Industrial Chemistry Library, Volume 10
Used Battery Collection and Recycling
Industrial Chemistry Library Advisory Editor: S.T. Sie, Faculty of Chemical Technology and Materials Science Delft University of Technology, Delft, The Netherlands
Volume 1
Progress in C 1 Chemistry in Japan (Edited by the Research Association for C 1 Chemistry)
Volume 2
Calcium Magnesium Acetate. An Emerging Bulk Chemical for Environmental Applications (Edited by D.L. Wise, Y.A. Levendis and M. Metghalchi)
Volume 3
Advances in Organobromine Chemistry I (Edited by J.-R. Desmurs and B. G6rard)
Volume 4
Technology of Corn Wet Milling and Associated Processes (by P.H. B lanchard)
Volume 5
Lithium Batteries. New Materials, Developments and Perspectives (Edited by G. Pistoia)
Volume 6
Industrial Chemicals. Their Characteristics and Development (by G. Again)
Volume 7
Advances in Organobromine Chemistry II (Edited by J.-R. Desmurs, B. G6rard and M.J. Goldstein)
Volume 8
The Roots of Organic Development (Edited by J.-R. Desmurs and S. Ratton)
Volume 9
High Pressure Process Technology: Fundamentals and Applications (Edited by A. Bertucco and G. Vetter)
Volume 10
Used Battery Collection and Recycling (Edited by G. Pistoia, J.-P. Wiaux and S.P. Wolsky)
Industrial Chemistry Library, Volume 10
Used B attery Collection and Recycling Edited by G. Pistoia
Via G. Scalia 10, 00136 Rome, Italy J.-P. Wiaux
Titalyse S.A., Route des Acacias 54 bis, CH-1227 Carouge, Geneva, Switserland
S.P. Wolsky Ansum Enterprises, 1900 Cocoanut Road, Boca Raton, Florida 33432, USA
2001 ELSEVIER
Amsterdam
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Preface
About 40 billion batteries were produced in the year 2000 and this number is increasing at approximately 5% annually. A large number of these batteries contain hazardous materials. Batteries also contain significant quantities of important materials. Consequently the uncontrolled disposal of batteries presents both a major risk to health and the environment and a significant waste of valuable material resources. Recognizing the importance of controlling battery waste disposal, worldwide government and industry efforts have been initiated to collect and recycle such wastes. Led by the OECD member states, legislation has been put in place mandating the collection and recycling of cadmium, lead and mercury batteries. Industry organizations have been established for the purpose of educating the consumer and developing collection/recycling programs. We may mention the Portable Rechargeable Battery Association (PRBA) and the Rechargeable Battery Recycling Corporation (RBRC) in the U.S.A., and the European Portable Battery Association (EPBA) and CollectNiCad in Europe. As a consequence of these laws and programs, increasing quantities of spent batteries are being collected and recycled. Recycling batteries with their varied chemistries is a difficult task. The success of the industry in meeting this challenge has been important to the advancement of this effort. We wish to express our deep gratitude to the contributors of the various chapters of this book and to the organizations and companies that have provided us general information and encouragement. Many of these groups have also contributed on a regular basis to the annual congresses organized first in the U.S.A. by one of us (S.P. Wolsky) - Seminar on Battery Waste Management - and later by others in Europe - Battery Recycling Congress. Our goal has been to present in one volume a systematic and updated summary of the important aspects of the battery waste issue. As such this book will be of interest to all those working in this important field.
G. Pistoia
J.-P.Wiaux
S.P. Wolsky
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vii
List of Contributors
J. DAVID, SNAM, 9 rue de la Garenne, F-38074, Saint Quentin Fallavier, France N. ENGLAND, The Portable Rechargeable Battery Association, 1000 Parkwood Circle, Atlanta, GA 30339, U.S.A. K. FUJIMOTO, Portable Rechargeable Battery Committee, Battery Association of Japan, Kikai,
Shinkou Kaikan Building 5F, 3-5-8 Siba-Kouen, Minato-ku, Tokyo 105-0011, Japan R. JUNGST, Lithium Battery R&D Department, Sandia National Laboratories, P.O. Box 5800, Albuquerque, NM87185-0613, U.S.A. W. McLAUGHLIN, Solid Team Inc., 148 Limestone, Claremont, CA 91711, U.S.A. D.G. MILLER, Toxco Inc., 3200 E. Frontera, Anaheim, CA 92806, U.S.A. K. L. MONEY, Inmetco, 245 Portersville Road, P.O. Box 720, Ellwood City, PA 16117, U.S.A. H. MORROW, International Cadmium Association, 9222 Jeffery Road, P.O. Box 924, Great Falls, VA 22066-0924, U.S.A. E. PAOLUCCI, Texeco, Via Pomarico 58, 00178 Rome, Italy A. PESCETELLI, Texeco, Via Pomarico 58, 00178 Rome, Italy A. TINE', Texeco, Via Pomarico 58, 00178 Rome, Italy N. WATSON, EPBA, Hazelwick Avenue, Crawley, Mallory House, West Sussex RH 10 1FQ, Great Britain D.B. WEINBERG, Howrey Simon Arnold & White, 1299 Pennsylvania Avenue, Washington, D.C. 20004, U.S.A. J.-P. WIAUX, Titalyse SA, 54bis Route des Acacias, CH-1227 Carouge, Geneva, Switzerland
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Table of Contents Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . List o f Contributors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Chapter 1. Environmental and Human Health Impact Assessments of
Battery Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1
H. Morrow Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2
Battery R a w Materials Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5
Manufacture o f Battery Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
10
Use and Maintenance o f Battery Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
15
Disposal o f Spent Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
17
Environmental and H u m a n Health Impact Assessments . . . . . . . . . . . . . . . 22 Cycle Life Analysis o f Battery Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
31
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
32
Chapter 2. Portable Rechargeable Batteries in Europe: Sales, Uses, Hoarding, Collection and Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35 J.-P. Wiaux Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
35
The European Market o f Portable Rechargeable Batteries . . . . . . . . . . . 39 Hoarding o f Portable Rechargeable Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 Batteries in Municipal Solid Waste ( M S W ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61 Collection o f Spent Rechargeable Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66 Collection Efficiency and Recycling Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
81
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
83
Chapter 3. Battery Collection and Recycling in Japan .............................. 87
K. Fujimoto Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87 Treatment of Spent Primary Dry Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88 Recycling of Spent Lead-Acid Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91 Collection and Recycling Activities for Portable Rechargeable Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
Chapter 4. Ni-Cd Battery Collection and Recycling Programs in the U.S.A.
and Canada . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
105
N. England, D.B. Weinberg, K.L. Money and H. Morrow Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105 The environmental issues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106 The NiCd Battery Recycling Problem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108 The Industry NiCd Battery Recycling Program . . . . . . . . . . . . . . . . . . . . . . . 109 The INMETCO NiCd Battery Recycling Process . . . . . . . . . . . . . . . . . . . . 113
Chapter 5. Environmentally Sound Recycling of Ni-Cd Batteries ............... 119 N. England
Introduction and Principal Findings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119 The Nature and Implications of Rechargeable Ni-Cd Battery Distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121 Ni-Cd Battery Recycling Esperiences Within the OECD ........... 123 The RBRC P r o g r a m - Canada and the U.S . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136 Lessons Learned w Recommendations for Action . . . . . . . . . . . . . . . . . . . . 137
Chapter 6. Nickel-Cadmium and Nickel-Metal Hydride Battery Treatments 147
J. David Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147 Treatment of Nickel Cadmium Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150 1. Types of Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
xi 2. Specific Processes for the Treatment o f Nickel C a d m i u m Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
155
T o d a y ' s Battery Recycling Companies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162 1. Europe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
162
2.
U.S.A . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
171
3.
Korea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
171
4.
Japan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Chapter 7. P r i m a r y
174
Battery Recycling in Europe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
N. Watson Battery Definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
177
Battery Collection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
177
Battery Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
191
Battery Sorting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
199
Integrating with Existing Recycling Operations . . . . . . . . . . . . . . . . . . .
209
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
222
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
223
Chapter 8. L e a d - A c i d B a t t e r i e s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
225
A. Pescetelli, E. Paolucci and A. Tinb Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
225
The Environmental and Health Impact . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225 Economical Aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
228
Lead Accumulator Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230 The Collection o f Spent Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
234
Comparison With Other Countries o f the European Union ..... 239 Collection Modes and Recycling Techniques . . . . . . . . . . . . . . . . . . . . . . 251 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Chapter 9.
Recycling The Lithium Battery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
D.G. Miller and W. McLaughlin
261
263
xii
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
263
Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
263
The Hazards and Safety Aspects of Recycling Lithium Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
267
Environmental Concerns of Recycling Lithium Batteries ...... 272 Sorting, Packaging, Storage, and Transporting of Lithium Batteries for Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 274 Lithium Battery Recycling Technologies . . . . . . . . . . . . . . . . . . . . . . . . . 277 The Toxco's Background and Processing Method . . . . . . . . . . . . . . . 279 Two o f Toxco's Typical Chemical Analyses . . . . . . . . . . . . . . . . . . . . . 282 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
Chapter 10. Recycling of Electric Vehicle Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
R.G. Jungst Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
295
Electric Vehicle/Hybrid Electric Vehicle Batteries . . . . . . . . . . . . . . 297 General Recycling Issues, and Drivers . . . . . . . . . . . . . . . . . . . . . . . . . . . . 304 Existing Methods for EV Battery Recycling . . . . . . . . . . . . . . . . . . . . . . 308 Optimized Recycling Processes for Advanced Batteries ........ 317 Recycling Prospects for Future Advanced Batteries . . . . . . . . . . . . . 320 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
Appendix A. Most Common Types of Commercial Batteries . . . . . . . . . . . . . . . . 329
Appendix B. Main Legislation on Battery Waste in the U.S.A. and E.U.
341
Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
369
Used Battery Collection and Recycling G. Pistoia, J.-P. Wiaux and S.P. Wolsky (Editors) 9 2001 Elsevier Science B.V. All rights reserved.
ENVIRONMENTAL
AND HUMAN HEALTH
IMPACT ASSESSMENTS
OF BATTERY
SYSTEMS
Hugh Morrow International Cadmium Association 9222 Jeffery Road Post Office Box 924 Great Falls, VA 22066-0924 USA
Abstract Total life cycle analyses may be utilized to establish the relative environmental and human health impacts of battery systems over their entire lifetime, from the production of the raw materials to the ultimate disposal of the spent battery. The three most important factors determining the total life cycle impact appear to be battery composition, battery performance, and the degree to which spent batteries are recycled after their useful lifetime. This assessment examines both rechargeable and nonrechargeable batteries, and includes lead acid, nickel cadmium, nickel metal hydride, lithium ion, carbon zinc and alkaline manganese batteries. Battery metals such as lead, cadmium, mercury, nickel, cobalt, chromium, vanadium, lithium, manganese and zinc, as well as acidic or alkaline electrolytes, may have adverse human health and environmental effects. The specific forms of these materials as well as the relative amounts present will establish the risks associated with that particular battery system. However, the degree to which such batteries are collected and recycled after their useful life may largely mitigate any such adverse effects. Landfill or incineration disposal options are not as desirable as recycling, but the risks associated with those options are not so unacceptably high as to require the phase outs of any existing battery technologies. Battery performance characteristics, likewise, are important in establishing the amount of potentially hazardous waste generated per unit of battery energy generated.
Rechargeable battery systems obviously enjoy a great advantage in this respect since they may be recharged and reused many times. However, other factors such as the battery voltage, ampere-hour rating, cycle life, charging efficiency and self-discharge characteristics may also be important in establishing the total amounts of hazardous waste generated per unit of battery energy and thus the total environmental impact per unit of battery energy. Safety issues have also become more important in recent years as more active battery chemistries have been developed. In particular, the presence of corrosive electrolytes and highly ignitable or explosive battery materials under certain conditions has become an issue which the battery industry must address. At present, it appears as if improvement in the recycling rates of spent batteries will produce the most substantial decreases in the environmental and human health impacts of battery systems. Introduction
Total life cycle analysis (LCA) is increasingly being utilized to establish the relative human health and environmental impacts of many products and processes. In these analyses, the total impacts, from the production of the raw materials for the product, through its manufacture, use and ultimate disposal are established, and then usually compared to other similar products. Environmentalists and regulators have used these principles to favor the displacement of one product in the marketplace with an allegedly "more environmentally friendly" product. Very often, however, it has been found that one product may exhibit high negative LCA impacts in one area, while another product may be deficient in another area. Such appears to be the case when various battery chemistries are compared. The components of a total life cycle analysis are generally agreed to consist of the following four basic steps: I.
Scope and Goal Definition
II. III.
Materials and Energy Inventory Environmental and Human Health Impact Assessments
IV.
Improvement Assessment
The scope and goal definition (Step I) is necessary in that most life cycle analyses may be as wide or as narrow as one wishes to make them. For example, one could define a
product life cycle analysis so widely as to include the production of the mining equipment used to mine the ore which produced the metal which went into the manufacture of the battery. Generally, however, these effects become normalized over so many other products as to become secondary effects of little consequence in the specific analysis of, for example, a rechargeable NiCd battery. The major area, however, which should be included, is the energy and emissions associated with the direct production of the raw materials used in the batteries. Thus, it is very important that the scope of a particular life cycle analysis be carefully defined and that comparisons between products be made on the basis of the same scope. In the case of batteries, the following stages are considered to be the major contributors to environmental and human health impacts and would be included in a life cycle analysis: 9
Battery Raw Materials Production
9
Battery Production Process
9
Battery Distribution and Transportation Requirements
9
Battery Use
9
Battery Recharging and Maintenance (Rechargeable Batteries)
9
Battery Recycling or Waste Management Option
Once these stages are established and the scope of the life cycle analysis reasonably well defined, then a complete materials and energy inventory analysis (Step II) must be performed on each of these stages to determine the overall materials and energy balances. As shown in Figure 1, the inputs of energy and materials on the left hand side for every stage in the manufacture, use and disposal of a battery are balanced by the outputs of usable products and environmental releases on the right hand side. To produce the least environmental and human health impacts, the environmental releases from all of these stages should be minimized. In carrying out life cycle analyses for battery systems, it becomes very quickly apparent that the inventory analyses for certain stages are insignificant compared to others. For example, the emissions associated with distribution and transportation of batteries and the appliances they power are spread out over so many billions of units as to be
Inputs
Outputs Battery Raw Materials Water Emissions
Battery& BatteryPack Production Procenes Energy
Airborne Emissions
Battery-Powered Devices & Applications Solid Wastes
Distribution & Transpo~ation Raw
Recycled Materials
Materials
Use, Recharging & Maintenance Usable Products
Recycling
Figure 1. Materials and E n e r g y I n v e n t o r y Analysis for Battery S y s t e m s
insignificant to the LCA of one single battery. Furthermore, sealed batteries have no emissions during normal use, and the emissions associated with the recharging of batteries depends very much upon the power generating infrastructure in a particular country. In countries dependent on high sulfur coals, the impact could be significant, but in countries with hydroelectric, nuclear, solar power or other clean energy sources, the emissions associated with recharging batteries are virtually non-existent. In any
event, these emissions, even in the case of dirty fossil fuels, also appear to be so spread out over so many applications as to have little effect on an individual battery's life cycle analysis. Each one of these stages will be considered in more detail below, but it appears as if battery raw material production, battery manufacture, battery performance during use, and battery recycling or disposal as waste are the most important stages in the comparative life cycle analyses of battery systems. The emissions associated with and the energy consumed during each of these stages will establish the environmental loading resulting from each battery system, which in turn may be converted into a human health and environmental impact analysis by assuming certain impact values for each of the materials emitted and energy consumed. A further factor particular to the evaluation of the life cycle analyses of battery systems is that their human health and environmental impacts must be normalized to the total lifetime energy output of the battery. In other words, impacts are expressed in terms of effects per kilowatt-hour of energy generated. This requirement is necessary since battery systems all differ considerably in their total lifetime energy output. Rechargeable batteries generally have higher total lifetime energy outputs than nonrechargeable batteries, and thus their environmental and human health impacts are lower. Put another way, it requires more non-rechargeable batteries to produce the same total lifetime energy as rechargeable batteries. Because the total lifetime energy of a battery system is important to its life cycle analysis, parameters such as operating voltage, ampere-hour rating, cycle life, charging efficiency and self-discharge characteristics may all become important factors in establishing a battery system's overall life cycle analysis.
Battery, Raw Materials Production Obviously, the first and most important factor in the inventory analysis stage is the overall composition of the battery system. Technically, a life cycle analysis can only be specifically performed on a specific battery composition, and there is often great variety in the compositions for batteries that nominally all belong to the same family. In addition, a rigorous life cycle analysis should consider every material in the battery, no matter how minute the environmental impacts may appear to be. The tendency in most life cycle analyses on battery systems to date has been to concentrate on the "hazardous materials" or "heavy metals" contained in those batteries while ignoring contributions which may arise from greater amounts of less high-profile substances. For example, life
cycle analyses of lead acid batteries usually focus on their lead content and ignore the sulfuric acid electrolyte. Most analyses of nickel-cadmium batteries dwell on the cadmium LCA contribution while minimizing the nickel and cobalt contribution. In a rigorous analysis, the contributions of every material must be considered. Some will indeed be found to be insignificant and have little or no effect on the final total impact, but others may have suprisingly large effects. Another factor which has yet to be properly evaluated and factored into battery life cycle analyses is the form of the material in the battery system itself. When evaluating the environmental and human health effects of battery materials, most analyses have assumed, for example in NiCd batteries, a single environmental impact value for nickel and all of its compounds or a single environmental impact value for cadmium and all of its compounds. Since these single values are usually derived from tests on a highly soluble species, they almost always overstate the environmental and human health impacts of the materials actually used in batteries. For example, in nickel-cadmium batteries, the relatively insoluble cadmium oxide is the compound normally used in the battery whereas the environmental and human health impact values are based on the highly soluble cadmium chloride. Thus, battery life cycle analyses usually represent the worst case scenario as far as human health and environmental impact are concerned. However, it is important to recognize the basis on which the environmental and human health impact values are assigned. In the case of zinc, for example, the surrogate compound used to derive impact values is zinc oxide which is a reasonable choice. In the case of some other metals, such as nickel and cadmium mentioned above, the impact values are based on the highly soluble species as surrogate compounds which very much overstates the relative risk. This problem has yet to be addressed in life cycle analyses of battery systems, and it is difficult to state how much it might affect them when it is addressed. These problems not withstanding, it is possible to examine general battery families and to make some analyses of these families based on generalized or average compositions, recognizing however that individual variations within the battery family may be considerable. The compositions of several such generalized battery families are indicated in Table I. These chemistries vary considerably, as shown by the three sets of data presented below (Fujimoto 1999, Morrow 1998 and Gaines 1994). This wide variation in battery chemistry is one of the primary reasons why it is so difficult to draw generalized conclusions about the relative environmental and human health impacts of one family of batteries compared to another family.
Table I. Various Nominal Compositions of Battery Families Battery, System Alkaline Manganese* Lead Acid* Nickel-Cadmium* Nickel Metal Hydride (ABs)* Nickel Metal Hydride (AB2)*
Nominal Composition, Weight Percent 30Fe - 20Zn - 15Mn 6 5 P b - 25H2SO4 30Fe - 30Ni - 15Cd 45Ni - 10Mg/A1 - 9Ce - 4Co 3 9 N i - 6 V - 6 Z r - 3 C r - 3 T i - 2.5Co
Nickel-Cadmium**
3 2 . 5 F e - 1 7 . 5 N i - 2 2 . 5 C d - 3Co
Nickel Metal Hydride**
4 2 . 5 N i - 1 7 . 5 F e - 7 . 5 C o - 12.5 Rare Earths
Lithium-Ion** Lead Acid*** Nickel-Cadmium(PBE)*** Nickel-Cadmium(FNC)***
2 2 . 5 F e - 1 7 . 5 C o - 7.5A1- 7 . 5 C u - 3Li 6 9 P b - 22H2SO4 14Fe - 26Ni - 18Cd 15Fe - 31Ni - 22Cd
Nickel Metal Hydride(ABs)***
4 4 F e - 2 9 N i - 5 Rare E a r t h s - 2 C o - 1Mn
Nickel Metal Hydride(AB2)***
4 4 F e - 2 4 N i - 7 V - 3 Z r - 2Cr- 1Ti
* Morrow 1998
**Fujimoto 1999
***Gaines 1994
The above data and data from other sources show some interesting trends in battery compositions over time. For example, the older NiCd batteries, which are the ones being collected and recycled now, tend to exhibit lower cadmium and cobalt values than the newer generations of NiCd batteries. There are also distinct differences in nickel and cadmium contents between industrial and consumer batteries. The battery industry generally agrees that consumer NiCds being collected today for recycling contained an average of 15% Cd. Industrial NiCds, on the other hand, may show a much wider variation, and levels from 7% Cd to 24% Cd have been noted in some industrial NiCds. Interestingly enough, a "Li-ion" battery actually contains very little lithium, and should more properly be designated an Fe-Co-A1-Cu-Li battery. These examples, however,
should be sufficient to demonstrate that using nominal compositions for battery life cycle analyses may introduce large factors of uncertainty into such analyses, and the compositional basis for any battery's LCA must be stated as part of the analysis results. The first analysis which obviously must be performed is to establish the emissions produced and the energy consumed during the production of the raw materials used for battery production. In the case of the metals utilized for the electrode materials in most batteries, the mining, smelting, and refining of the base metal, and their subsequent conversion into the specific form of the material utilized in the battery are the processes which must be addressed. Direct emissions of metals from the mining, smelting and refining of battery metals such as lead, cadmium, nickel, cobalt, zinc, manganese and many other metals are generally well-controlled and are subject to stringent regulation today. Metal emissions from the primary nonferrous smelters have diminished
Figure 2. Sources of Human Cadmium Exposure (Van Assche 1998) (the sources listed are arranged clockwise from: fertilizers, 42%)
considerably in the past twenty years as demonstrated by Canada's ARET (Accelerated Reduction and Elimination of Toxics) Program and the U.S. Environmental Protection Agency's TRI (Toxics Release Inventory) and 33/50 Programs. In addition, studies on the sources of human cadmium exposure, for example, indicate that only 6.3% of all human cadmium exposure comes from nonferrous smelting, principally zinc, lead and copper, and that only 2.5% arises from cadmium applications such as NiCd batteries. This data is shown graphically in Figure 2 and is based on studies in Europe (Van Assche 1998, Van Assche and Ciarletta 1992). Thus, it is clear that primary metals production processes do not contribute significantly to the environmental impact of the battery systems. A second environmental impact from the production of nonferrous battery metals arises because of the relative amount of energy utilized to produce a given quantity of the metal. In this case, the amount of energy necessary to produce a metric tonne may be related to the amount of greenhouse gases produced to create that energy. However, again, this may be too simplistic a view in that the amounts of greenhouse gases depend very much upon the types of fossil fuels used, air pollution control devices in place, and the nature of the energy producing combustion mechanisms. The energy consumed in the primary metal production of five common battery metals is summarized in Table II (Schuckert 1997). From an energy consumption standpoint, metals with low melting temperatures such as lead and cadmium, require less energy to produce, and thus have a lower environmental impact with respect to the generation of greenhouse gases. Metals which are produced by electrolytic processes or have high melting temperatures require higher energy inputs to produce and thus have higher environmental impacts with respect to greenhouse gases. Table II. Energy Consumed in Primary Metal Production Battery Metal
Ener~v (GJ/mt)
Manganese Nickel
54 200
Lead
25
Zinc/Cadmium
70
10 Nickel, for example, is produced by electrolytic processes and has a higher melting temperature, and thus requires higher energy to produce per metric tonne. However, in general, the levels of both metal emissions and greenhouse gas emissions which are produced in the production of battery metals are a small fraction of the total weight of the metals used in the battery. Thus, what is far more important in a total environmental impact analysis is whether or not a spent battery is recycled or disposed of by landfilling or incineration. If a battery is recycled, then the vast majority (>95%) of the weight of the battery does not produce an environmental impact. If the battery is landfilled or incinerated, then most of the materials in the battery are capable of producing an environmental impact. If all batteries were recycled to a similar degree, then compositional factors and primary metal production factors, as well as other factors to be subsequently discussed, would be more important. Finally, the conversion of the primary metal into the product and the form which are actually utilized in the battery system should be considered. For example, the electrode materials in lead acid batteries are normally cast lead or lead-alloy grids. The materials utilized in NiCd batteries are cadmium oxide and high surface area nickel foams or meshes. Technically, all of these factors should be considered to produce a detailed life cycle analysis. However, again, these differences are generally quite small compared to the principal variables- composition, performance and spent battery disposal option.
Manufacture of Battery, Systems Similarly, there is ample data available to demonstrate that the emissions associated with the manufacture of battery systems are minimal compared to those associated with the disposal of batteries into the environment. For example, studies have been made on NiCd batteries by both the Organization for Economic Cooperation and Development (OECD) and the Stockholm Environmental Institute (SEI) which indicate that the vast majority of cadmium in the manufacture of NiCd batteries partitions to the product and that only very small amounts are emitted to the environment. This result arises from both stringent regulations in place today, modem pollution control technology, and the general commitment to utilize valuable raw materials to the fullest extent possible. The partitioning of cadmium in the manufacture of NiCd batteries, according to the OECD (Organization for Economic Cooperation and Development 1994) and SEI (Stockholm Environmental Institute 1994) data, is summarized in Table III.
11 The SEI data is based mainly on earlier emission numbers for NiCd battery manufacturing, whereas the OECD monograph data represents updated emissions in the European Union as of 1994 compared to total volumes of cadmium utilized for NiCd battery production, based on information from the International Cadmium Association. All of this data indicates that most of the cadmium remains in the product and is not lost during NiCd battery manufacturing. A similar conclusion can be inferred with respect to nickel and cobalt, the other materials in a NiCd battery which might be likely to be regarded as "hazardous" and contribute to an adverse environmental impact. Iron, of
Table III. Partitioning of Cadmium in NiCd Battery Manufacturing Percent of Total Cadmium SEI Report OECD Monograph Industrial Consumer Industrial Consumer Air Emissions
0.10
0.00
0.01
0.01
Water Emissions
0.15
0.05
0.03
0.03
Solid Waste Product
2.75
2.45
0.50
0.50
97.00
97.50
99.46
99.46
course, is also present in major amounts, and, technically, should also be considered, but, as will be shown later, its environmental impact is quite low and therefore does not contribute significantly to the environmental impact of the NiCd battery system. Another set of data has been provided by a study on aqueous emission factors for cadmium in the Rhine River basin from 1970 to 1990 (Elgersma et al. 1992). This study was performed by the Delft University of Technology in the Netherlands and the International Institute for Applied Systems Analysis (IIASA) in Austria and was presented at the 1992 Seventh Intemational Cadmium Conference. This data, which is shown graphically in Figure 3, clearly shows that aqueous cadmium emissions for industrial NiCd battery manufacture have decreased from approximately 8 grams per kilogram of cadmium processed to less than 1 gram of cadmium per kilogram of cadmium processed in 1988. Similarly, aqueous cadmium emissions for consumer NiCd battery manufacture have decreased from 15 grams of cadmium per kilogram of cadmium processed in 1970 to about 1 gram of cadmium per kilogram of cadmium
12
Figure 3. Aqueous Emission Factors for Rhine River Basin, 1970-1990 processed in 1988. These 1988 aqueous cadmium emission levels correspond to approximately a 0.1% aqueous emission factor, in reasonable agreement with the data shown in Table III, and would probably be lower if based on 1995 or subsequent data. An additional point worth noting is that these significant decreases in NiCd battery manufacturing aqueous emissions were accomplished during the 1980s, the period of the highest growth rate in the NiCd market. In addition, two sets of data from the Battery Association of Japan (BAJ), formerly known as the Japan Storage Battery Association (JSBA), equally clearly demonstrate that the levels of cadmium emissions to air and water in Japan have decreased steadily over the period from 1980 through 1992 in spite of the greatly accelerated production of NiCd batteries in Japan during that same time period (Mukunoki and Fujimoto 1996). Japan is the world's largest producer of NiCd batteries, and currently accounts for over 70% of the world's NiCd battery production. If there is any country where potential environmental contamination by cadmium from NiCd battery manufacture should be
13
Percent of River Water Samples Above 10 ~g Cd/liter
Millions of NiCds Produced in Japan 1000
0.25%
8oc
i~i
.................................. -
600
0.20%
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1982
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Figure 4. Japanese River Water C a d m i u m Concentration and NiCd Battery Production
realized, it is Japan. Yet the data presented in Figure 4 for Japanese river
water
cadmium concentration and in Figure 5 for Japanese ambient air cadmium concentration respectively exhibit decreasing trends over these years in spite of eightfold increases in NiCd battery production. A more proper way of expressing average emissions associated with the manufacture of battery systems is to establish those emissions on the basis of the levels per KW-hr of battery energy provided, as the provision of stored energy is the function of a battery and batteries differ markedly in their ability to store energy. Such an analysis has been carried out (Geomet Technologies 1993) for industrial nickel-cadmium batteries intended for electric vehicle applications. These manufacturing emissions data are presented in Table IV.
14
Figure 5. Japanese Ambient Air Cadmium Concentration and NiCd Battery Production
Table IV. Metal Emissions in Production of NiCd Electric Vehicle Batteries* Grams Metal Emissions per KW-Hour Emission Sink
Nickel
Cadmium
Air
3.15
1.78
0.08
Water
2.28
1.31
0.05
Land Total
Negligible 5.43
*Source: Geomet Technologies
Negligible 3.09
Cobalt
Negligible 0.13
15 Typical industrial NiCd batteries utilized for electric vehicle applications have an energy density of 50 Watt-Hours per kilogram which corresponds to weight per unit energy of 20 kilograms per Kilowatt-Hour. Thus the metal emission levels associated with the manufacture of industrial NiCd batteries are roughly 0.04% of the total weight of the battery, in reasonably close agreement with most present day estimates which place total metal emissions during battery manufacturing between 0.01% and 0.1%. The data sets in Tables III and IV agree reasonably well, particularly if the decreasing levels of metal emissions with time are considered. Finally, a life cycle analysis conducted by SAFT (Comu and Eloy 1995) on nickelcadmium batteries for electric vehicle applications has established results comparable to those cited above. This study indicates that losses during the manufacturing process are likely to be on the order of 0.037% of battery weight for nickel and 0.008 - 0.019% of battery weight for cadmium, depending on the recycling options adopted. Once again, these estimates are consistent with other studies, and indicate very low environmental and human health impacts from the manufacturing stage of a battery's total life cycle analysis. Thus, the emissions associated with the manufacture of battery systems, like those associated with the production of the primary raw materials, are generally quite low, probably less than 1% of the total potential emissions if the spent battery were discarded entirely into the environment after use. While most of the data presented above are relevant mainly to nickel-cadmium batteries, which have been heavily studied because of regulatory and environmental controversy, the same general conclusions apply to other battery systems in general with some variations. Primary raw material production and battery manufacturing , in general, contribute only a small fraction of the environmental or human health impact that might be encountered in unconsidered waste disposal.
Use and Maintenance of Battery. Systems Rechargeable batteries are long-lived products which, in general, may be used many times over if they are charged and discharged properly. Non-rechargeable batteries are shorter lived products, but in some cases have higher initial energy density than rechargeable batteries. Since various battery chemistries, in general, will have different operating voltages, energy ratings and cycle lives (if they are rechargeable), each individual battery system will have different total lifetime energy characteristics. Even
16 within the same battery chemistry family, there will be variations to suit specific applications. Thus, an AA-sized NiCd battery may exhibit energy ratings from 500 milliampere-hours to 1,500 milliampere-hours depending on its intended use. Correspondingly, other properties, such as cycle life, may vary as well. In addition, total battery energy varies with battery size, the larger the battery in general the larger its total lifetime energy, other factors being equal. Therefore, it may be very difficult to establish an average set of performance characteristics for a battery family, but only to establish them for a very specific battery chemistry, size and type. Battery performance is importance because in determining any human health or environmental impacts of battery systems, these must be normalized to a unit energy basis, as previously noted for emissions associated with battery manufacturing. Thus, any emissions during any stage of the life cycle of the battery system must be divided by the total lifetime energy of the battery to obtain results which allow comparison amongst battery systems. The total lifetime energy of a particular battery system is the product of its voltage, capacity and cycle life. Strictly speaking, charging efficiency and self-discharge characteristics should also be taken into account, but in most life cycle analyses to date, they have not been. For example, the basic performance parameters of an AA-sized NiCd battery are summarized in Table V.
Table V. Basic Performance Parameters of AA NiCd Battery Parameter
Voltage Capacity Total Energy Cycle Life (80%DOD) Total Lifetime Energy
Range of Values
1.2 Volts 0.5 to 1.2 ampere-hours 0.6 to 1.4 watt-hours 700 to 1200 cycles 420 to 1680 watt-hours
Nickel-cadmium and nickel metal hydride batteries both operate at 1.2 volts, whereas alkaline manganese batteries produce 1.5 volts and lead acid batteries 2.0 volts. Lithium-ion batteries have an unusually high voltage, above 3.0 volts, which gives them a high energy density. Thus, all three of the parameters mentioned above - voltage, battery capacity, and cycle life - will be instrumental in establishing the life cycle
17 performance of a battery system. It is not just the composition of the battery alone which is important, and, as will be subsequently shown, it is the waste disposal option chosen for the battery which is perhaps even more important than either of these first two characteristics in determining life cycle impact. During the normal use and maintenance of a battery system, they are neither destroyed nor dissipated nor do they emit any harmful substances. Battery systems may be sealed or vented. If they are sealed, then no emissions occur during normal use and maintenance. If they are vented, then water vapor, hydrogen gas or oxygen gas may be vented, depending on the system and whether it is charging or discharging. A 1994 report (Stockholm Environmental Institute 1994), for example estimated that the dissipation rates for both industrial and consumer NiCd batteries were 0.01 percent per year. The International Cadmium Association believes, based on surveys of its NiCd battery producer members, that the dissipation rates are virtually zero, or so low as to be undetectable.
.~
However, a further consideration is the potential life cycle effect of each recharging cycle for the battery. The energy necessary to recharge a battery is generated by the primary power grid which generally operates on some form of fossil fuel. Combustion of fossil fuels result in the generation of greenhouse gases which can have an effect on a complete life cycle analysis, particularly if dirty fossil fuels are used or air pollution emission control devices are inadequate. In general, the emissions and life cycle effects associated with recharging are again small compared to those of battery disposal. One analysis (Schuckert et al. 1997) has measured the primary energy consumption during the production and utilization of both lead acid and nickel-cadmium batteries and their consequent effect upon carbon dioxide emissions and nitrous oxide emissions. In these cases, the amounts of energy required and greenhouse gases generated over the battery system's entire lifetime are lower for NiCd batteries than for lead acid batteries because of their higher cycle life, energy density and total lifetime energy even though the initial energy required to produce the NiCd battery is higher than to produce the lead acid battery.
Disposal of Spent Batteries In a life cycle impact analysis of battery systems, regardless of composition, performance and whether or not they are rechargeable, it is clearly the final disposal of the battery which determines its major environmental and human health impact. The
18 emissions associated with all the stages up to the disposal of the battery are perhaps only 1% to 2% of the total potential emissions if the battery is simply discarded into the environment. This figures changes, of course, if the battery is disposed of in a controlled manner such that emissions are minimized. Nonetheless, disposal is the key step in determining total environmental or human health impact. There are four possible options for the disposal of spent batteries- composting, incineration, land filling or recycling. Composting is obviously not intentionally utilized as most battery systems are simply not biodegradable. Incineration likewise is not a preferred option because of the low calorific value of batteries. They simply do not burn well, and their mass is not substantially reduced by the incineration process. However, incineration is utilized in some countries where land filling is not as viable an option to reduce volumes of combustible wastes. In Japan and some European nations which have little or no available landfill space, incineration of municipal solid waste (MSW) has become a necessity. Batteries which are invariably contained in municipal solid waste will not be reduced in volume by incineration and will most likely partition to the clinker ash or residue from the MSW incineration process. In some cases, small consumer batteries may be broken apart, battery materials oxidized or volatilized, and subsequently recondensed on the fine fly ash from the incinerator. Air emission pollution control devices should capture better than 99% of these fly ash emissions (Chandler 1995), but then the fly ash must generally be subsequently landfilled. All in all, however, incineration is not particularly well suited for the disposal of batteries, although it must be realized that incineration of the small consumer cells will invariably occur in some countries which utilize incineration for a large share of their municipal solid waste disposal. If, in fact, toxic or hazardous materials from batteries do concentrate in the fly ash from incinerators and that fly ash is captured by air emission control devices, then that ash must be disposed of as a hazardous waste in landfills. Ultimately what might be required is the derivation of a statistical probability of a specific chemical release of a specific concentration during a specific time period from the landfilled fly ash. There are, for example, provisional tolerable daily or weekly intakes (PTWIs) for certain materials established by the World Health Organization (WHO) which well might be used to limit the amounts of certain battery metals from land filling. Total life cycle impact analyses may be utilized to help establish those limits. However, it should also be mentioned that the WHO tolerable daily intake levels for cadmium range from 70 lag per day for the average 70-kg man to 60 lag per day for the average 60-kg woman.
19 Cadmium daily intake levels in most OECD nations have been decreasing steadily since the 1970s and today range from 10 to 20 pg per day, well below any levels of human health concem (Intemational Cadmium Association 1999). These relationships are shown in Figure 6.
Figure 6. Daily Cadmium Intake Levels for General Population
Thus, land filling of incinerator ash from batteries may not be a significant problem and releases through this waste disposal option may not be as great as feared by some. The two most likely options for the disposal of spent batteries today are land filling and recycling. Land filling is currently the most widely used option, as it is the most widely used disposal option for all municipal solid wastes in OECD nations. A recent report (OECD 1998) indicated that an average of 63% of the municipal solid waste in OECD
20 nations was land filled, an average of 17% was incinerated, and the balance of 20% was recycled or composted. However, even if batteries are land filled, it is by no means certain that this disposal option poses an immediate threat to human health and the environment. For example, a Swiss review by the University of Berne for the OECD (Eggenberger and Waber 1998) on landfill leachate data from landfills in Canada, Denmark, France, Germany, Italy, Japan and Switzerland indicated that the vast majority of leachate samples passed the World Health Organization's (WHO) recommended cadmium drinking water standard of 3 ~tg per liter. Some of the data included in this survey were obtained from 50-year old unlined landfills, which theoretically should represent a worst case environmental impact scenario. Thus, the present disposal of NiCd batteries in landfills does not appear to pose an unwarranted risk from the perspective of leaching cadmium into the environment and entering the human food chain. Even when considered on a long term basis, there is considerable doubt that the presence of land filled battery metals such as lead, zinc, and cadmium would have the catastrophic environmental effects which some have predicted. Studies on 2000-year old Roman artifacts in the United Kingdom (Thornton 1995) have shown that zinc, lead and cadmium diffuse only very short distances in soils, depending on soil type, soil pH and other site-specific factors, even after burial for periods up to 1900 years. Another study in Japan (Oda 1990) examined nickel-cadmium batteries buried in Japanese soils to detect any diffusion of nickel or cadmium from the battery. None has been detected after almost 20 years exposure. Further, it is unclear given the chemical complexation behavior of the metallic ions of many battery metals exactly how they would behave even if metallic ions were released. Some studies have suggested, for example, that both lead and cadmium exhibit a marked tendency to complex in sediments and be unavailable for plant or animal uptake. In addition, plant and animal uptake of metals such as zinc, lead and cadmium has been found to depend very much on the presence of other elements such as iron and on dissolved organic matter (Cook and Morrow 1995). Until these behavior are better understood, it is unjustified to equate the mere presence of a "hazardous" material in a battery with the true risk associated with that battery. Unfortunately, this is exactly the method which has been too often adopted in comparison of battery systems, so that the true risks remain largely obscured. These caveats notwithstanding, there is still little argument that the most preferred option for the disposal of spent batteries is obviously collection and recycling. Not only does this option greatly reduce any risk which may exist, but it conserves valuable
21 natural resources as well. Today, recycling is viewed as the best human health and environmental option for the disposal of spent batteries, and it is the fastest growing option. Lead acid batteries have already achieved impressive recycling rates, better than 90% in the United States, and growing all over the world. The questions surrounding recycling of NiCd batteries are not whether it is or is not the best disposal option, but only how to improve collection rates, how to finance collection and recycling programs to improve returns, how to label batteries to maximize collection, and how to measure recycling rates. With NiMH and Li-ion batteries, the issues are developing the recycling technologies to improve materials recovery. With the alkaline manganese and carbon zinc batteries, the questions revolve more around the economics of the collection and recovery processes. Obviously collection and recycling of a spent battery prevents the entry of the majority, probably greater than 98%, of the battery's weight into the environment after use. However, there are other environmental impact factors which also must be considered with regard to recycling. For example, when comparing battery systems, it is instructive to compare the relative energies required to recycle various battery systems. Nickeliron, nickel-cadmium and lead acid batteries are relatively easy to recycle because the reduction of nickel, iron, cadmium and lead oxides back to their pure metals requires less energy than the reduction of the oxides of other battery metals such as zinc, manganese, chromium, titanium, zirconium, lithium and the rare earth metals which are constituents of alkaline manganese, nickel metal hydride and lithium-ion batteries. Another factor is the emissions associated with the production of battery metals by the recycling process as opposed to production from virgin ore. There have been many studies to demonstrate that recycling requires far less energy input than production of metal from virgin ore (Gaines 1994), but there are also now studies to indicate that emissions from recycling are lower as well. One report (Geomet Technologies 1993) on electric vehicle NiCd batteries, for example, compares cadmium emissions from production and recycling and finds that recycling emissions are roughly 10 to 100 times lower. These results are summarized in Table VI. Considered from another point of view, three estimates of the degree of materials recovery from the recycling of NiCd batteries all place that recovery rate at greater than 99%. Similarly high recoveries would be expected for the recycling of nickel-iron and lead acid batteries, but recovery rates from recycling of alkaline manganese, nickel metal hydride and lithium ion batteries might be somewhat lower because of the high
22 Table VI. Cadmium Emissions from Production and Recycling NiCd Batteries* Production Emissions
Recycling Emissions
(grams Cd per KW-hr)
(arams Cd per KW-hr)
Air Water
0.28 to 3.6 0.40 to 2.4
0.0062 0.0014
Land
Negligible
Negligible
*Source: Geomet Technologies 1993
energies required and the difficulty of reducing some of the battery metal oxides present in these systems. For example, anywhere from 10% to 20% of the total weight of nickel metal hydride batteries might be lost in the slag during the recycling of these batteries due to the presence of very reactive metals (chromium, aluminum, magnesium, vanadium, zirconium, titanium, rare earth elements) which are strong oxide formers and very difficult to reduce. While it has been suggested that this slag could be utilized for other applications, some environmentalists and regulators argue that such "downgraded" applications do not constitute true recycling. Thus, it is possible to recover a very high percentage of the material in a spent battery, and no doubt recovery technology will improve in the future to allow high degrees of materials recovery from all battery systems. However, the efficiency of the collection process for spent batteries and the efficiency of the metal recovery process are both factors which will affect the overall environmental and human health impacts of battery systems.
Environmental and Human Health Impact Assessments Once a complete energy and materials inventory of all of the various steps in a battery's life cycle has been established, the next steps are to categorize the inventory items into various groups. In general, these impacts have been realized on three areas: 9 Natural Resources 9 Human Health Impacts 9 Ecological or Environmental Impacts
23 Determining the impact assessment requires classification of each impact into one of these categories, characterization of the impact to establish some kind of relationship between the energy or materials input/output and a corresponding natural resource/human health/ecological impact, and finally the evaluation of the actual environmental effects. Many life cycle analyses admit that this last phase involves social, political, ethical, administrative, and financial judgments and that the quantitative analyses obtained in the characterization phase are only instruments by which to justify policy. A truly scientific life cycle analysis would end at the characterization phase, as many of the decisions made beyond that point are qualitative and subjective in nature. The inventory analysis determines all of the energy and materials inputs in a battery's life cycle and all of the outputs which could have an environmental or human health impact. These outputs include direct emissions from all production and manufacturing processes, including emissions from the energy production processes, and from the use, maintenance, recycling or waste disposal of the battery. All of these emissions must then be considered on a normalized basis by dividing by the total lifetime energy of the battery. The results are total amounts of emissions per kilowatt-hour of energy. If the battery is not recycled, then virtually the entire weight of the spent battery must be considered as being dispersed into the environment, although as discussed previously, the true risk or immediate impact of land filled or incinerated and land filled batteries may be released over an extended period of time and only to a limited degree. The great controversy in life cycle analyses arises when specific impact assessment values are assigned for each particular material. There are many systems which have been proposed and the impact values vary widely. Strictly speaking, impact values should be very specific for the specific battery material involved. In practice, most systems employ generic categories such as "nickel and its compounds" or "lead and compounds" and employ human health and environmental impact data from surrogate compounds which are usually those which have been most studied in environmental and human health research. Unfortunately, this practice creates a worst case scenario analysis in that the surrogate compounds are almost always the highly soluble species of a metal compound, designed to yield rapid results in clinical tests, but not indicative of the manner in which battery compounds may behave. Thus, for example, cadmium chloride, the highly soluble cadmium compound and one often utilized in environmental and human health research, may be and often is used as the surrogate for all cadmium
24 metal and compounds, whereas the cadmium compounds present in NiCd batteries are the much less soluble cadmium oxide and cadmium hydroxide. Even worse, in many analyses, impact values appear to be assigned quite subjectively with no justification or methodology specified. Because of this problem, huge variations in environmental impact values exist from one method to another. Essentially, one can obtain any life cycle analysis result one desires simply by arbitrarily selecting artificially high or low environmental impact values. To have any validity at all, a life cycle analysis must be based on environmental and human health impact values which are rooted in quantitative, measurable indices of a material's effect on human, terrestrial or aquatic life. A 1997 comparison (Morrow 1997) compared the normalized life cycle analysis impact values for four rechargeable battery systems utilizing five different impact assessment techniques. Needless to say, the results were very inconsistent except that lead acid batteries consistently fared well because of their high recycling rate. All of the other battery systems ranged over the entire spectrum from relatively benign to the most toxic depending on the environmental impact assumptions chosen. For example, the five impact assessment evaluation methods reviewed in the 1997 comparison (Morrow 1997) were as follows: CML M e t h o d - Developed by The Centre for Environmental Science in Leiden, The Netherlands. The effects of water and air emissions of various chemicals on certain general areas such as eutrophication, energy depletion, greenhouse effect, acidification, winter smog, summer smog, heavy metals and carcinogenicity were expressed in terms of potential rather than real effects. EPS Method- The Environmental Priority in Product Design method was developed in Sweden by the Swedish Environmental Research Institute and the Swedish Federation of Industries. This system sets a value to a change in the environment through impacts on human health, biological diversity, production, resources and aesthetic values. Tellus Method- The Tellus Method is based on control costs of various air pollutants and considers factors such as carcinogenic potency ranking, oral reference dose ranking or a combination thereof.
25 Ecoscarcity M e t h o d - Defines a relationship for a given country of given area
between the critical level of a pollutant set by the limited carrying capacity of the natural environment and the actual anthropogenic emissions of that pollutant.
The
countries
evaluated by the
ecoscarcity method are
Switzerland, Netherlands, Norway and Sweden. 9 U.S. Environmental Protection Agency M e t h o d - Based on an analysis technique developed for EPA by the University of Tennessee, this method considers all major human health and environmental effects of the chemicals including persistence and bioaccumulation. It also includes weighting factors for the actual levels of emissions. These various evaluation schemes produce widely varying results. For example, in rating the metals utilized in various batteries systems, it was generally found that lead, cadmium and mercury consistently were listed as battery metals with the most adverse environmental or human health impacts. However, it was also noted that nickel, cobalt, chromium and even zinc were listed as materials of concern in some systems. Even more remarkable were some of the relative impact assessment values assigned to some battery metals relative to other battery metals. While this variation can be explained to some degree by the different bases used for the techniques, it also clearly indicates that a life cycle evaluation of a battery system will depend to a great extent upon the evaluation system chosen. For example, the relative environmental impact values assigned to six battery metals according to the five different evaluation techniques are summarized in Table VII. These values are all normalized to a maximum value of 100 which is the most adverse environmental impact effect to allow comparison across the five systems. There is really very little consistency across these environmental impact assessment methods except that the Swedish and Dutch systems rate cadmium the battery metal with the most adverse effects, while the Tellus and Ecoscarcity Methods rate mercury the most adverse battery metal. Zinc, manganese, nickel and even lead have relatively low effects except in the U.S. EPA system, which however is the one system which is most closely tied to actual quantitative assessments of environmental and human health toxicological end points. What is very surprising is the relatively low impact values for mercury in the Swedish and Dutch schemes given the general worldwide concern for mercury.
26
Table VII. Relative Environmental Impact Values for Battery Metals Utilizing Various Assessment Evaluation Methods Method
C__d_d
Ha
Pb
Ni
Mn
Z._.qn
CML
100.0
1.9
3.8
2.8
1.9
1.9
EPS
100.0
13.5
2.3
2.9
0.01
0.88
Tellus
65.2
100.0
21.3
5.6
0.15
0.15
Ecoscarcity
7.1
100.0
0.4
8.6
*
0.71
U.S. EPA
74.9
*
95.3
84.4
54.1
22.3
*Not evaluated by this method
Sweden and Netherlands appear to be much more concerned about cadmium and therefore their actions against nickel-cadmium batteries are not surprising. The conclusion must be that life cycle impact assessment values are, at best, estimates which are heavily biased towards particular area's, country's, organization's or individual's points of view and are often not really scientifically based. Of the five techniques considered above, only the U.S. EPA method appears to be largely based on scientifically established toxicological endpoints for human health and the environment, and even in the establishment of those endpoints, there are a considerable number of assumptions and judgments made as to the relative weighting factors utilized and surrogate compounds employed which affect the ultimate impact assessment.
Life Cycle Analysis of Battery Systems If the total energy and emissions of a battery during its entire lifetime production, use, maintenance and disposal are established, then divided by the total lifetime energy of the battery, the total emissions per kilowatt-hour of energy may be derived. These are separated into specific materials, usually elements, compounds or groups of compounds, for which specific environmental and/or human health impact assessment values are available. Utilizing these values, the overall relative life cycle environmental impact of a particular battery system may be established and compared to other battery systems. As previously discussed, these analyses involve many assumptions and
27 generalizations. In point of fact, accurate analyses can only be carried out on a specific battery composition with specific battery performance. Even then, the assumptions inherent in the impact assessment values, the manufacturing processes, the disposal options and all of the other steps discussed in this review create a large area of uncertainty. These uncertainties notwithstanding, it is useful and interesting to carry out an analysis on a specific battery to show how some of these variables will affect the overall analysis. At the 8th Intemational Conference on Nickel-Cadmium Batteries in Prague, Czech Republic, a paper (Morrow 1998) was presented which discussed the relative effects of performance and recycling on the life cycle impact assessment of nickel-cadmium batteries. An AA-sized NiCd battery with an assumed composition of 3 0 % N i - 15%Cd -
1%Co was studied even though the references and data in Table I clearly show that
these compositions could vary widely. The AA-sized consumer cell is, of course, a small (23-gram) sealed consumer cell, and thus there are no emissions during its use, maintenance or recharging, which would be small even if it were a vented cell. The range of performance parameters chosen were those previously presented in Table V. While the voltage for an AA-sized NiCd battery has remained the same over the years, the capacity of this cell and thus its unit energy have increased over the years. In 1990, the best AA-sized NiCd had a capacity of 0.5 ampere-hours, whereas in 2000, the best commercially available NiCd capacity in this size is about 1.2 ampere-hours. In addition, cycle life has generally improved, so that today's batteries have a higher total lifetime energy than yesterday's batteries. This statement is probably true of all battery systems, not just the nickel-cadmium system. If we assume that better than 98% of a battery's total environmental impact is contained in the battery itself and whether or not it is disposed of by incineration, land filling or recycling, then it becomes a relatively simple exercise to compute the environmental impacts of AA-sized NiCd batteries under the compositional and performance assumptions made above. A 23-gram NiCd battery will contain 6.90 grams of nickel, 3.45 grams of cadmium and 0.23 grams of cobalt. From previous analyses, these three materials in the NiCd battery will be the ones which will produce the largest adverse environmental effects even though there may be moderate amounts of steel, plastic, copper and electrolyte present as well. If we assume that the entire weight of the battery upon disposal represents an emission or output to the environment, then the "heavy metal waste" generated per kilowatt-hour of total lifetime battery energy is as
28 summarized in Table VIII. Two figures are shown, one for the lowest lifetime energy (420 watt-hours) and one for the highest lifetime energy (1680 watt-hours). It is immediately obvious that the highest energy NiCd exhibits the lowest amount of heavy metal waste generated when expressed in terms of grams per kilowatt-hour of total lifetime battery energy. The lowest energy NiCd correspondingly exhibits the highest amount of heavy metal waste per unit of lifetime battery energy. As expected, the amounts of the individual heavy metal wastes generated are directly proportional to the battery's assumed composition. If higher or lower nickel, cadmium or cobalt contents are utilized, then the values for those metals will shift in direct proportion.
Table Vlll. Heavy Metal Waste Generated for AA-Sized NiCd* Batteries Waste Generated, grams per KW-hr Element
Hi2hest Energy
Lowest Energy
Cadmium
2.05
8.21
Cobalt
0.14
0.55
Nickel
4.10
16.43
*Assumed Composition: 3 0 % N i - 15%Cd- 1%Co
Once the ranges of heavy metal wastes generated have been established for an AA-sized NiCd battery of an assumed composition, the next step in the analysis is to assess the environmental and human health impacts of those wastes. While there are many different techniques for assessing the environmental and human health impacts of various materials, the preferred method which will be utilized in this analysis is the one developed for the U.S. Environmental Protection Agency by the University of Tennessee (Davis et al. 1994). This method considers all the major human health and environmental effects including persistence and bioaccumulation which are really relevant to organic compounds but not to metals. This method also includes weighting factors for the actual total levels of emissions. Under this ranking and scoring system, "inherent hazard values" are assigned to various chemicals depending on their quantitative effects on human health and environmental toxicological endpoints. These human health endpoints include both acute and chronic effects, ingestion as well as
29 inhalation, carcinogenicity considerations and other effects such as mutagenicity and reproductive effects. A set of appropriate factors for aquatic and terrestrial organisms are similarly incorporated into the scoring system. The human health and environmental factors are then multiplied by the exposure potential which includes parameters expressing biological oxygen demand half-life, hydrolysis half-life and an aquatic bioconcentration factor. It is felt that this system is probably one of the better impact assessment systems available today because it assigns impact values based on quantitative scientific data rather than subjective "concem" over a chemical which is often based on perception rather than scientific data. On the other hand, the bioaccumulation and persistence factors have already been shown to be not particularly relevant to metals per se. In the future, altemative evaluation systems such as solubility and transformation characteristics of metals and metal compounds, and models such as the biotic ligand model will be found to be much more appropriate for evaluating the human health and environmental impacts of battery metals. If the environment impact assessment values for the U.S. EPA method shown in Table VII are combined with the heavy metal waste data for nickel, cadmium and cobalt shown in Table VIII, environmental impact assessment values per unit of total battery energy for each of the three metals may be derived. The sum of these three values then yields an approximate environmental impact value for an AA-sized NiCd battery of an assumed composition and an assumed range of performance and total lifetime energy. The lowest impact values are associated with the highest set of performance parameters of capacity and cycle life, while the highest impact values are associated with the lowest set of capacity and cycle life performance parameters. This data may be further analyzed to establish the respective impact values when various percentages of the NiCd batteries are recycled. Such an analysis is shown in Table IX for two levels of recycling, 0% and 40%. For each level of recycling, the range of impact values for each element corresponding to the highest and lowest performance parameters are shown. As expected, recycling of 40% of the NiCd batteries results in a 40% reduction in the environmental impact values associated with NiCd batteries. What is perhaps more surprising is that performance can have a marked effect on the total life cycle environmental impact associated with NiCd batteries. The data indicate that, if both capacity and cycle life of an AA-sized NiCd battery can simultaneously be realized at the top end of the assumed ranges, then total life cycle risks may be reduced by a factor of four compared to those batteries with performance at the bottom end of the assumed ranges.
30
Table IX. Environmental Impact Values per Kilowatt-Hour Lifetime Energy For AA-Sized NiCd Batteries at Two Recycling Levels Environmental Impact Values p e r K W - h r Element
0 % Recycling
4 0 % Recycling
Nickel
346 - 1384
208 - 831
Cadmium
154 - 614
Cobalt TOTAL
92 - 369
7 - 27
4 - 16
507 - 2025
304 - 1216
The relative contributions to the environmental impact values for AA-sized NiCd batteries are further shown graphically in Figure 7 as functions of both battery
r/3
=
~ g h Performance
2,500
1.620
a * "~.
~
L_ 5.A~;
Cobalt
~~!
Nickel
1,215
1,~0
810
~:~ 500 Z
Low Performance
405
405
3~
203
o 0%
20%
40%
60%
Percentage of NiCd Batteries Recycled
Figure 7. The Effects of Recycling, Performance and Composition on the
Environmental Impact Values for AA-Sized NiCd Batteries
I0!
80%
31 performance ranges, degree of recycling and the individual contributions made by the major battery metals. It is evident that high performance batteries have lower environment impacts than lower performance batteries. It is also clear that increased recycling rates drastically lower the environment impacts associated with these batteries. In the particular environmental impact analysis technique (U.S. EPA) used in this analysis, nickel contributes the greatest impact, followed by cadmium. Cobalt contributes very little environmental impact at all. The lower performance batteries are, in fact, the ones being collected and recycled today, and these results suggest that in today's situation, the most effective way to lower environmental impacts is to increase the recycling rate. Steady improvements in the performance of batteries will also mean that the batteries being produced today and collected 5 to 10 years from now will pose less risk to the environment than those being collected now. Finally, the individual environmental impact contributions of nickel, cadmium and cobalt in this example are based on assumptions and are somewhat fixed by the battery system. It probably will not be possible to vary, for example, NiCd battery chemistry in a manner significant enough to have as major an effect on total life cycle risk as the degree of recycling and battery performance have.
Conclusions
From the foregoing analysis, it is concluded that the most effective methods to reduce total battery life cycle environmental impacts are to increase recycling rates, to improve battery performance, and to lower hazardous material contents provided that this does not compromise battery performance. It is further concluded that the waste battery disposal step is, by far, the single most important factor in determining the total environmental and human health impact of a battery system over its entire life cycle. Finally, it must be noted that present-day environmental impact assessments of battery systems rely on enormous assumptions regarding battery composition, battery performance, and the environment impacts of battery materials. Until such a time as standards are developed for life cycle analyses of battery systems, it will be almost meaningless to compare battery systems on this basis, unless assumptions are clearly stated and analyses are applied in a uniform manner. It will also be necessary to accurately determine the actual contributions made in all of the various life cycle stages of a battery instead of being forced to assume that they are negligible because of lack of accurate and pertinent information.
32 References
Chandler 1995, "Cadmium in Municipal Solid Waste Management Systems," Sources of Cadmium in the Environment, Inter-Organization Programme for the Sound Management of Chemicals (IOMC), Organization for Economic Cooperation and Development, Paris, France. Cook and Morrow 1995, "Anthropogenic Sources of Cadmium in Canada," National Workshop on Cadmium Transport Into Plants, Canadian Network of Toxicology Centres, Ottawa, Ontario, Canada, June 20-21, 1995. Cornu and Eloy 1995, "Nickel Cadmium Batteries: Life Cycle Analysis in the Electric Vehicles Application," The Seventh International Seminar on Battery Waste Management, Deerfield Beach, Florida, November 8, 1995. Davis et al. 1994, "Chemical Hazard Evaluation for Management Strategies: A Method for Ranking and Scoring Chemicals by Potential Human Health and Environmental Impacts," Report prepared by The University of Tennessee, Center for Clean Products and Clean Technologies for the Waste Minimization, Destruction and Disposal Research Division, Risk Reduction Engineering Laboratory, U.S. Environmental Protection Agency, Cincinnati, Ohio, EPA/600/R-94/177, September 1994. Eggenberger and Waber 1998, "Cadmium in Seepage Waters of Landfills: A Statistical and Geochemical Evaluation," Report of November 20, 1997 for the OECD Advisory Group on Risk Management Meeting, February 9-10, 1998, Paris, France. Elgersma et al. 1992, "Emission Factors for Aqueous Industrial Cadmium Emissions in the Rhine River Basin: A Historical Reconstruction for the Period 1970-1988," Edited Proceedings Seventh International Cadmium Conference- New Orleans, Cadmium Association (London), Cadmium Council (Reston VA) and International Lead Zinc Research Organization (Research Triangle Park NC). Fujimoto 1999, "Collection and Recycling Activities for Portable Rechargeable Batteries in Japan," Proceedings of the 5th International Battery Recycling Congress, Deauville, France, September 27-29, 1999.
33 Gaines 1994, "Energy Use and Emissions in the Production and Recycling of Electric Vehicle Batteries," Report of December 13, 1994, Energy Systems Division, Argonne National Laboratory, United States Department of Energy, Argonne, Illinois. Geomet Technologies 1993, "Nickel-Cadmium Batteries for Electric Vehicles- Life Cycle Environmental and Safety Issues," Final Report No IE-2629 prepared for the Electric Power Research Institute (EPRI), December 1993. International Cadmium Association 1999, "Cadmium- A Problem of the Past, A Solution for the Future," International Cadmium Association, Brussels, Belgium and Great Falls, VA, 1999. Morrow 1997, "The abuse of life cycle analyses for comparison of battery systems," Materials Solutions for Environmental Problems, Proceedings of the International Symposium sponsored by the Materials Science and Engineering Section of The Metallurgical Society of CIM, 36th Annual Conference of Metallurgists of the Canadian Institute of Metallurgists, Sudbury, Ontario, Canada, August 17-20, 1997. Morrow 1998, "The Importance of Recycling and Performance to Life Cycle Analyses of Nickel Cadmium Batteries," 8th International Nickel-Cadmium Battery Conference, Prague, Czech Republic, September 20-21, 1998. Mukunoki and Fujimoto 1996, "Collection and Recycling of used Ni-Cd Batteries in Japan," Sources of Cadmium in the Environment, Inter-Organization Programme for the Sound Management of Chemicals (IOMC), Organization for Economic Cooperation and Development, Paris, France. Oda 1990, "In-Ground Burial Test for Ni-Cd Batteries," 2 nd Intemational Seminar on Battery Waste Management, Deerfield Beach, Florida, November 5-7, 1990. Organization for Economic Cooperation and Development 1994, Risk Reduction Monograph Number 5: Cadmium, OECD Environment Directorate, Paris, France. Organization for Economic Cooperation and Development 1998, Towards Sustainable Development: Environmental Indicators, OECD Group on the State of the Environment, Paris, France.
34 Stockholm Environmental Institute 1994, Accounting for Cadmium, Stockholm Environmental Institute, London, UK. Schuckert et al. 1997, "Life cycle engineering as an environmental management t o o l Comparison of nickel and lead traction battery systems," Materials Solutions for Environmental Problems, Proceedings of the International Symposium sponsored by the Materials Science and Engineering Section of The Metallurgical Society of CIM, 36 th Annual Conference of Metallurgists of the Canadian Institute of Metallurgists, Sudbury, Ontario, Canada, August 17-20, 1997. Thornton 1995, "Heavy metal migration in soils and rocks at historical smelting sites," Environmental Geochemistry and Health (1995), 17, pages 127-138. Van Assche 1998, "A Stepwise Model to Quantify the Relative Contribution of Different Environmental Sources to Human Cadmium Exposure," 8th International
Nickel-Cadmium Battery Conference, Prague, Czech Republic, September 20-21, 1998. Van Assche and Ciarletta 1992, "Cadmium in the Environment: Levels, Trends and Critical Pathways," Edited Proceedings Seventh Intemational Cadmium Conference New Orleans, Cadmium Association (London), Cadmium Council (Reston VA) and Intemational Lead Zinc Research Organization (Research Triangle Park NC).
Used Battery Collection and Recycling G. Pistoia, J.-P. Wiaux and S.P. Wolsky (Editors) 9 2001 Elsevier Science B.V. All rights reserved.
35
P O R T A B L E R E C H A R G E A B L E B A T T E R I E S IN E U R O P E : SALES, USES, HOARDING, COLLECTION
AND RECYCLING
Jean-Pol Wiaux Titalyse SA, Route des Acacias, 54bis, CH-1227 Carouge, Geneva, Switzerland
1. INTRODUCTION During the year 2000, the total worldwide battery market value reached approximately 30-35 billion euros.Four major market segments can be distinguished for the batteries: primary, starting lighting and ignition (SLI), industrial rechargeable and portable rechargeable. The primary battery sales account for one third of this market segment where the main technology is represented by alkaline batteries. This market is increasing on a 5% per year basis with no major change or technology rupture foreseen (Pilot - 2001). The second largest market segment is represented by industrial batteries where the leadacid battery used for stand-by in telecommunication or industry, railways, aviation is dominating. Nickel-cadmium batteries are expected to gain market shares thanks to their greater reliability and safety but also because of their uses in advanced applications with higher added value. The third market fraction is the traditional SLI battery application field which is under development due to an increasing demand for electrical and electronic applications in cars, like air conditioning systems and alterno-starters. To compensate the related demand for DC power, major car manufacturers have decided to increase the voltage of the battery unit from 12 volts to 42 volts. The last market fraction is represented by portable rechargeable batteries (PRB).
1.1.
Portable Rechargeable Batteries
The portable rechargeable battery market account for 20% of total batteries sales. It is a
36 market driven by the most advanced electrical and electronic equipment (EEE) in the fields of computing, communication, household equipment and all the portable electrical devices like cordless power tools, tooth brushes, dust busters, CD and MD players and the future generations of portable electronic equipment. This market segment was multiplied by a factor greater than 3 in the last ten years and is foreseen to maintain a significant growth in the near future. It is worth mentioning that nickel-cadmium (Ni-Cd) batteries have been the first type of portable rechargeable battery to take advantage of this market evolution. If a cumulative value is considered for the sales of Ni-Cd batteries from 1980, one reaches a total value of more than 150,000 tonnes of portable Ni-Cd batteries introduced in Europe between 1980 and 2000 (CollectNiCad- 2000). Until 1995, the largest fraction of Ni-Cd batteries introduced into the market was in household and electronic equipment. The emergency lighting units market has been in constant but moderate growth during the 1990's. From 1995, the cordless power tools application has taken a dominant position for these batteries (see also Figure 4) both in consumer and professional applications. A ten to twenty percent annual market increase has been observed during the last three years (Black&Decker 2001). Finally, the market share of Ni-Cd batteries in the electronic appliances has been replaced by Ni-MH and Li-Ion technologies as a consequence of a market driven evolution. One of the main features of this market is that the largest fraction (95%) of portable rechargeable batteries is sold incorporated in electrical and electronic equipment. Only a minor fraction (<5%) is sold individually as substitutes for primary batteries and/or as replacement batteries. 1.2. The Presence of Portable Rechargeable Batteries in the Environment
A very limited number of studies have been devoted to the analysis of the presence of batteries in municipal solid waste (MSW). The specific presence of Ni-Cd portable batteries has received some recent attention due to the increasing use of cadmium in batteries. In this context, Chandler's study is usually taken as a reference even if it was performed on a limited amount (2.5 tonnes) of materials (Chandler-1995). Several authors of scientific publications related to the composition of municipal solid waste have concluded, in a simplified intellectual approach, that, because Ni-Cd
37 batteries represent the major application for primary and secondary cadmium metal, the major source of cadmium in MSW streams is just Ni-Cd batteries. This statement is based on the implicit assumptions that: - there is a direct proportional correlation between the use of cadmium in Ni-Cd batteries and the concentration of cadmium in MSW. - there is no other source of cadmium in MSW streams than applications where cadmium metal is used. In order to present an alternative opinion to the erroneous assumption of these authors, this issue will be analyzed in this chapter on the basis of published data and field measurements. If portable rechargeable batteries that have been sold with EEE for the last ten to fifteen years are not introduced in MSW streams, their presence in other streams needs to be identified and evaluated quantitatively. The work carried out by two national collection programs for spent batteries and by CollectNiCad is presented in this chapter. (CollectNiCad is an industry initiated and financed program with a commitment to collect 5,000 tonnes of Ni-Cd batteries in 4 years [1999-2003]). It demonstrates the willingness of the portable rechargeable battery industry to clearly identify the presence of its products in the various market positions and waste streams (Figure 1). A consumer survey made on the hoarding effect in France and the evaluation of quantities of batteries in MSW in France and the Netherlands will be illustrated. Consolidated data on collection of portable rechargeable batteries will be supplied. The description of this issue via the Ni-Cd portable battery case will illustrate the effort and initiative taken by the industry to clarify this problem. Complementary information on the practice of landfill of spent batteries and the management of industrial waste streams will be supplied. Finally, the synergistic effect of the collection of batteries from the de-manufacturing of waste electrical and electronic equipment (WEEE) will be addressed. In order to give a broader perspective to this Section, reference is made to the recently published Euphemet study (Scoullos-2000) on Policy of Heavy Metals (Hg, Cd, Pb) in the European Community. From several scenarios considered by the authors of the report, one can extract two broad conclusions on the future of the rapidly changing
38 world of portable rechargeable batteries in general and of nickel-cadmium batteries in particular: 1. The Ni-Cd battery technology is hundred years old, but it has been through a significant market development only during the last twenty years. It can be considered, at the human scale, as a young technology we are learning to live with. In the last five years, a decline of the use of Ni-Cd batteries has occurred in low drain applications, while there was a large market development in high drain and safety applications. Consequently, when considering both the past and the medium term future of this technology, it cannot be classified as declining. 2. The authors of the Euphemet study support the concept that a controlled market introduction, where the close loop is secured by market actors, is one of the preferred options for the long term management of cadmium and its use in applications like batteries. In other words, marketing, collection and recycling of portable rechargeable batteries is a viable option to cadmium management in a sustainable economy when
industry's
strategy integrates
environmental
protection.
Figure 1. The Presence of Portable Rechargeable Batteries in the Environment
39 2. THE EUROPEAN MARKET OF RECHARGEABLE BATTERIES
2.1.
Battery Sales
During the nineties, the portable rechargeable battery industry has invested up to 5% of its turnover into the development of alternative sources of portable electrical energy. Figure 2 represents the market evolution of portable rechargeable batteries during the last ten years. In 1999, the total number of cells introduced into the market exceeded 3.0 billion cells. The data presented in Figure 2 demonstrate that the rechargeable battery industry has been committed to a technological development by which the offer to the end-user has been enlarged from two basic systems in 1990 (lead-acid and nickelcadmium) to five systems in the year 2000 (with the addition of nickel-metal hydride [Ni-MH], lithium-ion [Li-Ion] and lithium-polymer).
The evolution of the market according to the number of cells on a world wide basis is presented in Table 1 which has been compiled by Nomura Institute in Japan. For the year 2000, it has been estimated that Ni-Cd batteries have had a slight decrease in sales based on cells numbers. For Ni-MH batteries, there is an increase of more than 10% of the sales in the EU market. A higher market increase is observed for lithium-ion and lithium-polymer batteries. It is particularly difficult to evaluate the number of portable rechargeable batteries (cells) delivered in Europe due to the fact that rechargeable batteries are sold, by more than 95%, incorporated in electrical and electronic equipment. Consequently, many factors are influencing the reliability of data obtained from battery manufacturers. Indeed, the european rechargeable battery industry has no control of the transboundary movements of f'mished products with incorporated batteries. Early in 2000, CollectNiCad has issued the first data related to the number of Ni-Cd cells introduced into the european market according to market segments by applications (CollectNiCad 2000). The data compiled by CollectNiCad are presented in Figure 3. It has been calculated that approximately 340 million cells are sold effectively in Europe for an equivalent weight of 13,000 Tonnes. These cells are sold mainly assembled in power packs varying from 20 to 500 grams or more. An estimation of the european market for other types of cells has been made and is presented in Table 2. It is estimated that the number of Ni-MH and Li-Ion cells as well as portable lead-acid cells sold in Europe represent 25% of the world market. When the
40 market data are considered on a weight basis, one has to differentiate the cell weight according to the chemistry. Such a differential approach is also supplied in Table 2. The quantity of portable rechargeable batteries sold in Europe would be close to 35,000 tonnes or twenty percent of the total portable batteries market (primary and rechargeable).
Figure 2. Market Evolution of Portable Rechargeable Batteries in Europe (Pb-acid at the bar bottom, Li-polymer on top of the 1999 bar)
2.2. Evolution of the Applications of Portable Rechargeable Batteries Portable Ni-Cd batteries have experienced major changes in the last ten years. At the beginning of the nineties, these batteries, incorporated in EEE for household, leisure, audio- and video-communication equipment, were sharing the majority of the market. This is presented in Figure 4, which indicates the evolution of the relative percentage of sales for the last ten years. Emergency lighting applications were second and have maintained a constant position on the market. During the second half of the nineties, the EEE applications have required new technical features from rechargeable batteries
41
Average Weight I cell in grams
Millions cells/year
TotalW=ght Tonnes/y.
Market Share %
22 48 55 26 22 14
28 12 5 10 54 50 159
616 576 275 260 1188 700 3615
4.8 4.5 2.1 2.0 9.3 5.5 28.3
120
26
3120
24.4
Pow~ Tools (P.T.) CordlessTool
41
138
Olhers Medic~
20
Applications Bectd(~ and Bectronic r ~ _ . ~ ~ (~=r-~.=) l-busel'~d Equipment Dust Buster Toys Audio-Video SingleCells& Others Cordless Ph. Sub-total
Ughting (EL) Emergencylight
4
~lit~
s
Weight per Cell
37.8
200
1.6 1.6
12793
100
200
40
TOTAL C,~culatedAverage
44.2
338
Figure 3. Market Data for Portable Rechargeable Ni-Cd Batteries in Europe (1999) (data by application)
Table 1. Worldwide Production of Portable Rechargeable Batteries (millions of cells) (Source: Nomura institute and CollectNiCad 2000)
Yeas N-~ N-M-I U-Ion
1997 14~ 643 195
Total
333 2867
% 1988 % %_r % 5567~ 1 4 1 3 51.16% 1437 44.41% 1350 25(~A 7"/3 2 Z 9 9 % 1049 3 3 1 1 % 1233 7.60% 276 999% 411 129-P/~ Q(~,~ Q18 Q01% 1A9 Q09% 10 11.69% 303 1QS~A 333 94"PA 333 1(I).03% ~ 1 8 l(n(~/0 31684) 1(I103~ 3460
% 39CE% 3468% 17.34~ Q29% 86-PA
42 Table 2. Evaluation of Market Data for Portable Rechargeable Batteries in Europe (1999) (Source CollectNiCad)
European Market Portable Rechargeable Batteries CollectNiCad Evaluation NiCd NiMH (*) Sealed Pb Acid (*) Li-lon (*) Total
Cells Average 1999 Units Weight per cell in millions in k~l Tonnes 338 0.038 12844 260 0.02 5200 75 0.2 15000 103 0.018 1854 34898
(*) European market as 25% of the world market
PORTABLE
16000 ,,i
Ni-Cd
.
-
SALES
IN EUROPE
. . . . . . . . . . . . . . . . . . .
,,
14000
~" [~ ] POWERTOOLS Iv' 1 2 0 0 0 ~ = a=mG~cv _ ~'f~
BATTERIES
10000 8000
0
6000
O
4000
_
I 1 ~TOTAL ~~~>'~
-
2000 =E
0
-
.
--~
.
,,<
~
,~
q;
Figure 4. Portable Ni-Cd Sales in Europe: Historical Evolution and Forecast (Source: CollectNiCad)
q;
q,-..,
43 and substitution of Ni-Cd batteries with other technologies has occurred in this market segment. At the same time, the portable Ni-Cd batteries used for cordless power tool (CPT) applications have had an important market development due to the end user requirement for higher power and optimum cost/performance ratio. The portable rechargeable battery market has seen the appearance of technologies like Ni-MH, Li-Ion and Li-Polymer, as the market has required batteries with improved energy to weight and volume ratios in a given capacity range. By offering a lower weight, especially the lithium-based batteries were responding to this market demand. On the opposite, when high power and high current drains are required together with extreme operating temperatures, the Ni-Cd battery has reinforced its market position. 2.3. Ni-Cd Industrial Battery Market The stability of the industrial Ni-Cd battery sales during the last ten years has been confirmed (Figure 5). Uninterruptible power supply (UPS) applications are taking the largest market share. Railways applications will maintain their development in countries like U.K., France, Spain and Italy. The back-up power to photovoltaic units represents a speciality market in countries where the equipment has to be used in a wide temperature range. A large market was expected from the electric vehicle application, which did not developed to a significant level during the last five years. It is worth mentioning the industry initiative to secure 100% recycling of the batteries in this market segment. Indeed the industry remains the owner of the battery during its service life while the client is paying a leasing fee for its use. This commercial practise secures a 100% collection efficiency of the batteries at end of life. A speciality market exist in the aviation sector for engine start-up and emergency electrical power supply. Space and defence represent minor but stable market segments.
3. HOARDING OF PORTABLE RECHARGEABLE BATTERIES
In November 2000, a consumer survey was performed on the hoarding (home storage) of portable rechargeable batteries in France. The results are based on 1,010 "face to
44
Figure 5. Industrial Ni-Cd Sales in Europe: Historical Evolution (in each bar, from bottom to top: Railways, UPS, Aviation,
EV, Space&Defence) (Source CollectNiCad)
face" interviews performed in private households. The survey was performed with a sample of consumers representative of the french population. At the time of the survey, there was no national collection program in activity for the collection of all types of batteries but only private and/or community initiatives as well as a one-year-old program for the collection of rechargeable batteries initiated by SCRELEC. The portable electrical and electronic equipment referred to in the study as "equipment" includes a rechargeable battery and its charger. It was specifically addressed during the interviews under the french generic term of rechargeable equipment. In a similar approach, the replacement batteries mentioned in this report are portable rechargeable batteries. The interview was specifically oriented to the acquisition and ownership of portable electrical and electronic supplies ("the equipment") associated with portable rechargeable batteries and chargers. In this summary report, the results are presented for the following categories of equipment:
45 1. 2. 3. 4.
camcorders, portable audio (compact disc, walkman, etc), dust busters and kitchen aid equipment, shavers and toothbrushes,
5. home cordless phones, 6. mobile phones, 7. portable computers, 8. pocket organisers, 9. cordless power tools, 10. toys, 11. home alarm systems.
3.1.
Definitions
The understanding of the analysis of the results obtained during the survey requires a list of definitions that are presented below: 1. Acquisition Acquisition number = number of units (quantity) acquired per year. Penetration rate = number of households having acquired at least one piece of equipment. 2. Timeframe of acquisitions The time needed to acquire 90% of total number of units. 3. Home usage Home usage refers to equipment still in use and to equipment at home but in stand-by (not in use) mode. 4. Hoarding rate Hoarding rate = quantity at home (in use and not in use) / quantity of total acquisitions 5. Elimination modes of equipment and batteries Elimination modes = transfer to third party + collection + discarding in MSW. 6. Quantity available for collection Quantity available for collection = quantity of units collected + quantity of units discarded in MSW.
46 7. Collection efficiency
Collection efficiency = Quantity collected / Quantity available for collection. 8. Annual acquisition rate
Annual acquisition rate = number of units purchased per year.
3.2.
Acquisition and Penetration Rate
For the eleven major categories of equipment considered in this summary, 2,762 units of portable electrical and electronic equipment and 388 complementary "replacement" portable rechargeable batteries have been identified in 1,010 households (Table 3). The study supplies data on the penetration rate (number of households having acquired at least one piece of equipment) which is the highest for mobile communication equipment (61% for mobile telephones, 49% for home cordless telephones), while it is of 29% for cordless power tools and 20% for camcorder (Figure 6). The replacement batteries represents 14% of the total number of equipment identified. Nevertheless, the number of spare batteries (or packs) acquired reaches more than fifty percent of the purchased equipment for camcorders and toys and thirty percent for portable audio equipment (Figure 7). This type of equipment offers the possibility of exchanging the battery (or pack). The number of replacement batteries acquired is below 5% for dust busters, shavers, toothbrushes. In these last types of equipment, batteries are mainly incorporated and not exchangeable except by professionals. A distinction has been made between the original equipment purchase and the second hand acquisition (approximately 5% of total acquisitions). The multi-equipment effect is confirmed by the fact that the average number of equipment in households is higher than one for mobile audio equipment (1.3), mobile telephones (1.4), toys (1.4 on average), portable tools (1.2) and dust busters (1.2) as well as shavers and toothbrushes (1.2).
47 Table 3. Number of Acquisitions of Equipment and Replacement Batteries in 1,010 Households (France- November 2000)
INUSE
EQUIPMENT ATi-lOIrE NOrlN USE
BA'RERIES ACQtISI'nONS IN UNITS
BATIT~ES
206
171
34
118
85
PORTABLEAUDIO(1)
145
114
46
36
ous'raus'rERS & KA (2)
228
176
SHAVERS& T(X)11-~ (3)
239
195
HOVE CORDLESS~
567
514
MOBILEPHONES
853
813
PORTABLE
27
26
17
17
345
TOYS
ORIGINALE Q U ~ ~ S I T I O N S IN UNITS
B2UIPMENTTYPES
E(~~
AT~
22
48
27
42
28
322
18
44
32
113
72
30
63
40
I-K3VEALARMSYSTBVl
22
16
TOTAL Units Identitified
2762
2436
192
388
239
CORDLESS~
TOOLS
ANALYSISEquipment Total At Home Ratio At Home / Acquisitions
I
ANALYSlS Batteries Total At Home Ratio At Home / Acquisitions TOTAL BATI'ERIES Total at Home Ratio At ~ //k:cluisitions
Quantity 262;8
~
Percentage 9~ 1 Percentage
239 61.6
Batteries sold with E q u i ~
OJant~
and Re~acement Batteries
Percentage
2867 91
I
Units 3150
48 The study supplies information on the ratio of equipment still in use and the ratio that is kept at home but in stand-by (not in use) position. Among equipment that is still at home, an average of less than ten percent (8.8%) is not in use. But this ratio is widely distributed, being the highest for toys (29%), camcorders (17%) and mobile audio equipment (16%) that are recognised as not in use. It is the lowest for pocket assistant and alarm systems, all of which are in use.
Figure 6. Equipment and Replacement Battery Penetration Rates (number of households equipped with at least one piece in a given category)
3.3.
Timeframe for Acquisitions
The curve of Figure 8 shows the evolution of the number of acquisitions with time for camcorders. Equipment like camcorders, cordless power tools (Figure 9), dust busters, toys and home alarms systems have been acquired for a long period of time. When the time to acquire 90% of the equipment is considered, it is observed that the period extends over ten years for these types of equipment. As expected, for mobile telephones, 90% of the acquisitions have been made within the last five years which
49
Figure 8. Evolution of Acquisitions of Camcorder Units with Time
50 confirms the recent market penetration of the mobile communication equipment in France (Figure 10).
Figure 9.
Evolution of Acquisitions of Cordless Power Tools Units with
Time
3.4.
Home Storage Effect (Hoarding Rate)
The hoarding rate has been defined as the ratio between the number of units still at home (in use or not in use) and the total number of acquisitions expressed in percent.
Hoarding Rate = Quantity at home (in use and not in use) / Quantity o f acquisitions
The following results have been obtained from the data presented in Table 3. Home alarm systems: 73%. Dust busters, shavers and toothbrushes: 87% to 89%.
51 Camcorder, mobile phones and cordless power tools: higher than 95%. PC and pocket organisers: higher than 95%.
Figure I0. Evolution of Acquisitions of Mobile Phones Units with Time
When the total number of equipment declared is considered, more than 95% of the units are in a hoarding position on the average. The average hoarding rate for replacement batteries is 62%. It demonstrates that individual batteries and packs are discarded with a higher rate than batteries of first purchase directly associated with the equipment. A comparative evaluation of hoarding rates for equipment and replacement batteries is presented in Figure 11. 3.5.
Elimination Modes
There are three major elimination modes for equipment and batteries (Figure 12): 1. the transfer to relatives, friends, the exchange (trade) or re-sale (in all cases the equipment is re-introduced as an acquisition), 2. the take back to a collection point (available for collection),
52 3. the discarding in the MSW stream (available for collection).
Figure 11. Hoarding Rates for Equipment and Replacement Batteries
Elimination modes = Transfer to thirdparty + Collection + Discarding in M S W
The consumers have declared that 14% of the total number of acquisitions have been eliminated on the average. Considered separately, 11% of the equipment and 38% of the replacement batteries have been eliminated. From the total number of units (equipment and replacement batteries) that are eliminated, a first fraction equivalent to forty percent of the total quantity is transferred. This represents the preferred mode of elimination. This equipment is then re-introduced at home as a second hand acquisition. The second fraction or sixty percent of the quantity eliminated is available for collection. According to the type of equipment, one or the other of the elimination modes is favoured. For dust busters, discarding represents the majority of the declared cases. For cordless power tools, transfer is the preferred mode of elimination (resale, exchange
53 trade, giit, etc). This solution is also adopted in a preferential way for mobile phones and home cordless phones. In all cases, when combining collection and transfer data, they represent the large majority of elimination modes of equipment and batteries (more than two thirds of eliminated equipment and batteries versus less than one third for the MSW discarding mode).
Figure 12. Elimination Modes for Equipment and Replacement Batteries
It is interesting to note that even in a country without tradition for the collection of spent batteries (all types) and of waste electrical and electronic equipment, the collection mode represents one of the three major ways for discarding used equipment. (N.B. In France the official SCRELEC campaign did only start one year before the hoarding study was performed). When this survey was performed, the existence of this national collection program had not yet reached a high level of knowledge by the consumer. This survey has confh-med the correspondence (consistency) between this method of second hand acquisition and the elimination mode by transfer.
3.6. Quantity Available for Collection
When an equipment and/or a battery has reached the end of use, the consumer may discard it or take it back to a collection point. It becomes available for collection. Two
54 out of three elimination modes are considered when the availability for collection is defined:
1.
Collection
2.
Discarding in MSW
Indeed, it is not considered that the equipment which is transferred (w 3.5.) is available for collection. Quantity Available for Collection = quantity collected + quantity discarded in M S W
When the total number of equipment and spare batteries are considered, only 14% are eliminated and only 60% of those eliminated are made available for collection (less than 9% of total acquisitions approximately). The total flow of equipment and replacement batteries is presented schematically in Figure 13.
One half of the total quantity available for collection has been taken back to a collection point and the second half is discarded in MSW streams. Consequently, discarding in MSW is not the preferred method of elimination of spent batteries and equipment.
If a distinction is made between the management of the equipment and of the replacement battery, it is observed that only 5% of total equipment acquisitions are available for collection, while 38% of replacement batteries acquired are available for collection.
For equipment like dust busters (11.6%), shavers and toothbrushes (9.7%) the quantity available for collection is the highest. In the second place, toys (7.1%) and home cordless phones are found. The lowest rates of availability for collection are observed for portable audio (3.4%), mobile phones (1.1%), cordless power tools (2.3%) and camcorders (<1%).
Out of the fraction available for collection, the batteries are preferentially collected (65%) and the abandonment
in MSW (35%) represents a minority of cases. The
reverse is observed for the equipment where 68% are abandoned in MSW while 32% are collected.
55
Figure 13. Schematic Representation of the Flow of Equipment and Replacement Battery Acquisitions
This ratio obviously applies to a low number of units for equipment but it demonstrates the necessity to inform and assist the consumer on this issue.
3.7.
Collection Efficiency
The most appropriate concept to evaluate the success of spent batteries collection campaigns or programs is the collection efficiency that is based on measured data like the quantity of batteries present in waste (municipal solid and other industrial waste) and the quantity collected on a national basis from the various collection sources (national, private, etc). The Collection Efficiency has been defined in the following way:
56 Collection Efficiency = Quantity Collected~ Quantity Available for Collection where Quantity Available for Collection = Quantity collected + Quantity discarded in M S W
In both cases, batteries and equipment, the ratio between the quantities discarded in the MSW and the quantities collected (taken back to a collection point) is approximately identical at the level of 51% and 49%, respectively (Figure 14).
Figure 14. Quantity Available for Collection : Ratios Between Collection and Discarding.
3.8.
Annual Acquisition Rate
The annual acquisition rate is defined as the number of units acquired per year while the annual quantity available for collection is defined as the number of units that are available for collection per year.
For both equipment and replacement batteries, the annual acquisition rate (number of units acquired per y e a r - purchased or received as second hand) is significantly higher than the annual quantity available for collection
(number of units available for
collection per year either as being taken back to a collection point or as being discarded in MSW). This is the consequence of the consumer behaviour with a reliable (long life)
57 equipment to which he is attributing a high value. It is also the result of a multiequipment attitude. This phenomenon is presented in Figures 15, 16 and 17 for cordless power tools, audiovideo equipment and mobile phones, respectively.
From these data, it is concluded that the annual quantity available for collection represents only a minor percentage of the acquisition rate. As both rates vary with the type of equipment, there is no direct relation between the quantities of batteries and equipment introduced into the market and the quantities that the consumer is ready to eliminate either by participating to a collection scheme or by discarding in the MSW stream.
Figure 15. Comparison Between the Acquisition rate and the Annual Quantity Available for Collection of Portable Audio and Video Equipment
If one considers that the equipment discarded in the MSW represent only 50% of those which are available for collection, and if those available for collection represent less than 8 % of total acquisitions, then the quantities introduced in the MSW stream can
58
Figure 16. Comparison Between the Acquisition Rate and the Annual Quantity Available for Collection of Cordless Power Tools
only represent a modest percentage of the annual acquisition rate (that can be assimilated to the annual market introduction). This study shows that the concept of average lifetime of a battery or of the equipment is not appropriate. Indeed, the study demonstrates clearly that for certain categories of equipment, more than 90% of the units purchased within the last ten years is still at home. 3.9. Conclusions A summary of the results obtained in this survey is presented in Figure 18. 91% of the batteries with equipment and replacement batteries acquired by consumers are hoarded. Equipment and batteries that are not in hoarding are eliminated by three major modes: transfer, collection and discarding in MSW. For the equipment, a large ratio (40%) of the eliminated fraction is re-introduced in
59
Figure 17. Comparison Between the Acquisition Rate and the Annual Quantity Available for Collection of Mobile Phones
households by donation, re-sale and/or exchange while the second ratio (60%) is available for collection. For batteries, the ratio available for collection represents 38% of acquisitions and is preferentially collected rather than discarded. From the analysis of the results of this study, it is concluded that for portable rechargeable batteries associated to electrical and electronic equipment, the annual quantity available for collection represents only a minor percentage of the annual acquisition rate, representative of market sales. Both rates vary with the type of equipment, consequently there is no direct relation between the quantities of batteries and equipment introduced into the market and the quantities that the consumer is ready to eliminate either by participating to a collection scheme or by discarding the battery or the equipment in the MSW stream.
60
Figure 18. Graphic Representation of the Data Collected on the Consumer Behaviour with EEE and Replacement Batteries at End of Use
This result is confirmed by a detailed analysis of the batteries contents of MSW measured in the french countryside in the vicinity of Paris (November 1999). In 8,900 tonnes of MSW, the quantity of portable rechargeable batteries identified represented less than 5% of the volume introduced during the same year on the market (SCRELEC - Michaux 1999) A more recent study performed on 10,000 tonnes of MSW by STIBAT ( S T I B A T Bartels-1999) in the Netherlands has revealed that less than 10% of the portable rechargeable batteries are found in the MSW. This study, like another made previously in Japan (Fujimoto 1999 and 2001) shows that the concept of average lifetime of a battery is not appropriate. Indeed, it is observed that more than 90% of the equipment purchased within the last ten years is still at home, either in use or not. The most appropriate concept to evaluate the success of spent battery collection campaigns or programs is the collection efficiency that is based on measured data: the
61 quantity of batteries present in waste (municipal solid and other industrial waste) and the quantity collected on a national basis from the various collection sources. In this respect, this study demonstrates the coherence between data collected from two different sources: the measurement of quantities of batteries present in MSW and the evaluation of the quantities available for collection by this type of consumer survey. This study also confh'ms that the quantities of batteries purchased with equipment and left in hoarding remain the largest fraction of batteries introduced into the market during the last 10 years. It can be concluded that an efficient collection system should take into consideration several factors:
-
-
-
the large potential stock to collect, the low level of willingness of the consumer to eliminate the equipment, the need to control this hoarding by an appropriate public awareness campaign, the joint effort needed in collecting WEEE and spent batteries incorporated and/or sold to power this equipment.
4. BATTERIES IN MUNICIPAL SOLID WASTE In order to evaluate the impact of batteries that are neither in home storage nor collected, it is necessary to evaluate the quantities of batteries present in the municipal waste streams. The mass balance of portable Ni-Cd batteries introduced into the market is presented in Figure 19. The major flows of batteries are indicated in this figure: the the the the
quantities quantities quantities quantities
in hoarding, introduced in the municipal solid waste, introduced in the industrial solid waste, collected.
The large hoarding effect (75% to 80% of the batteries sold) leads to the accumulation of a large stock of batteries that are not introduced into the environment as long as they remain at end user locations. A significant fraction of Ni-Cd batteries are collected separately. It is estimated that more than 63 % (or 24,000 tonnes/year) of the quantity available for collection are
62
Figure 19. The Annual Mass Balance of Marketed Portable Ni-Cd Batteries (2000)
processed for recycling in dedicated processes for the recovery of cadmium and its reuse in new battery production. A smaller fraction (400 tonnes/year) of portable Ni-Cd batteries collected by industrial waste management companies is either processed with industrial waste and treated for recycling in non-dedicated processes like steel and lead recycling plants, or introduced legally in landfills according to local authorization procedures. Only a minor fraction (less than 800 tonnes/y- as estimated from measurements in three evaluation campaigns) of the annually marketed Ni-Cd batteries is collected with MSW. The difficulty faced by any collection program (national or private) is to evaluate the exact quantity of spent batteries available for collection as it is the fraction that can be collected. Indeed, batteries kept at home or in shops that are not available for collection are not a threat for the environment as long as they remain under the property and control of their owner.
63
4.1. The Battery Contents of MSW
According to studies published by several reliable sources, cadmium is present in the large majority of materials that are introduced in MSW. The material composition of MSW and their cadmium contents are presented in Figure 20. Recent studies (STIBAT-Bartels (1998) and SCRELEC-Michaux (1999)) performed on 10,000 tonnes of MSW have confirmed the low concentration of Ni-Cd battery in MSW which is in the range of 5.0 ppm expressed as a battery content. In other words, Ni-Cd Batteries represent only 0.0005 % (or 5 ppm) of the MSW content.
Figure 20. The Average Composition of Municipal Solid Waste and the Ratio of Spent Portable Batteries (results of measurement campaigns on 10,000 tonnes of MSW in France and the Netherlands (1999-2000) In Europe, the average concentration of cadmium in MSW has been evaluated at 6-12 parts per million (ppm) (French Society of Public Health (1999) and Maystre L-Y. (1995)). The average cadmium contents being 13.5% for portable rechargeable Ni-Cd batteries, the contribution of these batteries to the global cadmium flow represents less than 1.0 ppm. and remains inferior to 12% of the total cadmium contents. This result is presented in Figure 21.
64
Figure 21. The relative contribution of various materials to the total cadmium content of MSW (Calculated from the results of
measurement campaigns on 10,000 tonnes of MSW in F and the NL (1999-2000))
The dutch and the french studies on the Ni-Cd battery contents of MSW lead to the estimation that approximately 600 to 800 tonnes of portable Ni-Cd batteries are entering the MSW stream per year in the EU members states. It has to be compared with 13,000 tonnes annually on the market. A mass balance of the cadmium contents of Ni-Cd batteries introduced in MSW is shown in Figure 22. This fraction can lead to emissions of cadmium to the environment (atmospheric and water emissions). Today, in the EU members states these emissions need to be strictly controlled according to EU Directives on Waste (91/156/EEC), on Emissions from Municipal Solid Waste Incinerators (2000/76/EC), and from Landfills (99/31/EC). These emissions could be further reduced by an optimised collection efficiency of portable rechargeable batteries. 4.2.
Emissions from MSW Incinerators
According to the model developed on the basis of a quantity of 800 tonnes per year of Ni-Cd batteries collected in MSW, it can be observed from the analysis of Figure 22 that 23.8 tonnes of cadmium are processed in MSW incinerators in the EU countries.
65 The flue gas treatment should lead to the recovery of more than 98% of the cadmium as fly ash and wet sludge. These materials are stored in controlled landfills due to their heavy metal and other toxic material contents (Pb, Cd, Hg, As, Sb, dioxines, etc). According to this model, the atmospheric emissions of cadmium from Ni-Cd batteries treated in MSW incinerators are estimated to less than 0.5 tonnes/y in 2000. These data have been published in the last draft of the Risk Assessment Report on Cadmium and Cadmium Oxide (DRAR 2000) in November 2000. This value will be further reduced by two factors: 1. the efficient collection and recycling of Ni-Cd batteries, 2. the implementation of the EC Directive 2000/76/EC on emissions from MSW incinerators.
Figure 22. The Contribution of Ni-Cd Batteries to Total Cadmium Emissions
The current emission level of cadmium from MSW incinerators represent less than 2.0% of total atmospheric emissions of cadmium in the EU countries. The enforcement of the new EU Directive on emissions of cadmium gives a maximum permissible concentration of 0.05 mg/Nm 3. In these conditions, emissions associated to the
66 production of 5,500
m 3
of flue gas per ton of MSW incinerated would lead to a total
atmospheric emission below 100 kilograms for 22% MSW incineration capacity. Official reports from France and Switzerland (Chambaz D. and al. (1998), French Society of Public Health (1999)) confirm that municipal waste incinerators do not present any risk for the population as regards cadmium emissions. 4.3. Emissions from Landfills The second fraction of spent Ni-Cd batteries is introduced in landfills (as illustrated in Figure 22). The EC Directive on waste imposes a strict control of leachate emissions. More than 2,000 sites have been reviewed and 95% of them show cadmium concentrations in leachates below 5 micrograms per litre (Eggenberger 2000). This represents the recommended concentration of cadmium for drinking water by the World Health Organization (WHO). This low emission level from MSW landfills has been confirmed by Swedish researchers (Flyhammer 1996). Several sites may have higher concentration of cadmium emissions. These are industrial waste landfills and the origin of their cadmium emissions is not proven to be from spent batteries. Cadmium releases from landfills have been evaluated by the Draft Risk Assessment Report on Cadmium (DRAR 2000). They can be evaluated at less than 0.3 tonnes/y, this representing less than 0.8% of total emissions of cadmium in water in the EU countries. The major contributors to total cadmium emissions into surface waters are zinc and lead producers, fuel combustion for electricity generation, fuel combustion for road transportation, phosphate industries and non-ferrous metallurgy (DRAR 2000).
5.
COLLECTION OF SPENT RECHARGEABLE BATTERIES
5.1.
Collection of Spent Portable Rechargeable Batteries
Today, spent portable Ni-Cd batteries are mainly collected via four routes (Figure 23). The large majority comes through the sorting of batteries from general collection programs as those established in the Netherlands, Belgium, Germany, Austria and other EU countries. Municipalities in Sweden and professionals organisations in Denmark are
67 also contributing to their collection. Finally, in France a dedicated collection program for rechargeable batteries is in operation. Sorting Ni-Cd batteries from collected streams is a critical operation for those composition where zinc batteries are dominating. Industrial sorting technologies are in operation in Europe (Euro Bat Tri - 2000 and Wiaux -2000) but not in all countries and not with the same efficiency. It is believed that a significant fraction of Ni-Cd batteries collected are still processed with zinc batteries and are not accounted separately. In the future, the practise of separation of municipal waste before incineration will be more popular. Then, Ni-Cd batteries could be easily removed from municipal waste streams by using an electro-magnet overband in order to remove all Ni-Cd batteries together with other ferro-magnetic materials. This technology is currently used in the Netherlands (CollectNiCad 2001).
Figure 23. Collection Sources for Portable Rechargeable Batteries in Europe
As shown in Figure 23, the separate collection of portable rechargeable batteries reaches approximately 4,400 tonnes which are distributed between the four major chemistries: lead-acid (>2,000 tonnes), Ni-Cd (>2,000 tonnes), Ni-MH (< 500 tonnes) and Li-Ion (<100 tonnes). These data were recently presented by the major european recycler of portable rechargeable batteries (David 2001).
68
Figure 23. Comparison Between Collection Volumes of Portable Rechargeable Batteries (Consolidated data from recyclers for Ni-Cd; estimates from sorting results for lead-acid, Ni-MH and Li-Ion)
The evolution of the collected quantities of portable rechargeable Ni-Cd batteries are presented in Figure 24. The large increase during the last two years is mainly due to the recent development of collection programs in Germany (GRS) and France (SCRELEC) as well as the increasing efficiency of other national collection schemes (BEBAT, UFB, STIBAT, etc) The major collection programs in operation in Europe are presented in Table 4.
5.2.
Collection of Spent Industrial Ni-Cd Batteries
For industrial Ni-Cd batteries, the industry has established a "one for one" collection strategy that allows the take back of spent batteries at the time of sales as well as independently of sales. This principle allows the industry to pursue a collection target of more than 90% of the quantity of industrial Ni-Cd batteries introduced annually into the market (based on an annual average over the last ten years). The collected volumes obtained during the last six years are presented in Figure 25.
Table 4. Inventory of the Collection Programs for Spent Batteries in the EU Member States
Country
Austria Belgium Netherlands Italy
Organization
Status
UFB BEBAT STIBAT
Decree LawandVA Decree and VA
Year
91 96 95
Primary batteries MnZn Lithium(3) Button HgZn (2) S
Pb
Secondary batteries NiCd NiMH LiC(4)
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Switzerland Germany Denmark SDain Finland France
All batterv collection VA if not Ecotax All battery collection Major cities
All battery collection since april 1998 Tax Decree VA Decree
I 95 I
ECOVOLT SCRELEC
Portugal Sweden
Ministry
Decree Decree
94 89
UK Norway
REBAT REBATT
VA Decree
96 91
USA Japan
Remarks
1
RBRC
I
I
l
94 2000
x
l
x
l
x
I
l
X X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
I
X
X
X
X
Ni-Cd collection extended to all batetries and EEEqt. All battery collection since January 1998 Rechargeablebatteries Association created 09/09/99
X
Law
?
(1) VA = Voluntary Agreement (2) Mn-Zn = Saline and alkaline batteries
X
X
(3) Lithium = All primary lithium systems (4) Li-C = Li-ion
Collection before October 1996
70
Portable Ni-Cd Batteries Spent Portable Ni-Cd Batteries from European Sources collected separately and processed in Recycling Plants
2500 c~ 2000
o~
~
1
1500,',
" n / .~~ ~ooo_... m / I ~~176 / / I 0
1995
1996
1997
1998
1
I / I / I / 1999
2000
Figure 24. The Evolution of Collected Volumes of Spent Portable Ni-Cd Batteries
Figure 25. The Evolution of Collected Volumes of Spent Industrial Ni-Cd Batteries
71 5.3. Evolution of Collection Schemes
Earlier collection schemes for all types of batteries have been established on a voluntary basis in several european countries like Switzerland, the Netherlands, Germany and Austria. They were usually the result of private or community (municipalities) initiatives. We will not address the issue of collecting spent lead-acid batteries of the SLI type as it is treated separately in this book. On the basis of Directive 1991/157/EC, several collection systems were initiated with the objective to collect specifically button cells and portable Ni-Cd batteries. It is worth to mention that the collection of portable lead batteries was never addressed specifically while this category of portable rechargeable batteries represents an equivalent weight amount to Ni-Cd batteries in the european market. During the nineties, three collection systems were under development for portable rechargeable batteries: a dedicated collection scheme, a general collection scheme for all types of portable batteries (primary and rechargeable) and the collection of portable electrical and electronic equipment associated with the de-manufacturing in order to recover valuable components as batteries.
5.3.1. Dedicated Collection Scheme for Portable Rechargeable Batteries
Such collection systems were initiated on a national level in Sweden and Germany. In other countries, private initiatives were leading to the opening of collection systems for cordless power tools and other types of equipment: ECOELIT (Italy), BOSCH (Germany), REBAT (UK), ECOVOLT (France) are representatives of these initiatives. In Germany, the professional association Z.V.E.I. (Zentral Verband for Elektrische Industrie), has initiated a specific program for the collection of Ni-Cd batteries. This program was in operation between 1994 and 1998. The results of the Z.V.E.I. program are presented in Figure 26. The operation of a dedicated collection system for a single type of battery, like the program operated by Z.V.E.I. is facing three major barriers to collection.
72
Figure 26. Collection of Portable Rechargeable Ni-Cd Batteries
in Germany (Source" CollectNiCad)
1. For portable rechargeable batteries that are incorporated in pieces of equipment, the consumer is not willing to separate the rechargeable battery from the equipment. If this equipment has a potential life of more than ten years on the market, the amount of spent batteries collected will be very low. 2. The f'mancing of such a dedicated collection is addressed to less than ten percent of the portable battery market. 3. As consumers' demand is in favour of the collection of any type of battery regardless of its chemical nature, the volume of collected rechargeable batteries is equivalent to that of primary batteries.
5.3.2. The Collection of Portable Rechargeable Batteries Via a General Collection Scheme
To illustrate the impact of the collection of spent batteries of all types on the
73 efficiency of the collection of portable rechargeable batteries, the example of Germany is very illustrative. General collection schemes for all types of portable batteries (primary and rechargeable) from which rechargeable batteries like Ni-Cd batteries are sorted out in a specific stream has been initiated in several european countries. The impact of the startup of such a program as a follow-up of a dedicated scheme is illustrated in Figure 26 for the case of Germany. As a follow-up of the Z.V.E.I. collection scheme, a nation-wide collection organization (Gesammt Riichgewinnung System, GRS) was established in 1998 for the collection of all types of batteries. When a general collection scheme is operated, Ni-Cd batteries are sorted-out from other zinc and lithium batteries either manually or automatically (Euro Bat Tri 2000). The collection efficiency of portable rechargeable batteries is immediately increased when such a general collection scheme is implemented. Indeed, such an approach responds to consumer's requirements for a single message on the take back of all batteries. A comparison of the efficiency of collection of portable rechargeable Ni-Cd batteries in various EU countries is supplied in Figure 27. The information is presented with normalised data: grams of collected batteries per inhabitant per year. This way to present the results was first introduced by SNAM (SNAM-Linck 1998) and allows to compare the efficiency of collection programs in each individual european country. In Europe, during the most recent years, approximately 13,000 tonnes of portable Ni-Cd batteries were introduced annually into a market of 380,000,000 people: this corresponds to 5.0 grams per inhabitant per year. The collection is unevenly distributed among european countries as a result of the absence of collection programs in some of them.
5.3.3. The Collection of Rechargeable Batteries Incorporated in Portable Electrical and Electronic Equipment In 1999, in France, the Soci6t6 de Collecte et de Recyclage des Accumulateurs (SCRA) was founded with the objective to collect all types of portable rechargeable batteries. This program was rapidly extended to the collection of equipment in which batteries are incorporated. In 2000, the articles of association of the company were adapted to
74 include membership form major OEMs and retailers and the re-naming of the company as the Soci6t6 de Collecte et de Recyclage du Mat6riel Electrique (SCRELEC) did occur. The general principle of operation of the company is based on the responsibility of the importers/manufacturers/dealers to support the financial cost for collection, demanufacturing, sorting and recycling. This responsibility is covered by two french laws, the Decrees of 12 May 1999 (99/374) and 29 December 1999 (99/1171). SCRELEC operates on the basis of full transparency regarding the financial commitments of members and costs of the various operations controlled by this private collection company: collection, logistics, sorting, recycling, resale of materials. This is schematically presented in Figure 27.
All operations managed by SCRELEC are financed by the contribution of members according to their sales and by the re-sale of secondary raw materials obtained from the recycling operations. As SCRELEC is a non-profit organisation, the fee is adapted to current accounting balance. Members of SCRELEC are batteries manufacturers and importers, OEM (original equipment manufacturers) companies, national companies and importers as well as private label distributors.
SCRELEC has the duty to keep record of all types of primary and rechargeable batteries introduced into the french market and offers to authority a consolidated data base according to the technology and the application. Members have the duty to declare their annual sales according to the weight of batteries introduced into the market. A quarterly payment is organised and a legal statement made by SCRELEC certifies the active participation of each individual member to the program. Beyond the administrative and financial responsibility, SCRELEC acts as a control agency for the various operations related to the collection and recycling of spent batteries and also for the de-manufacturing of electrical and electronic equipment and the appropriate management of each type of component in recycling, re-use and/or discarding operations.
75
Figure 27. Collection of Portable Rechargeable Ni-Cd Batteries in European Countries (Normalised data on the basis of grams per inhabitant per
year; source: CollectNiCad)
The originality of SCRELEC's program is to integrate all actors of the recycling operations and to drive the system economically in all the steps. 5.3.4. Conclusions
As presented previously in Figure 24, collected quantities of portable rechargeable batteries have been increasing significantly during the last years and a continuous progression of collected volumes is expected as a result of several parameters: the private, national and regional initiatives for the collection of spent
.
batteries, the development of national collection and recycling associations in countries without collection organization in 2000,
.
the implementation of the WEEE Directive,
76 the increasing selectivity in the processing of industrial waste, the progressive abandonment of legal landfills for batteries in several EU members states, the increasing consumer awareness of the battery and the EEE collection issue.
.
5.
'1 ,,Consumers i ....
! r r: .i Distributors i :. ! "> ,.-, (, ,-Retailers ~ ~::. : I
Collection
Eqt. & Batt. '
[The
(Distributors-/Retailers, -
,,
,,
CommunitieS) ,
,
~,,
,
,
,
,,J
t
,,,
!
,,
:ManufactEmm:::;/ . .9. .
+
/
[: Eqt, il~ / M a f i ~ / i ~ r i ~ i : ] ! 1
........
Primary:baRerNs;i &Accumulators I ' .manUfacturers - i
t
[Materialsl <
I
Figure 28. The Collection and Recycling Scheme Under the Control of SCRELEC: Schematic Presentation of Operations, Logistics and Financials Aspects
6. COLLECTION EFFICIENCY AND RECYCLING RATE Each country establishing a collection scheme is trying to bring its own definition of recycling and collection rates. It appears that a standardisation at the european level is needed.
77 6.1. EU Legislation on Waste
The various european directives on waste management do not present a clear definition of terms as collection rates and recycling rates. There is a general trend to forget that recycling is a generic term for a sequence of operations starting with collection, consolidation, sorting, processing and finally re-use and/or recycling of recovered materials. Disposal in landfill is another end of life management of materials that cannot be re-used advantageously. A definition of the term "waste" is given in the Waste Directive 75/442/EEC as "any substance or object which the holder disposes of or is required to dispose of". A further reading of the text of Directive 91/156/EEC (presented as an amendment to Directive 75/442/EEC on waste) gives examples of the types of waste in Annex I (Q_6_ paragraph, Unusable parts, e.g. rejected batteries, exhausted catalysts, etc.) and also mentions, under Q 16, any materials, substances or products which are not contained in the above Q 1 to Q 15 categories.
In Annexes IIA and IIB, materials in "temporary storage on the site where they are produced" are not considered a waste.
So, if collection and/or recycling rates are evaluated, batteries in temporary storage should not be considered as they are not a waste. One should take into account the quantities available for collection and not the quantities introduced into the market. As we have seen in Section 3 of this chapter, a significant fraction of the rechargeable batteries remains in home storage (in use or not in use). As long as they remain is such a position they have not to be considered as a waste.
6.2.
United Nations and O E C D Environmental Indicators
In the absence of clear indications from the european directives on this subject, the recommendation is made to use the definitions proposed by the United Nations Department for Policy Coordination and Sustainable Development (UN 2000). In the list of Indicators for Environmental Aspects of Sustainable Development, the UN CSD Methodology Sheet gives a definition of the environmental indicator: Rate of
waste recycling.
78 The purpose of this indicator is to measure the proportion o f waste which is reused and/or recycled. The rate of waste recycling and/or reuse is defined as the volume of waste which is reused or recycled based on the volume actually I~enerated at source on a per capita basis. The unit of measurement is the percent. If one considers the specific case of spent portable Ni-Cd batteries, one can propose the following definitions. The recycling rate for Ni-Cd batteries is the ratio between the quantity of batteries processed for recycling over the quantity of spent Ni-Cd batteries generated at source and introduced in the waste stream by the end-user. In this approach, one can consider that the quantity of spent Ni-Cd batteries generated at source is equal to the quantity that the end-user is eliminating via several routes, like MSW and/or voluntary landfill (VL), and the quantity that is collected for recycling in dedicated processes or not. If we take the example of Ni-Cd batteries, one can consider for simplification two factors: The first one is the quantity of Ni-Cd batteries not processed for recycling but eliminated as a waste, Q. Q.
Spent Ni-Cd
SpentNi-CdN.R. where,
(1)
N.R.-- Q. MSW+ Q- VL--.
with Q. Msw = Quantity eliminated in MSW Q. VL--Quantity introduced in landfill The quantity of used batteries processed in recycling plants in Europe can be described by the following equation: Q. Ni-CdP.R.
--
Q. SNA~ Q. SAFT+ Q. ACCUREC+ Q. RECYCLER+ . . .
with Q. Ni-CdP.R.
--
quantity processed for recycling
(2)
79 In this equation, Q. ACCUREC, Q. SNAM, Q. SAFT represent the quantities of used batteries collected in various EU members states and effectively processed at SNAM, SAFT and ACCUREC that are the officially known recycling plants. Any other quantity processed at a new recycling plant could be included in this equation as Q. RECYCLER 9 This value, Q. Ni-CdP.R. corresponds to the quantity processed for recycling established on consolidated quantities processed during a fiscal year and is not related to any intermediate stock neither in the source country nor at the recycling plant. Using these measurable sources of information, a recycling rate (RR Ni-Cd-- equation 3) for Ni-Cd batteries can be established on a country by country basis in the EU. It can be easily transformed on a per capita basis, using a global or local EU member state approach. R R Ni-Cd(y) . . . =
(Q.
Ni-CdP.R.(y)X 1 0 0 / Q - s p e n t N i - C d ( y )
Indeed, according to the UN definition, the sum Q.
+
Q.
Ni-CdP.R.(y)
Spent Ni-Cd (y)
+
(3)
Q. Ni-CdP.R. (y)
represents the total quantity of spent Ni-Cd batteries generated at source.
6.3. Application of the UN Recycling Rate to Ni-Cd Batteries in Europe The first application of this formula was proposed by STIBAT and the results were presented in 1999 at the Battery Recycling Conference held in France (Deauville). STIBAT is controlling the market introduction of all batteries with a weight inferior to 1 kg. It has also the control of 100% of spent batteries collected by municipalities, professionals and private collection systems. In order to evaluate the flow of batteries escaping the collection circuit, in 1998 STIBAT has organised a campaign to measure the quantity of spent batteries present in MSW streams in the Netherlands. The application of formula 3 to the case of the Netherlands leads to a collection rate of 77% for used Ni-Cd batteries as illustrated in Table 5. The wider application of this formula on the european basis requires the measurement of used batteries in several major waste streams (mainly the MSW).
80
Table 5. Application of the Recycling Rate FormulaThe Netherlands' Case, 1998 (Source: STIBAT)
Year:
1. Ni-Cd
2. Q. Ni-CdP.R.
TOTAL
content in
(1998) (Tonnes)
1.+2.
Q. Ni-Cd P.R. /
(Tonnes)
TOTAL
141.4
163.7
77 %
MSW
gg
Ni-Cd
Source
(Tonnes) 1998
42.3
STIBAT
As it is presented in Figure 29, in Europe the quantity of spent Ni-Cd batteries processed for recycling has reached the volume of 2,040 tonnes in the year 2000. When compared to the quantity identified in MSW during the previous years (600 to 800 tonnes), it comes that the recycling rate of Ni-Cd batteries at the european level is higher than 70%. This calculation is presented in Table 6. It is obviously estimated that Ni-Cd batteries left in a hoarding position are not available for collection. Indeed, according to the UN definition, these batteries do not represent a waste generated at source.
Table 6. Application of the Recycling Rate Formula: Case of Europe, 2000 (Source: CollectNiCad)
Year
1. Ni-Cd
2. Q. Ni-CdP.R.
TOTAL
R R Ni-Cd
content in
(1998)
1.+2.
Q. Ni-Cd P.R./
M S W (1999)
(Tonnes)
(Tonnes)
TOTAL
2040
2840
72 %
Source
(Tonnes) 2000
800
CollectNiCad
81
Figure 29. Schematic Representation of the Mass Balance of Portable Ni-Cd Batteries in EU Members States (2000) (Source: CollectNiCad)
7. CONCLUSIONS The development of any program aimed at reducing the impact on the environment by a product, a chemical or a substance in general should follow some basic rules that have been issued by OECD under the generic term of Environmental Indicators (OECD Publications- 1998). These indicators can be global, sectorial and/or economic, nevertheless they are aimed at the realistic follow-up of a given situation. Prior to any elaboration of a program and of the follow-up of this program by environmental indicators, it is necessary to fix the rules of the system. In particular, it is needed to: have an agreement between the parties with a mutual understanding of the concepts and the definitions based on the so-called P S R - Pressure-State-Response - system,
82 -
have an identification of criteria which will validate the choice made for the parameters to be used in the indicators follow-up,
-
have a mutually agreed basis on criteria for (among others) the political justification, the analytical accuracy and the accessibility to measurements,
-
have established instructions relatives to the measurements of data, the collection of parameters and the calculation of indicators.
It is obvious that the evaluation of the collection and recycling efficiency of Ni-Cd batteries, and of portable Ni-Cd batteries in particular, is a difficult task to achieve. This is the reason why an agreement should not be signed if there is not a well documented and mutual understanding of the definition of data to acquire, parameters to evaluate and criteria like: collection rates, quantities available for collection, quantity found in municipal waste, recycling rates, hoarding, etc. Certainly, the methodology to adopt to evaluate the quantity of Ni-Cd batteries found in MSW becomes a critical parameter. The methodology to follow in order to measure this parameter is of prime importance. For instance, STIBAT has made this evaluation based on the quantities of batteries found in the small iron fraction of sorted municipal waste. In France, the campaign did measure the battery presence after mechanical sorting of the materials contents from garbage bags using a differential gravity technology. Can both results be compared? Can both methodologies be used? Are they complementary for our objective? The knowledge of the practise of waste management by consumers is a recent issue. Not all parameters of this dynamic process are known. It has been demonstrated in this chapter that there is no direct correlation between the quantity of rechargeable batteries (and equipment) purchased during one year and the quantity that are discarded or taken back to a collection centre. Data needs to be accumulated on an european basis on the quantity of batteries present in temporary storage at home and on the motivations of the consumer to eliminate these products from his daily environment. One can only draw definite conclusions on these issues when all parameters of the mass balance will be known. These include: the presence of batteries in home storage, the
83 composition of MSW and of industrial solid waste, the quantities collected and processed separately and with other streams, etc. During the last years, the rechargeable battery industry has started a significant data acquisition program at the european level: the first results of this program are presented in this chapter. They demonstrate that this industry is responsible for introducing those products on the market and for securing their management in the most environmentally friendly way at their end of life.
REFERENCES Black&Decker (2001): Communication to the EU Commission. Available from
CollectNiCad Secretariat. Avenue Marcel Thiry, 204. B-1200 Brussels, Belgium (June 2001). Chambaz D. et ai. (1998): Clean Municipal Waste Incinerators: A Dream or A
Reality? Published by the Federal Office for Landscape and Environmental Protection. CH-3000 Bern. Chandler C.(1996): Characterizing Cadmium in Municipal Solid waste. In:
Proceedings of the OECD Workshop on the Sources of Cadmium in the Environment, Saltsj6baden, Sweden 16-20 October, 1995, p. 393-398. CollectNiCad 2000-J-P Wiaux: Market Survey of Nickel-Cadmium Batteries. Available from CollectNiCad Secretariat. Avenue Marcel Thiry, 204. B-1200 Brussels, Belgium (February 2000). CollectNiCad 2001-J-P Wiaux: Market Survey of Nickel-Cadmium Batteries. Available from CollectNiCad Secretariat. Avenue Marcel Thiry, 204. B-1200 Brussels, Belgium (April 2001). David J. (2001): Can We Recycle 65% of the Components of Nickel Metal Hydride and Lithium-Ion Batteries? Proceedings of the International Congress on Battery Recycling. Montreux, Switzerland, May 2-4, 2001.
DRAR (2000): Draft Risk Assessment Report on Cadmium~Cadmium Oxide (2000). Belgian Rapporteur. Mr. M. De Win General Advisor. Ministry of Social Affairs,
84 Service of Risk Management. R.A.C. Vesalius. Pachecolaan, 19 Box 5. B- 1010 Brussels.
Eggenberger H. and Waber F. (2000): Cadmium Seepage Waters of Landfills: A Statistical and Geochemical Evaluation. Report prepared for the Federal Office for Landscape and Environmental Protection. CH-3000 Bem. Euro Bat Tri (2000): Description of an Automatic Industrial Spent Batteries Sorting Unit. Information available from Mr. D.Serre. Euro Bat Tri Sarl. BP 734. Rue de la Garenne, 9. F-38297 Saint Quentin Fallavier, Cedex, France Fiyhammar P. (1995): Heavy Metals in the Environment. Analysis of the Cadmium Flow in Sweden with Special Emphasis on Landfill Leachate. J.Environment. Quality, 1995 (24) 612-621. French Society of Public Health (1999): Municipal Solid Waste Incineration and Public Health: A Review of the State of the Art and a Risk Evaluation. ISBN - 2 911489 - 07 - 1. Collection Sant6 et Soci6t6, N~ - Nov. 1999. Fujimoto K. (1999): Collection and Recycling Activities for Portable Rechargeable Batteries in Japan. Battery Association of Japan. Proceedings of the 5th International Battery Recycling Congress, Deauville (France), September 27-29,1999. Fujimoto K. (2001): Progress in the Collection and Recycling of Portable Batteries in Japan. International Congress for Battery Recycling, Montreux, Switzerland, May 2-4, 2001. Maystre L-Y., Duflon V. et ai. (1994): Municipal Waste. Nature and Characterisation. Published in french under the title: D6chets Urbains. Nature et Caract6risation. 1994. Presses Polytechniques et Universitaires Romandes. CH- 1015 Lausanne. ISBN 2-88074-256-0 Miquel G. (2001): Parliament Office for Technological and Scientific Options. The Effect of Heavy Metals on Human Health and on the Environment. By G. Miquel.Senator. AssembMe Nationale N ~ 2979. Publication of April 6th, 2001. Paris. OECD Publications - 1998: Towards a Sustainable Development: Environmental Indicators.
85 Pilot C. (2001): The Battery Market 2000-2005. Batteries 2001. Proceedings of the Intemational Conference and Exhibition, held on April 16-18, 2001. Paris La Defense.
RIVM Report 481505015 (2000): Technical Report on Chemicals, Particulate Matters, Human Health, Air quality and Noise. W. Smeets et al. Report to the Environment Directorate General of the EC, May 2000. Sr
M., Thornton I. and Vonkeman G. (2000): EUPHEMET SYNOPSIS / EC
Project (contract no ENV4-CT97-0614), University of Athens, Athens 17-18 April 2000, Greece. Data and Trends in Production, Consumption, Use and Theoretical Background for Future Policies on Cadmium, Lead & Mercury. SCRELEC-Michaux J. (1999): Sorting of Batteries from MSW of the Montmorency/Paris Area, 1999. SCRELEC. Rue Hamelin, 17. F-75116 Paris, France. S N A M - Linck 1998: Collection of Ni-Cd batteries in EU Countries. OECD Workshop
on Ni-Cd Battery Marking. Mexico, December 1998. STIBAT - Bartels J. (1998): Batteries in MSW: Composition and Characterbation.
1998. STIBAT. Boerhaavelaan, 40 Postbus 190.2700 AD Zoetermeer, the Netherlands. TRAR (2000): Draft Targeted Risk Assessment Report on Cadmium~Cadmium Oxide as Used in Batteries (2000). Belgian Rapporteur. Mr. M. De Win General Advisor. Ministry of Social Affairs, Service of Risk Management. R.A.C. Vesalius. Pachecolaan, 19.Box 5. B- 1010 Brussels. UN 2000: United Nations Department for Policy Coordination and Sustainable
Development. United Nations Sustainable Development Program. Agenda 21: Indicators for Sustainable Development: Chapter 21. Environmentally Sound Management of Solid Wastes and Sewage-Related Residues. Rate of Waste Recycling and Re-use.Available on web-site: www.un.org/esa/sustdev/indisd/english/chap21 e.htm Wiaux J-P. (2000): Sorting Spent Batteries: A Review of Current Technologies. EPBA
Meeting on Battery Recycling, Brussels, May 2000. EPBA. 204 Avenue Marcel Thiry, B- 1200 Brussels, Belgium.
This Page Intentionally Left Blank
Used Battery Collection and Recycling
G. Pistoia, J.-P. Wiaux and S.P. Wolsky(Editors) 9 2001 Elsevier Science B.V. All rights reserved.
BATTERY COLLECTION
AND RECYCLING
87
IN JAPAN
Kinya Fujimoto Chairman, Overseas Environmental Committee Portable Rechargeable Battery Committee Battery Association of Japan, Kikai Shinkou Kaikan Building 5F 3-5-8 Siba-Kouen, Minato-ku, Tokyo (105-0011), Japan
INTRODUCTION In Japan, spent primary dry cells are allowed to be disposed of as general waste with noncombustible garbage. However, both disposal and collection of garbage by type are carried out by some municipalities at their own discretion. Recycling techniques for dry cells are now under research and development, but have yet to be set up, as economic, environmental and other problems are still pending. In view of the reuse of natural resources, however, efforts are being made to put recycling techniques for dry cells into practical use, in cooperation with industry people including metal refiners. Button type cells have been collected since 1984. The Battery Association of Japan (hereafter called BAJ) continues to promote and develop collection activities. For small-size portable rechargeable batteries, the collection of spent nickel cadmium batteries started in 1985 and has been pursued in combination with the collection of nickel metalhydride batteries, lithium ion batteries and small-size sealed lead-acid batteries. The collection rate of nickel cadmium batteries was over 40% in 2000. For lead-acid batteries for automobiles, the collection channels have been established and more than 95% are now collected and reused. Table 1.1 shows data on battery production by all japanese battery manufacturers. The volume of battery annually produced is impressive and claims for a continued effort aimed at avoiding their uncontrolled dispersion in the environment.
88 1. T ~ A T M E N T OF SPENT PRIMARY DRY CELLS
1.1 Relationship Between Dry Cells and Mercury Mercury contained in spent dry cells may be emitted through garbage disposal, thus causing environmental pollution. In this situation, the Ministry of Health and Welfare on July 1985 gave the prefectures an official notice called "Measures against the wastes which are difficult to treat", in response to reports from the Life Environment Council, the Waste Disposal Work Group, and the Appropriate Disposal Expert Committee. According to this notice, the main points concerning the disposal of spent dry cells are as follows.
Tablel.l. Production quantities by all japanese battery manufacturers (xlO0 million cells) 1991
1992
1993
1994
1995
1996
1997
1998
Manganese
25.2
24.9
24.0
22.1
21.8
18.7
16.3
15.6
Alkaline
8.3
8.9
9.4
8.9
9.8
11.1
13.9
14.6
Silver oxide
4.8
5.1
6.1
6.3
7.2
7.8
8.2
9.3
Lithium
4.5
4.9
5.8
7.0
7.8
7.1
8.6
9.2
0.5
0.5
0.5
0.6
0.5
Lead-acid batteries
0.6
0.6
0.6
0.6
0.6
0.5
0.5
0.5
Alk. accumulators*
7.7
7.6
8.8
8.8
8.7
6.9
7.0
5.9
0.7
2.0
3.1
3.6
5.8
6.4
0.3
1.3
1.9
2.7
Other primary cells
Nickel MH Lithium ion
*Alkaline accumulators: nickel cadmium batteries account for more than 99% a. Spent dry cells in general contain wastes which do not cause any problem in terms of preservation of the environment even if they are treated with other garbage. In addition, the reduction of mercury in alkaline dry cells, collection and disposal of button type mercury cells, etc. are expected to ensure the preservation of environmental life. Therefore, special measures do not need to be taken if the existing legislation is observed. b. In order to respond to the increasing social needs for a more comfortable and safer environment, the interested parties should work on basic ideas concerning the
89 measures for spent dry cells from their respective positions. However, measures taken by enterprises based on the reduction of mercury contained in garbage are considered the most appropriate. Based on this notice, the member companies of the Battery Association of Japan (formerly Dry Cells Association of Japan) made efforts to eliminate mercury in dry cells. As a result, the use of mercury was banned in April 1991 for manganese cells and in January 1992 for alkaline cells. Furthermore, the production of mercury cells was stopped at the end of 1995, replacing them with zinc-air cells. Moreover, in order to objectively evaluate the state of dry cells when landfilled as noncombustible garbage, the member companies of the Battery Association of Japan, entrusted the study of landfilled dry cells in 1985 to Fukuoka University. Based on the findings obtained over a 10-year observation, it was conf'mned that heavy metals including mercury from dry cells did not seep or spill into water tanks, according to environmental standards.
1.2 Reduction of Mercury With regard to cylindrical manganese and alkaline dry cells, which account for some 98% (on a weight basis) of all primary cells sold in Japan, no mercury has been used in the production since 1992.
Furthermore, as the production of mercury cells was
stopped at the end of 1995, the amount of mercury contained in the dry cells sold in Japan was equal to 1.4 tons in 1997, i.e. only 3% with respect to the 1985's total (45 tons). In addition, as button type cells (alkaline, silver oxide and zinc-air cells) still contain a small amount of mercury, BAJ will continue to reduce it and promote the collection and recycling of spent dry cells.
1.3 How Are Spent Dry Cells Disposed of ? As the Ministry of Health and Welfare gave the official notice "Measures against the wastes which are difficult to treat" to the prefectures on July 1985, the disposal of spent dry cells became the same as that of noncombustible general waste. However, since the method of collection differs with municipalities, their respective instructions should be followed. Most of the dry cells collected as noncombustible general garbage is landfilled. However, a number of them is sorted according to type and sent to Nomura Kosan Corporation's Itomuka mining station in Hokkaido for treatment. Since March
90 1997, approximately 10,000 tons of cells are collected from municipalities nationwide every year and recycled for mercury, scrap-iron and soft ferrite (magnetic material).
1.4 The Amount of Zinc and Manganese Used in Dry Cells In view of an efficient utilization of natural resources, recycling of the main materials used in dry cells is required, but other resources such as fuel, electricity, chemicals, etc. have to be consumed for this purpose. Therefore, a method of recycling while minimizing consumption of resources should be established. The usage of zinc and manganese which are the main materials of dry cells was approximately 20,000 tons for zinc and 30,000 tons for manganese in 1996. Each of them accounts for no more than 3% of Japan's total demand as shown in Table 1.2.
1.5 Dry Cell Materials The materials of dry cells vary with type and size, but consist of zinc (20%), manganese dioxide (30%) and iron (20%) on average. In order to recycle these materials efficiently and economically, it is necessary to treat them without consuming too much energy or increasing the environmental pollution. Recycling of spent dry cells is under research and development in various countries, but a technique fully complying with the above requirements has yet to be found.
Tablel.2. Main materials of dry cells (weight basis) Materials
Dry cell industry's usage (tons) 20,000
Total industrial usage (tons) 700,000
3
Manganese dioxide
30,000
1 million
3
Iron
20,000
10 million
0.02
Zinc
Share (%)
1.6 Recycling Technique for Dry Cells Under the present conditions, no recycling technique for spent dry cells has been established in the world, partly because of the limited appeal of recovering small quantities of zinc and manganese dioxide (table 1.2).
91 Recycling zinc from spent dry cells, for example, now requires about three times more energy than that needed for extracting zinc from its ores. Moreover, it may have an effect on the increase of CO2 in the atmosphere, calling for a prudent approach to recycling dry cells, from the viewpoint of prevention of global warming. At present, for the purpose of recycling dry cells, dry method, wet method, etc. are under consideration, but all of them remain very problematic in terms of energy consumption and economic effectiveness.
2. RECYCLING OF SPENT LEAD-ACID BATTERIES 2.1 Trends in the Market of Lead-Acid Batteries
Lead is used in batteries, inorganic chemicals, pipes, solders, electric wires, etc., but batteries accounted for 72% of the total usage of lead in 1997. Therefore it can be said that batteries play an important role in the recycling of lead. Lead-acid batteries are classified into motor vehicle batteries (for automobiles and motorcycles), industrial batteries (stationary batteries, traction batteries, etc.), small-size sealed batteries (for UPS and consumer products). Table 2.1 shows their shipments. It seems that the total shipment of lead-acid batteries has remained at much the same level in the past five years and that motor vehicle batteries, which accounted for 76.5% of all lead-acid batteries in 1997, have seen few changes, while industrial batteries and small-size sealed batteries have tended to gradually increase and gradually decrease, respectively. Table 2.1. Shipments of Lead-Acid batteries (tons)
1993
1994
1995
1996
1997
Motor vehicle
207,240
214,126
207,238
210,223
207,678
Industrial
36,318
36,528
38,420
43,864
46,996
Small-size sealed
20,009
20,771
19,439
18,050
16,957
263,567
271,425
265,097
272,137
271,631
Total
92 2.2. Recycling of Lead-Acid Batteries for Automobiles and Motorcycles (1) Lead Recycling Program Five lead-acid battery manufacturers announced a "Lead Recycling Program" in October 1996 and have implemented it. The main points of the program are as follows. a. The lead-acid battery manufacturers purchase at reasonable prices and reuse the recycled lead from battery waste. b. Introduce the collection through reverse channels of distribution. c. Request first-tier manufacturers to participate in the lead recycling efforts. d. Request battery sellers to take back the spent batteries free of charge (from general users). The collection rate is expressed as "collection/waste x 100 (%)". In 1997, collection rate of spent lead-acid batteries was 95%. (2) Collection System The Lead Recycling Committee discussed about the development of a low-cost lead collection system which should also comply with the Waste Disposal Law concerning cleaning and disposal of wastes. As a result, it was decided to adopt a "trade-in system in which battery manufacturers are discharge companies" as the best collection system. According to this system, the battery manufacturers collect spent batteries traded-in by battery sellers through reverse channels of distribution and deliver them to lead recycling and refining companies as intermediate treatment companies. Under the Waste Disposal Law, each seller is supposedly required to trade in and discharge spent batteries as a discharge company, but this is very difficult or almost impossible in terms of number of sellers (some 200,000 shops nationwide) and lead recycling and refining companies (19 companies nationwide), or requirement for each discharge company to have a qualified person in charge of control. Thus, the Committee concluded that sellers or wholesalers are to be the discharge locations for manufacturers and that manufacturers are to conduct the discharge from
93 sellers (or wholesalers) as their own discharge locations. Sellers (or wholesalers) which are the discharge locations are to notify their battery manufacturers of the collection by using a control card (the so-called manifest) when the number of traded-in spent batteries achieves a certain quantity (50 to 100 units). The battery manufacturers which are given the notice of collection are to entrust the collection of the spent batteries to a collection and transportation company in order to bring them to the lead recycling and refining company.
After that, the recycled
batteries are to be reused by the battery manufacturers. 2.3 Recycling of Industrial Batteries Industrial
batteries
are
used
for
telephones,
communications,
electric
transformations, various types of emergency power sources, etc. The Waste Disposal Law provides that "the companies shall properly dispose of the waste they produce with their commercial activities, as their own responsibility" (Clause 1, Article 3). Thus, the law requires the users themselves to properly dispose of the batteries as industrial waste. Industrial batteries used to be treated as valuables and be mostly traded-in by battery manufacturers (some users auctioned them). Since the beginning of 1990s, however, spent industrial batteries have been treated like automotive batteries. Battery manufacturers have taken measures on the assumption that spent industrial batteries are industrial waste and that the users are responsible for the disposal of the batteries. To comply with the regulations on industrial waste, effective from December 1998, BAJ prepared in March 1998 a guide for sales managers of battery companies outlining that industrial batteries must be disposed of by the users. BAJ is trying to give the widest diffusion to this guideline. Traditionally, the industrial batteries have been collected and recycled in a specific way without being dumped unlawfully, but the actual treatment has had a somewhat unlawful aspect (in terms of permission for disposal operators, etc.). In the future, BAJ thinks that a lawful and proper treatment will be done thanks to the cooperation between manufacturers and users in accordance with the guideline.
94 2.4. Recycling of Small-Size Sealed Lead-Acid Batteries Approximately 80% of all small-size sealed lead-acid batteries are estimated to be used for commercial purposes, such as UPS, and should be treated in the same way as industrial batteries, as stated above. It can be said that the remaining 20% are used in consumer products including headphone stereos, handy cleaners and electric reels. The general rule is that these batteries are collected through reverse channels of distribution. This assumes that spent batteries are brought by the users back to theshops. However, partly because the smallsize sealed lead-acid batteries have a limited distribution, the information for users is not spread enough. Furthermore, the fact that these batteries are produced in a small quantity and for various uses has not made the sellers themselves well enough informed. Therefore, it is estimated that the collection rate has been rather low. While the total amount of lead-acid batteries collected is known, no data is available for usage type or product type.
3. COLLECTION AND RECYCLING ACTIVITIES FOR PORTABLE RECHARGEABLE BATTERIES In the field of portable rechargeable batteries for such electronic devices, as cellular phones, personal computers and video cameras, many changes occurred in their respective markets. For over 30 years, NiCd batteries have mainly been used as the power source, but NiMH and lithium ion batteries were developed in the early 1990's and, since then, their demand has rapidly increased. For the collection and recycling of portable rechargeable batteries in Japan, both NiCd batteries and the products using NiCd batteries were specified as 1st and 2nd category products by the Law for the Promotion and Utilization of Recyclable Sources issued in June 1993. Since then, BAJ began a collection & recycling program of spent NiCd batteries. After that, other portable batteries like NiMH and lithium ion were gradually found in waste landfills. Considering that they contain so much valuable metals and that collection activity of NiCd battery should be further strengthened, BAJ made a decision to start a nationwide voluntary collection and recycling program for all types of portable rechargeable batteries. This began in July 1998.
95
3.1 Market Trends of Portable Rechargeable Batteries (1) Sales statistics by chemistry Table 3.1 shows the sales quantities of 3 different batteries. The NiCd battery sales have been gradually decreasing since 1994. On the other hand, sales of NiMH batteries in 1998 amounted to 640 million cells, with an increase ratio of 11%, and sales of lithium ion batteries were 275 million cells, with an increase ratio of 41%, with respect to the previous year. (2) Export ratio by chemistry Japanese manufacturers' worldwide sales amounted to 1,503 million cells in 1998. Nearly 80% (1,187 million cells) of them was for export. Table 3.2 shows the export ratio by chemistry in 1998. Although domestic deliveries account for 316 million cells, almost 50% is for re-export as products with the battery included. (3) Export ratios by continent The export ratios in 1998 are shown in Table 3.3. As for export to Asia, table 3.3 shows 34% for NiCd, 27% for NiMH and 36% for Li-ion. However, approximately 90% of the cells seem to be exported again.
Table 3.1. Sales quantities by all japanese manufacturers (million cells ) Year
NiCd
NiMH
Li-ion
Total
1994
880
199
---
1,079
1995
867
305
30
1,202
1996
703
358
114
1,175
1997
693
574
195
1,462
1998
588
640
275
1,503
Table 3.2. Export ratios by chemistry (%) NiCd
NiMH Li-ion
Average
Export
72
94
60
79
Domestic
28
6
40
21
96
Table 3.3. Export ratios by continent (%) Chemistry America
Europe
Asia
Japan
Total
NiCd
20
18
34
28
100
NiMH
25
42
27
6
100
Li-ion
14
10
36
40
100
(4) Domestic sales by application Domestic sales for 1998 amounted to 316 million cells, i.e. 21% of total. Table 3.4 shows the sales ratios by applications. In the field of security and emergency, only NiCd batteries were sold. However, in the fields of office equipment and communications, the Li-ion battery ratio was 69% and 53%, respectively. In the fields of home appliances, electric tools&toys and retail, the NiCd battery ratio was 51%, 84% and 63%, respectively. A ratio of 37% for NiMH batteries was found in retail (replacement). This seems to come from its use as the main power source for digital cameras.
Table 3.4. Sales ratios by application in 1998 (%) Categories Security&emergency
NiCd
NiMH
Li-ion
Total
100
0
0
100
Home appliances
51
13
36
100
Office equipment
18
13
69
100
Communications
35
12
53
100
Electric tools&toys
84
15
1
100
Retail (replace)
63
37
0
100
Others
87
10
3
100
3.2 Collection&Recycling Program of Portable Rechargeable Batteries (1) Background Only NiCd batteries are regulated by law. However, BAJ has started to promote a nationwide collection&recycling program including a voluntary system for NiMH and
97 Li-ion batteries. This program aims at conserving natural resources. Valuable natural resources are especially contained in the new chemistries of NiMH and Li-ion. These new chemistries were introduced and dramatically increased in volume and then new recycling technologies were developed and established. (2) Re-use of recyclable metals Table 3.5 shows the metal composition of rechargeable batteries. NiCd batteries contain such metals as Cd, Ni and Fe which are recyclable (80% of battery weight). NiMH batteries contain recyclable Ni, Co, Fe and rare metals (85%). Finally, Li-ion batteries mostly contain Co, Fe, AI, Cu and Li (65%). Table 3.5. Metal contents in portable rechargeable batteries Chemistry
Metal
NiCd
Ni
15-20
Cd
20-25
Fe
30-35
Ni
40-45
NiMH
Li-ion
Content (%)
Co
5-10
Fe
15-20
RM
10-15
Fe
20-25
Co
15-20
A1
5-10
Cu
5-10
Li
2-4
Total Metal (%)
Approx. 80
Approx. 85
Approx. 65
(3) Collection routes for portable rechargeable batteries In July 1995, BAJ prepared a nationwide NiCd collection program and promoted the related activities to establish an effective collection system based on the cooperation of relevant industries and consumer groups. As for the other rechargeable batteries, it was
98 discovered that they have almost the same sales channels as that of NiCd batteries. Therefore, it was considered that procedures using the same sales channels should be applied for NiMH and Li-ion batteries as well. Major collection routes are as follows. a. Reverse distribution by OEM (original equipment manufacturers) b. Battery shops collection c. Industrial waste collection d. Municipal collection (4) Separate collection by color coding system In order to help sorting and identifying unknown chemistries by children, students, housewives and consumers at the sales points, and to facilitate storage work at the recycling plants, BAJ
introduced a color coding system by chemistry and in 1998
published the book "Guide to Color Coding System for Portable Rechargeable Batteries". This book specifies the standard color number by chemistry as follows: a. NiCd battery : Pantone 389C b. NiMH battery: Pantone 1375C c. Li-ion battery: Pantone 312C (5) Recycling technologies for portable rechargeable batteries a. NiCd battery Cadmium evaporates by heating at approximately 800~ and is recovered as metal or Cd compound. After a refining treatment, Cd is used as secondary raw material for NiCd battery. On the other hand, Fe and Ni are regenerated as ferro-nickel compounds to be utilized as materials for the stainless steel industry. There are 4 recyclers for NiCd battery in Japan and they have over 20 years of operating experience. b. NiMH battery A recycling technology for NiMH batteries is now under development. Ni, Co and Fe are used for stainless steel products. There are now 8 recyclers in Japan, but they
99 are in the initial stage of commercial operation. c. Li-ion battery The most valuable element, Co, is separated from Fe, A1 and Cu by sieving. Co is then chemically treated to produce a cobalt compound. Fe and Cu/A1 are magnetically separated for re-use. There are 9 recyclers in Japan, but they are also in the initial stage of commercial operation. If the cathode materials are changed to Mn or Ni, additional developments of this new technology will be required in the future. A list of recyclers by chemistry is shown in Table 3.6.
Table 3.6. A list of recyclers in Japan Name of recycler
NiCd
NiMH
Li-ion
Toho Zinc
[]
[]
D
Japan Recycle Center
[3
[]
[3
Mitsui Metal
[] D
D
[3
D
D
[3
Nihon Mining Metal Sumitomo Metal Mining Kansai Catalyst Chemicals
[3
Nisso Metal Chemicals Horyu Chemicals
[3 D
[3
Kosumo Co.
@
[3
Santoku Metal
[3
[3
The mark [3 indicates the kind of battery recycled. (6) Collection results of portable rechargeable batteries Table 3.7 shows the collection results of spent NiCd, NiMH and Li-ion for the period 1994-1998.
100
Table 3.7. Collection results by chemistry (tons) Year
NiCd
NiMH
Li-ion
1994
630
. . . . . .
1995
641
7
---
1996
633
60
9
1997
692
184
49
1998
736
160
94
3.3 Hoarding Issue of Appliances with Portable Rechargeable Batteries (1) Background In the collection&recycling program of NiCd batteries, collection results for the sealed type for consumer use show a little increase (table 3.7). Therefore, BAJ made a preliminary study with the cooperation of 200 persons on typical appliances using portable rechargeable batteries. The results indicated that not all appliances were discarded into the waste stream after their life was over, with a ratio of 75% for video cameras, 44% for cellular phones, 47% for personal computers, and 57% for electrical toys. This means that a considerable volume of portable rechargeable batteries in the market are being retained by consumers. In other words, they are neither returned to the recycling chain nor sent to the f'mal disposal - the cells are being hoarded. (2) Necessary initiatives The current definition of collection rate is based on the sold and distributed weight of batteries and their service life. However, the service life of the batteries related to appliances should be regarded as very long when hoarded batteries are taken into consideration. In order to make collectable quantity clarified and also to make the collection effort properly evaluated, the hoarding rate of the batteries should be taken into account. (3) Survey on hoarding rates of appliances with portable rechargeable batteries Purpose of the survey
101 a. The purpose is to know how batteries for personal use are discarded and disposed of and to determine the effective useful life and hoarding rate of both appliances and batteries. 1,250 families were surveyed with a total of 3,414 persons. b. Appliances using the batteries under survey -
Home electric appliances such as video cameras, headphone stereos and electric shavers.
- Communication tools such as cellular phones, cordless phones and PHS. - Office equipments (laptop computers, word processors and PDAs). - Hobbies&toys (electric toys for children and amateurs). - Electric power tools. c. Summary of survey results Basic data obtained is as follows: -
-
Total number of appliances containing batteries. Total number of appliances with batteries disposed of.
- Years in use (effective useful life) for individual appliances with batteries. -
-
Number of appliances with batteries hoarded after the years in use. Number of appliances with batteries and separate batteries disposed of after the years in use.
-
Method of disposal.
- Number of spare battery packs for individual appliances. The total number of appliances using batteries was 5,352 and their ratio by kind of appliance was 25% for cellular phones, 22% for electric shavers, 17% for cordless phones, 13% for headphone stereos, 9% for video cameras, 8% for personal computers, 4% for toys and 2% for tools. Over 90% of the appliances using batteries indicated the same behavior: discarding of appliance with battery or hoarding of appliance with battery. Only
about 8% of the answers indicated a different behavior: discarding of
appliance without battery or discarding of battery without appliance. Therefore, portable rechargeable batteries have the same life cycle of the battery incorporating appliances. (4) Average years in use and hoarding rate According to the survey results, the average years of use for an individual appliance was calculated. The hoarding rate was also calculated from the difference between the total number of batteries and the number of batteries available for collection. Table 3.8 shows average years in use and hoarding rates.
102 Table 3.8. Average years in use and hoarding rate
Appliances
Average years in use
Hoarding rate (%)
Video cameras
6.4
83
Headphone stereos
4.2
71
Electric shavers
4.3
47
Cellular phones&PHS
1.5
59
Cordless phones
4.5
83
Laptop computers&WP
5.2
79
Electric toys
3.1
57
Electric tools
3.6
94 Average: 65%
"Average years in use" vary depending on the appliances. However, a high hoarding rate for individuals indicates that consumers do not discard or dispose of their own appliances with batteries. (5) New proposal for the definition of collection rates According to the results of the consumer survey, portable rechargeable batteries incorporated in portable electronic devices are kept at home with an average ratio of 65% after the effective useful life. Conventional collection rates have been using the sold and distributed weight of batteries. However, just because of the hoarding, this weight cannot coincide with the waste weight. Therefore, the real waste weight can be obtained by subtracting the hoarded weight to the distributed weight. Table 3.9 shows a comparison between conventional and new collection rates. (6) Final goal of "Hoarding" issue As mentioned above, in the consumer survey conducted by BAJ, 1,250 families were surveyed. Almost all their portable electronic devices and appliances using portable rechargeable batteries are widely used in the world market. In order to increase its reliability, repeating of such survey should be performed from time to time or when big changes in the market occur.
103 Table 3.9. C o m p a r i s o n of Collection Rates (CR)
Conventional: CR = A x100%
New with Hoarding: CR =
A
x100%
B(1-X ) A: Weight of batteries collected in collection chain B: Weight of batteries sold and distributed X: Hoarding rate B(1-X): Weight of batteries discarded as waste Value of X: 0.65 (65%) Case 1: a conventional CR of 20% becomes 57% Case 2: a conventional CR of 25% becomes 71%
The following is BAJ's position on hoarding issue. - A formula with a methodology based on precise statistical consumer data must be
established. - The public should be aware of the issue of spent portable rechargeable batteries and the necessity of a strong cooperation among consumers, relevant industries and government, so that hoarded batteries should be returned into the collection chain. - Most important action is to reach a national consensus among government, relevant
industries, consumer groups and battery industry about the definition of collection rates including the hoarding issue.
3.4 Final C o n s i d e r a t i o n s for Portable R e c h a r g e a b l e Batteries
In Japan, BAJ started collection and recycling program for all types of portable rechargeable batteries in July 1998. Their sales volume is still increasing with further development of portable electronic devices. In view of the utilization of valuable resources, their recycling technologies to produce secondary raw materials are being
104 established and are now under commercial operation. On the other hand, it is also important to take measures for preserving the environment. Accordingly, BAJ has conducted consumer surveys on how people handle batteries in use (discarding and hoarding). As a result, a value of the hoarding rate higher than expected was obtained. This means that the waste volume of portable rechargeable batteries is relatively low. However, this also emphasizes the need of a strong cooperation aiming at the return of hoarded batteries into the collection chains. Collection rate is one of the most important key factors for evaluating the environmental situation. With the introduction of the hoarding concept, the collection rates of spent NiCd batteries in Japan was in general found to be higher than 50%. By expanding the information and education programs to the public, an increase of collecting weight will be expected, not only for NiCd batteries but also for NiMH and Li-ion batteries. By continuing the above mentioned improvements, all types of portable rechargeable batteries will be environmentally friendly products in the coming recycling society.
Used Battery Collection and Recycling G. Pistoia, J.-P. Wiaux and S.P. Wolsky (Editors) 9 2001 Elsevier Science B.V. All rights reserved.
NICKEL-CADMIUM AND RECYCLING
105
BATTERY COLLECTION PROGRAMS
IN T H E USA AND C A N A D A
Norman England a, David B. Weinberg b, Kenneth L. Money c and Hugh Morrow d a
The Portable Rechargeable Battery Association, 1000 Parwood Circle, Atlanta, Ga
30339, U.S.A. b Howrey Simon Arnold & White, 1299 Pennsylvania Ave., Washington, D.C. 20004, U.S.A. c International Metals Reclamation Co., Inc., P.O. Box 720, 245 Portersville Road, Ellwood City, PA 16117, U.S.A. d International Cadmium Association, 9222 Jeffery Road, P.O. Box 924, Great Falls, VA 22066-0924, U.S.A.
INTRODUCTION Nickel-cadmium batteries are divided into two major classes - the small consumer cells that make up approximately 80% of the market and the large industrial batteries, which constitute the remaining 20%. The distinction between the two types of batteries, their applications and markets, and, most importantly, the total number of users of these two types is very important in establishing collection and recycling systems for NiCd batteries. Small consumer cells are typically used for portable household appliances, cordless power tools, hobbies and toys, emergency lighting, cordless telephones and many other types of portable communications devices. They are utilized by millions of consumers, tend to be discarded into municipal solid waste or stored at the end of their normal useful life, and are therefore more difficult to collect for recycling purposes. The large industrial NiCd batteries find application for railroad and aircraft starting, switching and signaling, standby power, electric and hybrid electric vehicles, and telecommunications distribution systems. They tend to be concentrated in a relatively few users, hundreds at most, and are therefore much easier to collect for recycling. It is therefore not surprising that industrial NiCd batteries are currently recycled at approximately an 80% rate while the consumer NiCd batteries are recycled at much lower rates, from 5% to 50% depending upon the specific
106 country and collection program in place. Therefore, the task for the NiCd battery industry is to collect and recycle the small consumer cells, and this discussion will focus mainly on the industry-sponsored efforts in the United States and Canada to collect and recycle these batteries.
THE ENVIRONMENTAL ISSUES The human health and environmental issues associated with nickel-cadmium batteries arise mainly from the ultimate disposal of the spent batteries. In general, occupational exposures to and manufacturing wastes and emissions from nickel, cadmium, cobalt and other materials in NiCd battery production are well regulated and controlled. There is virtually no danger of nickel or cadmium exposure during normal use of NiCd batteries. Even when NiCd batteries are disposed of in landfills, there is little danger of risk or exposure, at least in the short to mid-term, to nickel or cadmium from the battery's electrodes since they are always encased in at least two layers of steel or plastic or both. In the past twenty years, the space available for the disposal of waste in landfills has diminished rapidly, in some of the densely populated countries much more so than in others. In several countries in Europe and in Japan in particular, incineration and the human health and environmental issues arising from incineration have been instrumental in promulgating regulations affecting metal products. Since 1985 in the United States, some municipalities and local jurisdictions have made huge investments in solid waste incinerators to reduce the volume of disposal waste and because there just has not been sufficient space available for landfilling. However, these incinerators have not proved to be totally cost effective because of the additional expense of disposing of the incinerator's waste products, ash and slag. Unfortunately, these wastes and slags may contain levels of toxic materials that result in them being classified as "hazardous." The end result is an enormous increase in ash and slag management and disposal costs. In 1989, Franklin Associates published a report under contract to the U.S. Environmental Protection Agency on the sources of lead and cadmium in municipal solid waste (MSW) that clearly identified NiCd batteries as a major source of cadmium. Based on this report, which later proved to have exaggerated the NiCd
107 contribution to MSW, state jurisdictions, especially those with heavy commitments to new incinerators, began to propose legislation and regulation to divert NiCd batteries from the waste stream, and several even mandated NiCd battery collection programs which in turn led to voluntary action by some companies. However, shortly after issuance of the Franklin Report, EPA changed its test protocol for determining what wastes should be classified as hazardous. The new test protocol, the TCLP test, required that used NiCd batteries first be crushed or cut to a certain size much smaller than the size of the battery itself thereby exposing the internal nickel and cadmium electrodes, and then placed in an acetic acid solution for about a day to simulate the relative amount of nickel or cadmium leaching from the batteries into landfill leachate over a protracted period of time. Not suprisingly, used NiCd batteries failed the TCLP test and were classified as "hazardous waste." As a consequence, the transportation, storage and handling of used NiCd batteries immediately came under the jurisdiction of the United States' Resource Conservation and Recovery Act (RCRA) under which waste generators are required to obtain identification numbers from federal and state regulators, transporters must meet stringent regulatory requirements, and collection and recycling facilities need comprehensive and expensive permits. Such an array of regulatory requirements immediately halted the voluntary collection and recycling programs previously started for NiCd batteries even though some states were beginning to put legislation in place requiring collection and recycling. To add further to the confusion, RCRA requirements on used batteries did not apply to those generated from household wastes, but did apply to batteries from institutional generators. If a mixture of batteries from both sources were collected, then all were regulated. Previously, the U.S. EPA had specifically promulgated regulations that exempted used lead acid batteries from the regulatory burdens of RCRA in order to facilitate the already well-established recycling of automotive batteries. As a result, lead acid batteries enjoyed a recycling rate of better than 95%. NiCd batteries, however, were not included in this earlier scheme, and at the time the TCLP test was initiated, its potential impact on NiCd batteries was not recognized and no provisions were made to facilitate their recycling.
108 THE NiCd BATTERY RECYCLING PROBLEM
In April 1991, the NiCd battery manufacturers approached the U.S. Environmental Protection Agency with their problem. Even though they wanted to collect and recycle NiCd batteries to get them out of the municipal solid waste stream and needed to comply with several state recycling mandates as well, they were hindered from doing so because of the "hazardous waste" classification of used NiCd batteries. There was no technologically economical way to segregate exempted "household" used batteries from regulated "business" batteries, and too many of the mass market distributors whose cooperation was required to collect the batteries simply would have nothing to do with handling hazardous wastes. Even if collection systems could be set up, they would be economically prohibitive to manage when, for example, shipments of used NiCd batteries had to be transported by manifested hazardous waste carriers. Even though the U.S. EPA staff was sympathetic, no direct action was initially taken, and NiCd battery manufacturers proceeded to file a formal petition for rulemaking to reduce the regulatory burdens associated with the collection and recycling of NiCd batteries. Their proposal suggested that EPA either suspend or defer the application of the TCLP test to used NiCd batteries intended for recycling or that the exemptions granted for the recycling of lead acid batteries be extended to NiCd batteries as well. However, rather than adopt either of these suggestions, the U.S. EPA indicated that it would treat NiCd batteries within the framework of its ongoing effort to adopt rules to facilitate recycling of a number of other products including pesticide containers, mercury switches and fluorescent light bulbs. There were, however, potential problems and questions about recycling some of these products, which proved difficult and controversial. In spite of a groundswell of national support from NiCd battery manufacturers and users, little progress was made until political support was obtained from Capitol Hill. Even with bipartisan political support and fundamental agreement with the principles of the program, it was not until April 1995 that a final EPA regulation was issued and not until May 1996 that national legislation was signed into law, which facilitated a uniform, national NiCd battery recycling program in the United States. Thus, five years of intense effort and expense by the industry were necessary to implement what everybody agreed was a fundamentally sound idea in the first place.
109 THE INDUSTRY NiCd BATTERY RECYCLING PROGRAM
The plan proposed by the NiCd battery industry as early as 1993 and which today is being implemented by the Rechargeable Battery Recycling Corporation (RBRC) is known as the Charge Up to Recycle! program. RBRC is a not-for-profit corporation founded in 1994 and funded by rechargeable battery and product manufacturers to implement and maintain NiCd battery collection and recycling programs in the United States and, through a subsidiary, in Canada. The RBRC program has created various recycling plans for communities, retailers, businesses, and public agencies. For each group, RBRC pays or shares the cost of consolidating the batteries, shipping them to the processing facility, and recycling them. All NiCd batteries collected by these plans are sent to the sole North American facility capable of processing and recycling them, the International Metals Reclamation Co., Inc. (INMETCO). At their Ellwood City, Pennsylvania facility near Pittsburgh, nickel and iron are separated from cadmium in NiCd batteries and shipped to specialty steel producers to produce stainless steel. The recovered cadmium, at a 99.95 percent purity level, is sold for production of new NiCd rechargeable batteries and in other cadmium-containing products. INMETCO's recycling process is recognized by the U.S. EPA as being the "best demonstrated available technology" to recycle NiCd batteries. The Charge Up to Recycle! program contains several key elements which are specified both in the U.S. EPA regulation (40CFR, Part 273), various United States' state laws governing NiCd battery recycling, and in the "Mercury-Containing and Rechargeable Battery Management Act" of 1996. These include the following provisions: 9 Uniform Battery Labeling Requirements 9 Removeability of Batteries from Appliances 9 National Network of Collection Systems 9 Regulatory Relief to Facilitate NiCd Battery Collection 9 Widespread Publicity to Encourage Public Participation 9 Development of a Funding Mechanism for the Program
110 The uniform battery labeling requirements, as, for example, specified in the "Mercury-Containing and Rechargeable Battery Management Act", mandate that each regulated battery or rechargeable consumer product without an easily removable battery contain the three chasing arrows recycling symbol or a comparable recycling symbol, the designation "nickel-cadmium" or "Ni-Cd" and the phrase "Battery must be recycled or disposed of properly." On each rechargeable consumer product containing a regulated battery, which is not easily removable, the required labeling is "Contains nickel-cadmium battery. Battery must be recycled or disposed of properly." The easy removeability provision is also specified in the 1996 legislation and was an early requirement in several of the state NiCd battery recycling laws. These provisions were developed at the time when many NiCd battery power tools and appliances did not provide for easy removeability, mainly as a consumer safety measure. Since the early 1990s, however, battery operated tools, appliances and other devices have been designed so that in most cases the batteries are easily removable while still ensuring consumer safety. In fact, many manufacturers of battery powered tools today market replacement battery packs, which are interchangeable in a number of different tools. Only in certain systems such as computer memory backup and medical devices are the batteries permanently installed to avoid system failure. The Charge Up to Recycle? program features three different avenues of collecting used NiCd batteries for recycling: 9 Retail Recycling Plan (over 30,000 locations) 9 Community Recycling Plan (300 enlisted) 9 Business & Public Agency Recycling Plan (1,800 enrolled) By offering a different type of collection method to each target audience, this program is designed to obtain the maximum return of the small sealed NiCd batteries from each sector. These batteries could only have been collected by these mechanisms provided that the regulatory relief which is embodied in the exemptions granted under 40CFR, Part 273 for the storage, handling and shipment of used NiCd batteries intended for recycling was developed. Essentially, this regulation exempts the diffuse sources such as the retail outlets, county and municipality collection points, commercial/institutional generators, and individual consumers from any regulatory burdens associated with collecting and shipping their used NiCd batteries back to
111 centralized collection or "consolidation" points or directly to the NiCd battery recycling facility itself. In the Charge Up to Recycle! program in the United States today, Kinsbursky Brothers of Anaheim, California and INMETCO in Ellwood City, Pennsylvania are the two RBRC consolidation points for collected NiCd batteries, while INMETCO is also the NiCd battery recycler. Publicity and public awareness of the program has been generated through a number of means, and is increasing. To make the program work and develop the levels of NiCd battery recycling desired, widespread public education and outreach is required. This has been provided by a number of approaches including: 9 Prime Time Television Celebrity as Program Spokesperson 9 Nationwide Toll-Free Voice Automated Response System 9 Information and Collection Kits for Retail Outlets 9 Collection/Shipping Arrangements with Municipalities 9 Collection/Shipping Arrangements with Institutions/Corporations Finally, a funding scheme was implemented to pay for the recycling program, and it is paid for entirely by the rechargeable power industry. In order to assure equitable funding, entities at various levels of the manufacture and distribution chain (cell manufacturers, battery pack assemblers, battery marketers, and product manufacturers and marketers) may license the right to display the trademarked and EPA-certified
Figure 1. Trademarked RBRC Seal for Licensees
112 RBRC seal, shown in Figure 1, on their products. The licensing fee is proportional to the size of the cells incorporated in the product. The program also provides incentives for licensees to utilize their own distribution infrastructure to collect batteries and recycle them in a manner similar to that of the commercial/institutional generators. Licensees can receive a rebate of up to 75% of their original licensing fee based on the weight of batteries collected for recycling through their own infrastructure. To date, there are approximately 325 licensees signed up for the Charge Up to Recyclet. Program, including virtually all of the major producers and users of NiCd batteries in Canada and the United States. The RBRC program has the support of over 30,000 collection sites in the United States and Canada where consumers can drop off their used NiCd batteries for recycling. Participating retailers in the United States include ACE Hardware, Ameritech, BellSouth Cellular, Black & Decker, Car Phone Store, Cellular One, Circuit City, Radio Shack, Sear, Target and Wal-Mart. Consumers can locate the collection locations nearest them by calling 1-800-8-BATTERY (1-800-822-8837) or by visiting RBRC's website at www.rbrc.org. The RBRC Charge Up to Recyclet. Program was launched in Canada in 1997, and has now received the endorsement of Environment Canada and Natural Resources Canada. An EcoAction Network was established by Environment Canada to create public awareness for positive environmental actions taken by Canadians. The Network's objective is to demonstrate how entities such as RBRC are contributing to a healthier environment- and thereby encourage others to take similar actions across the country. This recognition acknowledges the proactive and voluntary action of the RBRC in developing and successfully implementing the program. The only battery management program of its kind in Canada, the RBRC program is available to all Canadians. Consumers can take their used NiCd battery to any of the more than 4,500 retail outlets that serve as collection sites. Participating Canadian retailers include Astral Photo Images, Authorized Motorola Dealers, Battery Plus, Black's Photography, Canadian Tire, Radio Shack Canada, Zellers, Personal Edge, and Centre du Rasoir.
113 The effectiveness of the RBRC program is demonstrated most clearly in the amounts of NiCd batteries collected for recycling in the program over the six years. These data are summarized in Figure 2. These data show an almost 52% increase in the collection of NiCd batteries in Canada and the United States from 1995 through 2001, an average of 8.6% per year improvement, and clearly demonstrate the effectiveness of the RBRC Charge Up to
Recycle! Program.
Figure 2. Nickel-Cadmium Batteries Collected for Recycling in North America
THE INMETCO NiCd BATTERY RECYCLING PROCESS The International Metals Reclamation Company, Inc. (INMETCO), located in Ellwood City, Pennsylvania, began operations in 1978 as a metals recycler. INMETCO is committed to the concept of sustainable development, which requires
114 balancing the need for economic growth with good stewardship in the protection of human health and the natural environment. Since 1978, INMETCO has been actively involved in the reclamation of various metallic secondary materials, including nickel, chromium, iron, molybdenum, cobalt and cadmium. Most of the secondary materials containing these metals reclaimed at INMETCO originate in the stainless steel industry, but since the introduction of the Cadmium Recovery Facility at INMETCO in 1995, a significant portion of the secondary materials also originate from spent batteries, especially NiCd's. In 1991, the U.S. EPA announced that the High Temperature Metals Recovery (HTMR) Process used by 1NMETCO was the Best Demonstrated Available Technology (BDAT) for treating electric arc furnace dust (EPA Waste Code K061), pickling wastes (K062), waste water treatment sludges from electroplating operations (F006), and spent nickel cadmium batteries (D006). INMETCO's High Temperature Metals Recovery process reclaims the nickel, chromium, iron, molybdenum and cobalt from the secondary wastes indicated above and produces a remelt alloy in cast pig form, weighing 25-30 pounds. The remelt alloy is shipped to most of the stainless steel manufacturers in the United States, as well as certain other international companies, for use as raw material feedstock in the production of more stainless steel. As an ISO 9002 certified facility, INMETCO, a fully permitted facility, is the only High Temperature Metals Recovery facility in North America dedicated to the recovery of nickel, chromium, iron and molybdenum from both hazardous and non-hazardous wastes. In the Cadmium Recovery Facility, INMETCO reclaims cadmium from spent NiCd batteries and produces a high purity cadmium shot known as Cadmet A or Cadmet B. The majority of recycled cadmium is returned to the battery industry for the production of new nickel-cadmium batteries. INMETCO's Cadmium Recovery Facility began operations in 1995, and since that time, INMETCO has been the only true recycler of NiCd batteries in North America.
High Temperature Metals Recovery, Process The INMETCO HTMR process uses industry standard equipment in a unique and patented process. At the heart of the INMETCO process is the use of coal or carbon products to reduce oxidized metal wastes to their metallic form in a rotary hearth furnace. The technology has been adapted to produce direct reduced iron from ore concentrates, carbon steel waste products, or a combination of these materials. The
115 High Temperature Metals Recovery process consists of four basic steps: (1) feed preparation, (2) reduction, (3) smelting, and (4) casting. Feed Preparation - In the feed preparation phase, both solid and liquid wastes are
drawn from storage containers and blended with other additives to form pellets for further processing. Coke or coal and/or other secondary carbon products are used as a reduction agent in the process, and are added at this point. A screw conveyer mixes and transports the resulting mixture to a pelletizing disk. Here, secondary liquids containing nickel and chromium are added to form green pellets. In the feed preparation phase, vented or industrial NiCd batteries are drained. Their electrolyte is used as a reagent in the wastewater treatment plant. The positive nickel plates are shredded and fed into the rotary hearth furnace and subsequently into the electric arc furnace for nickel and iron recovery. The negative cadmium plates are processed in the cadmium recovery facility. R e d u c t i o n - The blended feed materials are transferred to the rotary hearth furnace
operating at approximately 1260 degrees Fahrenheit. In the rotary hearth furnace, some of the carbon added during the blending stage reacts with the oxygen in the waste to reduce the metal bearing wastes to their metallic form. Gas produced in the process is discharged to a wet scrubber system. The scrubber water is then treated in a wastewater treatment plant on-site. This water is recycled back to the plant for reuse. The only products released to the atmosphere are essentially water vapor and the usual products of combustion. Smelting- The hot reduced feed is transferred from the rotary hearth furnace to the
electric arc furnace where the third major process occurs. The electric arc furnace performs a smelting operation to produce a nickel, chromium, and iron alloy. Lime, silica, magnesia, and alumina separate to form a slag/metal bath. Metal and slag are tapped periodically from the bath. The slag is collected and hauled to a slag cooling area. This non-hazardous slag may subsequently be used in building roads, parking lots, and commercial driveways. Casting- Casting is the final step. Molten metal is cast into pigs using a twin strand
pig caster. The bars of metal formed in the molds are called "pigs". Pigs are grouped into lots of approximately 20 tons and are shipped to stainless steel manufacturers to be used as remelt alloy for the production of stainless steels.
116
Cadmium Recovery, Facility NiCd consumer cells are small, sealed-cell batteries, which are most familiar to consumers, are rechargeable battery power packs for cordless drills, cellular and cordless phones, camcorders, household appliances, and battery-operated toys. The batteries in power packs are typically contained in a plastic case, which must be removed prior to cadmium extraction. The plastic is removed in a two-step process including INMETCO's patented rotary thermal oxidizer. In this process, the plastic, paper, and moisture are removed without fuming off cadmium.
INMETCO - INDUSTRIAL NiCds Ni-Cd Batteries Industrial Type
legative Plate~ Shred Ni-Fe
~tiol Cd Fume
:d Met
Figure 3. INMETCO Recycling Process for Industrial NiCd Batteries
117 After the plastic has been removed, the batteries are charged into a cadmium furnace and the cadmium is distilled off at high temperatures and collected. Negative cadmium plates from industrial batteries are also charged into the cadmium furnace for distillation of the cadmium. Carbon is added as a reductant. The charge is heated and the cadmium distilled, then collected in a water bath. The final cadmium product is in shot form. The cadmium shot is drummed, weighed, assayed, and shipped to the customer. The residue from the cadmium furnace, mostly iron and nickel, is shredded and fed to the nickel plant for nickel and iron recovery. Schematic diagrams of the processes utilized for the recycling of industrial and consumer NiCd batteries at INMETCO are shown in Figures 3 and 4.
1NMETC0
- CONSUMER
NiCds
Shred Ni-Fe Residual
Cd Fume
ti-Cr-Fe AIIo
Figure 4. INMETCO Recycling Process for Consumer NiCd Batteries
This Page Intentionally Left Blank
Used Battery Collection and Recycling
G. Pistoia, J.-P. Wiaux and S.P. Wolsky(Editors) 9 2001 Elsevier Science B.V. All rights reserved.
ENVIRONMENTALLY CADMIUM
119
SOUND RECYCLING
OF NICKEL
BATTERIES
N. England President and CEO, The Portable Rechargeable Battery Association, 1000 Parkwood Circle, Atlanta, GA 30339, U.S.A.
I.
INTRODUCTION AND PRINCIPAL FINDINGS Rechargeable nickel cadmium (Ni-Cd) batteries possess attributes that make
them ideal for powering portable appliances such as cellular and cordless telephones, portable household appliances, and power tools. Since their mass-market introduction in the mid-1980s, they have achieved wide consumer acceptance in all member states of the Organization for Economic Cooperation and Development (OECD). The 29 states are listed in the Appendix. Nonetheless, concern exists that after the useful lives of these batteries has ended, they may become a source of cadmium and nickel that reaches the environment. Recycling Ni-Cd batteries addresses this concern and also conserves valuable natural resources. However, used Ni-Cd batteries do not trade freely as commodities because the cost of collecting them for recycling exceeds the value of their reclaimed constituents. Faced with this challenge, companies that manufacture and use these batteries have developed and implemented collection programs in several national jurisdictions, and are now working to coordinate these activities intemationally.
There is now approximately a decade's experience with these programs, from which a number of lessons can be drawn. are as follows:
This paper does so. Its fundamental findings
120
A successful used Ni-Cd battery collection program requires support from several economic sectors and entities that operate a variety of convenient collection points -- retailers, product service centers, municipalities, and institutional generators. OECD member nations implement strict hazardous waste handling requirements to protect against the worst case environmental damage involving
dispersible
and
acutely
toxic
chemical
wastes.
When
governments apply these requirements to the collection of used articles that are not acutely toxic, such as Ni-Cd batteries, the result is to saddle the collector with complex legal requirements that create significant potential liability. This discourages the participation of the most necessary collector entities and complicates collection programs. Used Ni-Cd batteries are physically indistinguishable from new product. As a result, no environmental protection goal is achieved by requiring shipments to comply with hazardous waste transportation requirements. These requirements do cause prohibitive cost increases, however. There are only a handful of appropriate facilities in the world for reclaiming nickel cadmium batteries, and all are subject to scrutiny and permitting by their national governments.
Therefore, identification of an appropriate
recycling destination is simple and, so long as collected materials are routed to one of these facilities, the transboundary shipping requirements that make up the OECD "amber" scheme are unnecessary. Streamlining requirements for Ni-Cd battery collection and transportation is not inconsistent with applying stringent hazardous waste regulatory controls to the facility that recycles them. Economic
relationships
among
Ni-Cd
cell
manufacturers,
battery
manufacturers, manufacturers of Ni-Cd-powered products, and distribution channels are complex and varied.
As a result, effective collection
121 programs can most efficiently be implemented when industry groups voluntarily work out arrangements to allow the costs of administering to be shared equitably among all marketplace participants. The most important roles for government to play are to facilitate such voluntary action and encourage widespread participation by all manufacturers and marketers.
II.
THE NATURE AND IMPLICATIONS OF RECHARGEABLE Ni-Cd BATTERY DISTRIBUTION This section of this paper examines the key elements necessary in establishing a
successful rechargeable Ni-Cd battery recycling program.
As background, it is
important that the reader understand certain basic terminology and relationships.
Consumer use of the term "battery" in fact often extends to several different items. The basic building block of a "battery" is a " c e l l " - the combination of materials that produces electrical current in a predictable fashion. single cell.
Some "batteries" consist of a
More commonly, however, a series of cells are connected in a single
package. In the trade, this is commonly referred to as a "battery pack," but consumers often call it simply a "battery." Cells and battery packs can be included in products sold to consumers - such as portable telephones or power drills - or sold independently. In the trade, the former category is generally referred to as "original equipment manufacture" or "OEM," while the latter is referred to as "replacement." A number of channels of manufacture and distribution apply within each category.
Their principal shared characteristics are that they are multileveled,
intemational and dynamic. For example, an OEM battery pack included in a power tool may include cells manufactured in one or more countries (by a company or companies domiciled elsewhere), which were assembled into battery packs in yet another country or countries, by yet another company, and which then finally were assembled into the tool elsewhere (and by another company or companies). This last company may then place its own brand on the product, or supply it to yet another company which markets the product under its own brand.
122 The uninitiated generally characterize only the company whose brand appears on the product as the product manufacturer, but this obviously is not necessarily the case. Furthermore, even after the product is "manufactured," it may be sold directly to retailers, may be sold through one or more independent distributors, or maybe sold through both channels. Moreover, the same companies that supply component parts to the OEM product supplier may also supply it with replacement battery packs; may market those replacement products on their own; and/or may supply replacements to yet others to sell under their proprietary brand names.
In addition, there are some companies that
manufacture or assemble battery packs and batteries only for the replacement market. These replacement products may be marketed under the assembler's name or under that of some other entity. Varying cost and pricing considerations affect companies that participate at each level of this complex manufacture and distribution scheme.
Moreover, these
relationships are constantly changing. Additional dynamism arises from technological progress, which results in particular products being put to different uses over time. For example, five years ago rechargeable Ni-Cd batteries were the solution of choice to power all sorts of portable products, including computers, telephones and power tools. Today, batteries that rely upon chemistries other than nickel - cadmium have come to play an increasingly important role in many sectors, such as laptop computers and camcorders.
Thus,
distribution channels that were devoted to Ni-Cd batteries some years ago may now carry a relatively smaller quantity of such products or, in some situations, may no longer handle any Ni-Cd battery-containing OEM products at all.
At the same time, the
remaining OEM and replacement Ni-Cd battery marketplace has attracted additional suppliers. No governmentally-defined collection program can be expected to efficiently or effectively respond to these changing conditions or allocate responsibilities and costs among the numerous participants in product manufacture and distribution.
But quick
123 responses and cost allocations of this sort are a fundamental aspect of all marketplaces. Hence, collection and recycling programs can be expected to be most successful where governmental entities create an environment in which voluntary, private sector systems can succeed and then encourage widespread participation in those programs.
III.
NI-CD BATTERY RECYCLING EXPERIENCES WITHIN THE OECD
A.
The European Experience Well-established Ni-Cd battery recycling plants are operational in France,
Germany and Sweden. These plants, one of which has been in operation since 1977, recover the cadmium, nickel and iron from batteries collected throughout Europe and elsewhere across the world. The European Battery Directive, EEC 91/157, eslablishes a labeling requirement and requires separate collection for used Ni-Cd batteries marketed in Europe. Such batteries are also regulated as special waste when spent, imposing more costly handling requironents than apply to n~st recyclable products, but less than apply to hazardous waste.
The
European Battery Directive has spmred the collection of Ni-Cd batteries through a number of different systems. F~st, there are general public collection schemes run by governments in a number of European countries. Second, lhere are also numerous collection progrmas focused solely on Ni-Cd batteries fiat are being funded by the battery industry, in cooperation wilh government.
Finally, Ni-Cd batteries are also collected in programs
operated by OEM manufacturers that capture the appliance at the end of its life and fie battery that has been powering it as well. When these batteries are shipped across national borders for recycling in France, Germany or Sweden, all of the applicable OECD transboundary controls apply. Since the early 1990s, private seclor sponsored battery collection schemes have been operating in many counties in Western Europe, including Austria (UFB), Belgium (BEBAT), Germany (GRS), lhe Netherlands (STIBAT), Switzerland (BESO), the U.K. (REBAT), and France (ECOVOLT). Similar recycling organizations are being set up in Italy, Norway, Spain and Sweden. 1he number of units being collected increases each year.
124 However, these programs' operations are not all identical, in part because of the varied legal requirements that exist in the different countries. The divergent program approaches that developed across Europe have led to inconsistencies and inefficiencies that the European Portable Battery Association (EPBA) is seeking to address. example, some countries require the collection of all used portable batteries
For
(i.e.,
Austria, France, Germany, Netherlands, Sweden, and Switzerland), while other national collection mandates are focussed on used Ni-Cd batteries
(i.e., Denmark and Norway).
In the U.K., Ni-Cd batteries are collected on a voluntary basis. Efforts to extend the U.K. program to cover all portable rechargeable batteries under an industry established return company failed, in part because of disagreements over how to share the costs of collection among industry participants. Some of the disputes concerned paying for the collection of "free-rider" batteries
(i.e., batteries produced or imported by companies
that do not financially participate in the program).
Funding mechanisms to pay for Ni-Cd battery collection programs have varied from one EU country to the next, sometimes to the point of incompatibility.
For
example in Denmark manufacturers and importers of Ni-Cd Batteries are required to pay fees based on the number to be sold.
These monies are paid out to (15 Euro/kg )
collection companies who return spent Ni-Cd batteries to the government. Collection efforts have thus focused on the more urban, high population density areas because the collection results are the most profitable there, leaving more rural locations without collection. As a result, used Ni-Cd batteries that were originally purchased elsewhere in the EU -- including countries where collection organizations pay for collectionreportedly have been funneled to Denmark for the refund revenue. Consumers pay the fee indirectly by an increase in the cost of batteries. Sales of Ni-Cd batteries and battery powered tools reportedly have decreased in Denmark as a result of this deposit. In Norway, a new organization (REBATT AS) has undertaken the management of deposits collected from replacement Ni-Cd battery importers.
Monies are also
collected from sellers of OEM batteries, but these are put into the fund dedicated to electronic waste recycling. As REBATT AS collects OEM batteries, it invoices the
125 electronic waste fund for the monies necessary for their recycling. The fact that over 90% of the Ni-Cd batteries now marketed in Norway are OEM batteries makes this system very complex. The most common OEM collection programs are operated by the cordless tool industry. ~Spent Ni-Cd batteries, often along with the tool, are collected through reverse distribution schemes batteries).
(e.g.
the truck that brings new products returns with used tools and
Consumers may thus leave their spent batteries and/or used tools at
specialized trade or company outlets or service centers. Bosch runs such a program in Germany.
Black & Decker operates a similar one in the U.K.
An association of
manufacturers operate programs in France (Ecovolt) and Italy (Ecoelit).Computer batteries are collected by Siemens-Nixdorf in Germany.
Nokia and Ericsson are
cooperating with the cordless tool manufacturers to begin a new program in Finland this month. As examples of how such programs operate, the following discussion focuses on two OEM operated programs in the U.K. and Sweden.
I.
U.K. Pilot Collection Experience In 1996, a group of cellular phone manufacturers organized two year pilot
programs to collect end-of-life cellular phones and the batteries that power them in the U.K. and Sweden.
The group operated under the auspices of the European Trade
Organization for the Telecommunications and Professional Electronics Industry (ECTEL).
Many of the collected batteries were Ni-Cds which, in the case of the
batteries collected in the U.K., were sent to France for recycling at SNAM. The U.K. pilot was operated in conjunction with British Telecom outlets. Retail or distribution outlets were favored as collection points because of their widespread geographical coverage and accessibility to cell phone users.
The pilot program was
designed to make battery collection as trouble free as possible for consumers. A reverse distribution company, Loddon Holdings, was retained to handle the used battery collection and shipment operations in the UK.
Loddon had considerable experience
managing reverse distribution programs and familiarity with relevant regulatory compliance obligations, such as hazardous waste transportation and facility licensing.
126 Regrettably, in September of 1996, new special waste regulations took effect with respect to used Ni-Cd batteries. As a result, all of the participating retail outlets, as well as consolidation points, had to be licensed hazardous waste storage facilities and pay all associated fees.
Considerable expenditures of time, money and effort, were
incurred by program managers to ensure that all of the applicable special waste regulations were followed. These regulations require notification of the Environment Agency at least 3 days prior to each used battery shipment.
This seeming simple requirement rendered
collection very difficult. Batteries ready for pick up at some collection sites had to await the expiration of the three day notice. As those shipments became timely, a neighboring location might give the consolidator notice of another batch of used batteries that, added to the first, would make a full load.
These shipments could not be made together,
however, because of the timing of the notification requirements. Large inefficiencies resulted, especially in more remote parts of the U.K. where transportation costs were already large. The rules also set different requirements for large and small shipments.
A
vehicle visiting collection facilities is allowed a week to finish its rounds if its load is 400 kg. or less. If that load exceeds 400 kg. the batteries must reach their destination within 24 hours. This proved to be very disruptive of the normal method of making the rounds of collection facilities. Drivers had no ability to know whether or when a large shipment from one collection facility would completely disrupt the scheduled (and notified) collection run. In short, the UK program pointed up the considerable limitations and costs imposed by the UK's classification of used Ni-Cd batteries as special waste. 2.
Swedish Pilot Collection Experience The ECTEL participants also established a two-year pilot program in Sweden.
Used Ni-Cd batteries were collected in Sweden through the stores of five major retail chains. They were recycled domestically at the SAFT Sweden facility in Oskarshamn.
127 The Swedish pilot program was significantly easier to manage than the U.K program, largely because- notwithstanding the cadmium content of Ni-Cd batteries -end-of-life electronic products are not considered hazardous or special waste in Sweden. Thus, collected phones and batteries could be transported from retail outlets to consolidation points via common carriers. Retailers and consolidation points were also not required to have hazardous waste licenses. Shipping the batteries for recycling was even further simplified because the batteries were recycled domestically, so no OECD transboundary shipping requirements applied. The pilot program also highlighted the benefits of competitive pricing that arose from having a broader choice of contractors (consolidation facilities, haulers, etc.).
B.
The Australian Experience In Australia, there are Federal and state laws prohibiting the disposal of Ni-Cd
batteries in landfills, however, no mandatory collection requirements. The Australian Mobile Telecommunications Association (AMTA) has recently completed a six month trial that involved 140 retail stores in New South Wales collecting used mobile phone batteries. During the trial, AMTA collected over 100,000 batteries, which included Ni-Cd batteries, as well as other chemistries. The collected batteries were sent to a recycling facility operated by the Melbourne-based company, Ausmelt Limited. As a result of the success of the trial program, the AMTA membership (which includes handset manufacturers and suppliers, carriers, retailers and service providers) has decided to launch a national program that initially will involve over 600 stores. The national program will collect and recycle batteries, handsets, and all mobile phone accessories.
According to AMTA's executive director, the program also will be seeking to make
the
recycling
service
available
to
other
rechargeable
battery
suppliers/manufacturers in hopes that they may join the program and offer their customers the same service.
128 The trial program was funded by a $0.t56 (US$ 0.1017) levy on each battery sold, which in turn funded all batteries collected. The new national program wHI involve a higher levy. Thenew levy will be $1.00 (US$ 0.6518) per handset sold, or $0.45 (US$ 0.2933) per battery for those companies supplying replacement batteries and accessories to the market.
C.
The Mexican Experience A pilot program to collect used Ni-Cd batteries is currently underway in Mexico.
It was initiated in 1998, when a major electronic product manufacturer initiated a pilot program for the collection and recycling of used Ni-Cd batteries from 2-way radios. Under this pilot program, customers that returned used batteries to the company for recycling were given a discount on the purchase price of new replacement batteries. In six months over 10,000 Ni-Cd batteries were collected. Because no facility capable of processing these batteries and recycling their constituent metals exists in Mexico, the collected units must be sent to the U.S. or elsewhere for recycling. To do so, however, requires compliance both with the OECD transboundary shipping requirements (notification and tracking forms) and national requirements. To date, Mexican environmental authorities (the Instituto Nationale de Ecologia, or "INE") have required that the company register as a hazardous waste generator before export will be allowed. The company prefers not to do so, because of the implications of this characterization of their activities.
It thus is pursuing INE
permission to send the shipment without being identified as the generator. The company has also been involved in discussions with the INE about adopting a regulatory scheme more tailored to management of used batteries. Dialogue currently is underway about initiating a rulemaking to reduce the domestic hazardous waste management requirements to facilitate Ni-Cd battery collection and recycling.
It is
expected that a workgroup will be convened in the near future to discuss the development of relaxed INE regulations. The manufacturer has offered to expand the pilot radio battery collection program to full-scale status if more manageable standards for used battery handling are adopted.
129 In the meantime, the collected used batteries are being stored in a suitable consolidation facility.
D.
The U.S. Experience 1.
Background In the late 1980s, generalized commercial interest in promoting "green"
attributes of their products spurred the rechargeable power industry to begin implementing nationwide collection-for-recycling programs. In addition, thirteen of the fifty U.S. states enacted laws to facilitate the collection and recycling of used rechargeable batteries. The specifics of these laws varied, but the majority mandated used Ni-Cd battery collection and recycling. However, the difference between state mandates made impossible the adoption of identical programs in all of them. For example, some states specified what entities must act as collection points, while other states left the decision up to the rechargeable power industry. It also was uncertain in some states whether or not memory backup batteries were to be covered by the programs. The situation became even more complicated because of a change in the U.S. hazardous waste management law. In 1990, the U.S. EPA changed its test protocol for determining what wastes should be classified as hazardous. The new toxicity test, called the "TCLP test," required that materials be crushed or cut up to a small particle size and exposed to an acetic acid solution. The constituents of the leachate were then measured against standards for (among other elements) cadmium and lead.
The idea was to
simulate the release of the battery's contents into a landfill environment over a protracted period of time.
If excessive quantities of the hazardous constituents of
concern were measured, the waste material was to be regulated as hazardous.
However, no consideration whatsoever had been given to the implications of this change on Ni-Cd battery recycling. Because the new test required that materials be
130 ground up - thus breaching the integrity of battery casings -- used Ni-Cd batteries failed the TCLP test for cadmium. As a consequence, for the first time the transportation, storage, handling and recycling of used Ni-Cd batteries became subject to the hazardous waste provisions of the Federal Resource Conservation and Recovery Act (RCRA) and its attendant regulations.
These regulations require waste generators to obtain
identification numbers from federal or state regulators; waste transporters to meet stringent safety, insurance and licensing requirements based on worst case assumptions about waste spillage; and collection and recycling facilities to acquire comprehensive and expensive permits. But not all "waste" batteries were subjected to these requirements. By virtue of a historic policy-based exception, many RCRA requirements applicable to batteries from commercial generators did not apply to used batteries generated from households. Yet if a mixture of identical Ni-Cd batteries from household and commercial sources were collected, then all had to be regulated as hazardous waste. To further add to the confusion, in the U.S. environmental regulations are enforced by the states, but only after the U.S. EPA approves each state's enforcement plan for consistency with the Federal program. States also can be more stringent than the Federal requirements. Thus, when the U.S. EPA decides to relax a requirement, states must act affirmatively to implement relaxed requirements. Nothing in the U.S. federal system requires them to act, so state programs are frequently inconsistent with the Federal model. This complex array of regulatory requirements immediately resulted in the suspension of most voluntary collection and recycling programs previously set up or contemplated for Ni-Cd batteries.
The administrative and liability burdens were too
significant to be acceptable to the volunteer collectors. Because of the new classification of used Ni-Cd batteries as hazardous waste, large and small retailers refused to take part in their collection. Collection systems had become economically prohibitive to manage when the batteries had to be shipped under a hazardous waste manifest by costly hazardous waste carriers. Storing used batteries for a long enough period of time to allow for economic shipment was impossible because entities that store hazardous waste
131 in excess of 90 days were required to have hazardous waste storage permits. Even in states where collection was mandated, compliance efforts were frustrated. Moreover, even where used Ni-Cd batteries were collected, transportation costs skyrocketed. For instance, in 1991 shipping costs for truckload quantities increased by as much as 250 percent if a hazardous waste hauler ($3.00 to $3.50 per mile) had to be used in place of a common carrier ($1.40 per mile). Even greater increases applied to shipments of smaller quantities.
For example, the cost of shipping three 55-gallon
drums of used Ni-Cds from a generator in Minneapolis to International Metals Reclamation Company (INMETCO) in Ellwood City, Pennsylvania increased from $150.00-$200.00 for a common carrier to $1,273.00-$1,580.00 for a "backhaul" hazardous waste carrier (one that takes a load it would ordinarily not haul in order to avoid returning to its origin empty). The cost for a dedicated hazardous waste carrier was even higher, at $2115.00-$3,300 per load.
2.
Government & Industry Cooperation on Regulations In 1985, shortly after lead acid batteries first became regulated as hazardous
waste, the U.S. EPA had implemented rules that exempted collectors and transporters of used lead acid batteries for bona fide recycling from the regulatory burdens of the hazardous waste program. This allowed participation in established reverse distribution collection programs by retailers, distributors and transporters to remain strong. (The rate of lead battery lead recycling is now better than 95%.) Five years later, however, when the TCLP test was finalized, its potential adverse impact on Ni-Cd battery recycling was not recognized.
Consequently, no parallel
exemption was adopted. In April 1991, Ni-Cd battery manufacturers filed a petition with the U.S. EPA that proposed for Ni-Cd batteries the adoption of an exemption similar to the one applicable to lead acid batteries.
EPA staff promptly indicated that they agreed in principle with the industry proposal. However, rather than extend their existing lead battery recycling exemption to
132 Ni-Cds, EPA decided to address the Ni-Cd battery recycling issue within the framework of a broader effort to foster the recycling of several other widely used products that the Agency believed should not be disposed of in municipal trash.
Along with Ni-Cd
batteries, these included unused pesticides, mercury-containing thermostats, and mercury-containing lamps. Due to the controversy that surrounded some of the other wastes that were being considered for coverage - not Ni-Cd batteries - it then took the Agency nearly four years to develop and promulgate the rule. Finally, on May 11, 1995, EPA promulgated the "Universal Waste Rule." That rule's stated purpose was to reduce the amount of problem wastes entering the municipal solid waste stream and encourage their recycling or proper disposal.
The rule
significantly streamlined applicable regulations, including those related to generator notification, accumulation time limits, employee training, and shipping documentation. By allowing retailers, service centers, and institutional generators to collect and store used Ni-Cd batteries on site for up to one year, it opened the door for these entities to participate in collection programs. They also now could avoid the burdens and stigma of handling hazardous waste, hazardous waste generator notification, hazardous waste storage facility permits, shipping on a hazardous waste manifest, and using a hazardous waste hauler. Transportation became more feasible as well: common carriers may store spent Ni-Cd batteries for up to ten days at a transfer facility (loading docks, parking areas, etc.) without limitation. Movement of Ni-Cd batteries became subject to the same Department of Transportation (DOT) requirements that apply to the batteries when they are shipped as new products. Notably, the Universal Waste Rule did not reduce regulatory burdens on Ni-Cd recycling facilities.
They continue to be required to have hazardous waste facility
permits, facility closure plans and demonstrations of financial responsibility, employee training, storage requirements, and recordkeeping and reporting obligations. appropriate, as these facilities open the batteries and crush the constituents.
This is Such
activity, if done improperly, could represent a threat to human health and the environment.
133
3.
Inconsistency of State Regulations Requires Change in Federal Law By simplifying collection and making transportation more affordable, the
Universal Waste Rule served to encourage the establishment of a national collection and recycling program for Ni-Cd batteries. Under the U.S. federal system, however, this rule could not take effect nationwide until it was individually adopted by all fifty states. The industry and U.S. EPA were justly concerned that this could take many years. Furthermore, without changes in Federal law, states were free to accept the provisions of the new regulation or to continue to apply inconsistent requirements. To bring about a consistent and efficient used battery collection system, harmonization was necessary. (This situation parallels the current state of inconsistent regulatory requirements among the 29 OECD countries, where conflicting requirements have stifled efficient collection.) To this end, the industry approached the Congress and urged the passage of legislation to fix this problem by creating a standardized national system.
After
considerable effort, such legislation was enacted on May 13, 1996. Formally named the Mercury-Containing and Rechargeable Battery Management Act, but generally referred to as the "Battery Act", this law facilitates Ni-Cd recycling by, among other things, making the Universal Waste Rule effective immediately in all fifty states for all batteries covered by the Battery Act, including Ni-Cd batteries Acknowledging the steady increase in the use of rechargeable batteries, as well as potential environmental impacts resulting from their improper disposal, EPA issued a statement that it considered the law to be "a major step forward in the effort to facilitate the recycling of nickel-cadmium (Ni-Cd) batteries .... " Most importantly, the rule made possible the national collection program for used Ni-Cd batteries that today is being implemented
through
the
industry-supported
Rechargeable
Battery
Recycling
Corporation.
E.
The Canadian Experience Canada's federal transportation and environmental agencies, as well as regional
governments, classify Ni-Cd batteries as hazardous waste. As has been the case in the U.S. and many other countries across the world, this classification made it very difficult
134 for program operators to find entities willing to undertake the role of Ni-Cd battery collector. Nonetheless, industry proponents of collection for recycling, acting through the Rechargeable Battery Recycling Corporation of Canada (RBRC), a subsidiary of the U.S. Rechargeable Battery Recycling Corporation, in January of 1997 initiated a collection program. Due to regulatory constraints, the program was limited to retail take-back.
With the help of Environment Canada, Natural Resources Canada, and
Transport Canada, RBRC was able to convince the province and territory governments that retailers who collect spent Ni-Cd batteries should not have to register as hazardous waste generators.
This removed a substantial disincentive to retail participation in
RBRC's Canadian program, but RBRC wanted to expand the program to collect used batteries from businesses, institutions
(e.g., hospitals, police and fire stations),
government agencies, and municipalities and counties. On April 20, 1999, after two years of efforts to negotiate reduced management standards for non-retail program participants, Transport Canada issued to RBRC an Equivalent Level of Safety Permit (ELSP). The ELSP allows RBRC and its designated collectors and transporters to handle used Ni-Cd batteries as common goods (e.g., repeals package marking and recordkeeping and reporting obligations).
To get the
permit, RBRC demonstrated that its Ni-Cd program provides a level of safety that is equivalent to the Transportation of Dangerous Goods Regulations. On June 11, 1999, the Ontario Ministry of the Environment (MOE) gave RBRC a provisional Certificate of Approval (COA) that exempts RBRC from having to use a permitted hazardous waste facility to accumulate Ni-Cds prior to shipment to recycling facilities.
This COA was primarily intended to give RBRC a broader and more
affordable choice of consolidators. Unfortunately, the COA is only good in Ontario. Canada's remaining provinces and territories have yet to adopt a similar exemption. The OECD transboundary requirements for shipping used Ni-Cd batteries from Canada to the U.S. continue to make the RBRC collection program more cumbersome
135 and less cost efficient than it would be if streamlined controls could be applied to shipments to pre-approved facilities like INMETCO. The OECD requirements, as they are today, preclude retailers, service centers, municipalities, and other front line collectors from being able to even consider sending used battery collection boxes directly to approved recycling facilities within the OECD. F.
Transboundary Movement Within the OECD
Ni-Cd battery processing and recycling involves a number of processes, including physical component separation and applying chemical and/or thermal stresses to the resulting materials.
Some of these materials are toxic, and these operations
involve a number of workplace dangers. sophisticated and costly to operate.
Thus, these facilities are technically
Most nations require that operators obtain and
comply with hazardous waste treatment, storage and disposal facility permits. Because of these characteristics, and as noted above, only a handful of Ni-Cd recycling facilities exist in the world.
They are located in France, Germany, Japan,
Australia, the U.S., Korea and Sweden. Ni-Cd batteries collected in any other country must be shipped across national borders if they are to be recycled. Spent Ni-Cd batteries now move between OECD nations under "amber list" controls, plus any national controls imposed by the member nations involved. Amber transboundary controls are intended, among other things, to provide sufficient notice to the nation of import to insure that the shipments entering its territory are destined for a facility capable of managing them in an environmentally sound manner. Such controls also alert any transit nation to the fact that a cargo of recyclable material that presents a potential environmental threat is passing through its jurisdiction. Under the amber controls, shipments of used Ni-Cd batteries require 45 days' advance notification to receiving and transit counties. However, a general notification can be filed to cover multiple shipments from, through, and to designated countries for a one-year period.
Within thirty days of receipt of a notification, concerned countries
must consent to the shipment before it can commence. Shipments sent to pre-approved recovery operations require only ten days' advance notice to concerned countries.
136 The OECD notification form for amber wastes requires: generator, shipper and consignee identification information; a designation of the countries of import, transit and export; waste composition and quantity information; a certification that the information provided on the foregoing is complete and correct; a certification that legally enforceable contractual obligations have been entered into to provide for alternate management of the shipment if its disposition cannot be carried out as specified; and a certification that applicable insurance or financial guarantees are in force. The OECD movement/tracking form requires the same information related to generator, shipper and consignee identification; the countries of import, transit and export; and waste composition and quantity. It also includes a certification statement verifying the accuracy of the information on the form and confirming that all necessary consents have been received or tacitly obtained, and in the case of pre-authorized facilities, that no objections from the concerned countries have been raised. IV.
THE RBRC PROGRAM - CANADA AND THE U.S. As this topic is extensively treated in chapter 5, only a short summary will be
given here. The Rechargeable Battery Recycling Corporation is a not-for-profit corporation funded by rechargeable battery manufacturers and created to implement and maintain Ni-Cd battery collection and recycling programs in the U.S. and in Canada. The RBRC program, Charge Up to Recycle.t, has created various recycling plans to collect Ni-Cd batteries, which are then sent to INMETCO (Ellwood City, Pennsylvania) for processing and recycling. At the facility, the nickel and iron are separated from the cadmium and shipped to specialty steel producers for use in stainless steel products. The recovered high-purity cadmium is used to produce new Ni-Cd rechargeable batteries. Within the Charge Up to Recycle! program, three different plans for collecting used NiCd batteries are set up for retailers, communities, and business&public agencies. To
137 reach high recycling levels, widespread public education is carried out. The recycling program is paid for by the rechargeable power industry. To date, virtually all of the major producers and users of Ni-Cd batteries in Canada and the U.S. participate in the program, which also has the support of over 30,000 collection sites, where consumers can drop off their used Ni-Cd batteries for recycling.
V.
LESSONS LEARNED & RECOMMENDATIONS FOR ACTION
G.
Lessons Learned
1.
Difficulties in Establishing a Network of Collectors
One hurdle to be cleared in recycling significant numbers of used Ni-Cd batteries is to assure that the batteries are amassed in convenient locations for shipping to a reclamation facility. In every country studied, this collection objective has been the hardest to accomplish. commodities.
Many other recyclables are collected for their value as
These materials, whether old newspapers, scrap metals or lead acid
batteries, have positive economic value and are sought out by entrepreneurs seeking profit. In contrast, spent Ni-Cd batteries are useful as a source of raw materials when processed, but the combined cost of collection, transportation and processing far exceeds their raw material value. To an extent, this impediment can be overcome by identifying convenient points for consumers to drop off their spent batteries. These can be operated by government, the private sector or both.
Unfortunately, however, the initial experience of most used
Ni-Cd battery collection programs has been that regulatory constraints greatly impede this effort.
In many countries, because of their constituent cadmium, used Ni-Cd batteries either are now or were considered to be hazardous waste. This designation carries with it substantial burdens for those that handle such material. Generally these entities must meet requirements that were developed to address concems relating to such industrial wastes as used solvents, acids and the like.
They thus require operating and
138 transportation permits, must provide protective safeguards against spillage and loss, must demonstrate financial responsibility to guarantee cleanup of accidents, and so forth. The operators of those facilities best situated to collect used Ni-Cd batteries have universally balked at voluntarily undertaking the expense, complexity and liability associated with the these obligations.
Compelling entities that sell Ni-Cd batteries at
retail to take them back for recycling is little better; few welcome this burden, enforcement is difficult, and ultimately, retailers can simply discontinue selling new batteries rather than take on these problems. Since there are some appliances for which there is no alternative to Ni-Cd batteries power, consumers will resort to mail order or other avenues of obtaining the batteries that they need and have no feasible way to recycle them. 2.
Need to Assure Transportation to the Recycling Facility at Reasonable Cost
Once used Ni-Cd batteries have reached a collection point, the next step is to move them in bulk to the facility that is to process and recycle them. In many instances it is necessary to consolidate smaller loads before shipment to the recycling facility economically can take place. Transportation and temporary storage costs represent the largest overhead costs in a recycling program. These costs increase dramatically with the distance between the point of collection and the point of recycling. Furthermore, because there are currently only less than ten facilities capable of environmentally sound recycling of Ni-Cd batteries, these distances can be substantial. Moreover, when a material is designated as a hazardous waste, it is generally required that a specially permitted and bonded transporter be the only party to undertake the movement of hazardous waste. This is because hazardous waste is presumed to be capable of doing great damage to the environment if spilled and must be cleaned up by specially trained personnel. But the use of a designated hazardous waste transporter increases the cost of moving material in commerce substantially. At the same time, used Ni-Cd batteries require no different handling than that applicable to the new product. They simply do not present the unique risks that typify hazardous wastes: they are not liquid, semi-liquid or easily dispersible, acidic or corrosive, or otherwise dangerous to touch. If "spilled," they can be easily swept up.
139 Their potentially hazardous constituents are encapsulated and unavailable to the environment.
Those constituents can only be released by the processes (opening and
crushing) that occur intentionally. 3.
Need to Assure Predictable and Swift Transboundary Movement
Reclamation of metals from used Ni-Cd batteries requires use of complex industrial processes that demand substantial investment. Only less than ten facilities currently operate that can successfully perform this work. All are in OECD member nations, and each is carefully regulated by the governmental authorities of that jurisdiction. Because there are so few facilities recognized by OECD member states as capable of recycling Ni-Cd batteries, the necessity of moving them across intemational borders is evident. Where a nation has no such facility, the options for dealing with spent Ni-Cd batteries within its jurisdiction are limited to either exporting them for proper recycling or disposing of them (landfilling or incinerating) domestically. The former is environmentally preferable. Transboundary shipping requirements (i.e., notice and consent paperwork) are a potential impediment to such movement, however, if they are unnecessarily burdensome and time consuming.
This is important both from the perspective of encouraging
collection and shipment for recycling, and in order to assure the economic success of reclamation activities.
The facilities that process and recycle Ni-Cd batteries require a
degree of certainty about the availability and time of arrival of their feedstock. Delay or uncertainty of supply adds to costs and undermines the recycling process. H.
Recommendations 1.
Overly Stringent National Controls Should Be Modified
The burdens associated with collection, storage, transport and processing of spent Ni-Cd batteries and Ni-Cd battery manufacturing scrap are extremely important in determining whether or not a collection program will be viable. Economic penalties and
140 administrative complexities associated with collection and transportation of materials designated as "hazardous" may make the cost of collection impossible to bear. As noted above, where the administrative and/or economic penalties are high, retailers and others with desirable candidate collection locations are dissuaded from participating in the collection program. These candidates rarely are dependent on Ni-Cd battery sales for a substantial share of their profits. Thus, even if a government mandate requires that all locations selling Ni-Cd batteries participate in a collection and recycling program, they cannot be expected to incur unreasonable costs and obligations and may easily elect to discontinue selling new Ni-Cd batteries. Neither the consumer nor the environment benefits from this.
Consumers are likely to seek replacement batteries
outside the jurisdiction of the government applying the mandate and have no feasible place to recycle them. Comparisons in the U.S. show a shipping cost increase of a factor of 2 to 10 for the same used batteries, depending on whether they are characterized as hazardous or non-hazardous.
How steep the increase is dependent upon the shipment size and
whether it is a dedicated or backhaul trip. The regulatory provisions that are most responsible for this substantial cost increase are those requiring the batteries to be accompanied by a hazardous waste manifest and transported by licensed hazardous waste haulers. More affordable common carriers transport new Ni-Cd batteries, which are substantially identical to the used product.
There thus appears to be no environmental reason to preclude them from
similarly transporting properly packaged used Ni-Cd batteries that are accompanied by a standard bill of lading that identifies the shipment contents and the final recycling facility destination.
Such documents are used successfully to move material in
commerce where the primary concern is, as it is here, to make sure the goods reach the proper destination.
For just these reasons, several OECD member nations (such as Canada, Sweden and the U.S.) have created exemptions from otherwise applicable hazardous waste regulatory requirements to encourage recycling. In these nations, extensive industry-led efforts are underway to facilitate easy collection and transportation.
141 The OECD would exhibit considerable environmental leadership by producing guidance materials that recognize the value of a uniform and efficient system to channel Ni-Cd batteries to pre-authorized recovery_ operations. This guidance would recommend thr relaxation of hazardous waste requirements on the collection and transportation of used Ni-Cd batteries to those collection facilities recognized by the OECD member nation~ to be capable of environmentally sound reclamation of their constituent materials. National governments with environmentally sound and compliant facilities could be requested to certify their status to OECD. 2.
National Controls Should Be Harmonized
Economies of scale, and the concomitant limited number of recovery facilities, dictate the need for cross border movement of spent Ni-Cd batteries for recycling. Unfortunately, a lack of harmony between the regulatory regimes in the importing and exporting jurisdictions can result in a substantial impediment. Within the OECD there are many different such regimes. Where OECD member states differ significantly in their approach to the regulation of spent Ni-Cd battery collection, transportation and recycling, movements necessarily will have to meet the most stringent- and most cost prohibitive - regime. Again, action by the OECD to urge to the member nations to adopt uniform provisions to encourage Ni-Cd battery_ collection, and avoid characterization of the batteries as fully regulated hazardous waste would assist in solving this problem. Unnecessarily Burdensome Transboundary Requirements Should Be Eliminated
Amber list controls currently apply to all intra-OECD shipments of Ni-Cd batteries.
Such controls may make sense for batteries shipped between nations for
disposal in a landfill, because the nation of import necessarily requires an opportunity to verify that they are destined for a facility that has the capability to deal with them in an environmentally sound manner. For Ni-Cd batteries collected in intra-OECD commerce for recycling, however, these controls can impede efficient movement and result in
142 unnecessary storage time and administrative cost.
Indeed, time delays and
administrative burdens mount up incrementally when one is dealing with the recycling of a used material that has little or no economic value until it has been reclaimed. At some point, these additive burdens become sufficient to render recycling cost prohibitive. Many of these amber list controls are not necessary. For example, in the context of Ni-Cd battery recycling, used Ni-Cd batteries are no more hazardous to transport than new ones. Their potential hazard lies in their long term disposal in locations from which where the constituent metals theoretically might leach, or from incineration. Furthermore, as discussed above, there are only less than ten facilities in the world (all within the OECD) which are capable of recycling Ni-Cd batteries.
If the member
nations in which these facilities are located are satisfied that their operations are being operated in an environmentally responsible manner, advance notice of shipments serves no purpose. Thus, the only potential benefit of the amber scheme is to prevent shipment to other locations.
The Working Group on Waste Management Policy could take a
significant step in facilitating Ni-Cd battery_ recycling by recommending that transboundary shipments between OECD nations to these locations, or others recognized by national governments as acceptable, should be allowed to proceed under green list or significantly scaled back amber list controls. This reduction in control would only apply to shipments destined for facilities that have been identified by their home country's environmental authority as an environmentally sound facility, operating in full compliance with domestic environmental law and regulations. Shipments to these facilities under green list controls would represent no threat to human health or the environment.
To the contrary, using green list controls would
greatly facilitate an efficient system of removing these batteries from the environment and encourage businesses in OECD member nations to funnel batteries collected under national programs to the safest and best documented recovery operations. The environmental benefits of such a policy action are clear. To the extent that regulatory burdens are eased, including those related to intra-OECD transboundary
143 movements, more Ni-Cd batteries may become available for recycling. This increase in the availability of feedstock may well encourage the establishment of new, technologically advanced recovery facilities within the OECD, or the expansion and technological upgrading of existing facilities.
This increased recycling capacity also
would generate more recoverable material for use in place of virgin materials and decrease overall shipping distances.
4.
Government / Industry Cooperation Should Be Facilitated It is clear, in light of the complexity of portable electric product manufacture and
distribution channels and the rate of technological change, that any used Ni-Cd battery collection scheme must be able to accommodate changes in industry structure and product mix. The nimbleness thus required is readily supplied by market mechanisms, and difficult- if not impossible - for public agencies to match. Furthermore, the economics of material recovery, the cultural attitudes of the population being asked to recycle, the logistics of material collection, and the efficiency of various transportation options can vary considerably, even within nations. Attracting and keeping cooperative program participants is greatly enhanced if potential participants are given the opportunity to shape the program around cultural and economic realities of the marketplace in which the program is to function. All of these factors contribute to making voluntary programs, organized and implemented by product suppliers, the most attractive mechanism to obtain maximum rates of used Ni-Cd battery collection and recycling. Among other things, participants who voluntarily participate in programs are far more active and enthusiastic. They have a very real investment in the success of the program and will be more likely to suggest improvements designed to increase collection and recycling rates. Thus. governmental policies should be directed to encouraging voluntary_ arrangements. The OECD should act as facilitator for organizing such private sector and ~overnment interaction.
144 Funding is a particularly sensitive issue. All of the world's facilities that reclaim materials from Ni-Cd batteries at present are being paid to do so. That is, because of low metal prices, reclamation - even where the reclaimer has no responsibility for collection- is not currently profitable through the recovery of the metals alone. Thus, a funding mechanism for Ni-Cd battery collection and recycling programs must be established before a program can be realistically implemented.
The appropriate funding mechanisms will vary with national policies and historical factors. In some countries, there is historical precedent for the imposition of fees on retailers, and acceptance by consumers of this additional tax. But this is not always fair or reasonable. Fees must be proportional to the actual costs of collection, transportation and reclamation if they are to be accepted by the consumer and not distort the market. Similarly, these fees must be segregated from general govemmental revenue in order to allow accurate accounting of actual costs of recycling.
In Sweden, for example, fees paid on Ni-Cd battery purchases in Sweden far exceed the costs of a collection and recycling system. Indeed, they appear to have been imposed by the government as a punitive "tax" in an attempt to force Ni-Cd batteries out of the market in favor of batteries utilizing other chemistries. In this age of internet commerce and rapid mail order delivery, consumers that are given a significant monetary incentive to do so can just as easily buy their batteries outside such a program and avoid paying the punitive fee. Fees also should be collected at the time the new Ni-Cd battery or appliance is purchased. To do otherwise, that is to collect it at the time of consumer drop-off, creates a disincentive to recycling.
Yet, having the private sector implement these programs also faces difficulties. In the U.S. and Canada, for example, competition laws limit joint voluntary action to impose anything like an advance disposal fee.
The RBRC solution to this in Canada
and U.S. was to set up a voluntary funding scheme that is paid for entirely by the rechargeable power industry. Each participating battery manufacturer or battery user pays a licensing fee that is proportional to the total combined weight of Ni-Cd cells that the company markets in the U.S. and Canada. Licensees may display the RBRC seal on
145 Ni-Cd batteries, the devices powered by the batteries, their packaging and the instruction manuals for the devices. While this arrangement also requires a substantial investment in administrative support, the fact that business interests are in direct control of the administrative process maximizes its efficiency. While the attractions of voluntary systems are thus legion, they have one disadvantage: they rely on the good faith of all market participants to be truly equitable and fair. The problem of free-riders (i.e., battery and product manufacturers who do not support or participate in the program but who benefit from it) has been serious enough to generate significant concern among program participants and regulators.
Focusing
government attention on this segment of the marketplace, by requiring that companies support some sort of a voluntary system, may be a solution.
Another means of
minimizing the free-rider problem will be to promote participation in the recycling program as a product attribute. Through aggressive advertising campaigns, consumers should be alerted to look for Ni-Cd recycling program logos on batteries and products and to support collection efforts by buying paying participants' products. The overall program success thus far in North America is a function of sensible regulatory solutions that were developed and agreed upon mutually by both the rechargeable power industry and regulators. These entities, that can so often be at odds, put aside differences and cooperated to achieve an important environmental objective. The program has received considerable publicity and widespread public acceptance and the annual tonnage of batteries recycled has continued to grow. Appendix OECD's Member States
European Union: Austria, Belgium, Denmark, Finland, France, Germany, Greece, Ireland, Italy, Luxembourg, Netherlands, Portugal, Spain, Sweden, United Kingdom North America: Canada, Mexico, United States Pacific Rim: Australia, Japan, New Zealand, South Korea Others: Czech Republic, Hungary, Iceland, Norway, Poland, Switzerland, Turkey
This Page Intentionally Left Blank
Used Battery Collection and Recycling
G. Pistoia, J.-P. Wiaux and S.P. Wolsky(Editors) 9 2001 Elsevier Science B.V. All rights reserved.
NICKEL-CADMIUM
AND NICKEL-METAL
147
HYDRIDE
BATTERY TREATMENTS
J. David
SNAM, 9 rue de la Garenne, F-38074, Saint Quentin Fallavier, France
BACKGROUND
Ever since the nickel-cadmium battery came into existence, experts have been studying ways to recycle it. The first really widely-used batteries were of the open type. Their recovery at the end of their life was due to the ease with which they could be opened and the positive electrodes isolated so as to re-use the nickel. Until the 50's, companies showed little interest in recovering the cadmium, which was not considered hazardous; and the negative electrodes available weighed very little. Moreover, putting complete nickel-cadmium batteries in the furnace to produce nickelbased ferroalloys posed absolutely no problem. The cadmium was vaporised on the surface, where it burned to produce cadmium oxide, which was usually released into the environment. At best, some of the dust was picked up by relatively efficient filters, in the case of zinc, lead and other forms of dust. With the increasing demand for cadmium, for cadmium plating, pigments, and nickelcadmium batteries, the price of cadmium remained high. Prices in the range of 4 to 5 USD per pound were by no means uncommon, with operations in the cadmium market handled by dealers specialising in "minor metals" and speculating on the price at the first opportunity. In the 50's, electrochemical and hydrometallurgical processes were tested and used on a small scale for the production of recovered cadmium. The principle whereby the cadmium was extracted by distillation is described and used in the production of primary cadmium (coming from zinc ores). The first plants designed to recover the cadmium from nickel-cadmium batteries appear to have started up in the early 60's. These plants used distilling furnaces
148 charged with mainly pocket-plate negative electrodes and produced cadmium of fairly poor quality: 99.9% at best. The cadmium, which contained lead and nickel impurities, was nevertheless re-used for the production of pocket-plate nickel-cadmium batteries. The thermal process (cadmium distillation) became inescapable with the appearance of sealed cylindrical nickel-cadmium batteries. Just as it is economically viable, technically feasible and always practical to dismantle manufactured items weighing from 1 to 20 kg so as to separate out the electrodes and only process those containing cadmium, so it would be unthinkable to open up one by one sealed elements weighing from 30 to 150 grams. Whilst a pocket-plate negative electrode only contains iron, iron oxide and cadmium in the form of cadmium oxide or hydroxide, a sealed unit contains amounts of other materials, including powdered nickel and nickel hydroxide along with various types of organic matter. Hydrometallurgical and electrochemical processes are both far too complex for such a mixture. Plants were developed in the 70's: in Europe (2 in France and 2 in Germany), Asia, including Japan and Taiwan, and the USA. These were created either at the request of recycling companies specialising in the dismantling of industrial batteries, or at the request of the producers, mainly for the purpose of treating the waste produced by the manufacture of sealed units. However, the fact is that these projects were born, developed and then often disappeared as a result of fluctuations in the price of cadmium. It was in the 80's that plants specifically designed for the processing of batteries and waste from nickel-cadmium batteries came into their own. NIFE, in Sweden, had started work on its process in 1978, but it only became operational on an industrial scale in 1986. In Japan, NIPPON RECYCLE CENTER developed its process in the 70's, although its dedicated plant specifically designed to treat nickel-cadmium batteries only came into operation in Korea in 1984. Although the first cadmium distilling fumace built to operate the S.N.A.M. process goes back to 1965, the first S.N.A.M. plant was not built until 1982. NIFE, one of the two largest manufacturers of industrial nickel-cadmium batteries in the world, began recycling cadmium by treating its own waste before treating its customers' spent batteries.
149 NIPPON RECYCLE CENTER, first in Japan and then in Korea (HANIL joint venture)~ initially based its activities on treating waste from the manufacture of batteries in Japan. S.N.A.M. decided to build its plant in 1982 in order to treat waste from battery manufacture in the USA and France (SAFT) and then to process negative electrodes from nickel recovery companies engaged in the dismantling of industrial batteries. In all of this, it is quite astonishing that very few companies producing zinc, and thus inevitably producers of cadmium, took a really serious interest in recycling cadmium: - In Japan, in the late 80's, TOHO ZINC set up a plant for the pre-treatment of batteries and nickel-cadmium waste; this was designed to produce an impure cadmium oxide to be used in its primary cadmium production process. - MITSUI MINING, at the request of a Japanese manufacturer of nickel-cadmium batteries, developed a distilling furnace which has remained at the prototype stage. - In the USA, BIG RIVER ZINC developed a process designed to produce cadmium oxide directly from pocket-plate negative electrodes. It discontinued this process when the price of cadmium fell very sharply in 1991/1992. - UNION MINIERE was involved in the second S.N.A.M. plant in 1988, but withdrew in 1992. The situation of the nickel-cadmium battery manufacturers is different: they are rarely involved in the treatment of the waste they produce or of their customers' spent batteries, except for NIFE in Sweden and ENERGIZER in Florida, USA (which has a small unit basically designed to treat manufacturing dust and sludge from the wastewater treatment system). However, they provided the economic means for both the start-up and the growth of the main recycling companies currently in operation. The appearance of national organisations responsible for collecting and monitoring batteries and accumulators gave fresh impetus to companies recycling nickel-cadmium batteries and also initiated the recycling of NiMH and Li-Ion batteries. In Ellwood City, PA (USA), INMETCO organised its development on the basis of its collection system, largely due to the backing of the RBRC (Rechargeable Battery Recycling Corporation).
150 In Germany, ACCUREC started up with the collection nationwide of nickel-cadmium batteries (Arge Bat) and has ensured its growth with the collection of all types of batteries which took over in 1998 from Arge Bat under the name of G.R.S. BATTERIEN (Stifl-ung Gemeinsames Rticknahmesystem Batterien). Figure 1a gives examples of industrial NiCd cells, while Figure 1b show, collected consumer cells or packs.
T R E A T M E N T OF N I C K E L - C A D M I U M BATTERIES The technology used to treat nickel-cadmium batteries falls into two major categories: 9 The treatment of a mixture of batteries and accumulators 9 Technology specific to the treatment of nickel-cadmium batteries Most of the processes used to treat a mixture of batteries are regarded as being able to accept a more or less high quantity of NiCd, NiMH or Li-Ion batteries. With largescale collection services - such as those found in Germany, Switzerland, Belgium, Holland and so on - the current figure is 5 to 8% nickel-cadmium and NiMH batteries. These account for 1 to 1.6% nickel and 0.7 to 1% cadmium in the mixture. To more fully understand the advantages and disadvantages of the treatments involved, two types of process need to be distinguished: hydrometallurgical and thermal.
1/
TYPES OF PROCESS 1.1 - H y d r o m e t a l l u r g i c a l P r o c e s s
With hydrometallurgical processes, the presence of NiCd or NiMH batteries requires an additional stage in order to isolate the cadmium, in nickel-cadmium batteries, and the nickel found in certain batteries at a content of less than 0.1% and in the form of nickel steel or an electrolytic nickel coating. As a general rule, cementation of the cadmium is sufficient to extract a large part of it. Its presence in the mixture carries the risk that the zinc or zinc salts produced by the
151
Figure la. Industrial, Vented Open Cells
152
Figure lb. Collected Sealed Cells and Power Packs
153 process may contain an abnormally high quantity of cadmium impurities, which makes the zinc-based end-product more difficult to sell and contributes to reduce its value. As regards the nickel, it has to be isolated by precipitation or the preparation of a selective solution so as to separate it from the manganese. With the majority of these processes, a sorting operation is necessary. The basic purpose of these processes is in fact recycling of the chief components, zinc and manganese. The forms in which they are recycled and the market for which they are intended often preclude too high a content of one or another impurity, whether it be mercury, lead, cadmium and sometimes even nickel. The purpose of this mandatory sorting is to extract the type(s) of battery and/or accumulator responsible for these impurities. Very brief economic examination shows that, whatever the reason for sorting, its cost only increases fractionally if it is pursued beyond its initial objective. Moreover, the cost of treating nickel-cadmium batteries is quite c l e a r - the supplier contributes to the cost, i.e. that part of the cost not covered by recycling the nickel and the cadmium- and significantly below the cost for saline and alkaline batteries. Nickel-cadmium batteries: 0.2 to 0.3 euros / kg Saline and alkaline batteries: approx. 1 euro / kg With NiMH batteries, the advantage is even greater, since recycling the nickel far outweighs the cost of treatment and gives these batteries a positive value: 0 to 0.50 euros per kg depending on the price of nickel. This difference, added to saving an additional stage in the process, largely covers the extra cost incurred by sorting. In conclusion, even if the hydrometallurgical processes can in theory accept the presence of NiCd, NiMH and Li-Ion batteries, for both technical and economic reasons a sort is usually done in order to send the NiCd and NiMH batteries to treatment centres using specific processes. The most compelling example is the BATENUS process developed by PIRA in 1992 or thereabouts. In the laboratory, this process made it possible to separate all the metals, including lead, nickel, cadmium, lithium, etc.
154 At pilot level, it quickly became apparent that setting up a plant was becoming very complicated. In the end, the plant that had started to be built in Germany was never completed. Today, certain battery treatment centres, in Spain among other countries, are using a simplified version of this process, including a preliminary sorting operation designed to remove undesirable batteries and accumulators.
1.2 - P y r o m e t a l l u r g i c a l o r T h e r m a l P r o c e s s
With the pyrometallurgical, or thermal processes, the presence of nickel-cadmium and NiMH batteries does not, again, pose a problem in principle. Irrespective of the type of furnace used, the nickel contained in the batteries is combined with the ferromanganese that the process makes possible. However, the problem is the cadmium, which will be vaporised a n d - if the surface of the furnace is in contact with the a i r will burn to produce cadmium oxide which will be captured in the air treatment system. It will combine with the zinc oxide which already contains numerous impurities, including lead. Battery recycling plants using this type of process but without any preliminary sorting operation have 3 problems: The presence of highly reactive, if not explosive, batteries, including lithium batteries, can result in serious incidents. The presence of cadmium in the zinc-based end-product means that the product is not economically viable. A very poor "green" image: the air coming out of the furnace contains metals regarded as environmentally hostile and is often suspected of carrying dioxins. The particles coming from the filters are then handled successively by one, two or three specialised treatment centres. This sort of structure makes it very difficult, among other things, to trace the cadmium. As with the hydrometallurgical processes, and in the light of increasingly stricter environmental controls, plants of this type are seeking to treat only products that have been sorted and from which have been removed batteries and/or accumulators containing materials incompatible with their remits or with the risks they are prepared to accept.
155 In other words, the mixtures treated in plants which could accept any battery and accumulator mixes are in fact sorted. For both economic and environmental reasons, the NiCd, NiMH and Li-Ion batteries are usually separated and are no longer treated in these plants.
2/
S P E C I F I C P R O C E S S E S F O R T H E T R E A T M E N T OF N I C K E L CADMIUM BATTERIES
The methods specific to the treatment of nickel cadmium, and thus of NiMH, fall into three categories: -
Mechanical methods
-
Hydrometallurgical methods
-
Thermal methods
2.1 - Mechanical
Process
In Europe, two companies at least have tried to develop mechanical processes. - In 1989, M.G. Horn of IRELAND ALLOYS LTD presented to the 6th International Cadmium Conference in Paris the experimental study of a process based on crushing industrial battery plates followed by screening into different size grading values and magnetic separation. The purpose was to concentrate the cadmium so as to have to treat only a minimal fraction of the weight of the complete battery. The results, based on 3 tests, were as follows:
% Weight
% Cd Content
% Cd Distribution
Magnetic Part
60.9
Non-magnetic Part
2.3
19.8
2.2
Cd Concentration
36.8
20.6
83.8
4.7
14.0
156 In the magnetic part, the cadmium content was consistently above 1% except for pieces of 10 to 2 mm in which the cadmium content fell to 0.6%. In the non-magnetic powders, pieces of 20 to 5 mm had a content below 1% but only represented 4.5% by weight of the batteries. In other words, more or less all of the fractions had to be treated as they all contained cadmium. - In 1995, INTER-RECYCLING proposed in the USA the construction of a fixed centre and a mobile treatment unit based on a similar approach. This experiment was discontinued because of the impossibility of proving that there was no cadmium in the fibres produced by separator crushing and the flexible plastics. The designer never carried out tests on an industrial scale to confirm his theories: only the powder, 50% of the weight of the battery, was to be treated. The other fractions were free from cadmium and so could be sold as they were.
2.2 - H y d r o m e t a l l u r g i c a l P r o c e s s
The hydrometallurgical methods have been tested many times over, and one of them is still used to day by SAFT AB in their plant in Oskarshamn (Sweden) in addition to their thermal process and for the treatment of their sludge. The process is based on the following: -
Dissolution of the sludge. Cadmium electrolysis on a rotary aluminium cathode. The cadmium is then converted into cadmium oxide in their plant and used for the production of new batteries.
-
Nickel chloride production.
A process of this type is not economically viable in an independent recycling plant as it can only treat a low percentage of the waste from the production of nickel-cadmium batteries. And the process cannot in any event be used to treat used batteries.
157 Another significant experiment was developed by TNO in 1994. The flow sheet below gives details of the process (Figure 2), In 1995, LETO RECYCLING, which took part in this development, set up an industrial pilot plant. Unfortunately, it quickly became apparent that the cost of treating used sealed batteries was no lower than the cost of a thermal process. On the other hand, recycling the cadmium into a carbonate and nickel into chloride was less profitable than recycling the products produced by the thermal process, mainly owing to the low degree of purity of these products. TNO attempted to improve recycling by purifying the products by electrolysis. TNO was then producing pure cadmium cathodes and nickel cathodes with cobalt. The cost of retreating the end-products by electrolysis made the new experiment economically uncompetitive.
2.3 - Thermal
Process
These were the most commonly used processes in the past and with a few exceptions they are still in use today. They fall into two categories: 9 Open processes 9 Closed processes Figure 3 shows the thermal technology for the treatment ofNi Cd batteries.
2.3.1 - Open Processes
Open processes are based on the principle of direct ferronickel production and vaporisation of the cadmium, which is allowed to bum on the surface of the fumace. The cadmium is converted into cadmium oxide with a relatively high impurities content. This process calls for heavy capital expenditure, both for capturing the particles above the fumace and treating the captured air. It will be remembered that these fumaces work at a temperature of 1400~ and have to be charged with a liquid
158
NiCads ..............
....
Fe/Ni-scrap
diminution
...........
orgy,it l wash
wash
~~ ....Water ......
i
I s~ I-Cd/TBP =~....stripping .....1 ~ extraction ~= 9 I of Cd 1 i................. t~ "t ....1 ...............
"
[ ..........
i ' NaOH k Cadmium evaporation 1 Na.co,~ precipitation 1
t d
"~
.................... ....
i concen~ ................... 1 / ~nickseolluCtih/onride 20 %_H..CI.. ,/I /
cadmium [ carbonate
~,
............................. 1 ,eva.P,~176 1 i effluent
Figure 2. TNO - Hydrometallurgical Process for the Treatment of Ni Cd Batteries
159 heel. This necessarily means slow steady charging so as to avoid explosions caused by moisture in the batteries, among other things, when the furnaces are being recharged. No plant recycling nickel-cadmium batteries currently uses this type of process, not just because of the risks of explosion, but also because of the difficulty of capturing the particles. The standards in respect of the cadmium content of the air in treatment plants reach exposure limit values that it is very hard to comply with. In Europe, the threshold values are from 25 to
30/.tg/~m3.
In the USA, they range from 2 to 10 btg/Nm 3. The products obtained by these processes are ferronickel in the form of an alloy, which
Figure 3. Thermal Recovery Systems for Nickel Cadmium Batteries
160 could be recycled more effectively than that of the nickel-iron residues obtained by the same process, if these alloys could be titrated. Rectifying one or another content is practically impossible with an induction furnace, the type of furnace most often used. The inconsistency of the analyses meant that recycling could not be optimised. On the other hand, the cadmium was recovered in the form of very impure cadmium oxide, with high nickel, zinc and carbon contents. This made it necessary to add one or two distilling furnaces to the treatment furnace to convert the cadmium oxide into cadmium metal with an average purity of 99.95% and which still had to be refined to obtain a purity of 99.99%, or else sold unrefined at an unfavourable price. A variant of this process was developed in Australia by AUSMELT in 1998: their process used a closed induction furnace but with an air feed to burn the cadmium in the furnace and recover it in the form of cadmium oxide. The process produced nickel matte which had to be sent to the nickel refiners and highly contaminated cadmium oxides that had to be sent to the producers of primary cadmium. This required a higher investment than closed furnaces and the products extracted were somewhat less effectively recycled than the nickel-iron and cadmium metal residues.
2.3.2. - Closed Processes
The closed ftLrnace process is thus the process used to treat over 90% of the batteries and waste products from nickel-cadmium batteries. The principle consists of putting the products to be treated into a vessel placed in a chamber which is closed and sealed with the exception of an outlet for the following: the gases produced by the decomposition of organic materials, vaporisation of the water and decomposition of the hydroxides or oxides; the gaseous cadmium which has to be cooled to change into the liquid and then the solid phase in either a confined space or in water. Heating is usually done by heating elements. The temperature is built up gradually and
161 by stages so as to obtain, if necessary, the successive gasification of the different constituents, i.e. water, organic materials and cadmium. The purity of the cadmium obtained is between 99.9 and 99.95%. It usually needs to be refined to obtain a purity of 99.99%, the only readily marketable quality for, among other things, the production of nickel-cadmium batteries. The residue is an association of nickel and iron, not an alloy. Depending on the types of furnace and how they are used, these residues have a cadmium impurity content of 0.1 to 0.01%. The furnaces used can operate: at atmospheric pressure, in which case the distillation chamber is pressurised and the condensation chamber under negative pressure; these furnaces are both the cheapest and the simplest; -
at low pressure to help expel the cadmium from the gas distillation chamber; at very low pressure to speed up distillation (ALD furnace made in Germany). These are the most expensive furnaces, but they are also the fastest.
Energy consumption per kilo of batteries treated is the same in all three cases. The energy savings achieved with a high vacuum furnace, because it operates at low temperature, is in fact offset by the high amount of energy required in order to maintain the high vacuum. The constantly increasing use of sealed cells that cannot be disassembled and which have an organic materials content of 5 to 10%, has meant the introduction of two pretreatments. -
Removal of the plastic casing: Numerous power packs have a hard plastic shell accounting for 12 to 15% of their weight. The shell can be broken and separated from the individual nickelcadmium elements by means of, for example, a magnetic separator.
-
Pyrolysis or oxidation of the elements (or possibly of the power pack as is).
162 Pyrolysis is done in a sealed furnace, with no air coming in. The organic materials are broken down into simple organic chains (CHn) at a temperature below the cadmium distillation or cadmium oxide sublimation temperature. The gases obtained can be burned at high temperature (1000~
in a post-combustion
chamber producing CO2 and water vapour. It is important to wash the gases so as to prevent dioxins and inhibit the contaminants that could appear. The main recycling companies using these processes are mentioned below. 9 SAFT AB in Sweden, INMETCO in the USA, KOBAR in Korea, NIPPON RECYCLE CENTER in Japan use furnaces that process one tonne in 16 hours. 9 ACCUREC in Germany uses high vacuum fumaces that process 500 kg in 12 hours. 9 S.N.A.M. in France uses furnaces that work at atmospheric pressure and which process one tonne in 24 hours. These processes use very little water and do not call for high capital investment for the treatment of aqueous effluent. However, they do call for increasingly heavy investment in air treatment in order to comply with the increasingly stringent air discharge limits; these apply not only to cadmium but also to nickel, CO, CO2, NOx, dioxins and furans.
TODAY'S BATTERY RECYCLING COMPANIES
1/ EUROPE The companies involved in the processing of NiCd batteries at the industrial scale are: SAFT AB (Sweden), ACCUREC GmbH (Germany) and SNAM (France). The recycling capacity expressed in metric tons of NiCd batteries (industrial and portable) is presented below. A brief description of each company and of the technology used for recycling NiCd batteries is given below. The data presented are related to the treatment of batteries of european origin. In addition, the recycling companies are processing materials coming
163 from all around the world. The transboundary movement of used batteries for recycling purpose is submitted to the Basle Convention administrative rules.
Ni-Cd B A T T E R Y RECYCLING CAPA CITY OF PROCESSING PLANTS LOCA TED I N EUROPE
Companies
Recycling plant in operation from
Location
Capacity MT / year
ACCUREC GmbH
1995
Germany
2,500
SAFT AB
1978
Sweden
2,000
SNAM
1977
France
5,500
Profiles of the recycling companies are presented below. 1.1
ACCUREC GmbH
In 1995, ACCUREC GmbH decided to develop recycling technologies with the aim to recover raw materials from NiCd, NiMH and lithium batteries. Therefore a
new
process was designed of the highest level of technology: the VTR-process (Vacuum Thermal Recycling). The new developed recycling technology for Nickel-Cadmium batteries as well as the recycling technology for Nickel-Metal Hydride and Lithiumbased batteries was supported by the German Environmental Foundation DBU. The innovative technology is based on a "zero-emission-effect" where the vacuumtreatment guarantees a complete separation from the environment and avoid any air contamination by processed materials. For the first extension step of 1,000 t/y recycling capacity, a 2.5 million DM investment program has been made for research, development and industrialisation. Due to the new battery ordinance in Germany where it is mandatory to collect all types of batteries, the permit for the plant processing capacity was expanded up to 2,500 tons a year. In 1998 ALD AG (Aichilin/Leybold/Durferrit) became the major shareholder of ACCUREC. ALD Vacuum Technologies is the world leader in the field of design and manufacture of vacuum systems for metallurgical processes and vacuum heat
164 treatment. The ALD group of companies operates with 300 engineers and a revenue of 180 million DM for 1999. Looking for new activities, ALD now develops in cooperation with ACCUREC a zero emission treatment concept for recycling applications. The following types of materials can be treated in ACCUREC GmbH recycling plant: NiCd industrial vented cells with or without electrolyte. NiCd portable sealed cells, individual cells or powerpacks. Production waste from the production of batteries. NiMH sealed-cells, individual cells or powerpacks. Lithium batteries sealed cells, individual cells or powerpacks (pilot-plant). A schematic presentation of ACCUREC GmbH processes is supplied in Figures 4 and 5, for the treatment of industrial and portable NiCd batteries, respectively.
1.2
SAFT AB
The SAFT AB recycling plant at Oskarshamn/Sweden is fully integrated in the manufacturing plant for industrial nickel-cadmium batteries. It demonstrates the commitment of the major european NiCd battery producer to control the life-cycle of the products introduced on the market. Process development started in 1978 and the operation reached industrial scale in 1986 (Figure 6). The plant permit from the Court of Environment, dated 1996, includes treatment of 2,000 tonnes of used batteries while the present capacity is approx. 1,500 tonnes of industrial batteries
or
800 tonnes of industrial + 400 tonnes of portables.
Ni Cd batteries, portable as well as industrial, are received from the whole world. All internal production waste containing cadmium is treated at the plant (Figure 7). Based on the measurement prescribed in the Surveillance program, the yearly cadmium emissions of the recycling plant are estimated to approx. 0.2 kg to the atmosphere and approx. 0.5 kg to water (1999). The recovered cadmium (<99.95% pure) is directly used for the manufacturing of industrial batteries.
165
A C C U R E C GmbH (Germany) ...............................
]
/.tterystock/i
~-~
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BB_2_ ..... ~]~7_ .......... :
I
[ sort,ng
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il
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:
I
:el . . . . . lvt
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stock valuable goods
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t
-........................ BB3
'
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i, ..._ i v
cadm lum
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:
BB4
Figure 4. Schematic Presentation of the Ni-Cd Battery Treatment at Accurec GmbH: Industrial Cells ..............................
attery
stock
~
-'
BB__2 ........ _~_ ..............
NP'
I sorting
! /
I~......tationI I
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,- . . . . . . . . 1..~ I c ~ ..-- [plastic
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m
,~ ............ Y cells
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p .........
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cadm ium ,, .- -,-u ~_ . . . . . . . . . . . . . . . . . . . . . . . . . . BB 4
Figure 5. Schematic Presentation of the Ni-Cd Battery Treatment at Accurec GmbH: Portable Cells
166
Fig. 7
Recycling 9 Integrated in Battery Manufacture at SAFT AB
167 1.3
SNAM
S.N.A.M. was created in 1977, with a major activity in the extraction of the cadmium contained in waste originating from the production or recovery of nickel cadmium batteries. The first plant has been in operation at St Quentin Fallavier (Isere - France). The plant has received authorisation for the treatment of 1,500 tonnes of cadmium containing by-products. In 1988, S.N.A.M. has built a new factory in Viviez (Department of Aveyron - France) with a treatment authorisation of 4,000 tonnes of cadmium-containing waste. 9.*. Plant located in St-Quentin Fallavier (built in 1981)
This plant is authorised by prefectorial order AP 90.47.18 (dated October 3, 1990) to treat 1,500 tonnes per annum of products containing cadmium. The original 1981 permit was updated in 1990. Its current capacity is 1,400 tonnes with 6 distillation furnaces. It specialises in the treatment of used nickel cadmium sealed cells and those rejected during manufacture. 9:-
Plant located in Viviez (built in 1988)
The plant is authorised by prefectorial order AP 97.1750 (dated July 24, 1997) to accept and treat 4,000 tonnes of raw materials. Its current capacity is 3,300 tonnes with 9 distillation furnaces. It treats all types of waste but mainly nickel-cadmium industrial batteries and production waste. Together, the annual output of the 2 factories is over 700 tonnes of cadmium metal of a purity of 99.99 % by weight and more than 650 tonnes of nickel in the form of iron nickel residues (1,900 tonnes) or ferro-nickel. The balance is made of plastic materials (cases of the industrial batteries, plastic shells around the power packs etc.), of scrap iron (metallic cases of the industrial batteries, iron residues coming form the distillation of negative pocket plates). These products are valorised at a market value either for energy production or scrap. Figure 8 shows the general flow sheet of the SNAM process, while Figures 9 and 10 provide details of the recycling schemes of NiCd batteries and NiMH batteries, respectively.
Figure 8 : SNAM Process - General Flow Sheet
169 S.N.A.M. (France)
Ni-Cd Batteries Recycling Scheme
"~ ] industrial ]
!lectrolyte '~e-use
]Plastic
lectrode
II
] '
Sorting Single Cells /Pack____ss Plastic Ex___ternalCase S_ e p a rpr ~ __[ Recovery aratlo~B I
Nickel
Figure 9
Portable
I [
I~
ThermalTreatment .~ Metallurgical Treatment Fe-Ni
I
I
Ni-Cd 9 Battery Recycling at SNAM (France)
!~ H20 7 CO2
Cadmium
[
170
S.N.A.M. (France)
Ni-MH Batteries Recycling Scheme l Portable / Pack
/ !
-II-
External Case Separation II Thermal Treatment
C02
-IIShredding !i Magnetic Separation Iron Fraction
Leaching Selective precipitation Nickel and Cobalt recovery
Figure 10
Schematic 9 Presentation of a Ni-MH Battery Recycling Process
171 2/
U.S.A. : INMETCO
INMETCO is primarly a stainless steel recycler. They process about 50,000 tons of materials containing iron, nickel, and chromium per year, and return an Fe-Ni-Cr alloy back to the stainless steel industry for production of new alloys. As part of their recycling operation INMETCO has accepted both NiCd and NiFe batteries as well as EAF dust, electroplating sludges, and process wastes, all of which may contain some cadmium. The cadmium, and the other low melting elements, lead and zinc, are fumed off either during a rotary hearth furnace treatment or electric arc furnace melting operation. The zinc, lead and cadmium dust which is fumed off during these two operations is collected as a filter cake from a wet scrubber or as a bag-house dust. This Zn-Pb-Cd product is subsequently sent to Horsehead Resources Development Corporation where it is separated into zinc, lead, and cadmium and returned to the marketplace. INMETCO is capable of handling both portable and industrial NiCd batteries, and is permitted to recycle up to 10,000 tons of NiCd batteries per year. Since INMETCO is primarly a stainless steel recycler, the economics of their NiCd battery recycling process is not as dependent on current cadmium prices as are those of recyclers who are dedicated to NiCd battery recycling alone. Flow sheets of the INMETCO recycling processes for industrial and consumer NiCd batteries are presented in chapter 4 of this book.
3/
KOREA : NIPPON RECYCLE CENTER
NIPPON RECYCLE CENTER was established in Japan in 1976. In 1985, NIPPON RECYCLE CENTER made the decision to move their operation to Korea due to an increase in both production and consumption of NiCd batteries in this country. The strategy was to take advantage of this new market while strengthening the companies competitive position by reducing costs. HANIL METAL RECYCLE was thus formed as a joint venture based on the foreign capital inducement act. A new and enlarged plant was completed in 1987 in Korea's largest industrial park Changwon Kongup Kiji.
172 For the past 15 years, Nippon Recycle Center / Hanil Metal Recycle have been an important link in the recycling chain for NiCd batteries. In so doing they have contributed to enhancing the social utility of NiCd batteries. This plant discontinued operations in 2000 due to the difficulty of obtaining supplies from Japan. However, in mid-2001 a new company was formed, KOBAR Ltd., in a small town not far from Changwon City. Run by former technical executives from Hanil Metal Recycle, the plant uses greatly improved technology. Its initial capacity is limited to 1,000 tonnes/year.
4/
JAPAN
Toho Zinc and Kansai Catalyst In Japan, the largest cadmium consumer and the largest NiCd battery producer in the world, there is fairly extensive pyrometallurgical recycling of NiCd batteries. Both Kansai Catalyst and Toho Zinc integrate their NiCd battery recycling into the zinc cadmium refinery plant, and recover cadmium and iron nickel oxides from a rotary kiln process operated at 1000~ Industrial batteries are dismantled and sealed cells are first crushed prior to the high temperature treatment. The cadmium oxide is then introduced into the zinc refinery circuit where it is refined to high purity cadmium. The iron-nickel oxides are sold to the steel industry. Toho Zinc also has the capability of treating NiCd battery industry process sludges to recover nickel and cadmium by wet chemical methods. In this circuit, the sludges are leached by sulfuric acid, purified, and then treated with sulfur to produce a cadmium sulfide product which can also be introduced into the zinc refinery circuit for purification into high purity cadmium. The nickel is recovered and sold as a nickel carbonate. The recycling capacity of Toho Zinc is estimated at about 2,000 tons per year, while Kansai Catalyst is believed to be capable of recycling from 500 to 1,000 tons of spent Ni Cd batteries per year.
Nippon Recycle Center The other major Japanese recycling plant, JAPAN RECYCLE CENTER, dismantles or crushes industrial and consumer NiCd batteries which have been separated from
173 other cell chemistries. Plastic or steel casings are sent directly off for sale as scrap, while the crushed cells or dismantled electrodes are heated in a vacuum furnace at elevated temperature to volatilize the cadmium. The cadmium so collected may subsequently be refined to a higher purity metal or converted to cadmium oxide for battery industry use. JAPAN RECYCLE CENTER has a NiCd battery recycling capacity of over 2,000 tons of spent batteries and production scraps per year. At present, the Japanese NiCd battery recyclers have far greater recycling capacity than is utilized due to the low cadmium and nickel prices and an insufficient supply of collected NiCd batteries. In Figure 11, the Nippon Recycle Center process is presented.
Figure 11. Nippon Recycle Center Process - Japan
(This process was operating in joint venture at Hanil Metal Recycle (Korea) since 1999; Nippon Recycle Center in Japan operates this process exclusively)
174 CONCLUSION There is nothing new about recycling batteries and waste products from nickelcadmium batteries; but several developments have occurred in the last twenty years. National and intemational regulations are prohibiting to an ever-increasing extent the disposal of nickel-cadmium batteries on rubbish tips as well as their incineration along with household waste. A number of countries have already introduced collection systems: 9 either all batteries and accumulators undifferentiated (Switzerland, Germany, the Netherlands, Belgium and others); 9 or specifically nickel-cadmium or rechargeable portable batteries (USA, France, Denmark, Japan and others). The tables below show collection figures for Europe for both industrial batteries and sealed units and power packs. The objectives, which are tending to be govemed by increasingly stringent regulations, show that collection systems should increase very appreciably. In Europe, the annual tonnage of NiCd, NiMH and Li-Ion batteries is certain to increase fourfold in the period 2001 to 2008.
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Used Battery Collection and Recycling G. Pistoia, J.-P. Wiaux and S.P. Wolsky (Editors) 9 2001 Elsevier Science B.V. All rights reserved.
177
Primary Battery Recycling in Europe Neil Watson European Portable Battery Association, Hazelwick Avenue, Crawley, Mallory House, West Sussex RH 10 1FQ, Great Britain
Battery Definitions The term "general purpose consumer battery" can be used to describe any portable battery system. This includes both single cells, such as those used in torches, radios or other similar devices and "battery packs" used within mobile communication and cordless tools for example. The term covers both rechargeable chemistries, as well as the more abundant single use chemistries. The term "primary battery" is used to describe any single use battery system. These include, amongst others, alkaline-manganese, zinc-carbon, lithium, mercuric oxide and zinc-air chemistries. Primary batteries are lightweight and convenient, relatively inexpensive and consequently are used by households throughout the world to power portable electrical and electronic devices, radios, torches, toys and a whole host of other every day appliances. The most common primary batteries in use today are the zinc-carbon and the alkalinemanganese battery systems. Together, they constitute in excess of 90% by weight of the total consumer battery market in Europe. Consequently, particularly within the realm of battery recycling, the term "primary battery" is often used to describe just these two systems.
Battery Collection Historically lead-acid, silver oxide and industrial nickel cadmium batteries were collected by entrepreneurs and recycled at the end of their lives due to the economic value in the materials they contained. In the early 1980's primary batteries became subjected to increasing attention by environmental authorities and interest groups particularly in Scandinavia, Germany
178 and Benelux countries. Concern was voiced on the significance for the environment of disposing batteries containing mercury with normal domestic waste and particularly when such waste was incinerated. It was believed that mercury from waste batteries dispersed into the environment leading to hazardous concentrations in soil, crops and freshwater fish. Although several studies carried out in Europe, Japan and the USA concluded that mercury from batteries in waste does not pose a threat to the environment irrespective of the means of disposal, legislation was introduced to control the dispersal of mercury, cadmium and lead from waste batteries into the environment by separately collecting waste mercuric oxide, nickel cadmium and lead-acid batteries. Unlike lead-acid and silver oxide batteries, which have historically been collected and recycled due to their economic value, collection and recycling of general purpose batteries is currently undertaken at a cost to the waste generator. All responsible manufacturers whatever the industry, recognise a need to protect the environment and promote sustainable development. However this is rarely possible at zero cost. In the late 1980's many battery systems still contain a significant proportion of toxic elements whose environmental impact after use needed to be controlled. Some Member States began introducing measures for controlling the marketing and disposal of batteries. In view of this and in order to avoid the creation of barriers to trade and distortion of competition in the Community if this trend was allowed to continue, the European Council approved in March 1991 Directive 91/157/EEC "on batteries and accumulators containing certain dangerous substances". ,
European Legislation
The focus of European legislation for battery waste has been to reduce the impact on the environment of batteries containing heavy metals. Council Directive 91/157/EEC "on batteries and accumulators containing certain dangerous substances" was introduced with the aim of restricting the use of batteries containing cadmium, mercury and lead and controlling their disposal. Specifically the Directive prohibits the marketing of general purpose alkalinemanganese batteries containing more than 0.025% mercury (0.05% for special purpose types). Furthermore it calls for the marking and separate collection for recovery or
179 controlled disposal of batteries which contain more than 0.025% cadmium, 0.4% lead or 25 milligrams of mercury. The effect of this Directive on the european primary battery industry should have been limited, as neither alkaline-manganese nor zinc-carbon batteries contained significant quantities of these metals, certainly well below directive levels, if any at all. Neither alkaline-manganese nor zinc-carbon batteries contain any added cadmium. Cadmium can be present as a naturally occurring contaminant within the zinc component at up to 0.002% by weight. Lead is sometimes still used in both battery systems. In zinc-carbon batteries it is employed chiefly as an alloying addition to improve the forming characteristics of the zinc can, and additionally acts as a corrosion inhibitor. In alkaline-manganese it has found use as a plating alloy on the brass nail to reduce gassing. In zinc-carbon cells, the lead content is in the order of 0.02% and in those alkaline-manganese batteries where lead is still used, the addition is at a level of a few parts per million. Until the early 90's, mercury was added to both alkaline-manganese and zinc-carbon batteries to perform various functions within the anode. These included suppressing the hydrogen gas evolution within the cell, inhibiting corrosion and improving shelf life. Before 1985 mercury was added in concentrations up to 1% of total cell weight in alkaline manganese batteries and 0.01% in zinc carbon batteries. In
1985 the
european battery manufacturers began a programme to reduce the mercury content of batteries as far as technology would allow. By 1991, the year that the Directive was proposed, these had been so successful that mercury had been eliminated from all european produced zinc-carbon cells and reduced to below the 0.025% Directive threshold for alkaline-manganese cells.
The reduction programme continued until
1993 when mercury additions were completely eliminated from alkaline-manganese cells as well. Today only background levels of mercury remain within primary batteries. This is the naturally occurring mercury associated with the zinc components. Typically this is less than 2 parts per million and always less than 5 parts per million. 9
National Legislation
On a national level, the implementation of the European Union Battery Directive is far from harmonised. There currently exists a diverse, often complex, array of legislation
180 which is continuously evolving. Table 1 summarises the european national legislation situation as of May 2001.
In many countries the legislation simply enforces the
requirements of Directive 91/157/EEC, but in others the legislation goes beyond the Directive to encompass the collection of all consumer battery systems, regardless of their contents, and, where feasible, enforcing their recycling. Why is this? Although the European Directive 91/157/EEC does not include collection targets, Article 7 does charge Member States with ensuring the efficient organisation of collection programmes for those battery systems covered by the Directive. The problem arises because the general public, with limited experience of the different battery types, are unable to easily distinguish between batteries which should be collected separately and those which need not. This has resulted in either a poor response to dedicated collection programmes or non-Directive batteries being collected in error. Furthermore, as the Directive is limited to those batteries containing more than a certain amount of dangerous substances, it leaves the Member States free to act individually on those which fall outside its scope. Consequently in order to maximise the collection of the Directive batteries, some States believe the simplest solution is to legislate for the collection of all battery chemistries. The Directive batteries constitute less than 10% of the general purpose batteries marketed in Europe today. As these are typically rechargeable systems, they remain with the consumer far longer than the primary types. In those countries collecting all batteries, studies undertaken by the battery industry, in collaboration with the collection authorities, have shown that more than 95% of the batteries collected fall outside of the European Battery Directive. Should this solution therefore be considered to be taking a sledgehammer to crack a nut? From the simplistic viewpoint of meeting the requirements of the European Battery Directive, yes, but for the Member State, this solution has additional benefits. It can also be viewed as encouraging waste recycling generally and reducing political pressure
from environmental lobbying groups and other interested parties.
Furthermore waste recycling is considered to create more employment opporttmities than waste disposal. 9 The Response of the Primary Battery Industry Since the primary battery industry had invested heavily in making their products
181
Table 1. Summary of European National Battery Legislation, May 2001
182 environmentally inert, the primary battery producers were disappointed by some Member States' interpretation of the European Directive. They argued that primary alkaline-manganese and zinc-carbon batteries could safely be disposed of in landfill and therefore legislation to collect and recycle all batteries was unnecessary. This argument was based upon the conclusions of several international studies.
These
included the Institute of Risk Research study, University of Waterloo, Ontario, Canada 1 (1992) and ongoing landfill studies undertaken at the Fukuota University in Japan 2. The Canadian report concluded that dry-cell batteries do not represent a concentrated source of heavy metals in municipal solid waste and their disposal by landfill or incineration poses insignificant risk to human health. Furthermore they concluded that separate collection, storage and disposal of most household batteries produced more significant health related problems and that recycling of primary batteries was neither necessary nor needed. The Fukuota University study has charted the corrosion rate and mercury leaching potential from batteries buried in typical landfill conditions. The findings showed that after 9.5 years, the maximum loss of mercury from the battery containing test sites was 0.062% of the initial mercury content. Concentrations of mercury within leachate were measured between 0.0001 mg/1 to 0.00035 mg/1, significantly lower than the 0.0005 mg/l environmental standard. However political motivation frequently exceeds technical argument. Consequently the battery industry set up a working group under their european trade association, Europile (later to become the European Portable Battery Association - EPBA), charged with investigating collection and recycling of post consumer batteries in Europe. It quickly became apparent that if recycling of primary batteries was to proliferate across Europe, insufficient facilities and capacity were available to meet the anticipated demand. In the early 1990's, only two companies, both based in Switzerland, offered recycling of alkaline-manganese and zinc-carbon batteries. After investigation, the working group concluded that neither of these companies offered economically viable and sustainable solutions, as they required either large subsidies from Govemment or offered recycling at prohibitively high cost. A significant proportion of the cost of these two operations resulted from the need to capture and treat mercury. But since zinc-carbon and alkaline manganese batteries
183 were now free of added mercury, processes concentrating on treating mercurycontaining batteries were considered to have a limited future. With the aid of the intemational consulting group Arthur D. Little, the industry concluded that, once mercury was no longer added to primary batteries, the most effective and environmentally sound method of recycling them would be to utilise existing infrastructure within the metals industry. Recycling of other post consumer goods such as paper, aluminium cans, steel cans and glass bottles are regularly cited as examples of this integrated approach. This approach was only possible if the collected batteries could be guaranteed to be below 5 ppm of mercury. However, under the existing Battery Directive, 91/157/EEC, batteries were able to be imported into the European Union which still contained up to 250 ppm of mercury.
These imported batteries threatened the viability of the
integrated metals industry approach. Consequently the battery industry approached the European Commission with a proposal for a two stage approach to the issue of collection and recycling of primary batteries. This 'two step plan', proposed that if the European Union legislated for a ban on importation of primary batteries containing any added mercury, (step one), then cost effective and environmentally sound recycling of these batteries could commence four years later, (step two). This four year delay was necessary in order to allow the batteries sold before legislation to pass through the waste stream. This approach was approved by the European Union and adapted into law through a technical adaptation, 98/101/EEC, to the Battery Directive, which came into force on January 1st 2000. A revision to this Battery Directive has been proposed and is currently in the stage of inter-service consultation within the European Commission. The key proposals within this revision are as follows:
-
-
A marketing ban on all consumer nickel cadmium batteries from the 1st January 2008. All the standard size consumer batteries to be marked with a crossed out dustbin symbol on the battery label itself. This will include D, C, AA, AAA and 9V size batteries.
184 -
All battery types to be collected separately from other wastes. A collection targets of 75% is proposed.
-
By the end of 2004, all collected batteries must be recycled with a recycling rate of 55% of materials contained within them.
-
Member states are left free to define the responsibilities under this Directive. They are also free to employ economic instruments or deposits if they so wish.
The battery industry world-wide supports battery recycling so long as it is effective, environmentally sound and cost effective. The european battery industry, through the European Portable Battery Association, the EPBA, has voiced opposition to these proposals because it feels that they will not meet these aims. A huge financial burden would be placed on the battery industry in Europe in an attempt to reach a collection target which is unachievable. This collection target is also likely to create additional environmental burden rather than reduce it. Both of these issues are discussed further in this chapter. 9 Methods and Organisation of Battery Collection
The method of battery collection and economic instruments employed to finance the programmes differ from country to country. The driver for each system is the national legislation and in particular who is given responsibility for the collection and fmancing. Today, seven countries have battery collection schemes which impact primary batteries. These are Austria, Belgium, Germany, France, the Netherlands, Portugal, Sweden, and Switzerland. Belgium is the only country who pass the full responsibility for collection sorting and recycling, as well as publicity and awareness campaigns on to industry. Both Sweden and the Netherlands leave the responsibility for collection in the hands of the municipalities. All of the other countries share the responsibility for collection jointly between retailers and municipalities. All of the countries, with the exception of Sweden and Switzerland, will rely on industry to take responsibility for the waste management of the batteries.
Sweden
relies on the municipalities for waste management and Switzerland gives this responsibility to the recyclers themselves. Under the existing EU Directive, 91/157/EEC, no specific collection target is set. However some individual countries have imposed their own collection target.
185 Belgium had a collection target of 75% for 2000: this was not met. Consequently the belgian government have revised their target to 60% of sales by 2002, rising to 65% by 2004. The Netherlands have a collection target of 90% by 2004. These very high collection targets result in spiralling costs for the organisations with responsibility for collection. This is because a great deal of money needs to be spent on publicity and awareness campaigns to encourage the general public to return spent batteries. There is little evidence to suggest that these high collection targets are achievable. Two distinct financial management schemes can also be identified. The governments of Belgium, Sweden and Switzerland each define an environmental fee which is added to the price of every battery sold in order to finance the collection and recycling operations.
The remaining countries pass financial control onto the producers and
importers of the batteries, who are then responsible for recovering their costs from the market through sales of new products. In each of these countries, the battery industry has implemented collection and recycling associations, NCRA's, on behalf of the manufacturers, importers and retailers, who are impacted by the necessity to collect and recycle. Depending on national law, they are either in the form of an association, a federation, or a company. Each of the NCRA's is operated on a non-profit basis. It is not a legal requirement for any company or organisation with responsibility for collection and/or recycling to be a member of one of these NCRA's. Consequently in some countries, competing organisations have been set up to collect and recycle batteries. These are independent of the battery industry and generally profit orientated. - Germany
In Germany, the battery decree places specific requirements on the trade, municipalities and end users. Both the trade and municipalities must take back used batteries from the consumer free of charge. Furthermore the distributors are also obliged to notify customers that this is the case. Producers and importers of batteries are required to take back the returned batteries from these collection centres free of charge. They are also responsible for equipping the retailers and municipalities with suitable collection containers.
The decree even places a legal obligation on the
consumer to return spent batteries to one of these collection facilities. In 1998, the battery industry set up an organisation with responsibility
for the
collection of all batteries named Stiffung Gemeinsames Rticknahmesystem Batterien, (GRS Batterien). This is a federation which now represents more than 430 battery
186 producers and importers across Germany. They organise collection via trade and municipal collection centres as well as industry. They provide more than 130,000 return points for batteries to ensure that it is easy for the consumer to return used products. In addition they provide all of the collection containers and organise reverse logistics from the points of collection to the sorting facilities. The collection rate has grown from 5,700 tonnes in 1998, to in excess of 9,300 tonnes in 2000. Competing against GRS Batterien in Germany is Vfw-REBAT, a profit orientated battery collection company. This company also offers a nationwide collection and recovery/disposal service for the german market. They occupy a certain market share, particularly for special use batteries such as those used for agricultural fencing and signal lamps. Robert Bosch GmbH also operates battery collection but only in the field of battery packs for electrical power tools. GRS Batterien remain the largest organisation with responsibility for more than 80% of the market. The Netherlands Dutch legislation classifies a number of domestic products such as paints, medicines, -
pesticides and all types of batteries, as small chemical waste (KCA). Importers or manufacturers of these products are required to mark them with a special KCA symbol either on the packaging or on the product itself. The general public are informed that these products must not be disposed of with other household waste, but they are to be stored separately in a special KCA container, an ecobox. These wastes are collected separately on a regular basis by the municipality, and stored in one of more than 450 municipal depots. This is an example of a co-mingled collection system. The municipalities themselves are responsible for the adequate functioning and the costs of this part of the process. The battery industry takes up responsibility from the municipal depots, and the cost for the remaining steps in the process. These include the shipment from the municipal depot to a central storage facility, as well as the sorting and recycling of the batteries. The dutch legislation has been in force since 1995, the year after the battery industry established Stichting Batterijn (Stibat), the dutch NCRA. This makes Stibat one of the longest established collection and recycling associations in Europe. As in Germany, manufacturers or importers are not obliged to be part of a joint venture such as Stibat, for collection and processing; however a joint approach has considerable advantages over stand-alone solutions. members.
Today Stibat has over 450
187 Originally retum of batteries via the KCA collection system was only approved on the basis that high collection rates could be achieved. Targets set by the govemment were 80% by the 1st January 1996 rising to 90% by the 1st January 1998. It soon became apparent that these rates were unachievable. A number of factors can be identified which are responsible for this, particularly the fact that the general public either hoard batteries within the home or are ignorant of their responsibilities to retum used batteries via the KCA system. As the aim of the dutch decree is to prevent used batteries from being discarded through the household waste stream or simply into the environment, Stibat proposed a revised collection rate that takes into account a hoarding factor. This method of calculating collection rate assumes that the batteries which are stored within the home have no negative environmental impact. As the occurrences of batteries being discarded uncontrolled into the environment is negligible, the success of any collection process can be determined by its ability to keep batteries out of the municipal household waste stream. Using this method the collection rate for batteries in the Netherlands in 1998 was found to be 75%.
This calculation method has been accepted by the dutch
govemment. Stibat are still faced with achieving the exceptionally high collection target of 90% in 2003. Hence Stibat has now introduced additional collection schemes to improve the collection rate. These include reverse distribution as well as programmes with schools. Approximately 2,500 retail outlets are now participating in the take back scheme. Food chains are not included in this programme in order to avoid KCA waste being included in reverse logistics. Schools are offered an incentive programme whereby points are awarded per kg of batteries collected and these can be exchanged for equipment for the school. Over 2,000 schools participate in this scheme. - Belgium
Belgium has an "ecotax" law which subjects all batteries to an environmental tax of BEF 20 (C 0.5) plus VAT for each battery. This is regardless of the size or chemical system.
However, exemptions from this ecotax are possible if one of the two
following conditions is met. Firstly the battery manufacturer or importer must distinctly mark the battery and submit to a deposit valued at C 0.25 per battery. The obligations of collection and recycling will then be met by the taxpayer.
188 Altematively, a legally defined voluntary scheme for collection and recycling of batteries can be used. A deposit scheme for the retum of batteries has a number of drawbacks. Technically it would be unrealistic to expect manufacturers to mark products for a small market such as Belgium, when they are produced on a global scale. The scheme would be complex to administer, particularly with the risk of fraud resulting from batteries being returned which were purchased outside of Belgium. Battery manufacturers and importers therefore elected to collect and recycle or treat all batteries under a voluntary agreement with the government and in 1995 established Bebat to manage this scheme.
This scheme is funded through a collection and
recycling fee, which is set and only adjustable by Royal Decree and is presently set at BEF5 per battery ((~ 0.12). When a company joins Bebat, the Finance Ministry awards them temporary ecotax exception, which is conditional upon the collection objective being achieved for all Bebat members jointly within that year. Penalties are threatened for non-achievement. The Bebat collection scheme relies heavily on the reverse distribution model, utilising over 13,000 retail outlets.
An additional 5,000 collection points are available in
schools, education centres and youth clubs and 600 through container waste parks, operated by municipalities. Further collection points are present in the industry or other bulk users such as hospitals or the military. As with Stibat, a significant and growing proportion of the Bebat costs are being spent on public awareness and promotion. Once again, this is due to having to achieve, or strive towards, a very high collection target. - France
The legal obligation to separately collect all batteries for recycling came into effect from the beginning of 2001. Prior to this, only rechargeable batteries were required by law to be collected. As a result, two NCRA's were formed at different times by the battery industry. The first, Soci6t6 de Collect et de Recyclage des Accumulateurs (SCRA), representing rechargeable manufacturers and OEM producers, and the second Fibat, representing the interests of the primary battery manufacturers. Both of these organisations are now working together as a joint organisation called Soci6t6 de Collecte et de Recyclage des Equipments Electriques et Electroniques (SCRELEC) together with electronic equipment manufacturers.
189 The SCRELEC collection process is very similar to that operated by GRS Batterien in Germany.
Collection boxes of various types are distributed to collection points.
Currently two waste management companies have been contacted to collect the batteries from the various collection points including: stores, business or industrial sites and municipal waste facilities, and forward them to a sorting facility.
This
scheme is co-ordinated via a national call centre. SCRELEC has released an invitation to tender for the collection sorting and recycling of batteries in France. Several large retail chains have also set up their own independent collection schemes in collaboration with french recycling companies to meet their obligations under french law. - Austria
Austrian law requires retailers and wholesalers to take back used batteries from consumers free of charge. Municipalities are also obliged to accept used batteries from private citizens. Battery manufacturers and importers have established an organisation called Umweltforum Batterien (UFB) to administer the scheme for collection. It can handle sorting and disposal or recycling of batteries.
- Switzerland
National law on substances (Annex 4.10 dated 01.07.98) requires consumers to bring back used batteries or accumulators to point of sales or collection centres. Battery retailers are obliged to take back the types of batteries they sell. Municipalities too are participating voluntarily to establish separate battery collection points.
Collected
batteries are then transported to one of regional battery collection centres, which are operated by the battery recycler. A mandatory tax is paid by battery marketers to a private company, INOBAT, to finance the cost of collection, transportation, recycling and a public awareness campaign. - Sweden
The environmental protection plans of the swedish government focus only on those batteries containing mercury, cadmium and lead. However, all batteries are collected in order to maximise the capture of these hazardous materials.
The government
imposes a levy on nickel cadmium batteries, lead batteries and mercury containing button cells.
The money raised is used to fund collection and sorting, which is
undertaken by the municipalities. Mercury, nickel cadmium and lead batteries are sent for recycling and all other batteries are landfilled. Significantly, the swedish
190 government does not impose a collection target because it is believed not measurable. - Portugal
The separate collection of all batteries will commence in July 2001. Municipalities and retailers have the responsibility of collection from consumers, but producers and importers take responsibility for the batteries from designated depots. A mandatory collection target of 25%, based on annual sales by weight, has been set. The battery industry is setting up a collection and recycling company to manage its obligations under portuguese law. 9
Future Options for Battery Collection
A report commissioned by the UK Department of Trade and Industry, from the consultancy group Environmental Resources Management, ERM, entitled Analysis of the Environmental Impact and Financial Costs of a Possible New European Directive on Batteries 3, published in November 2000, raises questions about the principle of the separate collection of waste streams. This report studied collection of consumer batteries by three schemes commonly used around Europe: kerbside collection, takeback via retail outlets and the consumer returning used batteries to a municipal waste collection facility. The report considered emissions due to transportation, fabrication of special collection containers and effects on the climate, soil and water. It concluded that, while recycling of batteries does produce a positive environmental impact, separate collection of batteries produces a negative environmental impact, which far outweighs the positive benefits of recycling. This gap widens as the collection target increases. This report in itself is not conclusive. However it does stimulate debate on the separate collection of wastes in general. Further work is necessary in order to determine alternative solutions to reduce the differential between the negative impact of collection and the positive impact of recycling. One possible approach is to integrate the collection of primary batteries together with other suitable waste streams. Clearly such an approach will depend on the end use of the waste batteries, but the advantages in terms of minimising collection and transport impacts are obvious. The report findings also question the benefits of imposing high collection targets. The issue of collection targets has concerned the battery industry for some time. Of primary concern is the measurability of a collection target expressed in percentage terms. It is unrealistic to use sales statistics for any one given year as the baseline for such a calculation. This is because battery life is dependent upon the appliance in
191 which it is used. Most primary batteries for example, remain with the consumer for between two and three years. But it is not uncommon to find batteries returned in collection systems which are ten or more years old. Calculating the correct baseline is therefore very difficult and often questionable.
The battery industry has therefore
proposed collection targets based on a weight per capita, taking into account results achieved to date in countries with established collection processes, as well as the need to avoid unnecessary environmental burdens. Battery Recycling 9 Dedicated/Unsorted batteries
A number of waste handling companies dedicated to recycling batteries have developed as a response to the increasing battery legislation around Europe.
The
collection schemes, operating throughout Europe at the time of writing, collect mixed and sometimes very old batteries. Recent sampling undertaken at the Dutch battery collection facility in Rotterdam have shown that in excess of 90% of the primary batteries collected contain no added mercury. Consequently, despite the fact that the majority of batteries collected are mercury free, the overall mixture of batteries still contains mercury.
Until recently there has not been any quick and reliable method for
distinguishing between the older, mercury containing batteries and the younger mercury free batteries. As a result, the dedicated battery recycling companies have tended to concentrate on processing mixed or partly sorted batteries, within mercury tolerant processes. This approach has a number of advantages and disadvantages. The ability to process mixed or partially sorted batteries is attractive since the waste generator is required to undertake either none or only the minimum amount of preprocessing before sending the batteries for recycling. This reduces the up-front cost for the waste generator. But feeding unsorted batteries will introduce a number of undesirable elements into the process, not least of which is mercury. Mercury control and treatment is difficult and expensive. As all of the batteries are treated as if they were mercury containing, then an additional, unnecessary cost is added to the processing for the zero mercury added batteries. generator.
This cost is returned to the waste
Dedicating processes for recycling is always likely to result in a high processing cost as the entire capital investment must be realised against the waste being recycled. With unsorted batteries, the composition of the feed to the process is relatively uncontrolled, consequently the process is likely to produce variable quality products,
192 whose marketability and market value are limited. The alternative is to introduce further processing steps in order to improve the quality of the product pre-market, thereby adding further to the cost. 9
Hydrometailurgicai processes
Wet chemical, or hydrometallurgical processes for battery recycling differ fundamentally from pyrometallurgical approaches in that they aim to produce finished products with a high resale value rather than lower value material, which is further refined or used in a separate industry. This quest for greater added value is often borne out of necessity, to cover the high capital investment and operating costs. Early hydrometallurgical battery recycling processes concentrated on attempting to recycle a mixture of all batteries, both primary and secondary, without any sorting of the different chemistries. This approach often requires an increased number of process steps in order to eliminate or reduce the considerable number of impurities which would otherwise significantly reduce the value of the products or even make them unsaleable. Furthermore, since the input stream is constantly changing, a high degree of analysis and control is necessary while processing. This all adds to the complexity and therefore the cost of hydrometallurgical recycling of batteries. The technology being developed today accepts that pre-sorting can be beneficial to the hydrometallurgical recycling route. Zimaval, France, is a good example of selectively processing batteries by wet chemistry. The company specifically aims to recycle only three zinc bearing battery chemistries: alkaline, zinc carbon and zinc-air. Because the processing of these batteries also varies to a certain extent, they use sorting not only to remove other battery systems from the mix, but also to separate the three battery chemistries in order to batch process them. Zimaval have developed their own inhouse sorting technology to do this. Following sorting, the batteries are shredded. The zinc-air batteries, which are typically large industrial units, need to be cut and broken before processing. The alkaline and zinc carbon batteries are shredded in an automated unit. The former under sodium hydroxide and the latter under a water spray. The water wash is necessary to eliminate the chlorides within the zinc carbon cells before leaching. Plastics, paper and metals, both ferrous and non-ferrous are removed at this stage. The paper and plastics are segregated and sent off site for incineration with energy recovery, and the metals, once separated by eddy current techniques are sold.
193 The fines fraction, consisting mainly of zinc and manganese oxides and carbon, are leached in a sodium hydroxide bath. This selectively dissolves the zinc. Any amalgamated mercury present in the zinc precipitates out at this time and settles at the bottom of the reactor. This is periodically tapped off and sent for specialist treatment. After filtration, the zinc rich filtrate is allowed to cool naturally, then dendritic zinc is deposited by electrolysis. This is potentially a high value material used within the paint industry. The sodium hydroxide is recycled back into the alkaline leaching process. The filter cake consists primarily of oxides and hydroxides of manganese and carbon compounds. A sulphuric acid plus hydrogen peroxide leach is used to dissolve all of the manganese components as sulphates. Metallic impurities and hydroxides are also dissolved. The sulphuric acid is provided from recycling lead acid batteries. Carbon and some of the remaining impurities from the manganese dioxide remain suspension and are removed by filtration.
in
The filtrate contains zinc sulphate and manganese sulphate. The zinc sulphate precipitates out and is recovered. Sodium carbonate is then added and the manganese precipitates out as manganese carbonate, which is sold in the manganese industry The zinc-air treatment is somewhat simpler because the absence of manganese dioxide means that the acid treatment is not necessary. After the batteries have been opened, they are immersed in sodium hydroxide within a trummel. The fines, containing zinc powder, zinc oxide, carbon and lime are suspended in solution and undergo the same zinc treatment as described above. After washing, the large fraction consisting of polypropylene pieces, steel and carbon are sorted and recycled within specialist industries. The current capacity of the Zimaval facility is in the order of 4,000 tonnes per year. Erachem in Belgium also adopt the approach of selective hydrometallurgical processing. Their target is even more specific in that they recycle only the manganese and zinc fraction from the primary batteries. Following a battery sorting operation, the batteries are shredded and milled to liberate the fines fraction or 'black mass' which contains the zinc and manganese in the form of a complex mixture of oxides. This mixture is subjected to a sulphuric acid leach, before a purification stage, then sold as manganese and zinc salts and oxides. One important difference of this process,
194 compared to the Zimaval process, is the scale of the operation. Erachem, Europe are not dedicated battery recyclers, but are a chemical company who's primary interest is in the production of manganese salts for the battery, electronics and agrochemical industries.
They also produce carbon black, used in batteries, tyres and plastics
amongst other applications. The primary battery recycling is therefore undertaken by campaigns within the existing chemicals plant. Consequently it is difficult to calculate the exact capacity of the operation, but it is safe to say that this can be measured in tens of thousands of tonnes. The metal fractions are not lost with this process, but the responsibility for their recovery rests with the battery pre-processor. Today Erachem have partnerships with two pre-processors, Revatech in Belgium, who employ a dry separation methodology, and Duclos Environnement, France, who wet shred the batteries. 9
Pyrometailurgical processes
One of the first battery recycling plants available in Europe was the Batrec recycling plant in Switzerland. This plant operates a pyrometallurgical process developed by Sumitomo Industries in Japan. The process consists basically of three stages. The first is a pyrolysis of the organic substances, water and the mercury in the shaft furnace at temperatures of between 400 to 750 degrees centigrade. It takes up to four hours for the organics within the batteries to be evaporated and the mercury to be liberated. The organics are destroyed by burning in a post-combustion chamber. The exhaust gases are rapidly cooled down to prevent build-up of dioxins and washed in several stages before being released to the atmosphere. The mercury is further distilled and sold. Pyrolysis is followed by the smelting of the metallic factions within an induction furnace. The batteries are automatically fed into the introduction furnace, reductant and fluxes are added and the iron and manganese are melted to produce ferromanganese and the zinc evaporates. The liberated zinc then passes through a splash condenser where it is returned as zinc metal. The carbon monoxide produced as a by-product of the zinc oxide reduction is washed and fed back into the pyrolysis as fuel (energy recovery). The Batrec plant was built as a dedicated battery recycling facility, but with a flexibility towards a wide range of other mercury containing wastes.
195 However, as with most pyrometallurgical battery recycling processes, the high cost of mercury control has ensured that the processing cost has also remained high. Consequently, the use of the facility by organisations outside of Switzerland with the responsibility to collect batteries, is limited to mercury containing batteries or unsortable battery wastes. As a consequence all of the dedicated pyrometallurgical battery recyclers now take additional mercury containing wastes to reach their nominal capacity and remain viable. Batrec remain the most expensive primary battery recycling facility in Europe today. Operating costs for this process are in excess of 3,000 swiss francs per tonne when the process is being used at the capacity of less than 5,000 tonnes per year. However Batrec profits from a swiss Directive that forbids the exportation of wasteful recycling out of the country when a facility exists within Switzerland. Batrec, as the sole battery recycling facility within Switzerland, remain in a monopoly position. It is obvious that only those battery recycling facilities which offer economical processing will remain viable in the long-term within a competitive market. Any primary battery recycling facility which concentrates on mercury removal at high cost has a very limited lifespan. 9
Waste Stream Analysis
As previously discussed, the major battery manufacturers in Europe, Japan and the United States had all successfully eliminated mercury from primary batteries by 1993. Consequently the mercury burden on the environment from waste primary batteries has been significantly reduced and continues to reduce year on year. The question remained, "at what point in the future would all batteries which were sold before 1993 have been disposed of by the consumer?" If this date can be ascertained, then all primary recycling operations after that date need only concentrate on resource conservation and not toxic elimination. The battery industry developed a statistical method for determining the concentration of mercury in the waste stream at any point in time, and used this to predict the future date by which all of the mercury within primary batteries will have passed through the waste stream. This method, which
uses date code analysis was developed over a
period of many years through stockpile analyses in Germany, Sweden, Belgium and The Netherlands. It is employed annually in Europe to forecast the decline of residual
196 mercury in the collected batteries within The Netherlands, which is considered typical of other european battery markets. Manufacturers generally either stamp date codes on the base or side of the battery, or include a freshness code on the battery label. The age of each battery and hence the mercury content can be determined by recording the manufacturers code and converting this back to the year of manufacture. Some batteries can be assigned to manufacturing dates one year earlier than their actual year of manufacture as a result of using freshness codes, simply because the manufacturer will not replace his stocks of battery labels on January 1st each year. The mercury content of the batteries for each year of manufacture can be calculated from historical manufacturing information held within the manufacturers records. These in turn can be used to determine the mercury contents of the alkaline and zinc carbon streams within the sample. Some assumptions are made.
Firstly, when a manufacturer changed the mercury
content of a battery, all batteries manufactured in that year were taken as having the higher mercury content. Secondly, batteries which were corroded beyond the point of date code recognition were taken as having the highest mercury concentration for that battery type. Finally, all batteries manufactured before mercury concentration data was available were taken as having the same concentration as the year in which the first data became available. The first two assumptions are likely to bias the mercury content higher rather than lower than the actual level.
The third assumption
is
unlikely to cause any major fluctuations to the overall mercury content, since these batteries were manufactured before mercury reduction programs were introduced. In general this method of analysis will give a "worst case" mercury concentration. Sampling is undertaken at the Sortbat sorting facility in Rotterdam, The Netherlands. For the year 2000 analysis, every 200 th alkaline and zinc carbon battery was automatically sampled over a period of 4 weeks. The resulting sample was hand sorted and the Philips, Varta and Duracell batteries segregated for date code analysis. These manufacturers are used as a surrogate for all of the european battery manufacturers. Previous analyses have shown that the mercury reduction programmes between the major manufacturers followed similar lines and no significant error is introduced by doing so.
197 Most asian manufactured batteries arrive into the european market already installed in electrical equipment. These are mainly japanese produced alkaline or zinc carbon's, which have similar mercury content to european batteries, or are low quality zinc carbon batteries, imported in cheap toys. The low quality zinc carbon batteries were found by chemical analysis, to be within only a few parts per million of mercury different from those manufactured in Europe. Neither of these battery types are a significant contributor to the overall european market. The mercury content of the primary battery waste stream has been analysed in this way since 1995. Based on early data, a forecast has been made of the future anticipated mercury concentration of the stockpile and consequently the point in time at which the stockpile will become "mercury free". The forecast was made by taking a histogram of the age distribution of the batteries within the sample and calculating the overall mercury content. The mercury concentration for subsequent years is predicted by shifting the distribution forward by one year and re-calculating the overall mercury concentration. This process is repeated until the oldest cells found are manufactured in mercury free years. Using this method, the mercury level of primary batteries falls to background levels by 2004. This projection is given in Figure 1. The graph shows the average mercury concentration, (the solid line) bordered by an upper and lower anticipated limit (the two dotted lines). The upper and lower limit curves have been generated by assuming that highest mercury or the lowest mercury containing batteries for each particular year are found. Consequently we would expect the mercury concentration for primary batteries to fall between these two limits. The 1996 through 2000 analyses are superimposed on the curve. These indeed show that the annual measurements fall within the expected range (note the 1999 analysis was
198
Figure 1. Anticipated and actual decline in mercury levels within battery waste
not undertaken:
consequently, the 2000 analysis was taken early in the year and
therefore shown at a mid point between 1999 and 2000). In order to ensure that the mercury concentration of primary batteries will indeed fall to background, one must ensure that the european market is closed to the importation of batteries containing levels above background. The European Battery Directive, 91/157/EEC, still allowed for batteries containing up to 250 parts per million of mercury to be sold. The battery industry petitioned the European Parliament to close this loophole. In response, they introduced a technical adaptation, 98/101/EEC, which prevented the addition of any mercury in primary general purpose batteries sold in Europe. The battery industry in Europe has also added additional insurance to ensure that primary batteries manufactured with no added mercury can indeed be recycled without the need to allow for high cost mercury capture and treatment facilities. This has been done by introducing an invisible ink, only visible under ultra violet light, into the labels of all alkaline cylindrical batteries sold in Europe.
This allows rapid and
extremely accurate sorting of mercury free batteries out from the remainder.
199
This is a fine example of an industry working proactively and responsibly to ensure their waste is able to be recycled with the minimum amount of cost to the consumer or risk to the environment. As a result, future recycling technologies for primary batteries can concentrate on recycling for resource conservation, rather than toxic elimination. This has not been the case with most of the dedicated recycling processes operational today. Many of these recyclers have argued that the battery industry will never be able to guarantee that batteries being sent for recycling are indeed mercury free. This argument is used as justification for maintaining high costs because of the need to capture and treat mercury. It is very clear however that mercury within primary batteries is an historical problem and does not need to be a consideration for future, long-term, sustainable recycling options.
Battery Sorting Battery recycling is undertaken in order to: either remove toxic material from the waste stream, as is the case with mercury, lead or cadmium containing batteries, to recover materials with high commercial value, including nickel, cobalt and metal hydrides found in rechargeable systems, or for resource conservation, as is the case with mercury-free primary batteries. Battery recycling operations which seek to process all batteries collectively are either unable to recover the value from the high value materials at all, as they concentrate on detoxification, or their resale value is diminished as a result of impurities introduced from the other battery systems also being processed. In the latter case, expensive and complex purification processes are often necessary in order to reclaim even a small percentage of the materials value. It is therefore evident, that to maximise the benefits of both of these goals, some degree of pre-sorting is necessary before recycling. This is not a novel idea. Many commercial recycling processes operating today require sorting of the products before recycling. These include scrap metal for the steel industry as well as glass, paper and plastics recycling. The degree of accuracy required of sorting operations will be dictated by the purity requirements of the recycling facility. Most recycling facilities available in Europe today require sorting to some degree. Typically for recycling of primary batteries, the contamination by rechargeable systems such as nickel cadmium or lead acid, should be less than 2%. However, one tonne of mixed consumer batteries can contain anything up to 40,000 individual battery units of perhaps 10 different battery chemistries. These can vary in size from button cells with a diameter less than 7 millimetres and weighing
200 less than 0.3 grams, up to block batteries weighing a kilogram or more. With this in mind, one can clearly see that hand sorting of batteries, even on a small scale, is likely to be inaccurate and very time consuming. Consequently automated battery sorting technology has developed hand-in-hand with recycling technology. Accurate sorting relies on the identification of a number of different properties of a battery. These include the physical size and shape, the weight, the electromagnet properties and any surface identifiers such as colour or unique markings. These properties can be analysed in a number of different combinations in order to sort batteries into nickel cadmium, nickel metal hydride, lithium, lead acid, mercuric oxide, alkaline and zinc carbon batteries. Due to an voluntary marking initiative introduced by the european battery industry, it is now also possible to separate the alkaline and zinc carbon cells further into mercury free and mercury containing streams. With battery recycling operations ranging in size from 2,000 tonnes per year up to 20,000 tonnes per year and battery collection also increasing annually, it is also very evident that high speed is an essential requirement of a successful sorting facility. The third element for successful battery sorting is that the operation must be achievable at low cost. This means that large-scale facilities, in the order of 2 to 3,000 tonnes per shift, which have the added benefit of economies of scale, are preferred to smaller, more costly operations. Such facilities can be operated at a cost not exceeding $150 per tonne. One example of such an operation is the Sortbat sorting facility, operated by AVR Holding, in Rotterdam, The Netherlands. The plant is capable of processing 3,000 tonne per shift per year of post consumer batteries at an accuracy exceeding 99% for critical battery streams. Initially the machine was developed by the European Portable Battery Association to prove the concept of high speed battery sorting. However, around the same time, the need arose in The Netherlands to be able to recycle all battery types.
Consequently,
after discussions with dutch collection and recycling organisation - STIBAT, the EPBA agreed to build a prototype sorting installation which would provide enough capacity to satisfy this demand.
The ownership of the machine throughout its
development was to remain in the hands of the manufacturers and be leased by STIBAT. Consequently the battery manufacturers set up a non-profit making company, SORTBAT to oversee its development, installation and management.
201 The heart of the sorting line is an electromagnetic sensor which induces a magnetic field within each battery and measures either a voltage or a frequency response. The most successful electromagnet sensor technology available to date, and that used within this facility, is the Tri-Mag sensor developed and commercialised through a partnership between Titalyse S.A. of Geneva, Switzerland and Euro Bat Tri Sarl based in Lyon, France. Each battery is presented to the sensor by conveying it on two parallel polycord belts and transported directly through the centre of the sensor coils. This is illustrated in Figure 2. This transport method allows each battery to pass through the sensor in a very stable manner, thereby ensuring the accuracy of selection. The signal from the Tri-Mag is stored electronically and processed together with an accurate weight measurement. It is this combination of electromagnetic sensing and weighing which is responsible for the high purity levels achieved. Both measurements are carried out without the need to stop the battery. Consequently the operation is carried out at high speed. Today, each sensor is capable of measuring five cells every second, with mechanical handling being the rate limiting step. It is feasible that this speed could double in the future.
Figure 2. Battery on polycord belt and direction of travel
202 The process can be considered to be divided into four main stages. Stage I, hand sorting of large battery packs and removal of non-battery waste. Stage II, the dust and button cell removal. Stage III, where batteries are sorted according to size and stage IV, where the batteries are sorted by chemistry.
Sta~e I Batteries are first loaded via a bunker onto a band conveyor where block batteries, battery packs and non-battery waste are removed and sorted by hand. The batteries selected at this stage are those which are unable to be passed through the electromagnetic sensors in stage IV of the process. These include rechargeable battery packs and industrial batteries.
Stage II The remaining batteries are fed into a charging hopper which feeds a pocketed belt conveyor. This in turn deposits the batteries onto a cascade of sieves which have been carefully selected to remove dust and button cells. The remaining batteries are then fed onto a wide band conveyor which passes beneath a magnetic over-band conveyor which separates the magnetic fraction from the paper jacketed zinc carbon cells and batteries.
Stage III The over-band transfers all of the magnetic batteries onto a second pocketed belt conveyor and from there onto an additional hand sorting table. Here any remaining non-battery waste, rechargeable packs or damaged cells which evaded the initial hand sorting phase can be removed. They then pass onto a second series of cascading sieves which sort the batteries according to their physical dimensions. The main outputs from this section are the AAA, AA, C and D size cylindrical batteries most commonly used by the general public.
These are deposited into individual bunker feeders which
supply the batteries to stage IV on demand. Prismatic batteries, such as those used in smoke alarms and alkaline flat-pack cycle lamp batteries are also removed at this stage.
Stage I V This is the most technical stage of the process.
The size-sorted batteries are
individually fed from a vibrating bowl feeder onto the polycord belts. The supplies to the belts are regulated to ensure an even distribution of batteries to the sensors. The installation is equipped with four sets of polycords and sensors. One for C and D cells
203 combined, one for AA and AAA combined and two for AA size batteries only. This combination has been determined in order to balance the operation of the installation with the market mix of batteries sold in Europe. This balance is critical in ensuring the optimal operation to achieve the 3,000 tonne per shift throughput. Each battery in turn passes through a series of sensors. Measurements are taken 'onthe-fly' and stored in a programmable logic controller, a PLC. Decisions on battery chemistry are made based on inputs from each of the sensors as shown in Figure 3. Specialist batteries, which are generally shorter than general purpose batteries are selected by a simple size measurement. This is undertaken by the use of two throughbeam detectors fitted approximately 50 millimetres apart. Only standard consumer size batteries are allowed to pass this point. As the consumer size batteries continue along the polycords they pass beneath small magnetic over-band polycords which lift the battery off of the main line for a fraction of a second. These over-bands are connected to load cells which take up to 50 weight measurements of the battery as it passes across. These measurements are stored in the PLC, and used in conjunction with the information from the Tri-Mag sensors. All batteries over a set weight are rejected immediately, as these will be either lead acid or mercuric oxide. Immediately after weighing, the batteries pass through the Tri-Mag sensor. Induction coils induce a magnetic field within the battery and detector coils measure a voltage response which is converted to a unique alphanumeric signature which is also fed to the PLC. Within the Sortbat machine, this sensor is specifically used to differentiate between alkaline, zinc carbon and nickel cadmium batteries.
However due to the
construction of the outer casings, some specific batteries of different chemistries provide identical signature responses from the Tri-Mag.
Most of these conflicts
however are eliminated by reference to the weight measurement taken previously.
UVSensing The fastest sensor by far in the sorting installation is the Ultra Violet, UV detector. Two detectors per line look for a UV marker on battery labels which has been added
204
I Two stage Sieve
I
I
=Dust "-Buttons
I Reject I-, -znc:Paper
~ YES
Dimensional Sort I
//~y
~
,- Other:-
lindricals
gv, ~.sv,
Oversize
I Reject
Button Stacks Alkaline NiCd
"---I Weighing I
Record
Weight
I-----Specials:-
Ay,o .go
I Tri-Mag I YES
Reject
NO
H_qO:Cells Stacks
NiCd
I UV Detector I Hg Free:Alkaline
ZnC
NO
Check
Reject
Metal Jacket
r YES NO
/niJ:-
Check ~E_S
Alkaline:-
Weight
Metal Jacket PVC Label
? Undefined
Figure 3. Flow diagram illustrating stages II to IV of the Sortbat battery sorting installation
205 during manufacture. These markers, which are invisible to the naked eye, are being added to new batteries Europe-wide in order that they can be distinguished as mercury free and recycled in less mercury tolerant processes. The detectors, shown in Figure 4, are fitted with wavelength sensitive filters and calibrated to ensure that potential conflicts from other fluorescent inks are either minimised or eliminated. 9 Product Purity
The purity of the outputs is also very important to the recycling companies. Initially the machine was designed to sort critical streams to 96% efficiency. Table 2 shows the sorting efficiencies achieved today. These exceed the design specification in all cases and meet the current quality requirements of all of the recyclers in Europe.
Table 2. Purity of Output Streams with Respect to Critical Contaminants
9 Efficiency
Efficiency of processing operations can be calculated by comparing the theoretical throughput of the machine against the actual throughput within a given time period and stating this in percentage terms. This simple measurement takes into consideration all of the factors impacting the machine operation including downtime for non-routine maintenance and operator efficiency. Typically within an industrial environment, process efficiencies of 95% are normally targeted, with 85% being an acceptable efficiency level.
Within sorting installations, experience has shown that these
efficiency levels are very difficult to reach and the machine efficiency of the Sortbat equipment is in the order of 70%. Two factors are very influential in determining efficiency of battery sorting. The quality of the batteries to be sorted, and the balance
206 of the machine throughput in terms of individual cell sizes, versus the actual mix of cell sizes found within the collected cells. It is important to recognise that sorting of collected batteries is a waste handling operation. Rarely are batteries received into the installation in the same condition in which they were put onto the market. The batteries casings can be damaged by bulk handling or corroded due to storage in outdoor, humid conditions. Furthermore they will also contain a degree of non-battery waste, including packaging materials, nails, film canisters and a whole host of other foreign objects, which the equipment was not designed to handle. Consequently downtime due to blockages within the equipment can be frequent. This problem can be tackled in one of two ways. Firstly the machine can be modified, based on experience, to be more tolerant to frequently occurring problems resulting from battery condition. Secondly the problem of
waste and
condition of collected batteries can be addressed at source. For any sorting process to be operated efficiently, a combination of both of these approaches is necessary. The second and equally important factor is the balance of the design throughput of the machine to the actual market mix of batteries. Within the Sortbat machine design, each of the standard consumer cell sizes, AAA, AA, C and D, are either processed separately, or together with only one other size (i.e. AAA and AA together, C and D together). This choice is made in order to best fit the capability of the machine with the mix of batteries being collected from the market. Today the machine operated in The Netherlands has four separate sorting lines: one for a combined C and D stream, two for AA size only and one for a combined AA, AAA stream. Although this is a close approximation for the consumer battery market today, it is not perfect, and efficiencies can be seriously reduced if batches of single size only batteries are received for processing, during which time the lines for the other cell sizes lay redundant. Other successful battery sorting plants operate in Europe today based on similar principles to the Sortbat model. These include a 1,500 tonne per shift facility owned and operated by Trienekens, Germany, and a 1,000 tonne per year facility at Euro-BatTri, in Lyon France. The Trienekens operation uses two unique and patented steps during the size separation phase. This includes a rotating, angled disc to separate prismatic batteries
207
Figure 4. Sensor used to identify zero-mercury batteries
from cylindrical ones. Following this, the batteries are loaded into elevators and fed to a polycord based electronic separation stage almost identical to stage IV of the Sortbat process. This section is in fact a refurbished, redundant line from the Sortbat machine, although the central processing unit, as well as certain decision-making criteria, has been changed. The Euro-Bat-Tri facility was initially designed to pass batteries through the Tri-Mag sensor simply by dropping them under gravity down an inclined tube. This method however, imposed speed restrictions on the operation due to the down-stream mechanical handling involved in separating the selected batteries into their appropriate chemical streams. The facility is currently undergoing a complete refurbishment and the machine is being upgraded to a 10,000 tonne per year operation in line with the anticipated demand from the french market. This high capacity machine will also operate using the polycord transport principle. Other sorting principles are currently under development, including a vision based system and an X-ray system. The X-ray system is in the late stages of development
208 and should prove to be a very accurate and reliable sorting method.
Currently the
designers aim is to own and operate the system in-house and not to make the equipment commercially available. The problems with the commercialising such a system are likely to be the capital investment required in the X-ray sensor and the safety aspects of operating such equipment within a waste-handling environment. The principle of using vision for sorting is not new and is used very successfully in other fields. Cameras take images of the product as it passes and these are compared to a database of images stored within a central processing unit. Due to speed and memory constraints, the processor will not consider the entire image when making its decision on product category, but will concentrate on one or two unique identifiers only. When applying this technology to batteries, it is important to appreciate that many thousands of unique battery labels are marketed today.
These include main
manufacturer brands such as Duracell, Energizer, Varta etc., as well as private labelled batteries for retail chains. The database needs to allow for subtle differences in the battery label, such as a change in position of a visible date code, as well as more obvious ones such as a Duracell or Energizer label with or without an on-cell power meter.
Historical label changes need to be included too.
Each manufacturer has
potentially scores of changes to his main brand product label over the past ten years. For batteries, the unique identifiers could include, for example, the position of the '+' sign on a Duracell label compared to, say, the front edge of the letter 'D'. Each of these particular labels will need to be stored twice within the data base to allow for the battery being presented to the camera either top-up or bottom-up as this will alter the position and orientation of the unique identifier. These identifiers will be different for each individual battery label held within the processors memory. Early attempts to use this technology as a stand-alone battery sorting method have proved unsuccessful due to the vast processor power and memory required to operate at speed. Having said this, advances in computer processing power and memory seem to be made almost daily and the cost of these powerful new tools are decreasing too. This could therefore prove to be a valuable technology for future sorting operations. In the meantime, such systems are proving useful as an enhancement to the current sensor technology already in use today. Sortbat have recently developed a vision system to complement the selection of mercury free cells for low cost recycling. Due to the restrictions discussed above, this system will not be capable of replacing existing
209 sensors or detectors, but will concentrate on selecting certain label types which are known to be mercury free, yet pre-date the introduction of the ultra violet marker. These could include Philips 'Powercheck', Energizer and Duracell with on-cell testers and Varta batteries which have a '0% Hg, 0% Cd' ring around the cell.
Integrating with Existing Recycling Operations With the elimination of mercury from all primary consumer batteries, a less complex recycling route became available for them. Today alkaline and zinc carbon batteries can be successfully recycled within the existing metals industry. A number of options are available within this sector which can be successfully demonstrated to recycle batteries. The main area of interest for recycling spent primary batteries is the steelmaking Electric Arc Furnace (EAF). The melting of steel scrap within electric arc furnaces by the metals industry is an example of one of the world's largest and most successful recycling operations. This process is the starting point in recycling steel and zinc from the domestic, commercial and industrial sectors.
These include scrap from the
construction and automotive industries as well as white goods, food and beverage containers and numerous other end-of-life consumer products. Electric arc furnaces are operated worldwide at a large scale, typically 250,000 to 750,000 tonnes per year. An electric arc furnace consists of a dished hearth surmounted by a vertical cylinder (the side walls) and capped by a domed roof. The hearth and lower side walls are refractory lined to protect them from the liquid steel and slag. Generally the upper walls and outer roof are constructed of water-cooled steel panels. Three electrodes which carry the electrical power to the furnace enter via the roof.
The central roof area is consequently also made of refractory to prevent
arcing between the electrodes. Each furnace is also equipped with a door to view the operation and take samples, and a taphole through which the liquid steel is to be poured. Electric arc furnace fume and gases are extracted through a duct in the roof. The dust is extracted from the gas stream using a bag filtration system before the cleaned gases are vented via the stack. Power to the electrodes is supplied from a transformer operating at a secondary voltage between about 200 and 1,000 volts. Supplementary energy can be supplied from a combination of oxygen or carbon lances and oxygen fuel burners.
210 Scrap metal is charged batch-wise to the fumace from a scrap bucket by removing the roof and electrode structure and dropping the scrap in. Carbon, to aid the steelmaking operation and for extra energy, and lime, to form the basis of the slag, are also added at this time. The roof and electrodes are then brought back over the fumace shell and the charge is melted by energy supplied from the electrodes and supplementary devices. The steel begins to melt at temperatures around 1500~ and when most of it has been melted, a sample is taken to check the chemical analysis and determine alloy requirements. Two or more scrap charges are normally required to provide a full batch. During and after melting, chemical reactions occur between the contaminants and alloying elements in the scrap, the molten slag and the oxygen.
This leads to a
separation of the unwanted constituents from the liquid steel bath. These elements either dissolve in the slag or form gases which are extracted. The slag floats on the liquid steel and is usually removed by pouring off through the door. The steel is usually ready to 'tap' at between 1600 and 1700~ At this stage the tap-hole is opened, the furnace tilted and the steel poured into a refractory lined ladle where alloying additions or any further processing is undertaken before the product is finally cast. The cycle time of the EAF will depend upon the size of the fumace and the power input rate. Electric arc fumaces vary considerably in size from a one tonne total charge weight up to 300 tonnes. The fastest furnaces have 'tap-to-tap' times of around 30 to 40 minutes and power inputs of greater than 1 MW per tonne; slower furnaces may take 2 or 3 hours. This 'tap-to-tap' time is made up of charging, 'power-on time', refining, sampling, and tapping. One common misconception of the steel industry is that it produces steel products, together with a number of waste streams including slag, dust and millscale, which require disposal. But the truth is very different. Environmental awareness and economic necessity have prompted the steel industry to seek alternative solutions to disposal. Today the metals industry has evolved to the point where these traditional waste streams have become useful and valuable by-products. Furnace slag, for example, can be crushed, screened and sold as high-grade construction aggregate. Clean millscale is used in several applications, including the cement and ferro-alloy industries.
The
fumace dust, which is rich in zinc, is commonly sent to the zinc industry where it is processed within a Waelz kiln as part of the zinc metal recovery process. If the level of zinc in the dust is high enough, it can be treated directly within an Imperial Smelting
211 Furnace (ISF), thereby avoiding an entire processing phase and all of the associated environmental impacts. At most facilities, extemal companies are based permanently on the steel-making site to operate by-product recovery processes.
Table 3. The Effect of Primary Battery Additions to a Typical Steel Melt
CONSTITUENT
Manganese Zinc
MARKET EFFECT ON THE PROCESS MIX (%) 19.36 Mostly adds to slag bulk as MnO. Mostly concentrates in filter plant dust as ZnO, allows more profitable 16.72 recycling in Waelz kiln, etc.
Carbon
5.91
Recycled in liquid steel or as energy, may replace charge carbon.
Potassium hydroxide Steel
3.22
Adds to filter dust as K20.
21.62
Recycled in liquid steel adding to yield
Nickel
0.32
Lead
0.02
Tin
0.01
Brass
0.75
Paper
0.87
Bitumen
0.44
Plastics
3.00
Will burn to CO2, H20 and HC1; most of the HC1 will be bound to metals in the filter dust.
Zinc chloride
0.32
As for Zn metal.
Ammonium chloride
2.57
Oxygen Water
13.98
Decomposes to NO2, HC1 and H20 Majority attached to Mn in slag. Remainder forms oxides leaving the furnace.
11.00
Evaporates.
Mostly dissolve in liquid steel; a 1% battery addition might increase Cu in the melt by about 0.005% and Ni by about 0.003%. This is insignificant in most lower quality steels. Will bum to CO2 and H20.
The zinc carbon and alkaline batteries, without added mercury, have very good synergy with typical feeds used in the existing electric arc furnace recycling process. The steel, manganese, carbon and zinc, which constitute in the order of 65% of the batteries by weight, are all successfully recycled or reused within the process. The remaining constituents, moisture, paper, bitumen etc. are mostly harmlessly combusted
212 or vaporised by the steelmaking process. The effect of battery additions to a typical steel melt is given in Table 3. The steel components of the batteries melt down and report to the steel product. For every 1% addition of batteries by weight, the steel increases by approximately 0.2%. However the batteries also contain small amounts of residual metals such as nickel, tin and copper.
For a 1% addition of batteries, the total of these residual elements
increases by approximately 0.01%. This can be problematical to certain grades of steel, but for reinforcement and structural steels, this is insignificant.
However it is the
presence of the residual copper which ultimately restricts the addition of batteries to the electric arc furnace.
A 3% addition, resulting in a copper increase of
approximately 0.015%, is generally considered to be the limit for battery additions without adversely affecting the product. Approximately 6% of the battery weight is carbon. This will either be combusted directly adding to the available energy, or dissolve in the steel bath where it will be oxidised by injected oxygen prior to tap. In both cases, it is a useful addition to, or replacement for, charge carbon that is typically added at the rate of 0.5 to 2% of the scrap weight. Manganese dioxide in the batteries will normally be dissolved in the slag thereby increasing the slag bulk by about 250 kg for each one tonne of batteries added. For a typical steel/slag ratio this increase adds about 2.5% to the slag mass for a 1% battery addition. No significant effects arise either to the quality of the slag for the steel making process or for its processability and sale as an aggregate after use. It is possible that some of the manganese can be partially retained in the steel and reduces the need for alloy additions, particularly with low active oxygen in the bath. Otherwise the increased slag bulk leads to a greater quantity of slag for sale as road aggregate. The zinc component is an important addition for the steelmaker, both environmentally and economically. In all but the very fastest steel-melting units, the majority of the zinc will vaporise into the furnace off-gases and add to the zinc oxide level in the filter plant dust. For most furnaces, the increased zinc content of the filter dust can be up to 6% or occasionally even more, for each 1% addition of batteries. Where filter dust is sent to a secondary zinc processing plant, this increase is a very valuable benefit. The steel plant is charged for dust treatment by the zinc processor on a sliding scale which decreases as the zinc content increases. Therefore, for
213 steelmakers sending the furnace dust direct to a Waelz kiln operator, the added zinc from batteries undoubtedly reduces the dust processing cost for the steel plant. As Europe has a vast steel industry, there is more fumace dust generated compared to Waelz kiln capacity and as a consequence, some electric arc furnace dust is still landfilled.
The addition of primary batteries to the feed within these facilities
increases the prospect of the dust being taken for recycling by the Waelz kiln operators. Some steelmakers are adopting more innovative approaches to the problem of electric arc furnace dust recycling.
Within the UK, ASW Sheerness Steel re-inject a
proportion of their dust into the electric arc furnace to reclaim the iron units and further concentrate the zinc. This process, together with the battery additions, produces a dust that is high enough in zinc, that it can be sold directly to an Imperial Smelting Furnace without the need to pre-process within a Waelz kiln. Consequently the dust no longer generates a disposal cost, but is profitable. Nedstaal Staal B.V. in Ablasserdam, The Netherlands, also use the battery additions to augment the concentration of the zinc to a level where a percentage of the dust can be sent directly to an Imperial Smelting Furnace for recycling. In both of these examples, not only does the steelmaking company benefit from a reduction in cost, or even additional profit, but the environment in general benefits because a separate, intermediate processing stage is eliminated. This zinc enrichment stage, carried out within the Waelz kiln, is always separately located from both the steel plant and the imperial smelting furnace. Consequently the elimination of this step has additional environment benefits associated with reduced transport and logistics, in addition to the reduction in energy use and other environmental impacts associated with Waelz kiln operation. In all situations where the landfilling of filter dust is either prohibited or very costly, the 'added-value' of zinc in the dust from batteries is very significant. In exceptional, very fast fumaces, where 'power on' times are typically less than 30 minutes per heat, there is some evidence that the zinc may be partially dissolved in the steel bath and might ultimately result in problems while casting.
However, this
problem is very rare and in the vast majority of cases no effect is seen. The addition of batteries to the electric arc furnace steelmaking process is very simple. No modifications or additions are necessary for the installation. The batteries are
214 added into the charge bucket together with the scrap feed and fed to the furnace in the normal way without any pre-processing or additional operator requirements. Generally operators have found that the batteries are best added into the middle of a charging bucket to avoid any risk of batteries being ejected from the furnace due to venting when they are loaded. There are some costs associated with recycling of batteries within steelmaking electric arc furnaces. The addition of batteries to the scrap can sometimes result in increased power consumption. This varies up to about 0.5 MWh per tonne of batteries added, which is equivalent to 5 kWh per scrap tonne for a 1% addition of batteries. This increase in power consumption is very low and is usually within the normal fluctuations for most EAF's caused by variations in scrap composition. Adding this extra power to the furnace will also take a little extra time and, depending upon the transformer and power input rate, may increase power-on time by up to 30 seconds for a one tonne battery addition.
However, for most plants this time increase is
insignificant in terms of overall loss of productivity because other factors are more important in determining tap-to-tap times.
Additionally there is the possibility of
increased oxygen consumption by about 1 Nm 3 per scrap tonne, but this is normally offset by better energy efficiency due to the combustion of the carbon from the batteries. Table 4 shows an estimate of the cost advantages and disadvantages for each tonne of scrap charged with a 1% addition of batteries to an electric arc furnace.
The cost
estimates used within the table can be debated at length and could vary for different plants and locations. But generally the assumptions considered will give a 'worst case' scenario and therefore the benefits for most steelmakers are likely to be greater than that calculated. However, the overall effect is likely to be similar for any steelplant; the balance will either be neutral or slightly in favour of battery additions to the scrap. In addition to the cost balance shown in Table 4, the electric arc furnace operators benefit from an additional recycling fee of between C 50 and C 100 per tonne of batteries recycled, dependant upon quantity and other commercial factors.
At an
addition of 1% of scrap weight this is equivalent to a cost reduction of E 1 per tonne of scrap and, hence, typically equal to C 1.1 per tonne of product.
This is a very
significant additional economic benefit for the operator. In some cases, a proportion of this profit is allocated by agreement with local environment agencies, to additional environmental improvements within the facility.
215 Table 4. Estimated Cost Benefits and Disadvantages per Tonne of Scrap Charged for a 1% Addition
of Market Mix Zinc Carbon
and Alkaline
Manganese Batteries in a Typical EAF Benefit for a 1% battery addition (C /
Characteristic
Assumptions
scrap charge tonne)
Yield from steel to hot liquid (21.6%) Carbon value (5.9%)
Average scrap price = C 100/tonne
C 0.28
Variable cost to melt = C 30/tonne
• 0.05
Carbon cost = C 90/tonne Normally dust arising at 20kg/scrap
Zinc increase in dust (by only 4% Zn)
tonne C 0.51
Normally dust = 20% Zn Advantage of extra Zn = C 6 / %Zn in dust / tonne dust
Extra power (0.5MWh)
-C 0.25
Power cost = C 50/MWh
Extra Oxygen (1Nm 3)
-C0.10
Oxygen c o s t - E 0.1/Nm 3
Productivity loss
-C 0.25
Balance of costs
Loss of contribution = C 50/min Power input rate = 1 MWh/min
C 0.24
& benefits
9 Environmental Considerations for Electric Arc Furnace Recycling
Before permits were granted for battery recycling within electric arc furnace steelmaking operations, extensive trials were undertaken by the operators in collaboration with the battery industry. considerations
and
environmental
These trials included both processing
considerations.
Extensive
independent
environmental monitoring and environmental impact assessments were undertaken at several trial locations throughout Europe. At the first trial at Nedstaal B.V. in The Netherlands, the permitting authorities, The Provincial Executive of Zuid-Holland, applied the same requirements as for the Waste
216 Incineration Air Emissions Decree, the strictest environmental standard in the Netherlands.
The emissions
were monitored by Tauw Milieu, an independent,
government approved, environmental assessment agency.
Most importantly they reported that no dioxin issues were noted with the addition of batteries into the electric arc furnace. The dioxin level was measured from the electric arc furnace with and without the addition of batteries. With the addition, the level increased by only 0.20 x 10-8 kg/charge, and this was comparable with values measured previously during standard production. The NOx level fell by 10% to 5.49 kg/charge during the same trial. They therefore concluded that the dioxin and NOx levels remained within the normal fluctuations expected of steel plants due to the heterogeneous nature of scrap. These findings have also been confirmed by trials at ASW Sheerness Steel in The United Kingdom. With additions of batteries up to 2% of charge weight, the dioxin emission levels fell below the control level, measured with no battery additions. That is not to say that battery additions reduce dioxin emissions, but confirms again that emissions remain within normal fluctuation arising from changes in scrap quality.
For the Provincial Executive of Zuid-Holland, the dioxin level was not therefore considered significant. The other determining factors for the acceptance of batteries into the electric arc furnaces of Nedstaal B.V. were the mercury and cadmium contents. In both cases, the levels measured were well below the acceptance level of the stringent standards set within the Waste Incineration Air Emissions Decree.
Trials at Nervacero, Spain, measured the metals and heavy metal content of the emissions. Three comparisons were made between loads with battery additions and controls. These were: the sum ofPb, Cr, Cu and Mn in mg/Nm 3, the sum of Ni and As in m g ~ m 3 and the sum of Hg and Cd in ~tg~m 3. In each case the values were more than five times lower than the permit levels. Additionally the total particulate emission level did not increase and remained approximately four times lower than the permitted level. The use of the slag product is unaffected by battery additions.
The slag produced
during battery recycling in the USA passes US EPA, TCLP tests. Slag produced while recycling batteries in Europe continues to be sold as construction material. Adding batteries creates no additional health and safety issues for plant staff. The batteries are added along with the steel scrap into large charging containers. These are
217 loaded directly into the furnace mechanically. There is no need to shred or pre-treat the batteries before addition to the furnace.
The environmental arguments for using the existing metals industry to recycle batteries rather than developing dedicated processes are strong. The industry is subjected to stringent environmental regulations, which control the emission of potential pollutants to atmosphere, water and land. Additionally the use of products and by-products are also subjected to tight regulatory control. Adding batteries to the feed streams of the metals industry, at the levels recommended, do not significantly affect the process, its environmental controls, or the markets available for the products. Indeed in many instances, adding batteries to the process enhances the by-products and will help to ensure that they are recycled, rather than landfilled, in the future. The metals industry has a massive infrastructure with established markets for all of its products and by-products. The industry has enough capacity to recycle all of the scrap batteries produced globally many times over. Consequently the battery industry can be very selective over who they send batteries to for recycling. The companies selected by the battery industry for partnership will recycle all of their by-products that are affected by battery additions. The steelmaking electric arc furnace produces approximately 40% of the steel required for modem living. Consequently it is a very stable industry with an environmental control system firmly established, and readily able to respond to any additional environmental controls imposed on it in the future. This is already a well-established recycling route for many other multi-metal, end-of-life consumer products. Recycling batteries within these processes does not add any additional burden to the operators because they are already used to handling varied feeds within their processes.
9 Other Integrated Recycling Approaches Within the metals industry, some small consortiums or individual companies have sought to manage the growing environmental waste problems within their industry in a responsible manner, by dedicating equipment and resources to manage waste problems in-house. As with the steelmaking routte, primary batteries can also be successfully recycled within these processes. One obvious disadvantage of these processes, compared to electric arc furnace steelmaking, is availability. These processes are unique in their approach and often small scale, compared to the very large electric arc furnaces producing steel. Although the primary focus of some of these operations
218 remains almost exclusively in-house waste, other companies have embraced the opportunity offered by recycling wastes for other industries including batteries. DK Recycling und Roheisen GmbH, of Duisburg, Germany, operate a blast furnace to produce foundry pig iron from iron containing dusts and sludges. This process is unique in that unlike conventional blast furnace operations, DK are able to cope with significant amounts of zinc.
Zinc typically forms accretions on the furnace wall
leading to clogging and increased furnace wear. Through a specialist knowledge in the handling of zinc in the blast furnace and careful attention to certain operational parameters, DK Recycling are able to take wastes where the zinc burden is up to 300 times higher than conventional blast furnaces. The sludge from the gas cleaning plant occurs as a pure zinc concentrate, which is sold to the zinc industry. Today DK Recycling und Roheisen GmbH recycle mercury free manufacturing scrap from primary battery manufacturing facilities and are undergoing further trials to extend this service to collected post consumer batteries. Valdi is a subsidiary of a foundry company, AFE Metal, and a special industrial waste handler, Tredi. This company has grown out of the environmental branch of Feursmetal, one of the foundry sites within the AFE portfolio. In 1990, AFE Metal was faced with a scheduled closure of the facility handling the waste from the Feurs foundry. This gave the company four years in which to develop alternatives to their waste handling problem.
They embarked upon a research and
development project which included reducing raw material consumption, reorganising wastes within the plant and developing in-house recycling processes. The project was so successful that in 1995, AFE Metal decided to extend their know-how to other foundries and similar wastes. In 1997, the decision was taken to diversify and set up a specific company, Valdi, to operate the recycling processes. Today Valdi recycle various metal or mineral containing by-products into ferro-alloys within a dedicated 10,000 tonne per year facility in the Feurs foundry.
Primary
batteries have been included as one of the recycleables within the facility since 1994. Batteries are continually fed into a 3.5 MVA electric arc furnace via an automatic feeding system during the melting process. Unlike the electric arc furnace steelmaking route, which can only facilitate batteries up to approximately 3% of the feed, the Valdi process loads batteries into a furnace which is void of steel except for a small heel,
219 which is maintained to begin the melting process Only lime and reductant are added to the furnace together with the batteries to reduce manganese dioxide and neutralise the gases produced. The iron, manganese and zinc contained within the batteries are all reduced within the bath.
The iron and manganese are diluted with the liquid heel and the zinc is
vaporised, where it is re-oxidised on contact with the oxygen in the air, in just the same way as in conventional steelmaking processes. The manganese, iron and steel combine to form a ferromanganese, which is less pure than traditionally produced ferromanganese, but still able to be used in several applications including the production of high resistance castings such as teeth for mechanical diggers. The zinc oxide is captured within a bag filter plant and sold to a zinc reclaimer. The electric arc furnace has been specially adapted in order to cope with the high volume of zinc oxide evolved and to control fugitive emissions.
An additional
extraction port has been added to the roof of the furnace to help to extract the zinc oxide and the entire furnace is contained within a 'dog-house', an enclosure designed to restrict environmental emissions within the working space (Figure 5). The 'doghouse' is also fitted with a forced ventilation fan, which improves the extraction process. These additional environmental controls, together with an activated carbon injection system and specially designed bag filters, allow Valdi to process batteries containing up to 500 parts per million of mercury without any adverse effects on the local environment.
The ability to process batteries containing some added mercury
makes Valdi unique among the integrated metals industry processing routes. The electric arc fumace dust produced by Valdi is contaminated to some extent by the mercury. This means that the dust cannot be sent for processing within the pyrometallurgical zinc industry.
The dust is therefore sent for processing via a
hydrometallurgical route, however this is a far more expensive option. The slag produced from the process is recycled as an aggregate in much the same way as the steelmaking electric arc furnace slag. The industrialisation of these processes has won the company the EUREKA prize of Lillehammer, for outstanding environmental achievement in 1999. Valdi do not intend to stop here. The current capacity of the Valdi process is approximately 5,000 tonnes
220
Figure 5. Vaidi Furnace contained within a 'Dog-House'
for used batteries. They have ambitious plans to extend the recycling of batteries to a second facility at Le Palais, also in France. Valdi see that one of the biggest problems of recycling batteries within their furnaces is the water content.
With batteries containing up to 10% moisture, a significant
proportion of the energy required by the furnace is used to dry the batteries. This is
221 not an efficient use of the energy. Furthermore when processing large quantities of batteries in this way, there is also a risk associated with rapid expansion of gases during the drying process. Consequently Valdi intend to install an upfront multiple hearth furnace in their new facility to produce direct reduced iron, D.R.I., from the batteries and then melt this within an electric arc furnace to produce ferromanganese. In addition to improving the melting efficiency of the furnace, this step also brings additional advantages. These include better separation of zinc from pollutants within the gas phase, lowering dust volume, and increasing the zinc concentration. With the inclusion of this new facility, Valdi's capacity will increase to approximately 15,000 tonnes of batteries per year. 9
Waelz Kilns
Within the zinc industry Waelz kilns are used to concentrate the zinc oxide within the electric arc furnace dust coming from the steel industry. The Waelz kiln is a large rotating furnace operating under oxygenating conditions at approximately 1300 degrees centigrade.
Under these conditions the zinc content of the electrical arc
furnace dust is increased from between 20 to 25% by weight, to 55 to 60% by weight. This upgraded dust is then either converted into zinc metal by smelting or electrolysis, or used in the rubber or animal feed industry. The only by-product of the Waelz kiln is a slag, which is suitable for civil engineering applications or as an additive in the cement industry. The Waelz kiln operation is subjected to the same stringent environmental standards as the EAF steelmaking process. Trials have been undertaken in Europe and the USA to determine whether these same standards are met when operating with mercury free primary batteries as part of the feed. Independent environmental assessments have shown that there is no increase in the emission of solids to the atmosphere and these are well below statutory requirements. With the addition of batteries, the total particulate emission level, measured during trials in Spain, did not increase and remained 30% below the permitted level. Furthermore, treating batteries does not increase the heavy metal content of the emissions.
As for the electric arc furnaces, the heavy metal content of emissions are
measured as the sum of Pb, Cr, Cu and Mn in mg/Nm 3. With the addition of batteries at up to 15% of the charge, no increase in the normal operating levels was measured. In both cases the values were more than 10 times lower than the permit levels.
222 As expected, the manganese content of the slag increased, but this was not deleterious and the leachability of the slag did not increase.
A waste is considered toxic when a
leachate shows a value for the ecotoxicity standard, ECs0, of greater than, or equal to, 3,000 mg/1. In all cases, the EC50 value was less than 200 mg/1.
Conclusions
Europe is, and will remain, at the leading edge of battery waste management. The European Union is keen to see the expansion of battery collection and recycling and continues to propose new legislation in an attempt to harmonise efforts across Europe. It would appear however that because the Member States remain free to be able to impose economic instruments or deposits at will, and the Directive fails to define individual responsibility, it is unlikely to achieve this aim. Many innovative and diverse processes have been developed over a number of years to tackle the growing problem of battery waste. Some have been proposed simply to resolve issues on a national level, while others are clearly looking to the future and much larger volumes. As with any competitive market, the processes which will prove sustainable in the long-term will be those which are able to adapt to changes in battery compositions and remain economically viable.
The elimination of mercury from
alkaline and zinc carbon batteries, for example, increases the opportunities for recycling and reduces the need for dedicated facilities concentrating on the control of hazardous materials. Integrated waste management schemes, rather than a dedicated schemes, would appear to be an alternative way forward for many used consumer products. In light of the findings in the UK Department of Trade and Industry report, collecting similar waste streams together, the comingled approach used for small household chemical wastes in the Netherlands for example, would appear to have significant environmental benefits over dedicated battery collection schemes operated elsewhere. Alkaline and zinc carbon batteries would appear to be ideal candidates for such an approach, given that they can now be recycled in the metals industry together with other metal bearing waste.
Not only will this provide the most
environmentally beneficial solution, but it would also provide the most economically viable solution.
223 References
1. Assessing the Environmental Effects of Disposal Alternatives for HousehoM Batteries, Institute for Risk Research, University of Waterloo, Ontario, Feb. 1992 2. Behaviour of Mercury in Used Dry Batteries Buried in Landfill Sites, Urban City Cleaning, Vol. 49, No. 212, June 1996. 3. Analysis of the Environmental Impact and Financial Costs of a Possible New European Directive on Batteries, Environmental Resources Management, November 2000.
This Page Intentionally Left Blank
Used Battery Collection and Recycling
G. Pistoia, J.-P. Wiaux and S.P. Wolsky(Editors) 9 2001 Elsevier Science B.V. All rights reserved.
225
LEAD/ACID BATTERIES A. Pescetelli, E. Paolucci and A. Tin~
Texeco s.r.l., Via Pomarico 58, 00178 Rome, Italy*
Introduction
The world is getting increasingly aware of the need to limit the consumption of nonrenewable resources and the production of waste. This requirement is accomplished by taking advantage of recycling technologies and re-using the materials at the end of their useful life. In this framework, recycling of the largely used lead/acid batteries, containing metals, chemical compounds and other harmful substances, is a correct way to put into effect these concepts. Collecting and recycling these batteries with high efficiencies, currently underway in all developed countries, allows the drastic limitation of environmental pollution while contributing to the availability of significant lead volumes to meet the industrial demand. At the same time, recovering lead from batteries significantly reduces the need to depend on its primary resources, i.e. lead ores, thus delaying their depletion. 1.
THE ENVIRONMENTAL AND HEALTH IMPACT
Lead and sulphuric acid are dangerous substances for both the environment and human health. Exposure to Lead
Exposure to lead may occur through inhalation or ingestion, with a significant impact on individuals according to their age, sex, diet, work, etc. It has long been recognized that lead may cause relevant damage to people, particularly children and pregnant women. The lead absorption capacity of children is higher than that of adults, * Tel.: +39 06 50 33166- fax: +39 06 50 32832 Web: http://www.texeco.it/-Email:
[email protected]@flashnet.it
226 arriving at as much as 50% of the ingested lead, i.e. some five times more. The reference dose (RID) for chronic exposure - inhalation or ingestion- has been set at 0.0035 mgPb/Kg/day. RID means the daily maximum dose allowed without measurable effects on human health. There is a vast literature on the damage caused by exposure to lead. Hereafter the main adverse effects are mentioned. 9 A limited exposure to high doses can have a severe impact on the kidneys, brain and digestive apparatus. 9 Extended exposure to low doses may have negative effects on the central nervous system, blood pressure, kidneys and D vitamin metabolism. In particular, children experience a reduction of growth rate and their learning capacity. 9
High levels in blood may damage the male reproductive apparatus, while pregnant women may experience abortion and/or reduced foetal growth.
9
Lead is classified as a "probable cancer-inducing subtance for human beings". Research work on animals has shown that even ingestion of low doses may induce kidney cancer. However, it is worth mentioning that international institutions such as EPA and WHO have still to quantify the cancerogenic potential (or Slope Factor, SF), i.e. the slope of the plot: probability of a tumor vs.
lead dose.
People dealing with lead are obviously more exposed than others, even if measures are taken to minimise the risk. The lead level in the blood of these workers is periodically checked and, if 60 ~g/100ml of blood are exceeded, they must leave the department or even the job.
Sulphuric Acid Sulphuric acid is a very uncommon component of industrial products sold on the market, although some quantity of it can be found in some industrial residues from which is recovered, whenever possible. The sole, widespread products carrying significant quantity of acid are the lead/acid accumulators; to avoid acid dispersion in the environment it is necessary their recycling. Every year, large volumes of new accumulators are put in the market to replace equivalent volumes of spent batteries. As an accumulator contains 25% by weight of an electrolyte solution at 15% sulphuric acid, the quantity that could be dispersed in the environment is very high.
227 To give an example, 150,000 tons of spent batteries are annually produced in Italy, i.e. 37,000 tons of electrolyte of which 5,600 tons are sulphuric acid. Considering that part of the acid is absorbed by the active mass of the accumulator, the free acid at risk of dispersion accounts for 72% of the total, i.e. 4,000 tons/year. Sulphuric acid is highly corrosive and irritating, particularly to skin, eyes and internal organs, e.g. breathing and digestive apparatuses. Contact of the electrolyte solution with skin may cause severe bums that may be lethal if covering a large part of the body. Mists or aerosols containing high acid concentrations may cause redness, irration and, for protracted exposures, serious bums and blindness if eyes are not duly protected. Acid ingestion may bum mouth, throat, oesophagus and stomach. Typical symptons are sickness, vomiting, collapse and even death. Due to its low vapour pressure, sulphuric acid may is dangerous by inhalation only when present in mist or aerosol. Inhalation may result in severe lung damage. OSHA (Occupational Safety and Health Administration, U.S.A.) has fixed to 1 mg/m 3 the exposure limit in a working place. The International Agency for Cancer Research (IACR) has ascertained that protracted exposure to high acid concentrations in mists or aerosols is carcinogenic. Besides these effects on human health, sulphuric acid may have an adverse impact on the environment. It may pollute both surface and ground water. When spilled from accumulators, it may even be more dangerous due to the presence of lead compounds dissolved in it. At high concentrations, it may distroy any kind of aquatic life. Sulphuric acid is included among the substances subjected to the Emergency Planning and Community Right-to-Know (U.S.A.). Acid release to the environment exceeding 1 pound must be annually declared and is included in the Toxic Release Inventory (TRI).
228 2.
ECONOMICAL ASPECTS
The Macroeconomical Reference Framework
The lead market has recently undergone significant structural changes, which are summarised as follows. The environmental issue has impacted the production system, accelerated the obsolescence of old technology of primary lead production from its ores and triggered the research of new products with lower lead content or absolutely lead-free.Therefore, pigments, paints and anti-detonating compounds are now lead-free, while the lead content of hunting ammunition has been significantly reduced. The production of lead accumulators absorbs 70% of the lead metal produced in the world. A small number of international corporations control 80% of the production of lead accumulators. The volume of lead produced from secondary materials, mainly batteries, has grown remarkably in the developed countries. Traditional lead-bearing ore deposits (galena) are almost exhausted, so that polymetallic complex ores must be mined. This makes lead dependent on the economics and market of other metals. The volume of accumulators produced annually determines in turn the volume of spent batteries to be treated by the smelters; so the battery producers fix annually the quantity of secondary lead they can receive back. World production of secondary lead (50-60% of the total) plays a significant role in controlling the official lead price. While battery collectors and smelters can benefit from rising prices, battery producers cannot. This situation could induce the producers to collect the spent batteries through their own distribution network, thus reducing the cost of recycling. Furthermore, the producers might even run smelting plants of their own to further limit the final cost of secondary lead. Some battery producers already collect spent batteries and sell them to smelters saving on the recycling costs; others collect and recycle in their own metallurgical plants. In the medium/long run, this action of the battery producers may result in their independence from the lead producers. Obviously, there is no general solution
229 for each case, since countries differ in terms of macroeconomy, nature and dimensions of the territory, environmental strategies.
The Market and its Evolution
The world lead production at the beginning of the year 2000 amounted to 6 million tons/year, with 60% of it coming from secondary lead, especially from spent accumulators. The production of secondary lead started a few decades ago, affecting the traditional lead market based on metal extracted from ore. Such dramatic change can be explained as follows. Fast development of people and goods mobility, mainly thanks to the improved surface infrastructures. The replacement of lead in several applications, once its harm had been ascertained. Short life of car accumulators, involving their replacement and recycling of scrap-lead as a raw material. In this way developed countries are considering the scrap-lead source as "lead mine", cheap to exploit and almost inexhaustible. Producing lead through recycling is a process economically more appealing than doing the same from ores. This change in philosophy took some time to be assimilated- until the new process became economical and safe both for the workers and the environment. To this end, the regulations imposed by public administrations have proved critical to help change the former approach. In the medium/long run, the lead market is expected to grow thanks to an increased demand for cars (i.e. of the accumulators equipping them) especially in Asia and Eastern Europe. The demand for industrial accumulators will also be continuing steady especially for telecommunication systems. Every year, about 3,900,000 tons of lead are used to produce accumulators. Taking into account that 65% of the accumulators weight is lead, some 6,000,000 tons of accumulators are thus produced every year. If the conservative estimates of an annual growth of 3-4% are conf'Lrmed for the automotive sector, this will result in 10,000 tons/year of accumulators within
a few decades and the same quantity should
theoretically be available for recycling.
/.~..~
230 Qualitative Market Evolution
The well known harmful nature of lead has determined over the last decades a dramatic disappearance from the market of those products and chemicals containing this metals. The present use of lead according to the sector is given in Table 1. Lead accumulators (for stationary use, traction or starting) largely prevail.
Table 1
Application
%
Batteries Pigments and other compounds Semifinished products Cable coating Ammunition Alloys Gasoline additives Miscellaneous
73 11 6 2 2 2 1 3
It is expected that in the future lead-containing compounds will be used only in special applications where it will be difficult to find substitutes with the same physical and chemical characteristics, production costs and possibility of recycling. At the present stage of technological development, it can be anticipated that lead will mostly be used in the field of radiation protection and in accumulators. 3.
LEAD ACCUMULATOR STRUCTURE
The electrodes, commonly named grid, are made by a lead alloy frame to improve both strenght and hardness of the grid supporting the so called active mass. This active mass is made by mixing very fine Pb powder with lead oxide (PbO or Pb304) and diluted H2SO4. After drying, the mass composition turns basically into lead sulphate and unreacted lead oxides. The final electrodes are formed by spreading the
231 mass over the grids and charging them through electrolysis in H2804. This gives rise to the formation of Pb at the negative and PbO2 at the positive electrode, while the concentration of sulphuric acid increases. During discharge, the electrochemical reactions are reversed, thus producing PbSO4 at both electrodes, while the acid concentration decreases.
The Battery Components The main components of a lead/acid accumulator are: 9 metallic Pb alloyed with Sb and/or Ca; 9 Pb oxide; 9 an electrolyte containing diluted H2SO4; 9 plastic materials to form separator and case. The weight rate of the above components is as follows: 9 Pb: 60/65%; 9 diluted H2SO4: 20/25%; 9 plastic materials: 10%:
Technological Evolution of Lead Accumulators Several years of research have led to a marked improvement of both the quality of the components and the production technology. The battery producers have been oriented to achieve a better performance coupled with an extended life, while reducing costs. In this respect, the environmental constraint has played an important role, as the producers have been forced to use materials more suitable from a technical and economical viewpoint, and easily recyclable as well. Lead accumulators are used in various applications, such as starters of intemal combustion engines, electric traction (forklifts, wheelchairs, etc.), power generation units (power plants, telephone exchange stations, railroads, hospitals, etc.).
Car Accumulators The lead/acid batteries used in cars have undergone significant changes with time, thus paralleling the car evolution, particularly in terms of electric and electronic
232 equipment. Until mid 70's, the accumulators were basically formed by: 9 positive and negative grids with Pb/Sb alloys (4-6% Sb). The battery producers used to buy such alloys from the smelters- and the origin of this lead was both primary and secondary. The Sb was specifically selected for the alloy to make the smelting easier and, at the same time, to facilitate handling of the grids during the manufacturing process; 9 active mass of lead oxides and metallic lead (that converts into lead sulphate after mixing with acid and curing): this mass is prepared from high-purity Pb by the battery industries; 9 separator: until a few years ago, PVC-based separators were used. This material has caused serious problems to the recyclers, as the pyrometallurgical smelting process determines the release of chlorine into the air. Accordingly, it has proved necessary to install upstream equipment to remove any other material from the the electrodes; 9 casing: a typical material was ebonite, a highly cross-linked rubber featuring high acid resistance and structural strenght. The ebonite case, too, has generated problems to the recyclers because, like PVC, it had
to be separated before
smelting and also because it was not suitable for recycling. The situation improved when polypropylene replaced the ebonite. Its low specific gravity makes fully possible a separation from other components as well as its recovery with a purity grade that allows its recycling. A major result was brought about by the introduction of maintenace-free batteries. Their success in the market is due to the following benefits for the consumers: 9 the use of an easily castable Pb/Ca alloy (3% Ca) for both the positive and the negative electrode; 9 the removal of Sb from the grids; 9 the use of a separator wrapping the positive electrode to avoid short-circuits; 9 the elimination of the space once destined to collect the active mass at the bottom of the battery. These advances have positively influenced not only the way to produce batteries but also the technique of recovering lead and its alloys from spent accumulators. Indeed, the Pb/Ca alloy is produced from soft high-purity Pb and, because of the great
233 affinity of Ca to O2,undergoes a quick modification.Therefore, the treatment time must be as short as possible and the alloy cannot be stored for too long. From the environmental viewpoint, a significant step was achieved by replacing PVC with polyethylene (PE), thus avoiding any chlorine in the air.
Industrial and Stationary Accumulators These batteries, largely used in industrial and consumer applications, have had the same development of car batteries, in spite of the differences between the two classes in terms of size, shape of the electrodes (fiat or tubular) and alloy composition.
Future Developments In the near future, sealed lead accumulators, based on the oxygen recombination, will increasingly be used as car batteries (replacement) and in stationary applications as well. The sealed batteries are classified in two categories: one with spirally wound electrodes in a cylindrical metal container and the other with flat plates in a prismatic container. Both are equipped with a pressure valve to release the excess of gas, if necessary. The cylindrical cells vent at high pressures (typically 105 Pa) and are normally referred to as SLA (sealed lead acid), while the prismatic cells vent at lower pressures and are called VRLA (valve regulated lead acid). A minor amount of electrolyte is required by both systems. These new accumulators initially experienced self-discharge problems at the negative electrodes,
now solved by removing the
excess of oxygen from the plates. Future applications of lead accumulators will include the production of alarm systems and electric cars. In the 90's, the Advanced Lead Acid Battery Consortium (ALABC) was set with the participation of battery producers and lead smelters. The consortium aims at stimulating and co-ordinating the research at global level to produce new batteries suitable for use in electric cars. Higher specific energy, longer life time, reduced initial and maintenance cost are the main targets. These lead accumulators might be a good alternative to other electrochemical systems. Despite its lower energy, the lead accumulator has still remarkable advantages in terms of reliability, cost and recyclability.
234 4.
THE C O L L E C T I O N OF SPENT BATTERIES
The European Union Regulations on Spent Batteries The main purpose of the EC Directive 157/91 is to set a common regulation among the member states regarding the recovery and disposal of batteries containing dangerous substances. In particular, the above directive refers to batteries exceedings these limits: 9 25 mg Hg/cell 9 0.025% Cd (total weight) 9 0.4% Pb (total weight) 9 0.025% Hg (alkaline batteries) The directive defines the spent battery as an exhausted power source that has to be recycled or disposed of by means of procedures set up by the member states and aimed at limiting the danger for the environment and human health. The member states have to establish programs for the gradual reduction of toxic and/or harmful substances in batteries, and implement techniques to eliminate them. Furthermore, the directive proclaims the efficient organization of a separate collection of this waste and the setting up of appropriate storage facilities. At the same time, the states are asked to provide financial support to boost both collection and recycling actions. These actions must: 9 be agreed upon with the interested parties, i.e. battery producers, collectors, recyclers; 9
be based on sound criteria as to their cost and environmental protection;
9
assure a reasonable competition.
Furthermore, the states should inform the consumers about: the risk associated with the uncontrolled disposal of spent batteries; the procedure to properly remove batteries from their equipment; the labels applied on each battery. In particular the labels should mention: heavy metal contents, requirement of a separate collection and the possibility of recycling.
235 The member states cannot veto, or take any measure to limit, the sale of any battery if it is produced in accordance with the EC Directive 157/91. The Italian Way to the Collection and Recycling of Lead/Acid Accumulators
The italian legislation has adopted the EC directives on environmental protection through the establishment of non-profit consortia. Such consortia are managed by: a) people involved in the production, distribution, use of such goods that later will become lead waste; b) operators in charge of collecting, recycling and/or disposing of the waste. The aim of the the legislator in this field was to maximise waste collection by making it compulsory and to have it recycled by fixing annual targets. For some types of particularly dangerous waste, collection is compulsory and cannot depend on market fluctuations - a bonus is granted for collection. There are currently 5 consortia and the one in charge of lead wastes is COBAT. This consortium takes care of spent lead/acid accumulators and any other kind of lead scrap. COBAT Institution
This consortium is a non-profit organization participated by private companies involved in any step of the accumulator's life, i.e. 9 lead batteries producers and/or importers and dealers (30% share); 9 new battery retailers taking back also the spent ones (10%); 9 spent batteries and scrap-lead collectors (10%); 9 spent batteries and scrap recyclers (50%). The members of the consortium have the obligation COBAT to reach the consortium goals.
to operate solely through
As it will be later pointed out when reviewing the european scenario, other institutions have been established in addition to COBAT. The italian policy seems to have fully implemented the principle of the 'shared responsibility' v i s a vis the environment through the invol-cement of operators with different, and sometimes opposed, interests. The by-law of the consortium obliges anyone detaining spent lead/acid batteries (and scrap-lead) to transfer them to the consortium either directly or through
236 collectors appointed by COBAT. The accumulators have to contain the sulphuric acid solution. Thus, the consortium grants collection, transfer and recycling of the batteries by means of the structures of its members. In this way, metallic lead and recyclable plastic materials are recovered, sulphuric acid is neutralized, and the final slag is properly land filled. In short, the main tasks of the consortium are: 9 to ensure collection and stockpile of spent batteries and scrap-lead. This scrap may generate from battery production systems and/or the recovery of secondary lead; 9 to deliver the above materials to companies in charge of recycling, even if they are located abroad; 9 to ensure the disposal of the above materials, should recycling not be possible or economically feasible; 9 to carry out market studies and technical-scientific research to improve the technology of recovering lead; 9 to advertise the obligation of collecting and recycling spent accumulators. The consortium activities are supported by: 9 proceeds of the sale to the recycling companies of used batteries and scrap-lead; 9 administration of its own assets; 9 the levy imposed on each battery collected. Such levy is a key economical tool able to convert into business a simple service activity. All producers and importers working in Italy are subject to pay this levy. The Collection Network
The operators appointed by COBAT establish the collection network. They take care of collecting, storing and, in some cases, delivering spent batteries to the recycling plant. This service is provided cost free to waste producers. All industrial, commercial and small companies, whose activity generates used batteries, are compelled under the law to collect and put them into special containers. Furthermore, they must keep note of any used dangerous waste.
battery on the special book for
237 The collectors must transfer to the consortium via computer all relevant data, so as to allow COBAT to set up a database (Decobat). In this way, COBAT is able to trace the waste in real time passing from the producers to the recyclers, via the collectors and carriers. Besides its primary collection network,
COBAT relies on private and municipal
collection structures. Their nature makes it easy to reach the end consumer and to take care of dangerous waste from the beginning. Collection Cost for Car Accumulators
The collection cost for a car accumulator has been calculated at 0.10 E/kg. This covers all costs, more or less the same throughout the European Union, from the extraction of the battery from the car until delivery at the recycling plant. The main share of the cost is taken by the transport because specially equipped trucks and suitable logistics are required. Data on the Collection
COBAT collects 176,000 out of 185,000 tons (95%) of used batteries annually produced. It is reckoned that 60-65% of the above amount is composed of metallic lead or lead compounds. Car batteries consist of 150,000 tons of the above amount. The recycling plants provide for neutralisation of the sulphuric acid (30 million litres/year) and recovery of lead (about 100,000 tons Pb) which is then returned to the market. This complete cycle provides several economical and environmental advantages to the community. Recycling 9 Criteria for Assigning the Batteries to the Recycling Companies
The battery price is fixed by Cobat and is the same for all recyclers. Thus, a procedure has been set up to assign the batteries annually collected to the recyclers. Texeco, an italian consulting company, has been appointed to develop and test this procedure in practice. A mathematical model was developed to evaluate the plants in terms of recycling capacity, care of the workers' health and compliance with environmental regulations.Therefore, the six plants operating in Italy receive their share of spent batteries according to this model. Whenever a facility undergoes a
238 change affecting its productivity, the new scenario is monitored and the relevant annual share is adjusted. 9 Recycling Costs for Car Batteries
The recyclers buy spent batteries from COBAT at a price of 0.06 C/kg. This revenue and the above-mentioned levy allow COBAT to break the balance sheet even, since the collection cost which is kept more or less steady at 0.10 C/kg. The recyclers' costs are formed by: 9 cost of the batteries (0.06 C/kg), i.e. 0.10 E/kg of lead (63% of the battery weight); 9 industrial cost of production, i.e. 0.31 C/kg; 9 costs for delivering new batteries to the clients, etc. The overall costs of the recyclers amount to 0.44 C/kg, this representing the breakeven point (BEP) for high-level european recyclers. 9 Costs of Slag Disposal
There are two types of slag: 9 smelting slag (iron and sulphur compounds, silica and soda from rotary kilns): 0.09 C/kg; 9 plastic materials (e.g. ebonite, PVC and polyethylene): 0.18 ~/kg. The price difference is due to the different land filling cost based on volume rather than weight. Therefore, a weight unit of slag has a volume corresponding to only a fraction of plastic material with a similar weight. 9
Recycling Organization
The metallurgical treatment of spent lead/acid batteries, and the recovery of lead metal, benefits the community both in terms of energy saving and balance of trade. The lead price is fixed daily according to the London Metal Exchange quotation and does not change across the European Union. It is customary to set aside for foreign recyclers a small percentage (2-5%) of batteries. Of this amount, italian recyclers have a pre-emptive right to buy, provided the bidding price is the same.
239 All italian plants use a chemical-physical process to separate the solid fraction and neutralise the solution, while a thermic process is used for smelting and refining. Two of them also use a chemical process to lower the sulphur content in the metal, thus reducing emissions released by the molten phase. The italian metallurgical industry has introduced innovative recycling technologies, later adopted in other european and non-european countries. All plants comply with the severe environmental rules and have a total recycling capacity of about 380,000 tons/year of spent batteries. This capacity, largely exceeding the estimated input, ensures the continuing operation if treatment problems arise. The extra capacity is also available to treat scrap-lead and batteries sourced from the european market. Battery recycling creates lead-containing wastes which are classified as dangerousin particular, smelting slag and slurries from sulphuric acid neutralisation. COBAT supervise the recyclers to ensure that they send this particular waste to landfill or use it according to the law.
5. COMPARISON WITH OTHER COUNTRIES OF THE EUROPEAN UNION The comparison is made among E.U. countries on the following basis: 9 consortia-based, i.e. country in which there is a participation by all subjects involved throughout the battery life (Italy, Sweden, Norway, Austria, Denmark and the Netherlands); 9 non consortia-based, i.e. country in which battery recovery takes place in a freemarket regime (France, Germany, United Kingdom and the other european countries). - Countries Not Using Consortia-Based Systems Germany
Regulationsfor Spent Battery Collection Primary and rechargeable batteries are still a matter under discussion, even at the political level, because of their content of heavy metals. The german producers have self-imposed the following targets:
240 9
producing batteries with low or zero content of dangerous substances;
9
collecting from the dealers spent batteries containing heavy metals.
Batteries free of toxic substances are not included in the collection system and enter the municipal waste stream. The first target above has been hit, while the second has been missed as only 30% of sold batteries have been returned. The experience gained with other recycling systems has shown that the recycling rate only increases if there is financial incentive or if the system is simple and cheap for the consumers. A regulation set in 1996 obliges: 9
the consumers to return the spent battery to the dealers or to public collectors;
9
the dealers to accept all batteries from the consumers and to give notice of their obligation;
9
the producers/importers to accept back and recycle all batteries;
9
the producers to label the batteries as indicated in the E.U. Directive 86/93.
A levy of 7.75 E is applied to any car battery bought without returning the spent one. Furthermore, dealers and producers/importers may form associations to eliminate spent batteries. The elimination of household batteries has been compulsory since 1974. The regulation distinguish dangerous spent batteries from other types, in agreement with Directive 157/91. The waste collecting companies, too, have the obligation to take back spent batteries from the consumers. The battery producers are obliged to monitor and analyse the results obtained with the collecting operations. They must submit an annual report to the authority for waste management. In practice, this regulation compels the producers to participate in the recycling process and introduces the "producers responsibility".
Recovery About 200,000 tons of lead are consumed every year for accumulators, as shown in table 2 (all figures in tons). The levy to support recovering of spent batteries amounted to 7.75 • for car accumulators in 1998. Every year, 80% of spent batteries is recovered. The data for lead/acid batteries in 1997/1998 are reported in Table 3.
241 Table 2
Year
Production of Refined Lead
1989 1990 1991 1992 1993 1994 1995 1996
390,000 405,000 363,000 354,000 334,000 332,000 314,000 238,000
Consumption of Refined Lead
Consumption of Lead for Accumulators
450,000 448,000 413,000 412,000 352,000 351,000 360,000 341,000
178,000 195,000 205,000 223,000 210,000 216,000 207,000 193,000
Table 3 Origin Domestic Production Collection Import (East Europe) Export (France) Recycling
Weight (Tons) 220,000 200,000 15,000 20,000 195,000
The recovery costs are reported in Table 4. From these data, one can see that the average cost for the recovery of spent lead/acid batteries in Germany is 0.52 C/kgPb. This includes collection, recycling, slag and plastics disposal. France
Regulationsfor Spent Battery Collection
242 Until 1996, in France a dedicated regulation for batteries and accumulators was still Table 4
Step
Cost ((~/kgPb)
Collection
0.15
Lead Recycling
0.34
Furnace slug disposal
0.02
Plastics (Ebonite,PVC, PE) disposal
0.01
missing. The law governing the recovery of lead/acid accumulators, issued in 1996, is based on the following assumptions: 9 batteries containing Hg, Cd or Pb cannot enter the municipal waste stream; 9 such batteries cannot be disposed of or recycled through unauthorized facilities; 9 dealers must accept any kind of spent batteries; 9 producers/importes have to organise the recycling or disposal of such batteries to the extent of their production/import volumes; 9 producers/importers/dealers are allowed to enter into mutual agreements and/or with waste operators or secondary producers to organize the recycling or selective disposal of spent batteries.
Targets The following are the targets fixed by legislation: 9 reach a collection rate of at least 85%; 9 bind the interested parties to reach 100% as soon as possible; 9 set up a network among car dealers to receive spent accumulators, including the ones bought in supermarkets; 9 force the waste operators to collect the accumulators even if containing sulphuric acid.
243
Recovery France has not issued a specific law to apply EC Directive 157/91 yet; for the moment a partly hybrid collection system controlled by main commercial operators is in place. The annual lead consumption for batteries is about 160,000 tons with a collection rate of 70%. In table 5, data on lead production and consumption (tons) are reported. Table 5
Year
1989 1990 1991 1992 1993 1994 1995 1996
Production of Refined Lead 267,000 260,000 283,000 284,000 259,000 261,000 297,000 301,000
Consumption of Refined Lead
Consumption of Lead for Accumulators
244,000 255,000 252,000 246,000 226,000 237,000 262,000 255,000
154,000 164,000 169,000 166,000 156,000 170,000 192,000
The data for lead/acid batteries in 1997/1998 are reported in Table 6. Table 6
Origin Domestic Production Collection Import (from Germany) Export (to Spain) Recycling The recovering costs are reported in Table7.
Weight (Tons) 190,000 160,000 20,000 10,000 170,000
244 Table 7
Step
Cost ((~/kgPb)
Collection Lead Recycling Slag, ebonite, PVC, PE disposal Total recovery cost
0.15 0.29 0.01 0.45
United Kingdom
The Commerce and Industry Department looks after the application of a law, issued in 1994, imposing a label on the batteries, as indicated in EC Directive 86/93. There is actually no regulation in place on collection/recycling, which takes place in a freemarket regime. The recycling rate exceeds 80%. Data related to 1997/1998 are reported in table 8.
Table 8
Origin Domestic Production Collection Import (from Sweden) Recycling
Weight (Tons) 160,000 150,000 15,000 165,000
The recovering costs are reported in Table 9. Spain
Directive EC 157/91 has been put into effect by royal decree of January 1996.
245 Table 9 Step
Cost (E/kgPb)
Collection
0.13
Lead Recycling
0.28
Slag disposal
0.01
Portugal Directive EC 157/91 has been put into effect with the decree of August 1994. The program for lead/acid batteries is based on the following: 9 minimum collection rate: 75%; 9 information to the consumers with support of the Environment Ministry; 9 obligation for producers, importers, dealers to take back all spent batteries up to their production or sales level; 9 registration in the company books of any data related to production, sale and collection of lead/acid batteries.
Luxemburg In 1993, Directive 157/91 was adopted. In the specific regulation: 9 the consumers are informed about the possibility to buy rechargeable batteries or batteries with low heavy metal content; 9 producers/importers/dealers are obliged to receive back all spent batteries, to be recycled later on. In 1994, the volume of lead batteries collected amounted to 398,000 tons, while 74,000 tons of other batteries were also collected.
246 - Countries Using Consortia-Based Systems Sweden
The law on battery collection was issued in 1989, thus anticipating the EC directive of 1991. According to this regulation, the waste collectors, battery producers and secondary producers (only one at the present time) are organised in the Retturbat AB. The battery dealers are responsible for the collection and must accept all batteries returned by the consumers and bring them to a site indicated by the municipality. The waste operators then deliver these batteries to the smelter. The producers/importers pay a levy of 4.24 (~ per car battery to the Environment Ministry, which returns part of it to Retturbat AB in order to sustain collection and treatment. Thanks to this system, the recycling rate in Sweden has exceeded 95% in 1996. Sweden has also proposed to modify EC Directive 157/91: producers/importers should be more involved, the public authority should supervise, and the incentive for battery replacement should be increased. Furthermore, Sweden has proposed to make a distinction between primary batteries and accumulators. It can be said that in Sweden, as well as in Italy, Directive 157/91 has been fully implemented. Norway In 1993, the Environment Minister has signed an agreement with the consortium of battery collectors, producers and importers to set up a system granting an efficient collection of all spent lead accumulators. The levy paid by the consumer for car batteries of 20 amperes minimum is about 3.10 C, an amount considered sufficient to allow a good support to the system even when lead prices are low. More than 95% of spent batteries are annually collected. The Netherlands
The application of Directive 157/91 has occurred as part of a plan for dangerous waste disposal (1993-2003). Lead accumulators are collected and stored by 70 waste operators. Furthermore, the collection of cars to be scrapped is organized by Auto Recycling Netherlands BV with a levy of 116.22 C per new car, thus allowing a satisfactory recovery of their batteries.
247 In 1995, was founded STIBAT to collect and recycle spent batteries. Its targets were: 80% in 1996 and 90% in 1998. The program is supervised by LMA (Landelijk Meldpunt Mvalstoffen), a governmental agency. STIBAT, the Environment Ministry, the municipality association, dealers and distributors act in a co-ordinate way at country level. Batteries collected from STIBAT are recycled also abroad, e.g. in Sweden, Germany, U.S.A., France, U.K., Belgium, Switzerland. Austria
The regulation on spent batteries took place before Austria's admission to the European Community. The 1990 decree of the Environment Ministry obliges dealers to take back from the consumers all types of used batteries. The austrian regulation is more strict than that of the E.U. one. Data for the lead accumulators are reported in table 10.
Table 10
Origin
Weight (Tons)
Domestic Production Collection
12,000 11,500
Import (East Europe) Recycling
18,000 29,500
Denmark
Battery collection is carried out according to an agreement between the Environment and Energy Ministry and the association for lead battery collection (1996). The target is to reach a collection/recycling rate of 99.9%. While the dealers are obliged to take batteries back free of charge, the collectors receive 0.1 C/kg of battery. The total amount the collectors annually receive is 1.3 million C, an interesting incentive to collect spent batteries.
248 Comparison of the European Countries' Data 9 Collection
The recycling rates for 1997/1998 are reported in table 11.
Table 11
Country Italy
% >95
Germany France
80 70
Sweden
>95
Norway
>95
The Netherland
90
Greece Portugal
90 75
Austria
<80
United Kingdom
>80
The data mostly refer to the number of replacement batteries, which is equivalent to that of the spent ones. Data on spent batteries are not always available, as the collection system is often irregular as it is managed by private operators. Furthermore, spent batteries often cross borders, e.g. France-Germany, East EuropeGermany or Austria, France-Spain, Scandinavian Countries-United Kingdom, and this factor determines some uncertainty as to whether the figures are correct.. The collection costs are summarized in table 12. 9 Recycling
The costs for lead recycling are reported in table 13.
249 Table 12
Country Italy France Germany Austria United Kingdom
Cost (E/kgPb) 0.10 0.15 0.15 0.15 0.13
Table 13
Country Italy France Germany United Kingdom
Cost (C/kgPb) 0.32 0.29 0.34 0.28
These recycling costs refer to lead for the production of ingot lead or standard Pb/Sb alloy; other alloys have extra costs. ,
Sulphuric Acid Disposal
The above costs include disposal of the acid. The acid contained in a spent battery is accepted in all countries but is not paid; its weight is not taken into account when determining the dry total weight of the spent batteries. Only in Italy, "free" acid is accepted, i.e. the acid that leaks from broken batteries and accumulates at the bottom of the containers. Its acceptance is imposed by COBAT with the aim to limit acid dispersion in the environment, although the collectors prefer to sell acid-free batteries to the recyclers.
250 9
Slag Disposal
As previuosly mentioned, there are two types of slag: from smelting (iron and sulphur compounds, silica and soda from rotary kilns) and from plastic materials (ebonite, PVC, PE). The disposal costs depend on the slag volume rather than its weight. Accordingly, disposing of a given weight of smelting slag will be cheaper than disposing of the same weight of plastics which are lighter and need more space. In table 14, the cost given is average for both types of slag. Table 14
Country
Cost (•/kgPb)
Italy France Germany United Kingdom
0.02 0.01 0.02 0.01
9 Total Recovering Costs
It is now possible to calculate the total costs for battery recovering (table 15). A complete comparison among european countries is rather diffult due to the lack of reliable official data and since there is no entity such as COBAT, controlling the phases and costs of recycling. Information is directly provided by the operators who have some difficulties in obtaining the right figures.
Table 15
Country Italy France Germany United Kingdom
Cost (C/kgPb) 0.44 0.45 0.51 0.42
251 From this comparison, it is evident that the free-market regime is not always able to ensure lower costs. Furthermore, it has to be considered that, in this regime, only what is economically convenient is collected. For a complete comparison, one has to take into account such factors as power, ecological costs, taxes, facility maintenance, etc. Looking at table 11, it can be noted that the recycling rate is higher in those countries with a consortia-based system. Lower rates in other countries are explained because the collection is directly linked to lead price; therefore, when the lead price diminishes, collection becomes less attractive as in this case the impact of transport cannot be further reduced, and the overall collection cost vis a vis lead price is higher. Free competion may therefore show some negative aspects, especially if one considers that acid-free batteries are paid better than others. On the contrary, the overpricing-based system is able to meet the costs of a complete recovery and, at the same time, to protect the environment.
6. C O L L E C T I O N MODES AND RECYCLING TECHNIQUES Collection Modes
The systems used to collect and store spent accumulators are not the same in the various countries. The lack of uniformity has to be ascribed mainly to the nature and small dimensions of the operators. However, as an example the italian situation is described below. 9
Primary holders
Primary holders storing spent batteries are obliged to hand them free of charge to authorised companies. The primary holders are fined if batteries are left in a public space. Secondary holders (such as scrap-metal operators and car electricians) assure their storing in safe conditions, i.e. the batteries will not be broken and acid and/or Pb compounds not spilled. 9 Collection Authorised transportation companies take back the used batteries from secondary holders. These companies should have available a truck fleet to be able to reach
252 secondary holders everywhere, especially in the big towns. Furthermore, the trucks must be equipped in such a way to grant loading and transportation without any spillage of dangerous substances from the batteries. To this end, all trucks are equipped with stainless-steel acid-resistant containers shaped so as to contain any spilled acid. Once the batteries are collected, the trucks reach the collection center and the batteries are stockpiled in storage areas whose floors are lined with acidresistant materials. These areas must be sheltered and aerated, and located so to allow an easy loading of the batteries on bigger trucks for delivery to the recycling plants. Any acid spilled during the loading/tmloading operations is collected in special containers and sent to the recycling plants.
9 Transport to the Recycling Plants Battery transport is carried out according to the criteria indicated below: 9 location of the recycling plants; 9 volume of batteries assigned by COBAT; 9 volume of batteries received by the collection centres; 9 transport cost minimisation: The COBAT databank allows monitoring of the flow of spent batteries to the recycling plants. In this way, it is possible to meet the recyclers' requirements and to optimise the number of voyages to reduce the risk of environmental damage.
The Production Cycle- Recovery Technologies The current recycling technology used world-wide involves various steps. The first operation requires the non-metallic components to be separated from the metallic fraction by crushing and physical sorting. In this way, reusable organic components are recovered and dangerous substances, such as PVC, are not fed into the furnace. Attempts to treat the batteries bypassing this preliminary step have been made at the industrial level (shaft furnace); however, no advantageous result from both economical and environmental points of view was achieved. The treatment process involves the following steps: 9 physical treatment;
253 9 smelting/reduction of lead-bearing products; 9 refining the lead obtained by smelting to meet the market specifications; 9 alloying. 9
Physical T r e a t m e n t Facilities
Until the early 60's, Pb recovery from spent batteries was carried out by shredding the battery manually and detracting the plates along with the separators and part of the ebonite cover. The plates were delivered to the lead reduction plant. The ebonite case was washed in a drum and lead sulphate recovered. After drying, the lead sulphate was fed into a reduction furnace. The washed ebonite was dumped. This method was unsatisfactory in terms of workers' health (prolonged exposure to lead) and lead recovery (as plates treated were not clean since they contained 8-10% plastic materials, and due to the simultaneous reduction of Pb/Sb grids along with the active mass). In the middle 60's, the major italian producers of secondary lead patented and operated an automated battery shredding facility. This technology, later modified to take into account the increasing use of polypropylene cases containing more electrolyte, was in use till late 70's-early 80's. Since then, the same producers have modified the existing shredding facility to adapt it to the new battery type
(as
mentioned, with a polypropylene case and more acid) and to comply with the more restrictive regulations. 9
Sink and Float Separation
This process takes place in two phases. In the first, the batteries are shredded, the active matter is separated and dried, and the acid is neutralised. In the second, lead is separated from ebonite (or polypropylene) with the so-called 'sink and float' process.
Battery Shredding A payloader feeds a hopper with batteries. From the hopper, by means of a conveyor belt, the batteries fall into a rotating cylinder were the cases are broken with the help of big iron beams inside. In the same cylinder, the resulting scrap is dried by a gas burner. The end of the cyclinder is provided with two sieves. The first sieve allows
254 the recovery of the dried active mass, which is sent through a belt to a series of containers. The second sieve allows the retention of the coarse parts, such as partly broken cases also sent to containers. The part containing ebonite (polypropylene), separators and lead is conveyed to the 'sink and float' unit.
Separation of the Components A slurry made of the active battery mass is fast stirred in a pool. Its density and viscosity are frequently checked. This slurry is conveyed to a separating drum, flowing upstream with respect to the scrap. Then, the slurry drags the shredded containers and the plastic separators which begin to float because of their low specific weight as compared to the slurry. At the end of the drum a rotating sieve separates the slurry from the plastic materials. The shredded containers proceed to the second section were they are washed by recycled water. On the other hand scrap-lead leaves the drum and reaches a rotating sieve for washing. After that it falls onto a conveyor belt and is stockpiled. Periodically and altematively, the slurry carrying also the active matter is drawn from the tank and sent to a couple of draining tanks, of which one is continually being replenished and the other depleted. Here, water drains the material and is then eliminated into a sewer, while the active mass is from time to time collected, dried and added to the one already separated by the rotating sieve. 9 Hydrodynamic Separation and Carbon
This unit has two sections, the first allowing shredding and separation, and the second allowing sulphur elimination from the active mass. Sulphur is present as lead sulphate and is recovered as sodium sulphate, used in the soap industry.
Battery Shredding and Separation of the Components The incoming batteries are stored in a special concrete place lined with acid-resistant asphalt, having a storage capacity is 4,000-6,000 tons of batteries. Here, acid drains from those batteries broken during the unloading operations. Sometimes, the batteries are crushed on purpose by means of a crawler. The drained electrolyte is collected in one or more pits, from which it is conveyed to reservoirs. The batteries now partly emptied (6-12% residual electrolyte) are fed to a hopper, from which they are belt-conveyed to a special hammer mill for shredding. The resulting lead paste,
255 mostly PbOx and PbSO4, is transferred from the mill to a wet sieve (mesh: 1-1.5 mm) were it is separated from other components. The mixture of grids, polyethylene (PE) separators, polypropylene (PP), PVC, wood and other materials is sent to the hydrogravimetric separator. Due to a strong water flow, PP floats at the top of the equipment, while the grids sink to the bottom. PE, PVC and other residues leave the separator through an opening and can possibly be treated to obtain a further separation. At this stage, the following products have been obtained: 9 active mass+water: about 60% of the incoming battery weight; 9 grids (95% lead): 28%; 9 PP (its percentage depends on the type of case): 97% of initial PP weight; 9 PE+PVC+other residues (variable percentage): The grids are stored and then sent to feed the kiln. PP flakes can be marketed as such or extruded by special equipment to obtain granules, later sold to manufacturers of plastic products. In Europe, the commercial value of extruded PP reaches about 6080% of its original value. The PE/PVC mixture is land filled. Several plants limit the physical treatment to this phase and send to fumaces the lead mixture Carbonatation process
The lead paste is pumped into a reaction vessel. By adding Na2CO3, the following reaction occurs: Na2CO3 + PbSO4 ") PbCO3 + Na2SO4 Once the reaction is finished, the paste passes through a filter-press and a desulphurated material with 12% water is obtained. The solution containing sodium sulphate is crystallized to obtain anhydrous Na2SO4 and the hot water is recycled. This second phase has the advantage of transforming lead sulphate into carbonate, minimising SOx emissions and making unnecessary the use of special scrubbers. Furthermore, the lead sulphate requires large amounts of reactants in the furnace, while the lead carbonate only needs coal. Therefore, the advantages are:
256 9 no SOx emission; 9 few reactants needed; 9 increased kiln productivity: 30%; 9 proceeds from selling Na2SO4 to soap and glass industry allow the compensation of about 85% of the cost of Na2CO3 used. This technique is still in use in several plants. However, marketing Na2SO4 is becoming more and more difficult, especially as far as the soap industry is concerned. So, the use of this technique depends on the economical, technological and environmental conditions of a recycling plant. A flowchart describing all the treatment steps carried out in the plant is reported on page 33. Metallurgical Plants 9 Smelting/Reduction
Smelting is the key process in the cycle of spent lead batteries recovery. The fumace can be of different types: reverberatory fumace, used in the metallurgical industry not only for lead, but also for copper, steel, etc. These furnaces have a radiant vault and a refractory lining of chromium-magnesium bricks, with lateral oxy-fuel burners and are fed by a loading hopper. The feed made of metallic lead, lead compounds, reducing agents and slagging agents is carefully pre-mixed; rotary kilns, widely used by virtue of their flexibility in terms of operation and maintenance. In a plant, normally two such kilns of different sizes are installed. The number of batteries to be treated determines the one to be used. The burner is set on one of the kiln headers and is made retractable as the charge is introduced through the same opening. The combustion fumes leave the side opposite the bumer. Since rotary kilns are widely used, the following description of the process refers to them.
257
BATTERY MIX
u I CRUSHER I INDUSTRIAL WATER
I GR DS
I
POLYPROPILENE
I SULPHATED PASTE
r I
RECYCLING WATER I
I HYDROGRAVIMETRIC I SEPARATOR
I
t~ -~
PRESS FILTER
P.V.C. + WASTE
J .......
PASTE
Na2CO3 WASHING WATER INDUSTRIAL
u
I
v
I
REACTIONTANK
PASTE + SOLUTION u
WARM WATER TO WASHING
! PRESS FILTER
I
u
I SOLUTION TANK I~[ I CONDENSATOR I
H20 VAPOR
I
q WARM WATER ; TANK
I MOTHER LIQiOR
BURGE
CRYSTALLIZER 2" I
u
I EVAPORATION AND I CRYSTALLIZER 1"
VAPOR
CRYSTAL + MOTHER LIQUOR
CRYSTAL +
MOTHE~LIQUOR
I CENTRIFUGE I DR ....
FVAPOR
ICENTRIFUGEI ~
LIQUOR
DR ER FVAPOR
~
DESULPHATED PASTE
I
258 The amount of charge introduced in the kiln, especially in terms of reactants and slagging agents, is a function of whether the lead paste carbonatation was made before smelting. In the absence of carbonatation, the feed mix is made up of metallic lead, lead sulphate, coal, soda, scrap-iron, silica (sand) and/or glass. These materials are charged without pre-mixing but sequentially, according to their function: soda, lead and its salts, carbon, scrap-iron. The charge is fed from the burner side keeping the kiln slowly rotating. The oxy-fuel burner is stoked with methane. The charge components give rise to reactions eventually leading to metallic lead: NazCO3 + 2PbSO4 + Fe + 9C "-) 2Pb + FeS + Na2S + 9CO + CO2 The maximum temperature is 1000~
The yield in terms of lead is about 90%.
Fe and Na2CO3prevent the formation of SO2 (sulphides are formed instead), thus the combustion fumes have SO2 levels below the permitted limit. Once the reaction is over, lead and slag are sequentially cast from the casting hole in the middle of the kiln. Molten lead and slag are cast in ladles on a train perpendicular to the kiln and kept under suction.The whole cycle- charging, reactions and casting lasts about 3 hours. The fumes are conveyed to a fume scrubber, before sending them to a filter. Sometimes, a special scrubber for SO2 is also used, to eliminate possible excess. The plants equipped with a carbonatation unit benefit a great deal from the production. In fact, as the charge is mainly made of metallic Pb and PbCO3, the amount of necessary Fe, C and slagging agents is lower. Furthermore, reaction time and temperature are also reduced, lead yield is higher and SO2 emissions are negligible. An increase in the production capacity by 30-35% may be estimated with respect to the treatment based on sulphur-containing lead. However, as mentioned above, carbonatation brings about higher operation costs and the need to sell sodium sulphate. Nevertheless, the last-generation plants designed for the production of primary lead are able to treat sulphur-bearing lead from spent batteries. These are direct-smelting plants which are suitable to treat lead sulphates, which, after the addition of lead concentrates, are directly reduced to metallic lead without problems. In Europe, there are three plants of this kind. Although based on different technologies, a feeding mix
259 made up of lead concentrates and lead sulphate from batteries is used in all cases. A plant built with Kivcet technology is operating in Italy; another one (QSL technology) is in Germany; a third (Ausmelt technology) is in France. 9
Refining/Alloying
From the smelting of lead ores or spent batteries a metallic lead is obtained which has to be refined, i.e. purified from other metals, so as to obtain 99.9% grade lead. Those metals are treated in special facilities to recover them. Usually, lead concentrate carries precious metals, sometimes in economic concentrations. Lead can be refined either electrolitically or thermally. 9
Electrolytic Refining
With this process, the smelted lead is cast as anode and electrolysed in a fluosilicic acid solution. By this process pure lead is collected as cathode, while any other metals remain on the anode and are recovered as anodic slurry, further treated to recover single metals. 9
T h e r m a l Refining
With this method, the refming process takes place in open kettles, usually quite large, heated by a direct flame underneath. Plants producing lead from spent batteries prefer this process because the investment and direct costs are lower and there is a small quantity of secondary metals. Refining can be performed either continuously or in batches, according to the production requirement of the plant. In particular, smelted lead is cast into ingots and sent to a kettle were it is smelted again to free it from copper (decopperizing) by skimming the surface with a bucket. Afterwards, the molten lead is channeled to other kettles were it is further separated from other impurities/metals, again by skimming. Each kettle
is provided with
stirrers and pumps to pour molten lead into the next kettle. The phases of the continuous process are: 9 Decopperizing; 9 detinning (with soda and NaNO3, with or without Harris' machine); 9 deantimoning (with oxygen and Harris' machine); 9 alloying (Pb/Ca, Pb/Sb, Pb/Sn);
260 9 final refining and casting. The ashes generated during the ref'minig phase, after sorting, are recycled to the kilns. Lead metal is cast into ingots, after checking its grade, using an automatic casting machine. At the end of this machine an automatic machine stakes the ingots.
Comparison of the Production Technologies The technological advances in the recycling plants cannot be understood without considering the advances that have involved the batteries they are treating. Batteries have undergonemajor changes in their performance and materials. The replacement of ebonite with PP for the case and of PVC with PE for the separator has been quite an important step. The new generation of batteries has allowed the recyclers to reduce the amount of material to be land filled, to improve working conditions within their plants and to to recover and market organic products, so that the overall costs can be reduced. All modem technologies are based on the following phases: crushing the battery, sorting non-metal components and treating the metal. The technological differences as to the first and second phases are not so relevant, as such facilities are now well known and easy to get in the market. As to the third phase, possible alternatives are: 9 direct treatment of lead and its compounds in the smelting/reducing kilns. This solution cuts the costs, but limits the capacity of the kilns, while increasing the costs of ecological facilities; 9 carbonatation of the lead salts before smelting. This solution calls for higher expenses for equipment and their management, with the risk of not getting back a satisfactory revenue from the sale of sodium sulphate. Nevertheless, this alternative allows for a 30-35% increase in production capacity and a reduced cost for ecological facilities; 9 sale of lead sulphate to primary smelters, and also its partial or total tolling by reduction plants (i.e. treatment cost for recyclers account). If sold, lead sulphate would dramatically reduce recyclers' expenses; if tolled, the production capacity of the recyclers would increase, as it would only depend on the shredding facility size, which however is usually oversized in this kind of plant. On the other hand, should the lead sulphate be sold, the recyclers would lose market shares for the trmal product and their production would become less
261 autonomous. In case of partial or total tolling, the recyclers should pay not only for smelting, but also for delivering the sulphate to the plant and taking back the refined metal. These considerations highlight how the right choice stems on economical rather than technical parameters. Therefore, the final choice is up to the management. If only the technical aspects were considered, the last two options (carbonatation, sale/toll) would appear more reliable.
CONCLUSIONS The growing interest of government, industry and ordinary people toward the environmental problems has made possible the issue of regulations to protect the environment and human health. In this respect, the high collection rate of spent batteries in the developed countries (European Union for instance) is a significant achievement. It is everyone's hope that the developing countries can soon bridge the gap, as lead pollution is not halted by the country borders. The lead market has undergone major changes, so that great attention is devoted to its recovery and recycling. The technological advances in the lead/acid accumulators field have made lead recovery easier and safer for the environment. At the same time, the lead metallurgy has become environmentally friendly as well. Lead is a material with excellent electrochemical properties. As long as its toxicity is kept under control, and this is entirely possible, lead will be useful and used for many years to come.
This Page Intentionally Left Blank
Used Battery Collection and Recycling G. Pistoia, J.-P. Wiaux and S.P. Wolsky (Editors) 9 2001 Elsevier Science B.V. All rights reserved.
RECYCLING
263
THE LITHIUM BATTERY
D a v i d G. Miller a and Bill M c L a u g h l i n b
a Toxco Inc., 3200 E. Frontera, Anaheim, CA 92806, U.S.A. b Solid Team Inc., 148 Limestone, Caremont, CA 91711, U.S.A.
INTRODUCTION Prior to discussing the practicalities of recycling lithium batteries, it is necessary to first provide a background illustrating the types and characteristics of lithium batteries. Following the background section, this chapter will focus on: 9 9 9 9 9 9
The hazards and safety aspects of recycling lithium systems The environmental concerns of lithium recycling Sorting, packaging, and transporting the batteries for recycling Components of the batteries with regard to recycling Current recycling techniques Typical chemical analyses
BACKGROUND
The never-ending search for the most efficient battery (lightest weight, highest energy) has gone on since the batteries were initially developed. The LeClanche cell, lead acid and carbon zinc batteries sustained the portable electric world until the latter part of the 20 th century. During this period the technology base of electronics began drastically expanding due to breakthroughs in microelectronics, software, digital systems, communications technology, and electric transportation. It seems that each year brings us the conveni~ence of some new device that is battery powered. In the past 20 years the desire for a better battery has turned into a necessity. In the past 40 years this quest for the perfect battery has had amazing results. The development and refinement of many battery types such as the alkaline, silver zinc,
264 lithium primary, nickel metal hydride, and lithium secondary systems has made tremendous progress. In addition to consumer types, many other systems are also evidence of intensified battery development efforts. These include, but are certainly not limited to, nickel hydrogen, magnesium silver chloride, zinc air, and several types of lithium and calcium based thermal systems, only to name a few.
This search however, is limited by certain restrictions. Among these restrictions, are the fundamental laws of physics and chemistry. One such rule is that each element (or compound) can only achieve its well defined maximum, positive or negative, electrical potential. Lithium and sodium, are the two lightest metals and also have the
265 highest electrochemical potentials at 3.04 and 2.71V, respectively. This makes both appear to be great candidates as an anode material. Under this premise, much interest and emphasis was placed on the development and design of some of the earlier sodium sulfur batteries in military applications and electric vehicles. The sodium and sulfur couple was, in fact, very good but, in a practical battery, very poor. The downfall of the sodium based battery was the high heat generated (and necessary) for normal operation. The battery case breached in many situations releasing molten sodium and resulting in a flaming mass of burning metal. In a nutshell, sodium was found to be too reactive for any battery purpose other than very specialized low vibration, remote military applications. Throwing out sodium as the perfect anode, lithium is the next obvious choice. Thus the lithium generation of batteries was born. The military was in many ways the test bed for this high-energy lightweight electrical system. In primary (nonrechargeable) systems the lithium anode was tried with many cathodes including thionyl chloride, sulfur dioxide, manganese dioxide, carbon monofluoride, sulfuryl chloride, iron disulfide, as well as many that never made it into practical applications. Some of these proved successful and are still used today, many proved to be failures for one reason or another and development ceased. Along with the benefits of the light lithium metal come several disadvantages. One of the inescapable characteristics of elemental lithium is that it will react with air or water exothermically. The batteries also were found to react violently when heated too much, when charged, when pierced, when over discharged, or when short-circuited. The contents were sometimes violently reactive in air and water and generated highly flammable hydrogen gas. It was also found that the reason the lithium primaries could not be charged was based on the plating characteristics of the lithium metal. Indeed, it does not plate evenly and begins to form tiny spikes or dendrites. As the charge is continued, these dendrites can grow long enough to pierce the separator material causing a direct internal short. This pinpoint short is believed to create a tiny area of molten lithium which quickly spreads throughout the anode surface. There is a thermal runaway followed by venting (the battery over heats and ejects the inner cell contents, sometimes violently). This physical characteristic seemed to be an impasse for the development of a rechargeable lithium battery system. For over thirty years lithium primary batteries gained consumer and industrial awareness. They became well known for their performance in very diverse military
266 applications. They gained a reputation for their long shelf life, constant voltage, wide operating temperature range, and low self-discharge characteristics. They provided the highest voltages for the longest duration at half of the weight of many other conventional systems. Unfortunately, these earlier primary batteries (especially the liquid cathode cells) also became known for their reactivity and obvious safety concerns. During the 90's came one of the biggest breakthroughs in rechargeable batteries since the development of the Nickel Cadmium: lithium ion batteries, with liquid or polymeric electrolytes, were developed. These lithium rechargeable batteries operate on the premise that the electrical potential of lithium metal is approached, but lithium metal is not present. Indeed, Li § from one lithium compound in the anode is transferred to another lithium compound at specific sites on the cathode during discharge. The reverse occurs during charge but the adverse plating of the lithium metal does not occur because the lithium ion is not allowed to form lithium metal. There is only approximately 0.1 V difference between the fully charged battery voltage and the voltage necessary to plate lithium metal. If charging of the battery is continued beyond the fully charged voltage, Li § begin to plate on the surface of the anode in metallic form and can result in venting similar to primary lithium batteries. It is for this reason that successful lithium rechargeable systems have charge control circuitry. Lithium batteries can be categorized into many types. Several of the most common types are listed below. This is not a complete list nor is it meant to be. Soluble Cathode:
Lithium/Thionyl Chloride Lithium/SulfurDioxide Lithium/Sulfuryl Chloride
Solid Cathode:
Lithium/Manganese Dioxide Lithium/Iron Disulfide Lithium/Carbon Monofluoride Lithium/Iodide
Thermals:
Lithium/Iron Disulfide
Lithium Rechargeable:
Carbon/LithiumCobalt Oxide
267 Carbon/LithiumManganese Oxide Carbon/LithiumNickel Cobalt Oxide Lithium Metal/Polymer Each type is unique in electrical and chemical characteristics. Each type also has special recycling techniques that must be considered. By over looking a difference in chemical composition, size, or reactivity, tragic environmental and safety concerns can be quickly realized.
It is also necessary to understand the battery types to
maximize an efficient and cost effective commercial business. Lithium batteries are not all the same, they are not an inert waste even if lithium is not in elemental form, and they require special packaging, storage, handling, processing, and personnel training.
THE
HAZARDS
AND
SAFETY ASPECTS
OF
RECYCLING
LITHIUM
BATTERIES As seen in the previous section there are numerous types of lithium batteries. In this section, we shall look at the generic hazards of primary (with liquid or solid cathode) and rechargeable batteries. There is much controversy over the reactivity of several individual chemistry types. It is the authors opinion that there are inherent hazards associated with any battery type or energy source and in most situations the hazards and size are directly related. In a similar scenario, lithium batteries in general cannot be categorized into being more or less hazardous than any other chemistry without knowing the exact type and size of the systems to be compared. The hazards of any battery system increase with size (as mentioned above), but in contrast, depending on the type, a smaller lithium system may be much more reactive than a larger lithium system of a different type.
Hazards of Primary Batteries In the case of the primary lithium systems, the hazards for the most part involve the safe processing and management of the elemental lithium and associated hydrogen gas. Eliminating the random very violent reactions is paramount when considering the safe processing of the batteries for recycling. Once lithium and hydrogen are controlled, the components within the battery can be exposed, separated, neutralized, reprocessed, and
268 separated again or re-manufactured into marketable materials. Primary lithium batteries exhibit the following hazards.
1) Because the reaction of lithium with water quickly generates hydrogen and heat, and because a lithium battery can spark if shorted, there is extreme risk for fire, flames, and violent deflagration. Violent deflagration simply means that the destructive pressure wave generated when a battery vents has a slight rise-time when plotted versus time. A pressure wave from an explosion, on the other hand, has zero rise-time. It should be noted that to the common observer, under abusive circumstances, lithium primary batteries may certainly look like explosive. 2) Soluble-cathode lithium primary batteries most times contain very toxic cathodes and flammable solvents. These types of batteries are seldom seen outside of the military in sizes larger than a button/coin cell. They are common in some heavy industrial or remote processes including oil-drilling operations. many military forces throughout the world.
They are extremely common in
269 3) Any lithium primary battery under the right (or wrong) circumstances can vent fire and flames similar to a torch. 4) The hazards of a lithium primary system increase by magnitudes as the size of the battery increases.
Large lithium primary batteries or cells of any type can be very
dangerous if not handled properly.
Hazards of Secondary Batteries Recycling lithium rechargeable battery systems does not involve elemental lithium under normal conditions. It is the authors belief that a fully charged large nickel metal-hydride battery has the potential to be much more reactive than a comparably sized lithium secondary. The metal-hydride battery worst-case hazards include the possibility of very high hydrogen concentrations within the battery case. In certain situations this could result in a violent hydrogen reaction (this violent reaction, by the way, would not be considered deflagration but instead is an actual explosion). Because there is no elemental lithium, many of the hazards of processing lithium ion systems are similar to other non-lithium battery systems. There are also new hazards and, as in the case of the primary lithium batteries, each type must be evaluated. The lithium ion rechargeable systems are much less reactive than lithium primary systems for several reasons: 1) There is no elemental lithium (under normal use scenarios), thus there is very little hydrogen generated. There is the possibility of elemental lithium being produced if the charge control circuitry has failed. This possibility cannot be overlooked in the case of a commercial recycling facility. 2) The electrolytes are less reactive than most soluble-cathode primary batteries. Sulfur dioxide, thionyl chloride and sulfuril chloride are extremely toxic and quickly fume when exposed to moisture (forming very acidic mists). 3) There is very little free electrolyte in lithium secondary systems, thus reducing the possibility of spilling acidic liquids. The hazards of the lithium secondary systems are described below and must be considered in any recycling process.
270 1) The non-aqueous electrolyte is primarily composed of flammable organic solvents. 2) Large heavy batteries can consist of many cells with high cumulative voltages. This naturally increases the risks of electric shock and crushing injuries. 3) The battery electrolyte is toxic. 4) The presence of elemental lithium can sometimes occur if the charge control circuitry fails. Hazards Considerations
Lithium batteries when new or fully charged are capable of possessing large amounts of electrical energy (as do many types of batteries).
When received at a
recycling facility, most of this energy should be dissipated since the majority of batteries sent for recycling should be depleted. A commercial recycling facility cannot count on this being the situation in all cases. Consumers and industry alike mix new and used batteries in many applications. They change the batteries of several systems (i.e. radios, flashlights etc.) even though only one actually needs new batteries or they replace one or two cells instead of replacing all of the cells from a system. As a result, batteries received for processing vary in depths of discharge from fully depleted to fully charged. Multi-cell batteries should always be treated as fully charged to avoid serious injury. This electrical energy can also (and will eventually) create a spark. Sparking can occur under abusive circumstances such as terminal-to-terminal shorting or internal shorting due to piercing or crushing the case. In the presence of a spark the electrolyte, packaging material and other combustible material will cause a fire. Some organic electrolytes have a low vapor pressure and will quickly evaporate into the air. The organic vapors must be managed to reduce the risk of personnel exposure as well as to prevent the formation of extremely flammable environments. In a similar scenario, there is no sorting equipment available that can distinguish between the various chemistries of lithium batteries. Consumer collection or recycling facility efforts many times depends on manually sorting the various types of batteries. Batteries are shipped with the wrong shipping or safety documents and may even be mistaken for other types of batteries all together. The point is that a recycling facility must be prepared for the worst case scenario when it is least expected. A facility must put a high priority on screening, quality control and safety.
271 Worker and personnel safety should always be considered in a recycling environment.
Battery safety consists of many common sense concepts as well as
several that are not common sense. 1) Wear eye protection. 2) Wear safety shoes. 3) Wear long sleeves when working with neutralization chemicals or battery electrolytes. 4) Use chemical resistant gloves, apron, and face shield when working with the electrolyte or vented batteries. 5) When working with a large battery disconnect the cells. 6) Do not wear metal rings, watches, or necklaces that may come in contact with the electrical terminals of the batteries. 7) If cutting electrical wiring, cut one wire at a time to prevent shorting the battery. Use care when disconnecting cells not to short-circuit the terminals with wrenches or other metal objects. The cell cases in many situations are one side of the electrical circuit. With this in mind, never remove the protective plastic cell coating. 8) Remove all non-essential combustible material from the processing area. Remember that secondary fires cause most damage resulting from a lithium battery fire. 9) Always work in pairs or keep in contact with other workers via intercom. 10) Practice fire response in accordance with an approved response plan. 11) Practice spill response in accordance with an approved response plan. 12) Make sure fire extinguishers are accessible, clearly marked, and are the correct class for the types of fires anticipated. Graphite powder based extinguishers are the correct class for lithium primaries and can also be used for lithium ion. Copper fire extinguishers should not be used for soluble-cathode lithium primary batteries. Make sure personnel are familiar with extinguisher locations. 13) Supplied air or respirators with organic filters (for lithium secondary batteries), and acid filters (for lithium primaries), should be readily available if exposed to battery electrolytes. Respirators are not recommended for long term exposure or exposure to unknown concentrations of electrolytes. 14) Always have a copy of the battery Material Safety Data Sheet (MSDS) on file and available. 15) When disassembling a battery into cells, always refer to an electrical schematic if at all possible.
272 16) In most situations it is best to store the batteries in a sprinkler-controlled area. The batteries can and will start the fire but only vent reactive materials for a brief period. The chance of water actually coming in contact with elemental lithium is very remote. The water will cool most batteries in close proximity to the fire and also will prevent secondary fires as a result of the battery fire. Water should not be used on very large lithium batteries (above 1000 Ah per cell) but these batteries comprise much less than 1% of the lithium battery population and are only used in military and government applications.
ENVIRONMENTAL CONCERNS OF RECYCLING LITHIUM BATTERIES All batteries should be recycled. Lithium batteries are no exception. Even when discharged, the batteries contain some form of lithium, organic solvents, and other chemicals most of which are toxic. When not fully discharged, the batteries have the potential to start fires. Aside from the known environmental concerns of today, it is not unlikely that in the future new environmental requirements or concerns may evolve from the disposal of batteries. In one eastern block country there is a huge problem with lead acid batteries contaminating ground water. One middle eastern country had a landfill f'tre that burned out of control for many days due to lithium batteries. In North America several lithium-recycling facilities have been shut down for environmental reasons. The only sure solution is appropriate recycling. Everything in the battery when new is still contained in it when completely discharged. Incineration, pyrometallurgical and hydrolysis methods eliminate reactivity but in many situations ultimately generate a hazardous waste. This may be wastewater, sludge, bag house waste, or ash. Prior to the processing of any lithium battery for recycling, the battery's material safety data sheet should be reviewed, and, if necessary, a complete analysis should be performed to determine the waste products. Components and chemicals are unique to each manufacturer and not each type of lithium battery. Many are similar but none are identical. Compounds that can cause serious concern if overlooked include chrome, arsenic, fluorine, mercury, organic solvents, asbestos, lithium, and others. At the end of this chapter are two typical battery analyses performed by Toxco Inc., exemplifying the
273 in-depth planning which must occur prior to receiving batteries for recycling. A similar analysis of the anticipated reactions has been developed for each lithium battery type.
So, if one is trying to select a lithium battery recycling facility, what does he look for to make sure the facility is in compliance with environmental requirements? It should have: the required approvals/permits from the designated authority; air discharge permits (if there is any form of air emission), and water discharge permits (if there is any effluent being released). If a recycler states that a facility permit is not necessary he should be able to provide proof of such, in writing, from the competent environmental authority. If one plans on processing larger volumes or extremely hazardous systems the best method of evaluation is a site visit to review the facility and environmental permits. A typical visual audit should include: 1) A review of environmental approvals and permits. 2) 3) 4) 5) 6) 7)
An inspection of the general cleanliness and housekeeping of the facility. A review of the receiving log and hazardous waste manifest log (if applicable), A review of personnel training and qualifications. A review of emergency accident/incident plans. A review of the background and facility history. A review of the corporate structure.
274 SORTING, PACKAGING, STORAGE, AND TRANSPORTING OF LITHIUM BATTERIES FOR RECYCLING Sorting, packaging, storage, and transporting of lithium batteries is discussed in detail since the success of all battery waste management facilities can be quickly affected by these practices.
These processes seem trivial to the actual recycling
methodologies but they are not. The liabilities, safety concerns, and physical damage can be very great if certain steps are not strictly adhered to. authors
opinions and interpretations.
The following are the
Governmental requirements
should be
investigated for the packaging and transportation in your area for your specific needs. There is no automatic mechanism that can sort the various types of lithium batteries. There are expensive automated systems that can sort lithium from nickel, alkaline, etc.
As a result, lithium types must be either sorted by the user or at the
processing facility. This is usually a very tedious and time-consuming process. This process is necessary since some lithium systems can and will contaminate processes. Several types and sizes of lithium batteries and other also have the potential to react violently. If not properly sorted, facilities, personnel, and equipment can be placed at high risk. Improper sorting can be extremely costly at a minimum. Packaging is probably the most overlooked cause of fire or incident. The batteries must be packaged according to strict requirements. The cells or terminals must be insulated with a nonconductive material to prevent short-circuiting against each other or against the sides of metal packaging. The batteries are then placed into an approved metal drum, wooden box, fiberboard box or other approved packaging group II container. The batteries must also be suitably cushioned to reduce vibration and shock during transport. The cushioning recommended is absorbent vermiculite. The inside of the packaging should be lined with a heavy plastic/polypropylene liner. The outside of the package should be labeled with a "Miscellaneous" Class 9 label. Leaking or vented cells must be packaged separately to prevent spills. The transport of lithium batteries varies from country to country.
In most
countries the batteries must be shipped as a hazardous waste UN3091. Only transport companies approved and permitted are allowed to transport hazardous waste and the waste must be labeled and manifested as hazardous waste.
There are exceptions
depending on the type of battery and the quantity of lithium contained within the
275 battery.
In the US several types of common household have been classified as
Universal Waste.
The Universal Waste rule allows the batteries to be shipped via
common carrier using a standard bill of lading. With the development of the lithium ion battery the transport rules are being modified or at least reviewed.
The current
argument is that lithium ion batteries do not have the same characteristics of reactivity
as the lithium primaries of earlier years. Authors note: It is the belief of the authors that the secondary lithium batteries should have been named "light metal" vs. "lithium" rechargeable. They have been scrutinized regarding safety when in fact they do not exhibit the same violent properties of their primary lithium cousins. As the newer lithium rechargeable batteries are evaluated and worst case scenarios are reviewed this fact will be proven and incorporated into transport requirements (hopefully soon). Requirements for the transport between countries involves the import and export authorizations of the environmental agencies of the respective countries involved. The storage requirements for lithium batteries are very similar to those of other batteries. They should be kept out of direct sunlight or high heat. They should be kept covered and clearly marked. In a recycling environment safeguards must be taken to reduce the risk of fire. All combustible material that is not essential should be removed from the area. Batteries should not be stored near explosives, flammable liquids or other non-compatible materials. The storage area should be made of metal or concrete
276 and all materials in the storage area such as insulation, roofing etc. should be reviewed and replaced with a non-flammable substitute. For many years the storage of lithium batteries was considered to be the same as for lithium metal. Sprinkler-type water fire suppression systems were not recommended.
Through experience it is known that
although there is lithium metal in many batteries, this does not cause the most fire damage. In most cases it is the combustible packaging or building materials that cause the majority of battery-related fire damage. For this reason it is recommended that the storage (and processing area) be controlled with sprinklers. Most batteries are small and vent quickly. They also are contained in metal outer battery eases. The reaction from water with a small amount of lithium is considered negligible compared to secondary fire damage. The water will eliminate secondary fires in storage and will act to cool the cases of other batteries within the immediate area. An example of the ideal storage area (used by Toxco Inc as well as many facets of the military) is seen below. This structure is made completely of poured concrete and has an earthen covered roof. For extremely large volumes of batteries another good idea is to store batteries in several such areas vs. storing in one large area. This prevents catastrophic incidents. The areas should also be away from processing equipment and located in a remote site away from personnel.
277 LITHIUM BATTERY RECYCLING TECHNOLOGIES In the recent past most lithium batteries were either put into a landfill or incinerated. Many of the larger lithium primary systems had no known method of disposal, much less recycling. The older large primary lithium batteries were, many times, so reactive that open detonation was used as an effective disposal method. The recycling technologies are only now being fully developed.
The
marketability of the components and the labor dollars invested to process the batteries are the driving considerations. Many research oriented agencies have proposed recycling methodologies which consider the battery chemicals as simply chemicals. Usually the battery characteristics are either overlooked completely or given inadequate planning. The neutralization of chemicals is the primary focus and either economics or safety is limited (at best). For these reasons many lithium battery recycling operations have started but most could not sustain either economic or physical losses. Some of the secondary lithium cells produced today contain cobalt compounds. Cobalt is a valuable metal openly traded for $10-$15 per pound on the open market. At this price, cobalt recovery is the primary goal of several recycling facilities that only accept lithium ion batteries. The authors fear that as other cheaper materials are found, many of these types of facilities may lose their economic justification. Currently, there is only one company in the world that has a long history of recycling all types and sizes of lithium batteries. There are two common types of lithium battery recycling. One type involves processing smaller primary lithium and lithium ion cells in an existing or modified pyrometallurgical processes.
Batteries are fed into an electric arc furnace or metal
smelting type operation. A facility of this type may accept many types of metal wastes and simply blend in batteries. In a pyrometallurgical process electrolytes, paper, plastics, and most other non metal components are burned off and the combustion products are captured in fume scrubbers, bag houses, and other pollution control devices. The primary goal of the pyrometallurgical recycling facility is the recovery of cobalt, ferrous, and some non-ferrous metals. The final product will usually be an ingot containing a mixture of metals. This ingot, free of many battery impurities, is usually sold to downstream secondary metal smelters who specialize in the refining and separation of unique metals. The advantages of a pyrometallurgical process are:
278 1) It is very economical especially when batteries are blended with other waste streams. Recycling costs are similar to incineration costs. 2) Flammable electrolytes pose no threat and may actually add to the efficiency of the process by supplementing the fuel source. 3) Some marketable metal, cobalt, and/or electricity are usually gained from the process. The disadvantages of this type of facility include: 1) The process produces large volumes of ash and air emissions similar to any large smelting operation. 2) The process operates only with the input of large amounts of fuel or electricity. 3) Items not recycled include aluminum (which will be oxidized), lithium, organic electrolytes, carbon, paper, and plastics. 4) Some of the waste products from the process must be disposed of as hazardous waste. 5) The process is not suitable for many primary systems due to the corrosive characteristics of the electrolyte/cathode as well as the reactivity of the battery. Facilities that do not fall into the pyrometallurgical category involve wet chemistry processes. Only two such processes are known and only one has processed high volumes of all types of lithium batteries. These processes generally produce cleaner recycled products, less waste from the process, and are dedicated strictly to processing lithium batteries. Advantages of this type of process are (these advantages have been verified only for the Toxco Inc process since little is known about a developing european wet chemistry process): 1) Recycling of more materials (lithium, aluminum, plastics, and electrolyte solutions) is possible since combustion of the battery is not part of the process. 2) There are negligible air emissions from the process. 3) There is no hazardous waste generated from the process. 4) The process can be used for all types and sizes of lithium batteries. The disadvantages to this process are: 1) Large volumes of chemicals must be handled by properly trained personnel.
279 2) Special batch processing is necessary for some types of batteries or other lithium wastes.
THE TOXCO'S B A C K G R O U N D AND PROCESSING M E T H O D
Toxco, a Southern California environmental firm, developed the most successful lithium recycling processing technique for all lithium batteries regardless of size or type. The process was developed and brought to commercial use in 1992 to meet the need for lithium battery recycling in military systems. It has been strongly improved over the years and has resulted in many U.S. patents. The essence of the processes is the lowering of the reactivity by reducing the temperature of the batteries. Typical chemical reaction rates are halved for every 10~ C (17 ~
drop in temperature. So lowering the batteries to 15~ C reduces the reactivity in
half. Further lowering to 5 ~
reduces the reactivity to 88of its original reactivity.
Placing the batteries in liquid argon or liquid nitrogen reduces the reactivity to less than 1/250,000th of their room temperature reactivity. At these temperatures the batteries are close to inert and can be safely handled regardless of their specific chemistry. Once frozen the batteries are mechanically reduced in size either by shearing, cutting, or shredding. At this point the battery materials are basically divided into three paths: the soluble components including virtually all the lithium possible pass into the bath; the insoluble constituents float, sink, or remain in suspension. Those constituents that sink are primarily recoverable metals. Those that float or remain in suspension are largely waste such as fiberglass, paper, carbon, etc. with no residual value. The dissolved material is then processed through a series of wet chemistry baths and filters to yield lithium carbonate which is a basic building block compound for the lithium industry. Cobalt is recovered in a similar manner and is sold with the lithium carbonate and scrap metal on the open market. The overall process provides an effective technique for recycling lithium batteries. As time passes, if the materials within the batteries can be standardized, there may be opportunities for an even greater percentage of recyclable materials possibly to include the plastic casing or the electrolyte. It should be noted that recovering a useable form of energy from the electrolyte is currently very optimistic. Recovering battery grade electrolyte is currently considered neither cost effective nor efficient. The objectives of the Toxco process were to:
280 1) Recycle all types of spent lithium batteries regardless of size; 2) Recover marketable lithium and other materials such as nickel, case metals (both ferrous and non ferrous), cobalt, and other valuable components in the batteries; 3) Provide an environmentally sound and legal recycling method thus protecting future generations; 4) Provide a safe disposition for the batteries; and, 5) Generate positive revenue for the company that would sustain growth and continued operation. These requirements have all been met. When the company began, acquiring the necessary environmental approvals and permits for a site using a brand new method to recycle a potentially explosive material was quite a challenge. After failing several times to obtain permits in 20 different U.S. states in 1992, Toxco obtained a temporary permit from the Province of British Columbia in Canada. This initial permit was conditional on the success of the methodology. Obviously, the process was a success and the permit was soon made permanent. The U.S. EnvironmentalProtection Agency and Department of Defense, the Canadian Ministry of the Environment, and similar groups around the world currently approve of the facility. There is no hazardous waste generated when lithium batteries are recycled at Toxco Inc. There is no municipal sewer system in the processing area and air emissions are collected via a direct-capture-system over each of the reaction areas. These fumes are processed through three air filters connected in series; the first is a wet bed fume scrubber which removes particulate material, the second is a traveling bed filter to further remove particulate material, and the third treats the emissions chemically. Each year Toxco is required to hire an outside environmental audit firm to test the emissions for conformance with their permit. The 1999 results are presented in Table 1. As one can see the emissions are quite minor in comparison to the allowable limits. The original Toxco facility near Trail, British Columbia began as a 33,000 square foot warehouse on 11 acres of land. Only 15,000 square feet was used as battery processing and the rest remained storage space. This facility has since grown to over 40,000 square feet of processing area dedicated to lithium battery recycling. A second Toxco facility has also been set up in Baltimore (Ohio) and a third is planned in the near future.
281
282
Table 1: Average 1999 Toxco Emissions Data Constituent
Allowable Limits
Li/SO2
Li/SOC12
Li/Cobaltite
MK-50
mg/m 3
Batteries
Batteries
Batteries
Torpedo
50
10.1
Boilers Particulate FI*
1.59
<0.05
SO2,
50.0
1
H2S*
0.2
0.015
HCI*
35
-
NH3,
75.0
5.04
Cd**
8
0.31
Cr**
13
Li**
1500
3.4
7.0
10.5 <0.05
-
-
0.5
-
-
0.039
-
-
2.9
-
-
-
-
0.98
-
0.3
0.3
1.9
8
8
3
41.2
79.8
1.6
3.0
S**
12,000
350
1200
<100
<100
Zn**
2,900
15.0
22.8
16.6
39.9
Opacity(%)
20
0
0
0
0
*mg/m 3
**gg/m 3
T W O OF T O X C O ' S T Y P I C A L C H E M I C A L ANALYSES *
I. Lithium Sulfur Dioxide Battery Analysis One of the most common lithium primary battery chemistry is lithium sulfur dioxide. It is lightweight and is used in a wide range of communications devices. The lithium sulfur dioxide battery provides power over a wide temperature range (-20 to +140 ~ F) and has rather constant output until depleted. The basic chemical reactions for these lithium sulfur dioxide battery packs are shown below. (Samuel C. Levy while at the Sandia National Laboratories under a grant from the U. S. Department of Energy developed this analysis). *The following analyses and conclusions are applicable to the Toxco process only and should not be applied to other recycling processes without careful examination by a qualified professional.
283
1.1. Battery Constituents The BA5590 consists of 10 lithium sulfur dioxide (Li/SO2) 'D' cells wired in a cardboard container which also contains diodes, electrical and thermal fuses, a connector, and a resistor with a manual switch to fully discharge the battery prior to disposal. When fresh, each battery contains the following materials: Chemical Lithium metal Sulfur dioxide Acetonitrile Lithium bromide Carbon black
Weight (~ams) 23.5 242 58 18 --50
Other materials within the battery include the nickel-plated cold rolled steel cans,-500 g, plus small amounts of copper, nickel, aluminum, molybdenum, Teflon, polypropylene and glass. During discharge, the lithium reacts with the sulfur dioxide to form lithium dithionite via the following reactions:
284 Anode:
2Li ~ 2Li + + 2e-
Cathode:
2SOz+2e- ~ 5204 "2
Cell:
2Li + 2SO2 ~ Li~S204
Since this cell design has a slight excess of SO2, all of the lithium will be reacted when the battery is fully discharged. Therefore, contents of a discharged cell should be: Chemical
Weight (grams)
Lithium Dithionite
-~240
Sulfur dioxide
-25
Acetonitrile
58
Lithium bromide
18
Carbon black
-50
The inert materials of construction will be the same as in a fresh battery. The actual batteries that arrive at the Lithium Recycling Center will be somewhere between the two levels of constituents shown above. 1.2. Recycling Process The following chemical reactions are likely to occur when the batteries are shredded and immersed in an alkaline water bath. 9
Lithium dithionite will undergo alkaline hydrolysis: 3Li2S204 + 6LiOH ~ 5Li2SO3 + Li2S + 3H20
f.w.
3(142.01) 6(23.94) 426.03
143.64
5(93.94) 469.70
45.94 3(18) 45.94 54
A fully discharged battery will have 240 g of lithium dithionite; therefore approximately: 469.70 = x 426.03
240
x = 264.60 g Li2SO3 per battery
285 and 45.94 = x
x = 25.88 g Li2S per battery
426.03 240 9
will be formed in the alkaline bath.
Sulfur dioxide is highly soluble in water forming sulfurous acid H2SO3.
S02 + H20 ----~H2SO3 64.06 18 82.06
f.w. Therefore, 82.06
=
x = 32.03 g H2SO3 per battery will be present in the water bath.
x
64.02 25
(CH3CN)is highly soluble in water.
9
Acetonitrile
9
Lithium bromide is extremely soluble in water. The other materials will be unreactive with, and insoluble in, the alkaline aqueous solution.
The above discussion assumes a normal discharge mode for the BA5590 batteries. It also assumes that the intemal resistor has been engaged by the manual switch to completely discharge all the units. There may be instances, however, of defective cells within a battery or exposure of a battery to abusive conditions that result in lithium metal remaining in the battery after discharge. In these infrequent cases the lithium may catalyze the polymerization of acetonitrile with the concomitant formation of lithium cyanide. Trace amounts of heterocylic organic nitrogen compounds have also been identified in these cells, e.g., dimethylquinoline, 4-amino-2,6dimethylpyrimidine, 2-amino-5-phenylpyrazine, and 6-phenyl-2-pyridone. Batteries exposed to certain abusive conditions may experience thermal runaway -
a series of coupled exothermic chemical reactions involving metallic lithium, lithium
dithionite and possibly sulfur, resulting in the formation of sulfides. At the elevated temperatures resulting from these reactions, these products may further react with the carbon in the cathode to form carbon dioxide (CO2) and carbon disulfide (CSz). Carbon
286 dioxide is not an environmental concern. Although carbon disulfide is poisonous, it is soluble in water to the extent of ~0.1 g/100 g H20 at 20~
and ~0.26 g ~ 2 0 at 0 ~
Thus, if any is present in the batteries it will be small enough in quantity that it should all end up in solution. 1.3. Air Emissions Recycling of lithium sulfur dioxide batteries which have been discharged normally should not result in any toxic air emissions since all of the products are either soluble in the alkaline quench or remain as unreacted solids. Recycling of batteries that have been exposed to certain abusive conditions may evolve some gas during the quenching operation. These gasses may include hydrogen, from the reaction of any remaining lithium with the water, and carbon dioxide. These gasses are nontoxic and environmentally benign. Although hydrogen is flammable and can be explosive when mixed with air, this should not present a problem under the conditions to be found during this process. Since the number of batteries exposed to abusive conditions is not known, it is impossible to determine the amount of gases generated. 1.4. Chemical Reactions in the Water Bath The lithium sulfite and lithium sulfide formed by the hydrolysis of lithium dithionite will react further in the water bath. 9
The sulfide will be readily oxidized to sulfate: SO3 "2 + 02 + H 2 0 --> SO4 "2 +
9
And the sulfide oxidized to thiosulfate: S2 + 202 + H20 --~ $203 -2 + 2OH-
2OH-
Both products will remain in solution and should not pose a health or environmental threat.
If ingested, sulfate and thiosulfate have a cathartic effect on
humans. Thiosulfate is also used as an antidote to cyanide poisoning. The dissolved sulfur dioxide will react in alkaline solution to form either lithium bisulfite LiHSO3 or lithium sulfite Li2SO3, both of which will be readily oxidized to sulfate.
287 Acetonitrile is a toxic material, the lowest published toxic dose for humans being 570 mg/kg. A slow kinetic process may eventually convert the acetonitrile to acetic acid. Lithium bromide will remain in solution.
Large doses may cause central
nervous system depression in humans as well as disturbed blood electrolyte balance. The products formed in defective or abused batteries will most likely occur in small quantities and remain in solution. Unless there are extenuating circumstances, e.g., a large number of abused batteries in one lot, the environmental risks should be minimal. Concentrations of the products formed in the water bath cannot be calculated since neither the volume nor the numbers of batteries to be quenched at any one time are known.
2. Lithium Manganese Dioxide Battery Analysis The Li/MnO2 cell was one of the first lithium/solid cathode systems to be used commercially. 2.1. Battery_ Constituents The model 2/3A battery is a cylindrically shaped bobbin-type battery, 1.6 cm in diameter and 5 cm long. The battery is a solid cathode type with a nominal 3.0 volt rating. It has low to moderate power capability. The battery is not pressurized and doesn't need a hermetic seal. It is generally used for portable electronic equipment, photographic equipment, watches, calculators, etc. obtained. The cathode is manganese dioxide pressed onto nickel wire mesh grid.
Lifetimes of up to 10 years are
(MnO2) mixed
with carbon and a binder
The anode is a sheet of lithium metal.
The
electrolyte is a mixture of propylene carbonate, 1,2 dimethoxyethane, and lithium trifluoromethane sulphonate.
These layers are wound in a "jelly-roll" with a
polypropylene separator and placed in a stainless steel container. As manufactured, each battery contains the following materials:
288 Material
Weight (grams)
Lithium metal
0.5
Manganese Dioxide
8.2
Carbon, binder, screen
1.5
Electrolyte 1,2 dimethoxyethane
1.2 (est.)
propylene carbonate
0.4 (est.)
lithium trifluoromethane sulphonate
0.2 (est.)
Metal and plastics
4.2
The total weight of the cell is 16.2g. These cells are frequently configured as a 6V twin pack. The twin pack is a plastic shell. The cell reactions for this system are:
Cathode reaction:
L i - - - > Li+ + e MnIVO2 + Li ++ e _ m > (Li+)MnInO2
Total cell reaction:
Li + MnWOz ~-----> (Li+)Mnrnoz
Anode reaction:
2.2. Recycling Process During shredding, there may be some fumes formed if lithium metal remaining in the cells is ignited. These will be lithium oxide fumes. Some fine particulates (dust) may be carried in the ventilation stream. However, the components of the cells are nonvolatile solids or low-volatile liquids and are not expected to produce significant emissions during shredding. The following reactions are likely to occur when the batteries are shredded and immersed in an alkaline water bath. Un-reacted lithium metal will react with the water,
fw
2Li + 2(6.94)
2H20--=> 2(18.0)
2LiOH + 2(23.94)
H2 2.0
13.88
36.0
47.88
2.0
289 The amount of hydrogen produced will depend on the state of discharge of the battery. The hydrogen formed will be ignited by lithium burning on the surface of the treatment solution to form water. MnO2 is insoluble in caustic solution and will precipitate. The discharge product Li MnO2 will react in the alkaline bath to form lithium hydroxide and manganic oxyhydroxide: 2LiMnO2 2(93.87) 187.74
+
2H20 _ m > 2LiOH + 2(18.0) 2(23.94) 36.0 47.88
2Mn(OH)O 2(87.94) 175.88
The quantity of LiMn02 present will be governed by the degree of discharge of the battery. Mn(OH)O is insoluble in water and is stable to disproportionation. The same products will be formed in the reaction bath whether the batteries are charged or discharged except for the relative proportions of MnO2 and Mn(OH)O. The Mn(OH)O will only be formed from discharged batteries. Propylene carbonate will hydrolyze in alkaline solution to propylene glycol and lithium carbonate: C2H6CO3 +
2LiOH ~ >
C3H6(OH)2
102.09 102.09
2(23.94) 47.88
76.11 76.11
+
Li,CO3
73.89 73.89
The propylene glycol is totally miscible with water. The lithium carbonate is insoluble and will precipitate with other lithium salts. 1,2-dimethoxyethane is soluble in water but is essentially non-reactive. As the concentration of the 1,2-dimethoxyethane builds up in the reaction tank solution, some may start to volatize. However, it is expected that any that does volatize will be ignited by the lithium burning on the surface. The combustion products will be carbon dioxide
290 and water. The carbon dioxide will be absorbed in the caustic scrubber solution to form lithium carbonate which will precipitate with other lithium salts. 2C2H4(OCH3)2 + 1102 ~ >
8CO2 + 10H20
Lithium trifluoromethane sulphonate is a very stable and soluble salt. It will dissolve in the reaction tank solution until its solubility limit is reached, then precipitate with the other lithium salts. 2.3. Air Emissions The shredding and treatment of Li/MnO2 batteries will result in minimal air emissions. Some Li20 may form from metallic lithium igniting on the surface of the reaction tank solution or in the shredder. Some MnO2 may be carried in the exhaust stream as a dust. pressure.
Propylene carbonate is a high boiling liquid with a low vapour
Any vapour that does form will be readily absorbed in the air emission
scrubbers. 1,2-dimethoxythane is a moderately volatile liquid. Any vapour that does form will be captured in the scrubbers and retumed to the reaction tank.
Any that
volatilizes from the reaction tank will be ignited along with the hydrogen given off from the lithium reaction. It is expected that only minor quantities of sub-micron sized fume will pass through the air emission scrubbers. No gases are expected.
2.4. Biological Effects The components and reaction by-products of Li/MnOz batteries have generally low toxicities. 9
Lithium metal is a hazard because of its violent reaction with water. No
toxicological data is available. Exposure can cause severe bum. 9
Lithium oxide (LizO) is corrosive. Exposure or inhalation causes severe
irritation or bums. No toxicological data is available.
291 9 Lithium triofluoromethane sulphonate has low toxicity but may cause mild skin or upper respiratory irritation. 9
Manganese dioxide and manganic oxyhydroxide have low toxicity but may
cause respiratory irritation. 9
1,2-dimethoxythane has low toxicity but may cause dizziness, difficult
breathing or nausea if handled. Skin contact may cause irritation. Propylene carbonate is non-toxic but may cause irritation with prolonged contact. 9
Propylene glycol is non-toxic and has been used to replace glycerol in food
products and cosmetics. Normal safe-handling procedures should prevent any risk to workers dealing with the solids or solutions. Air emissions will be controlled through the ventilation system. No environmental risks are expected.
CONCLUSION Lithium batteries have developed over the past 30 years to become one of the most promising new battery systems. Primary and secondary lithium batteries have gained widespread use in communications, portable tools, military devices, and industry. The next five to ten years will continue to show heavy lithium battery growth in standard uses as well as development into new applications such as electric and hybrid electric vehicles. Although lithium batteries have been shown to be safe in many applications, there are many conditions that will increase the hazards.
These hazards can be
overcome during recycling by any commercial facility through diligent continuous review of handling and processing. The successful facility must not allow recycling, storage, handling, and transportation procedures to become routine. These procedures must be continually revised and checked to verify accuracy and efficiency.
Once a
recycling facility considers their processes as perfect and without flaw, an accident or incident becomes possible.
292 Each type of lithium battery requires slightly different processing/handling. The specific reasons for differing processes may be due to the environmental concems of the materials within the batteries, the size of the batteries, the reactivity of the batteries, safety concerns, differing states of charge of the batteries, and/or different materials to be recovered. An analysis of each battery type should be performed and the results should be reviewed for chemical compatibility of the process, flammability, toxicity, reactivity, safety, and for environmental concerns. The recycling of lithium batteries regardless of size or chemistry is a complicated process. There have been many incidents involving these high-energy batteries and the simplest most obscure aspects of the procedure usually cause these incidents. Toxco Inc., to date, is one of the oldest and most successful lithium battery recycling companies in the world. Although many companies recycle some types or sizes of lithium batteries recovering one or two materials from the battery, Toxco Inc.
293 has the only process in the world that recovers case metals, lithium, and cobalt (if present) from any type or size of primary or secondary lithium battery.
Recycling
lithium and all other batteries is quickly becoming a necessity. As the natural resources of the Earth become scarcer, reutilization of materials will be required. As landfills are used and space becomes limited conservation of this space is required.
As ground
water, soil, and the air become more contaminated alternatives to landfills and incinerators must be developed.
Our sons/daughters and their sons/daughters will
appreciate the progress our generation made to overcome recycling obstacles in an effort to safeguard their future well being.
This Page Intentionally Left Blank
Used Battery Collection and Recycling G. Pistoia, J.-P. Wiaux and S.P. Wolsky (Editors) 9 2001 Elsevier Science B.V. All rights reserved.
RECYCLING
OF ELECTRIC
295
VEHICLE BATTERIES
Rudolph G. Jungst Lithium Battery R&D Department, Sandia National Laboratories, Albuquerque, NM, 87185-0613, U.S.A.
INTRODUCTION Electric vehicles (EVs) first appeared in the late 19th century at about the same time that internal combustion (IC) engine-powered vehicles were introduced. Electric motor and steam technologies were actually more advanced and more reliable than the early gasoline engine [1 ]. William Morrison of Des Moines, Iowa, built the first successful electric car produced in America in 1890 [2], and by 1900, 38 percent of U.S. automobiles were electric. Almost 34,000 electric cars were registered in the U.S. in 1912, the year of their peak acceptance [3]. Quiet operation, reliability, and easy starting and operation were their major selling points. Nevertheless, the limited range and speed of electfics combined with the lower purchase price and low fuel cost for cars powered by gasoline led to a rapid decline in use of electric cars, particularly as the IC engine was improved. By the 1930s, gasoline-powered vehicles dominated the market. With the oil crisis of the 1970s, interest in altemative fuels for vehicles, including electricity, experienced resurgence and serious development efforts resumed. However, these efforts were difficult to sustain during a period of fluctuating oil prices, and only small numbers of EVs that were conversions of IC-powered cars were produced. In the early 1990s, regulatory requirements emerged for the first time as a major factor with the establishment of the California Zero Emission Vehicle (ZEV) initiative. The United States Advanced Battery Consortium (USABC) and more recently the Partnership for a New Generation of Vehicles (PNGV) were formed to address technical challenges to the commercialization of viable electric and hybrid electric vehicle (HEV) power sources and systems. The active participants in these groups have included the major U.S. automobile manufacturers, the U.S. Department of Energy (DOE), and the Electric Power Research Institute (EPRI). As a result of these and other efforts, small numbers of advanced, purpose-built EVs have been offered to consumers in certain areas (e.g.,
296 under manufacturer memoranda of agreement in California). The limited range of pure EVs, particularly with lead-acid batteries (the only option available at first), and their high
capital
cost
continue
to
be
the
major
impediments
to
wide-scale
commercialization. Therefore, much research has been and continues to be directed toward advanced batteries, fuel cells, and other energy storage devices (capacitors, flywheels, etc.), as well as hybrid power plant designs. Advanced batteries include those technologies that were not commercialized by about 1990 (e.g., nickel/metal hydride, lithium-ion). The U.S. DOE, as a major participant in the USABC and PNGV programs, has been working to address infrastructure barriers to the commercial acceptance of EVs since the early 1990s. As an outgrowth of a workshop held in 1991 on sodium-beta batteries [4], a Working Group was established to identify and recommend solutions to commercialization barriers in the areas of battery shipping, battery reclamation and recycling, and in-vehicle safety [5]. The Advanced Battery Readiness Ad Hoc Working Group, as it is now known, continues to provide a forum for discussion of these issues. The purpose of this chapter is to review the current state of recycling technologies for EV and HEV battery power sources. We will use the term recycling to include materials that are reclaimed for use in different products as well as the materials that are reclaimed and transformed into new batteries. A practical method for recycling batteries and other energy storage components from EVs is viewed as essential for the successful implementation of this transportation technology. Toxic materials are found in many battery technologies (e.g., lead, cadmium, nickel). Disposal of EV batteries may be allowable by regulations in some cases, but is likely to be costly and detracts from the environmental benefits of a zero-emission vehicle. The battery is a major cost component for EVs, and therefore disposal is doubly expensive, especially if the waste contains valuable materials. Recycling provides an opportunity to reduce life cycle costs through recovery of high-value materials and avoidance of the cost of hazardous waste disposal. Most developers of power sources for EVs therefore have a goal of recycling as much material as possible at the end of life. Less demanding, secondary uses for the energy storage device may extend its term of operation, or in some cases refurbishment could also be considered. Eventually, however, the battery must be processed in such a way that all the valuable and/or hazardous components and materials can be recycled.
297 E L E C T R I C VEHICLE/HYBRID ELECTRIC VEHICLE BATTERIES EVs depend entirely on the battery system for their power, while HEVs combine a battery system with some other power source (e.g., internal combustion engine, fuel cell) in order to maximize efficiency and increase range. Batteries for EVs and HEVs are much different in scale than those commonly used in portable consumer electronics such as cell phones or laptop computers. EV battery packs typically generate 300 to 350 volts, with 10 to 30 kWh of stored energy for EVs and 1 to 5 kWh for HEV applications. The power to energy ratio is 2 to 4 times greater for the HEV-battery design than that for EVs. The batteries are usually made up of multi-cell modules connected in series/parallel arrangements, although the number of individual cells, battery mass, and battery volume vary somewhat with the design and the type of battery chemistry used. Relatively few consumers would be expected to perform their own battery maintenance, and almost none could replace one of these large batteries themselves. The problem of handling is compounded by the fact that large numbers of EVs and HEVs may come into widespread use. Nominal characteristics for several recent types of EV/HEV battery packs and their associated vehicles are shown in Table 1. Originally, most of the battery packs were of the valve-regulated lead-acid (VRLA) type, which suffers from the disadvantage of a relatively low specific energy (Wh/kg). VRLA-powered vehicles therefore usually exhibit more limited range and payload capacity than those using advanced battery systems. As shown in Table 1, more than a 40% improvement in battery pack energy can be realized by substituting a nickel/metal hydride (Ni/MH) battery for VRLA in the same vehicle. This can be achieved with no increase in battery weight or volume. For most four-passenger family size EVs, the battery weighs about 500 kg and occupies a 200-L volume. HEV batteries only need to be about 10 to 20% of this size and weight because of their lower energy storage needs and the exclusive use of advanced battery chemistries. The configuration of the battery also varies widely with the vehicle design. In some instances (e.g., the EV 1 battery shown in Figure 1), the battery fits in a T-shaped tunnel within the vehicle. In other vehicles (trucks and vans), a fiat battery pack is placed beneath the floor so as not to take up so much of the internal cargo space. Typical configurations of some of the current or proposed battery packs are shown in Figures 1 through 7.
Table 1 Typical EV/HEV Battery Pack Characteristics
298
Vehicle
Battery Type
EVMEV
Pack Power (kW) 83 88 90 83 88 90
Pack Pack Pack Modules/ Calculated Total Pack Energy Voltage Capacity Pack Pack Mass (kg) (Ah) Volume (L) (kWh) (V) GM EV1 26 16.5 VRLA EV 473 205 53 312 GM EV1 546 205 26 60 312 18.7 VRLA EV GM EV1 468 193 26 77 343 26.4 NiMH EV Chevrolet S 10 473 205 26 53 312 16.5 VRLA EV Chevrolet S10 546 205 26 60 312 18.7 VRLA EV Chevrolet S 10 26 27.4 468 193 85 343 NiMH EV 18.7 Ford Ranger 870 39 60 312 VRLA EV Ford Ranger 25 28.5 Ni/MH EV 485 95 300 Chrysler Epic 27 27.5 85 324 VRLA EV Chrysler Epic 30 31.2 Ni/MH EV 62 1 93 336 Mercedes A Class 1 30 370 104 289 Na/NiC12 EV 24 Toyota Ecom 43 144 77 28 288 8.4 Ni/MH EV 24 Toyota RAV4 90 449 189 288 28.3 Ni/MH EV 95 12 32.4 Nissan Altra 360 230 94 345 Li-ion EV 4 41 Nissan Hyper-Mini Li-ion 116 77 90 120 10.8 EV 21 Toyota Prius Gen 1 Ni/MH 44 40 1.8 HEV 15 6.5 288 Toyota Prius Gen 2 NUMH 22 38 274 1.8 HEV 25 39 6.8 GM Precept 45 90 60 28 12.5 350 4.4 NiMH HEV Li-Polymer HEV 43 GM Precept 81 70 7 10.4 350 3.6 Ni/MH Honda Insight HEV 20 0.9 12 22 7 6.5 144 NilMH = nickehetal hydride, VRLA = valve-regulated lead-acid, Na/NiC12= sodium/nickel chloride, Li-ion = lithium-ion, Li polymer = lithiumpolymer
299
Fig. 2. GM Ovonic Ni/MH Battery for the Chevrolet S10 Pickup Truck.
300
Fig. 3. Ford Ranger Truck Ni/MH Battery.
Fig.4. DaimlerChrysler Epic Minivan Advanced Lead-Acid Battery.
301
Fig. 6. Nissan Altra EV Li-lon Battery Module
302
Fig.7. Second Generation Toyota Prius Ni/MH Battery Pack.
The types of batteries predominantly in use at this point are lead-acid and Ni/MH, although a few lithium-ion (Li-ion) systems are starting to appear. As the number of HEVs increases in the near term, the number of Ni/MH systems is also expected to increase. It is the standard energy storage unit in the later models of the GM EV1. Nickel/metal hydride batteries are also used in Ford Ranger and DaimlerChrysler EPIC EVs and in the Toyota and Honda HEVs. However, a niche market for lead-acid systems is likely to remain for lower cost EVs used for commuting short distances. Lithium-ion batteries are used in the Nissan Altra EV, but their use has not expanded as significantly to date as has the N i g H battery system. Although Ni/MH systems appear to offer the best prospects for near-term implementation in spite of high costs, Li-ion or lithium-polymer may eventually provide better performance with a lower battery weight. This assumes questions regarding safety issues associated with the reactivity of lithium and life expectancy issues can be resolved satisfactorily. In the long term, lithium batteries may therefore replace Ni/MH as lithium battery costs are reduced and performance improves. Safer versions of the lithium battery such as lithium-polymer are also being developed and are already available in small cells. Other battery chemistries (e.g., soditma/nickel chloride (Na/NiC12), nickel/zinc (Ni/Zn)) may be found in small numbers, but will
303 probably not be dominant factors in the market over the next 5 to 10 years. Fuel cells are another type of power source that may find increased use in alternative-fuel vehicles in the future, but will not be commercially available in automobiles for several years. Growth of the EV market is a key factor that will determine which power sources are available for recycling over the next 10 to 15 years. The onset of the anticipated exponential growth in the number of EV/HEVs on the road has proved difficult to predict, and this has made developers and recyclers reluctant to invest in establishing dedicated recycling facilities. The changing mix of power sources over time could render a dedicated recycling process obsolete before a significant increase in the number of vehicles occurs. An approach that uses an existing recycling process that is not solely dependent on the EV battery waste stream has been the primary strategy used thus far. However, these processes are not always able to reclaim all of the valuable battery materials. Projections of the number of EVs that will be sold in the U.S. vary considerably depending on the source. An EV population in the U.S. of several hundred thousand has been predicted to occur within a few years ever since the mid-1990s [6]. In 1997, one estimate for 2005 totaled 320,000 vehicles, based on ZEV-mandated programs in California and other states [7]. More recent projections, however, estimate 50,000 EVs per year starting in 2005. This lower projection reflects vehicle estimates resulting from the California Memoranda of Agreement Program, as well as a court decision precluding other states from implementing ZEV programs more restrictive than that in California. Early in the year 2000, the actual EV population in California, the state with the most active ZEV program, was 2300 [8]. The total EV population in the U.S. was about 5,000 late in the year 2000 according to the Electric Vehicle Association of the Americas. This situation may begin to change soon because the ZEV program in place in California in late 2000 requires about 22,000 EVs to be offered for sale by 2003. In addition, the commercial introduction of HEVs by Toyota and Honda could add substantially to these numbers if they become popular. Honda increased the number of Insight vehicles that would be made available for sale in the year 2000 to 6500 based on strong early demand [9]. Clearly, however, an EV population of several hundred thousand in the U.S. is still years away and more time will elapse before the batteries in those vehicles reach end-of-life. Incentives to commit resources toward development of dedicated recycling facilities will therefore likely remain low for some time.
304 GENERAL RECYCLING ISSUES, AND DRIVERS
Economics and Planning Economics is an important consideration when designing a recycling process. Some generic constraints that determine whether recycling is economically viable have been discussed [5]. These include the ability of the market to absorb the large quantity of recycled material that could result in the long term assuming that it is not recycled directly into new batteries. Market size is likely to differ for each of the specific materials that can be recovered. Price collapse or possibly an inability to sell the reclaimed products at all could be the result if a limited market is flooded with recycled material. A fundamental precept of chemical process economics (the Exclusion Principle) states that high-priced materials tend to have limited markets, while high volume materials have low unit prices [ 10]. It is therefore unrealistic to expect to enter a large size market for a particular commodity and command a high unit price. Another general expectation is that the establishment of a new, large scale recycling process dedicated to a particular advanced battery chemistry will most likely take a long time. This is due to two factors: 1) the time required to obtain operating permits from the Environmental Protection Agency (EPA) for an unfamiliar process, and 2) the fact that financing will be difficult to obtain for such a project until there is an established waste stream. In fact, a recycling process that is capable of handling a variety of waste streams is much more likely to be implemented since the EV market and the types of power sources that will be used in EVs are relatively uncertain at this point.
Partnerships Because of the necessity for innovative approaches in the recycling arena, partnerships involving waste processors have begun to emerge. For example, Toxco, Inc., a major recycler of lithium batteries world wide, has formed an alliance with Kinsbursky Brothers, Inc., the largest non-lithium battery management firm in the U.S. By joining forces, battery and vehicle manufacturers can be offered a comprehensive and efficient battery management program through a single source. Automobile and recycling companies have also formed alliances. Because of its use of the Li-ion battery in its Altra EV, Nissan reviewed future recycling capacity for spent Li-ion batteries. The company formed a partnership with Toxco after finding that a significant lithium battery recycling capacity shortfall could be anticipated. Toxco would share a percentage of its long-range processing capacity with Nissan, and also
305 provide additional capacity in Califomia as larger quantities of Nissan EVs appear on the California highways. An additional benefit derived from the Nissan-Toxco agreement is that it has provided renewed enthusiasm for a lithium recycling facility in California. In 1992, it was difficult to obtain a permit for a lithium recycling facility in California because of strict solid and hazardous waste disposal regulations. However, the current regional director of the California Department of Toxic Substances Control has visited the Toxco facility in British Columbia (BC) and met with the BC Ministry of Environment regulators [17]. As a result of that review, a lithium battery recycling facility in California is now considered feasible.
Environment, Safety, and Health Another important consideration for recycling is the toxicity and reactivity of materials. Because EV batteries are large, heavy, operate at high voltages, and frequently contain toxic, corrosive, or reactive materials, health and safety issues must be considered when handling them and may present limits on how to recycle them as well. These issues are all manageable as long as careful planning is done in advance. Most battery maintenance will be performed by trained personnel while the system is in the vehicle, and replacement batteries will most likely only be available through auto dealers or specialty shops. The control provided by the need to use trained installers and the significant cost of the battery means that virtually all batteries will be returned for recycling at end-of-life. A training package to address accident scenarios, including a video, has been prepared for emergency response personnel [11]. This kind of safety information will become more available as the number and types of EVs proliferate. Chemical hazards broadly fall into two categories: 1) physical and health hazards from exposure to these materials during battery handling and dismantlement, and 2) environmental hazards from disposal. If these materials are considered hazardous waste because they are listed by the EPA or categorized as characteristic wastes, then they can only be disposed of in specially designated landfill facilities. Characteristic wastes are classes of materials that are identified as exhibiting leachability, flammability, and corrosivity/reactivity. This adds to the cost and could justify further expenditures to reclaim or recycle these materials even if they are not inherently valuable. An assessment of the health impacts from reclamation of automotive batteries was completed for the California EPA, and a report was issued in 1999 [12]. This study compares the relative impact of recycling nine different types of EV batteries in terms
306 of cancer, toxicity, and ecotoxicological potential. The methodology is semiquantitative and was based on the protocol developed by the Office of Environmental Health Hazard Assessment, a division of the California EPA. Table 2 shows the health and environmental impact score that was developed for each battery constituent. Antimony, arsenic, cadmium, lead, and nickel are the five materials with the highest scores (i.e., the most negative impacts). A health/hazard score for each battery type was then determined by multiplying the constituent score by the estimated amount of emissions to the air and a battery life factor in terms of grams per mile of battery pack usage. The scores were then totaled for each battery type and recycling process as described in Reference 12. These health~azard scores are primarily determined by the human health impacts.
A log-scale graph of the normalized
healtl~azard scores is shown in Figure 8 for different battery types and recycling processes. Generally, the healtl~azard score is highest for batteries containing significant amounts of materials with a high health impact or that are potentially emitted in large amounts by the recycling process. The advanced battery chemistries such as Ni/MH and Li-ion appear to offer improvement over conventional battery systems because they incorporate less hazardous materials and may use hydrometallurgical rather than pyrometallurgical or smelting processes for recycling. A closer examination of hazardous waste characteristics of battery materials does reveal differences between battery chemistries. The toxicity of conventional battery materials such as lead, antimony and cadmium are well known, and therefore they are usually recovered as much as possible rather than disposing of them. Strict emission controls are required to prevent their release into the air or water. The problems with advanced battery systems in this regard are not quite so severe, but there still may be reactive, corrosive, or toxic materials present that must be dealt with during the recycling process. Both Ni/MH and Li-ion batteries do contain hazardous materials. Nickel/metal hydride battery packs, of course, contain nickel, which is a suspected carcinogen in some forms. However, the only hazardous material in a Ni/MH battery, as defined by federal regulations, is the potassium hydroxide (KOH)-based electrolyte (corrosive). The only characteristic hazard of any consequence for the electrode materials in these batteries is toxicity. The hazard level is determined by a test called the toxicity characteristic
307
Table 2. Relative Health Impact of Major Battery Components Material
Health Impact Score
Material
Health Impact Score
Arsenic
65
Fluorine
22
Cadmium
57
Zinc
21
Lead
56
Aluminum
20
Antimony
51
Carbon Black
20
Nickel
45
Vanadium
18
Cobalt
35
Tin
13
Manganese
33
Sulfuric acid
11
Phosphorus
33
Sulfur
9
Copper
31
Iron
8
Chromium
30
Zirconium
7
Lithium
25
KOH
5
Chlorine
23
Titanium
4
Sodium
23
Plastic
3
Note: A higher number indicates a greater effect.
leaching procedure (TCLP) that measures the tendency of metals to leach from the waste under conditions that could be encountered at a landfill. TCLP tests on two different types of AB2 metal hydride alloys showed that the metals in the leachate were either unregulated or below EPA standard limits (chromium) [13]. In regions such as the State of California, however, stricter regulations are in place, and the batteries would be considered hazardous waste there because of the presence of a standard for nickel (20 mg/L). European Community (EC) standards for nickel (2.0 mg/L) are also exceeded. Similar results were found in a more recent measurement where only Ni and Zn, which have no EPA standards, were found in significant concentrations in the TCLP leachate from Ni/MH batteries [14]. Lithium-ion batteries also contain hazardous materials. While lithium intercalated in carbon is somewhat less reactive than lithium metal, it still does react with water to produce lithium hydroxide (LiOH) and hydrogen (H2). Moreover, cycled Li-ion cells could contain lithium metal plated on the surface of the anode if they have been
308
Fig. 8. Normalized Health/Hazard Scores for Various Battery Types and Recycling Processes. subjected to overcharge conditions. The hazard posed by the remainder of the Li-ion battery is mainly in the toxicity area and depends on the specific battery design. The Liion chemistry is not as mature as Ni/MH and several variations of the cathode and electrolyte could be found. Metal oxide cathode materials could contain cobalt, nickel, manganese or, more rarely vanadium. Mixed metal cathodes are becoming more common. Electrolytes are composed of fairly innocuous organic carbonates and a lithium salt. TCLP testing has been done on several types of lithium batteries, and the results show that they would not be considered hazardous waste by EPA standards [14,15].
EXISTING METHODS FOR EV BATTERY RECYCLING As part of a broad assessment of the general recyclability of automotive batteries done in the mid-1990s, a report on recycling technology was prepared for the California Environmental Protection Agency Air Resources Board [ 16]. Ten different EV battery technologies were ranked based on their performance and recyclability. The battery chemistries that were included in this study are presented in Table 3. Because the recycling capacity available for some of these batteries was minimal in 1995 and the
309 market for some of the materials that would be recovered was also too small and unstable to support the recycling effort alone, a mandatory deposit of $100 to $150 per battery was suggested. This figure was believed to be large enough to ensure return of the batteries to central collection sites, but not so large as to trigger theft or a battery black market.
Table 3. Battery Chemistries Included in Recycling Technology Assessment Lead-acid (all types)
Lithium/iron disulfide
Nickel/cadmium
Lithium-ion
Nickel/iron
Lithium-polymer
Nickel/metal hydride
Zinc (zinc-air, zinc/bromine)
Sodium/sulfur Sodium/nickel chloride
performance and recycling technology. The recycling attribute categories of technology, infrastructure, market conditions, and regulatory constraints were used to rank battery technologies and the associated weighting factors assigned to each specific attribute are shown in Table 4. Each battery was scored on a scale of one to five for each recyclingrelated attribute. A score of five indicates the best performance characteristics, and a one indicates the worst performance or characteristic. A total score was calculated by multiplying the individual score for each attribute by the weighting factor for that attribute, and then summing the products. A summary of the final recycling score received by each of the batteries included in the study is presented in Table 5. The higher scores indicate better recycling characteristics.
Lead-acid batteries received a high score by virtue of being a commercial product with an established recycling infrastructure. Nickel/metal hydride and nickel/cadmium are also widely available commercially and are routinely recycled. Zinc batteries are sold in large quantities and little or no hazardous waste and pollutants are produced by processing. Most of the battery technologies farther down the list are ranked lower because the batteries are not commercial products and recycling processes are not developed any further than a bench scale. In the case of sodium/sulfur batteries, the market outlook for recovered products is unfavorable.
310 Table 4. Recycling Attributes used to Rank Battery Technologies
Recycling Attribute
Weighting Factor
Ease of battery dismantling Fraction of output that is recyclable/reusable Fraction of output as hazardous waste Scale of existing technology Size of batteries currently handled Existing recycling facilities Existing collection infrastructure Distance to recycler Market for recycled product Value of product Disposal costs Hazardous material status Toxic metals content Difficulty in permitting new or expanded facilities Effect of air emissions on permitting
Conventional Batteries 9 Lead-acid (Pb-acid)
The lead-acid battery has been the rechargeable energy storage technology of choice since the earliest development of EVs because of its widespread availability, relatively low cost, and generally user friendly characteristics. Consequently, an infrastructure for collection and recycling of these batteries already exists. In fact, recycled lead forms a significant percentage of the lead used in fabricating new batteries. Because the market for lead-acid batteries is already extremely large, even a significant penetration of the EV application by this battery chemistry is not expected to have a noticeable impact on the ability of industry to continue the present high recycling rate. A study was conducted in 1996 and confirmed this low impact of increased EV use on
311 the lead-acid battery recycling infrastructure by projecting the increased amount of recycled lead that would result [ 18]. Although most of the regulations that are currently spurring market development are viewed as encouraging advanced batteries rather than
Table 5. Summary of Scores for Battery Recycling Battery Technology
Total Score (180 Maximum)
Conventional lead-acid
153
Sealed bipolar lead-acid
153
Nickel/metal hydride
147
Nickel/cadmium
146
Zinc-air
146
Zinc/bromine
140
Lithium/iron sulfide
135
Lithium/iron disulfide
135
Lithium-ion
132
Sodium/sulfur
119
Sodium/nickel chloride
114
Aluminum-air
114"
Iron-air
112"
Lithium-polymer
101
* All attributes could not be ranked. lead-acid, lead-acid will likely have a niche role to play in coming years. The annual amount of waste expected from EV batteries in the U.S. was projected out to the year 2005 based on a set of reasonable assumptions in order to compare with the capacity for secondary lead recovery. The long-term trend in U.S. secondary lead recovery capacity is slowly upward, but the existing capacity in 1996 was taken as a conservative estimate. The following assumptions were used in arriving at this projection: 9 A total U.S. EV population of 2000 in 1994 [19] 9 EV sales of 200,000 in 2003 [20] 9 A 3-year replacement schedule for lead-acid batteries in EVs 9 Market share for lead-acid batteries decreasing from 100% in 1995 to 30% for 2000 and beyond
312 9 Improved energy density for lead-acid batteries from 30 Wh/kg in 1995 to 50 Wh/kg in 2005 9 Battery mass per EV of 500 kg in 1995 and decreasing with improved energy density 9 Battery mass is 73% lead In retrospect, most of these assumptions were good, but there were a few that were not. It now appears that EV sales in 2003 will more likely be 10 to 15% of the 200,000 predicted by the Energy Information Agency in 1996. Since a large fraction of these vehicles could well be hybrids using advanced battery technology, the constant 30% market share for lead-acid batteries beyond 2000 is probably also too high. A less important factor is the predicted decrease in battery mass per vehicle as energy density improves. Although this trend may occur at some point, it is probable that the desire for more on-board energy storage will continue unabated for at least the near term. The introduction of advanced batteries with higher energy density has not led to consistently lower weight batteries, but more otten than not the incorporation of more battery capacity. Nevertheless, the assumptions were conservative in the sense that the predictions based on them likely represent an upper limit for the impact on the lead-acid battery recycling industry. The mass of lead in scrap EV batteries is projected to increase as shown in Figure 9, reaching about 16,000 metric tons in 2005. This can be compared to Figure 10, which shows the amount of lead from battery scrap and the total amount of lead recovered from scrap in the U.S. through the year 1995 from U.S. Bureau of Mines data. Total secondary lead is nearing 1M metric tons per year. The predicted EV battery lead mass in 2005 is only about 1.5% of the secondary lead recovery capacity in 1996 and will actually be less than that in 2005 once the future growth in secondary lead recovery is included. Clearly EV battery waste will remain a very small portion of secondary lead production well beyond 2005. Nearly all of the secondary lead is recovered by thermal smelting, which does raise concerns regarding air and water pollution. Emission control devices are necessary to prevent the release of lead particulate to the environment, and in at least one case a backup battery has been installed to ensure that these emission controls continue to operate in the event of a power outage from the local electric utility [21]. However,
313
16000
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
14000 12000 .~. 10000 8000 6000 =[
4000 2000 0 1996
1997
1998
1999
2000
2001
Year
2002
2003
2004
2005
Fig. 9. Projected Mass of Lead in EV Batteries to 2005.
Sec~
1200
1000
o c
"~
800
t
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
TotalScrap
...............................................................
600
I
,I=
4OO
r:S:r::
200
..................
Year Fig. 10. Lead from Battery Scrap, Total Lead Scrap, Secondary Lead Recovery Capacity, and Lead Scrap Export in the U.S. when such a large mass of lead is processed, it is virtually impossible to prevent the release of small amounts during the processing. Nonthermal methods such as electrowinning have been investigated for secondary lead recovery and in some cases
314 have been shown to be technically feasible [22], but these methods have not been widely adopted, mainly due to high costs. More detailed information on recycling processes for lead-acid and other batteries can be found in other sections of this volume. 9 Nickel/Cadmium (Ni/Cd) Another conventional battery technology that has been considered for EVs is Ni/Cd. Although capable of somewhat better performance than lead-acid in some respects, this battery is also more costly and does not equal the performance levels possible with advanced battery systems. It is unlikely to see widespread use in EV applications in the U.S. although there are reported to be more than 10,000 EVs using Ni/Cd batteries presently on the road in Europe [23].
Because of the toxicity of cadmium, which
precludes disposal, and the value of the nickel, there are well-developed processes for recycling of Ni/Cd batteries. Most of the facilities in Europe are dedicated Ni/Cd battery recycling plants. The combined recycling capacity world wide was about 25,000 metric tons of Ni/Cd batteries per year in 1993, but this was significantly underutilized because of inefficient collection systems and low prices for nickel and cadmium. Both pyrometallurgical and hydrometallurgical methods are used to recycle cadmium from a variety of waste materials in plants in North America, Europe, and Japan [24]. Cadmium is relatively easy to separate from other materials because of its low melting point and chemical activity. Since 1995, consumer and industrial Ni/Cd battery recycling in the U.S. has been primarily done at the International Metals Reclamation Company, Inc. (INMETCO) using a process licensed from SAFT NIFE. The cadmium is distilled from the plates using a low temperature thermal process, and the material is used for new battery production. The nickel content of the battery goes into the standard INMETCO stainless steel remelt alloy production. In general, this thermal recovery process makes up the majority of the world recycling capacity. The cadmium is recovered and purified as the metal or can be converted to cadmium oxide. Hydrometallurgical recovery processes operate on a broader variety of waste products and frequently recover other metals in addition to cadmium. They generally employ dissolution by acid treatment followed by selective extraction methods such as precipitation or ion exchange to separate the products. The economics in the
315 hydrometallurgical case may depend on materials other than cadmium, which may not be the major species present. Cadmium recycling appears to be well developed and capacity is more than adequate to handle any near-term growth that could reasonably be expected due to growth in the EV market.
Advanced Batteries
9 Nickel/Metal Hydride (Ni/MH) Nickel/metal
hydride
batteries
can
be
partially
reclaimed
today
through
pyrometallurgical processing, although the focus is primarily on the nickel, chromium and iron fractions. Rare earths and other metals typically contained in the hydride alloy are not separated and form part of a slag that is eventually sold as aggregate for road construction. The principal facility of this type in the U.S. that accepts Ni/MH battery waste is operated by INMETCO. A variety of wastes from the stainless steel industry have been processed in rotary hearth and electric arc furnaces by INMETCO to produce a standard remelt alloy that can be used by stainless steel producers. Nickel/metal hydride batteries are compatible with the INMETCO process due to their high nickel and iron content. Because batteries are only a fraction of the waste stream, the amount of battery waste that is available is not important to continued operation of the process. This recycling process is thus well suited to the current period of uncertainty while EV/HEVs establish a foothold in the market. At present levels of waste generation, there is no fee levied to process Ni/MH scrap, but none of the inherent value is returned to the waste generator, either. In Europe, S.N.A.M. has developed several processes to separate and recycle AB5 hydride alloy from Ni/MH batteries [25]. One process separates 60 to 85 percent of the hydride alloy for reuse in batteries, while the remainder and other metalic components are recycled as nickel-iron scrap. Another simpler process deactivates the hydride alloy and the residue can then be sold for production of nickel or nickel-cobalt alloy. 9 Lithium-ion (Li-ion)
Recycling capabilities for lithium batteries have advanced significantly since the early 1990s. Initial methods focused mainly on deactivation and safe disposal rather than material recovery because of the prevalence and well known reactivity of lithium metal in the primary batteries that made up the bulk of the commercial product at that time
316 [26,27]. The tremendous growth in the rechargeable lithium battery market has stimulated efforts to reclaim the most valuable components of Li-ion cells such as cobalt, and progress has also been made in finding ways to reuse the lithium salts. Although EV-size Li-ion batteries have not been fielded in significant numbers, other opportunities to dispose of very large lithium primary batteries have required development of handling techniques that should also be useful for EV battery modules. For example, a four-year project to dispose of more than 4,500 large lithium batteries for the U.S. Navy and Air Force was begun by Toxco in 1998 [28]. The Li/thionyl chloride primary batteries each weigh 570 pounds, which is the same general size as an EV battery. The first commercial Li-ion battery technology was produced by Sony and they are also the only Li-ion battery manufacturer to develop their own recycling process [29]. Production of Li-ion batteries by Sony began in 1991 and a battery-recycling project began the next year in conjunction with Sumitomo Metals and Mining Co., Ltd. The Sony Li-ion cell contains a lithium cobalt dioxide (LiCoO2) cathode and cobalt comprises 15 to 20% of the battery weight. Since cobalt is a relatively expensive material compared to the other battery constituents, its recovery is the primary objective in the recycling process. Besides the cobalt, which is recovered as cobalt chloride, iron and copper are also recycled from the used Li-ion cells, but the lithium is not reclaimed in the Sony process. If the cathode is changed to another material at some point, a major impact on the recycling economies could occur. Toxco, Inc. has developed processes to recover lithium as lithium carbonate from lithium batteries and other types of lithium-containing wastes [30]. As much as 98% of the available lithium can be recovered, along with a similar fraction of the available cobalt (Co) and much of the aluminum (A1), iron (Fe), and nickel (Ni). The lithium carbonate can be returned to lithium production and Pacific Lithium, Ltd. has done this. More recently, Toxco has acquired facilities to convert the lithium carbonate back into electrolyte salts for lithium batteries. Clearly, it is feasible and profitable to recycle the cobalt cathode and lithium components of these batteries. Recycling of the more valuable constituents of Li-ion EV battery modules should follow in a straightforward manner using the processes developed on the strength of the rapidly growing market for the smaller Li-ion batteries in portable electronic devices. A preview of the handling constraints that will be posed by larger EV modules has been obtained from the work on large lithium/thionyl chloride cells [28,31]. These must be
317 sliced apart under cryogenic conditions to reduce and safely control reactivity until the lithium is deactivated.
OPTIMIZED RECYCLING PROCESSES FOR ADVANCED BATTERIES
9 Nickel/Metal Hydride (Ni/MH) Preliminary studies have been conducted on altematives to the pyrometallurgical processing of N i g H batteries. Hydrometallurgical treatment provides metal salts as products, which may offer market stability benefits in certain circumstances compared to the primary metals produced by smelting. Another advantage is that the separation and recovery of other valuable constituents such as titanium, vanadium, zirconium, and rare earths may become possible. The U.S. Bureau of Mines (USBM) conducted exploratory research on hydrometallurgical processing options for several years [32,33], concluding that these options are indeed feasible for battery scrap containing either AB2 or AB5 hydride alloys. AB2 metal hydride electrodes typically contain about 54% Ni + Co, 42% Ti + V + Zr, and 4% other elements (A1, Cr) by weight. The AB5 electrode consists of a LaNi5 type alloy on a nickel substrate. The alloy contains about 33% rare earths, 10% Co, 50% Ni, 0.12% Fe, and 6% other metals (Mn, Al). USBM evaluated several different leaching protocols and acid solutions for extraction efficiency on whole batteries, cracked batteries, and components. A two-stage leaching process was found to be particularly effective for concentrating the titanium (Ti), vanadium (V), zirconium (Zr), and chromium (Cr) species in solution. Preliminary precipitation tests to recover partially separated metals from solution were run using pH adjustment, carbonate precipitation or oxalate precipitation, although the optimum methods for producing the highest purity products were not determined. Nickel and cobalt could be recovered by electrowinning or solvent extraction as well as by precipitation techniques. Operating revenue that could be generated from chemical separation or physical/chemical separation processes for recycling Ni/MH batteries was compared to a pyrometallurgical process in a report prepared for the National Renewable Energy Laboratory (NREL), a DOE facility located in Golden, Colorado [34]. The pyrometallurgical process has similarities to the process operated by INMETCO. Revenues (or costs) were estimated for both AB2 and AB5 hydride alloy battery designs. Other general assumptions in the cost calculations were that the plant was sited in California and was processing 30,000 metric tons of EV batteries annually.
The
chemical process is based on an acid leach of the battery materials, followed by
318 precipitation of all but the nickel and cobalt, which are recovered by electrowinning. The major products recovered are nickel-iron scrap, steel scrap, polypropylene and nickel metal. In the physical/chemical separation process, the battery electrodes are physically separated prior to chemical processing and the metal hydride alloy powder is recovered and returned to hydride alloy producers. The rest of the procedure is very similar to the chemical process. For the pyrometallurgical process, all of the battery electrodes and powders are smelted to form a ferronickel product and a slag that is enriched in hydride alloy constituents. Slag from batteries containing AB2 alloy could be smelted further to produce ferrovanadium while rare earth producers may be interested in the enriched rare earth content of the slag from AB5 batteries. The only other products are steel scrap and a very low-grade ftmaace slag remaining after the smelting of the ferrovanadium product. In the most favorable case (physical separation/chemical process), the revenue from the recovered products obtained by the recycling process was predicted to be between $16.70/kWh of batteries processed for the AB5 alloy and $18.50/kWh for the AB2 alloy. This is largely because of the value of the credit assumed for the physically separated hydride alloy scrap, although the process is still predicted to generate a small amount of revenue without it. The revenue of $9.50/kWh from the chemical process is second best for the AB5 alloy, and the pyrometallurgical process comes in third at $4.15/kWh. For the AB2 alloy, the pyrometallurgical process looks better at $7.50/kWh, but the chemical process does not generate revenue at -$.50/kWh. The better cost performance of the chemical process in the case of the AB5 alloy is a result of both somewhat lower processing costs and a significantly higher product credit because of the cobalt content. Little follow-on evaluation has occurred for Ni/MH battery recycling processes since the earlier studies described above were completed in about 1994 in spite of the potential benefits that were shown [35]. Mitsui Mining and Smelting Company Limited reported one additional study in 1995 [36]. Nickel, cobalt and rare earth elements were the major materials that were targeted for recovery from the battery. Following mechanical processing, a sulfuric acid leach was applied as the first step in a hydrometaUurgical process. Rare earth elements can be separated by the double salt method and then other impurities (copper, zinc) removed by solvent extraction or sulfide precipitation. The f'mal solution contains nickel and cobalt, which are recovered in high purity by electrowinning. A conceptual flow diagram of the process was presented, but continuous testing and other evaluations had not yet been done.
319 Optimization of the hydrometallurgical-type processes is far from complete, and feasibility and pilot scale-up experiments must still be performed. In order to capitalize on the value of cobalt in the AB2 battery system (worth approximately $18 per pound), and the value of rare earth materials for industrial applications (worth approximately $8 to $10 per pound) [7], a more detailed examination of the economics associated with hydrometallurgical processes is needed. Two factors that seem to be contributing to the low level of interest are the current low prices in the primary metals market and the slow increase in the number of fielded EV batteries. Operators of existing commercial smelting operations are unwilling to accept small, infrequent shipments of battery manufacturing scrap, and returns of end-of-life batteries from the field are expected to be miniscule for some time yet. Even waste processors that are willing to accept small waste shipments, such as INMETCO, will not pay for the scrap at the current level of volume and price. Research on improved, more comprehensive recycling processes is not occurring because profits in the near term will be too low to justify the investment. However, the relatively high cost of the Ni/MH battery system makes it important to maximize the recycling credit that can be obtained, and this will only happen with the development of a more comprehensive recycling process. 9 Lithium-ion (Li-ion) and Lithium-polymer (Li-polymer) One of the future recycling needs for the Li-ion battery chemistry involves testing of improved methods for recovering alternative cathode materials. Because the economic incentive to reclaim these materials will likely be less than for cobalt, it will be important for the processes to be highly efficient and necessary to use inexpensive reagents. Other opportunities are in recovery of carbon anodes. It is preferable to process them back into new battery anodes because this would be the most valuable use for the carbon material. However, this will be a difficult task requiring extensive study before feasibility can be proven. The lithium-polymer version of these batteries is another area where work is needed. Lithium-polymer batteries are being rapidly developed for portable consumer electronics applications and may be used in the future for EV/HEVs since the polymer design mitigates safety concerns regarding lithium metal in large cells. Some work to develop recycling processes is under way, but no details have been published and no process test data have been made available. Although many of the constituents are shared in common with the Li-ion battery system, the presence of a solid polymer
320 electrolyte introduces new materials with unique properties. This may complicate physical disassembly of cells if that is needed as part of the recycling process, but also may present opportunities to increase revenues from recycling. Investment in recycling process improvement will continue to be difficult to obtain for lithium batteries since most of the high-value constituents are already accounted for, and there are only small numbers of prototype lithium-polymer batteries in the field.
RECYCLING PROSPECTS FOR FUTURE ADVANCED BATTERY SYSTEMS 9
S o d i u m / S u l f u r (Na/S)
Much of the effort to develop the Na/S battery was aimed at its use in electric vehicles. Current applications of this advanced battery system are now mainly in the stationary battery area, but feasibility studies were done on the recycling of this system before the EV development efforts were suspended. Sodium/sulfur batteries contain reactive and corrosive materials, but not toxic ones. By treatment of the battery waste, the reactivity problems can be removed. The major difficulty in recycling this chemistry is that most of the constituents have low value or are difficult to recover in a form that could be used in a high-value application (e.g., the beta" alumina electrolyte). A patented proposed recycling scheme has been evaluated on a pilot scale and found to be acceptable from a cost and technical standpoint [37]. This process replaced incineration, which was used earlier in the development program, but judged too expensive for large numbers of batteries. In the recycling process, the batteries are shredded and the soluble constituents extracted with water. The resulting sodium polysulfide solution is acidified to generate hydrogen sulfide, which can be converted to sulfur in a small-scale Claus process reactor. The remaining Na2SO4 solution can be converted to sulfuric acid and sodium hydroxide, which are sold or used in the process. Insoluble ceramic, graphite and metal cell case materials are also recovered. Sulfur recovered in this way was recycled into new Na/S cells that showed identical performance to cells built with virgin sulfur. Estimated processing costs were deemed acceptable at $6 to $10/kWh of batteries based on a 5,000 (metric) ton per year plant size. This compares favorably to the $40 to $60/kWh incineration cost. The relatively low value of the recovered materials prevents this recycling process from being completely self-supporting. Other more valuable forms of sulfur could be recovered with a modified process, but markets for them may
321 be limited because of the Exclusion Principle. A detailed examination of the cost benefits in this area has not been done. A specification was drawn up for a pilot recycling plant (250 tons/year) that would meet German safety and environmental standards, but the plant was not constructed because the quantity of returned batteries was insufficient to support it. Analyses of solution from laboratory-scale recycling were carried out for chromium, which is regulated for toxicity, and levels were found to be below EPA limits. TCLP tests on cells also show amounts of leachable chromium that are within EPA standards. 9
Sodium/Nickel Chloride (Na/NiCI2)
The Na/NiCI2 or ZEBRA battery is another high temperature system that resembles Na/S in some respects. However, the design of the system reduces operational hazards from certain failure modes such as cell shorting. This battery has been road tested in about 90 vehicles [38] including the Mercedes A-class EV, although it is not currently slated for commercialization. A recycling process for the battery has been outlined and appears to be feasible. Detailed cost analyses have not been done, but the presence of nickel offers a stronger possibility of recovered value than for Na/S. The sodium/nickel chloride cell, if completely discharged, no longer contains dangerous (reactive) materials since the products of the cell reaction are NaC1 and nickel [39]. The battery is therefore shorted before beginning the recycling process. Soluble components such as NiC12, NaC1, and NaAIC14 are leached out aider slicing the cells into pieces. These soluble components are further separated by precipitating the nickel as nickel sulfide and subsequent crystallization of NaC1 and NaA1Cl4 from the solution. The insoluble case material and ceramics undergo mechanical sieving and magnetic separation, and the valuable components such as the metals are recovered for metallurgical processing and subsequent reuse. Unfortunately, the relatively expensive beta" alumina ceramic electrolyte would most likely go to very low-value uses at first or be sent to disposal. The cost would likely be strongly influenced by the price of nickel, since that is the most valuable constituent. Recovery of all the nickel is important if the process is to be carried out in locations that regulate nickel for disposal. A preliminary evaluation of recycling costs showed that these are just about offset by the value of the recovered materials [40].
322 9
Nickel/Zinc (Ni/Zn)
Ni/Zn batteries with reasonable cycle lives for motive power applications are being developed. Enough progress has been made that small batteries have been proposed for electric scooters and other light transportation applications. Upgrading to larger packs for EVs may occur with further development and experience since the battery would be relatively inexpensive and environmentally friendly. A detailed recycling plan has not been formulated for this technology, but the battery does not contain any particularly hazardous materials. The untreated batteries would be considered hazardous waste because of the corrosive alkaline electrolyte, but this could be recovered or treated to eliminate that problem. Although no TCLP tests are known to have been done on this battery, it seems likely that enough nickel could leach to cause the waste to be considered hazardous due to toxicity in regions where nickel is regulated. Since there are no other regulated materials in this battery, the waste would not be hazardous according to EPA regulations. The only impediment to recycling could be economic in that the single high-value material is nickel. However, the INMETCO smelting process fits well with the battery system because it recovers both nickel and zinc. Nickel/zinc batteries have been recycled by INMETCO with no apparent difficulty. *
Zinc-air
Mechanically rechargeable, zinc-air batteries have been tested in Europe in postal trucks [41]. In this system, spent zinc anodes are removed from the battery and electrochemically reprocessed. A replacement battery containing charged anodes is loaded into the vehicle to minimize refueling time. Although a recycling process has not been designed, the battery materials are non-toxic and should be easy to handle. The cells do contain KOH electrolyte that would have to be neutralized. Besides the zinc anodes, which are continually recycled during the life of the battery, the materials of construction are steel, carbon, plastic, copper, and nickel. No recycling cost estimates have been made, but the recovered materials would not be very high in value so the process would have to be inexpensive to be economically viable.
SUMMARY Electric vehicle batteries present recycling challenges because of their large size, potentially large numbers, uncertain timetable for implementation, and varied chemistries. Most battery chemistries contain materials that would be considered
323 hazardous waste by virtue of reactivity, corrosivity, or toxicity. On disposal, reactivity and corrosivity can generally be dealt with by appropriate treatment of the battery waste. However, toxicity can cause problems and additional cost for waste disposal if the offending species cannot be reclaimed to a high degree by a recycling process. Ultimately, the choice of the recycling process and its effectiveness is shaped by economics. The goal is always to recycle as much as possible, but it may be too expensive to recover some materials or they may have little value to begin with. Disposal may ultimately be the most cost-effective solution for those low-value materials that do not have hazardous waste characteristics. Batteries that do not contain a large percentage of valuable or reusable materials are particularly vulnerable to these issues. A review of the battery chemistries in use in EVs today or that possibly could be used in the future shows that nearly all have some rudimentary recycling potential. Many can be recycled to a high level, at least on a laboratory or pilot scale. There appear to be no situations that totally preclude recycling. What is presently missing is the optimization of the recycling processes needed to recover maximum value and scale up to a high material feed rate. This is perhaps unavoidable given the past history and continued uncertainty regarding the development of the EV market. Battery recyclers have proven resourceful in the past and just as in the case of the lead-acid technology, the advent of large numbers of EVs and HEVs will stimulate development of improved recycling technology. However, the dominant EV power source 10 to 20 years from now may use different materials or even be a new technology, so much remains to be done.
ACKNOWLEDGEMENTS Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy under contract DEAC04-94AL85000. Funding for this work was provided by the DOE Office of Transportation Technologies. The author gratefully acknowledges Thomas Evashenk, California Air Resource Board; David Hermance, Toyota; Paul Gifford, GM Ovonic; Gary Roque, Nissan; George Shishkovsky, DaimlerChrysler; Larry Simmering, Ford; Laura Vimmerstedt, NREL; Carol Hammel, NREL; Members of the Reclamation/Recycle Sub-Working Group; and Imelda Francis, Technical Editor, Just Do Information Technologies (Just Do IT).
324 REFERENCES
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325 14. P. Klimek, "Solid Waste Characterization of 'New' CECOM Rechargeable Batteries," presented at the Advanced Battery Readiness Ad Hoc Working Group, February 18-19, 1999. 15. D. Smith, "Sony Electronics Incorporated-Update on Li-ion Battery Environmental Issues," presented at the Advanced Battery Readiness Ad Hoc Working Group, March 4-5, 1998. 16. S. Unnasch, M. Montano, and P. Franklin, "Reclamation of Automotive Batteries: Assessment of Health Impacts and Recycling Technology, Task 1: Assessment of EV Battery Recycling Technology," Acurex Environmental Corporation, March 1995. 17. G.M. Roque, W.J. McLaughlin, "Preparing for the EV's and the Electric Vehicle Batteries," presented at the 11th Seminar on Battery Waste Management, Deerfield Beach, Florida, November 1999. 18. Vimmerstedt L., Jungst R.G., and Hammel C. "Impact of Increased Electric Vehicle Use on Battery Recycling Infrastructure," presented at the 8th International Seminar on Battery Waste Management, October 1996. 19. Electric Vehicle Association of the Americas (EVAA), EVAA World Wide Web site http://www.evaa.org. 20. "Supplement to the Annual Energy Outlook, 1996," Energy Information Agency, U.S. Department of Energy, Washington, DC, EIA tip site (flp://flp.eia.doe.gov), 1996. 21. G.W. Hunt, and C.B. John, "A Review of the Operation of a Large Scale, Demand Side Energy Management System Based on a Valve-Regulated Lead-Acid Battery Energy Storage System," presented at the Electric Energy Storage Applications and Technologies Conference (EESAT 2000), Orlando, FL, September 2000. 22. R.D. Prengaman, "Recovering Lead from Batteries," JOM: Journal of the Minerals, Metals, and Materials Society, Vol. 47, pp. 31-33, 1995. 23. Electric Vehicle Progress, Vol. 22 # 12, p. 2, June 15, 2000. 24. H. Morrow, "The Recycling of Nickel-Cadmium Batteries," The Battery Man, October 1993. 25. J. David, "Battery Recycling '99," presented at the 1l th International Seminar on Battery Waste Management," Deerfield Beach, FL, November 1999. 26. J.P. Guptil, "Disposal of Lithium Batteries and the Potential for Recycling of Lithium Battery Components," presented at the 5th International Seminar on Battery Waste Management, Deerfield Beach, FL, November 1993.
326 27. W.J. McLaughlin, "Recycling of Large Lithium Batteries," presented at the Advanced Battery Readiness Working Group Meeting, Washington, DC, March 1998. 28. W.J. McLaughlin, "Lithium Recycling and Disposal Techniques," presented at the 5th International Seminar on Battery Waste Management, Deerfield Beach, FL, November 1993. 29. K. Murano, "Recycling of Lithium Ion Batteries," presented at the Ad Hoc Advanced Battery Readiness Working Group Meeting, Washington, DC, April 1997. 30. W.J. McLaughlin, "Recycling of Lithium Batteries and Other Lithium Wastes," presented at the Ad Hoc Advanced Battery Readiness Working Group Meeting, Washington, DC, April 1997. 31. W.J. McLaughlin, "Deactivation, Disposal, and Recycling of Large Lithium Batteries," presented at the Ad Hoc Advanced Battery Readiness Working Group Meeting, Washington, DC, April 1997. 32. J.W. Lyman, and G.R. Palmer, "Investigating the Recycling of Nickel Hydride Battery Scrap," J. of Metals, pp. 32-35, May 1993. 33. J.W. Lyman, and G.R. Palmer, "Recycling of Nickel-Metal Hydride Battery Scrap," presented at the 186th Meeting of the Electrochemical Society, Miami Beach, FL, October 1994. 34. J.C. Sabatini, E.L. Field, I-C. Wu, M.R. Cox, B.M. Barnett, and J.T. Coleman, "Feasibility Study for the Recycling of Nickel Metal Hydride Electric Vehicle Batteries," Golden, CO: National Renewable Energy Laboratory, TP-463-6153, January 1994. 35. R.G. Jungst, "Recycling of Advanced Batteries for Electric Vehicles," presented at the 1lth International Seminar on Battery Waste Management, Deerfield Beach, FL, November 1999. 36. T. Yoshida, H. Ono, and R. Shirai, "Recycling of Used Ni-MH Rechargeable Batteries," Proceedings of the Third International Symposium on Recycling of Metals and Engineered Materials, pp. 145-152, 1995. 37. J. Rasmassen, "Sodium Sulfur Battery Disposal and Reclamation at Silent Power Limited," presented at the DOE Ad Hoc Electric Vehicle Battery Readiness Working Group, August 30-31, 1994. 38. C.-H. Dustman, "ZEBRA| for the U.S.," presented at the DOE Ad Hoc Advanced Battery Readiness Working Group, April 3-4, 1997. 39. H. Hammerling, "Recycling of Sodium/Nickel Chloride Batteries," presented at the DOE Ad Hoc Advanced Battery Readiness Working Group, August 30-31, 1994.
327 40. C.-H. Dustman, "Latest Advancement on the ZEBRA Battery," presented at the DOE Ad Hoe Advanced Battery Readiness Working Group, March 4-5,1998. 41. R. Putt, "Zinc-air Battery System," presented at the Ad Hoc Advanced Battery Readiness Working Group, March 21-22, 1996.
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APPENDIX A MOST C O M M O N TYPES OF C O M M E R C I A L BATTERIES*
* The information contained in this appendix has mainly been taken from: "Handbook of Batteries", D. Linden Ed., McGraw-Hill, Inc., New York, 1994. "Handbook of Battery Materials", J.O. Besenhard, Ed., Wiley-VCH, Weinheim, 1999.
330 Batteries can be divided into two broad categories:
Primary batteries: 9Zn-carbon 9Alkaline Zn-MnO2 9Zn-silver oxide 9Lithium
Secondary batteries: 9Lead-acid 9Sealed Lead-acid 9Vented industrial Ni-Cd 9Sealed Ni-Cd 9 9Li and Li-ion
Major Applications of the Batteries Listed Above. Primary batteries 9Zn-carbon: portable radios, instruments, toys, watches, flashlights. *Alkaline Zn-MnO2: calculators, radios, tape and cassette recorders; in general, replacement of Zn-carbon whenever a better performance is required. *Zn-Ag20: watches, calculators, hearing aids, cameras, space applications (in large
sizes). 9Lithium: watches, calculators, cameras, memory backup, toys, pacemakers, military applications. Secondary batteries 9Lead-acid: vehicles (SLI and traction), aircrats, submarines, forklifts, uninterruptible power sources, telephone exchange stations. 9Sealed Lead-acid: power tools, portable electronic equipment. 9Vented Ni-Cd: industrial power applications, communication equipment. 9Sealed Ni-Cd: power tools, portable electronic equipment, cameras, railroad equipment. 9Ni-MeH: several portable applications, e.g. computers and cellular phones, EV traction. 9Li and Li-ion: as for Ni-MeH.
331 In figure 1, the world market by battery type is presented.
A S u m m a r y of the Characteristics of Commercial Batteries
Primary batteries 9 Zn-Carbon
These batteries are the most widely used, also by virtue of their low cost. The anode is high-purity Zn and the cathode is battery-grade manganese dioxide. The electrolyte may be either a solution of ammonium chloride (Leclanch~ cell) or zinc chloride. The overall cell reaction may be written, in simplified form, as: Zn + 2 Mn02
-)
ZnO'Mn203
However, the products which can be found in spent batteries reveal more complicated reactions involving the electrolyte. For instance, in cells with NH4C1 as primary electrolyte, such products as MnOOH, Zn(NH3)2C12, Zn(OH)C1 can be found, whereas in cells with ZnC12 the formation of MnOOH, Zn(OH)C1, ZnC12.xZnO is possible. Leclanch6 cells may be divided into general purpose (intermittent low-rate discharge) and industrial heavy duty (intermittent medium/heavy rates) grades. Zinc-chloride cells also afford continuous discharge and have, in addition, an extra/superheavy duty grade for continuous medium/heavy rates. The zinc-carbon battery is made in two basic shapes, cylindrical and flat, and is available in many sizes. The weight can range from 6g to 900g and the capacity from 300 mAh to 40 Ah *
Alkaline Zn-MnO2
This battery has several advantages over the Zn-carbon battery: higher energy density, better performance at low and high rates, longer shelf life, and better dimensional stability.
332 The anode is powdered Zn metal, the cathode is electrolytic UnO2 and the electrolyte is a concentrated solution of KOH (35-45%). The total reaction on continuous discharge and to 1e/mole MnO2 is: Zn + 2 MnO2 + H20 "-) Zn(OH)2 + 2 MnOOH At low rates or intermittent discharges, the reaction is: Zn + 3 UnO2 "-) 2 ZnO + Un304 The initial voltage of these batteries, as well as the one of Zn-carbon cells, is about 1.5 V. To prevent Zn corrosion and passivation, mercury has long been used to amalgamate the anode. As is well known, Hg has been eliminated or greatly reduced, and replaced with indium, bismuth or other additives. Alkaline batteries are constructed as cyclindrical or button cells. The capacities of the former range from 0.6 to 22 Ah, while those of the latter vary from 35 to 160 mAh. 9
Zn-Silver
Oxide
This high-energy density battery is ideal for use, as button cell, in such electronic devices as cameras, calculators and watches. It features a fiat, constant voltage of 1.5 V and a very low self-discharge The anode is Zn metal, the cathode silver oxide (most commonly as Ag20) and the electrolyte an alkaline solution (20-45% KOH or NaOH). The overall reaction is: Zn + Ag20 --) 2 Ag + ZnO Button Zn-Ag20 cells have capacities ranging from 10 to 200 mAh. 9 Li
Li primary batteries have entered the market in the 70's and have since gained increasingly high market shares in a variety of applications. Li batteries have several pleasant characteristis, such as: high voltage, high energy density, wide temperature range, good power density, flat discharge curves, excellent shelf life. Li batteries can be divided into 3 categories:
333 soluble cathode (SO2, SOC12) solid cathode (MnO2, CFx, FeS2, AgV2Os) solid electrolyte (LiI) The first category features high to moderate power, and sizes ranging from 0.5 to an impressive 20,000 Ah. The second category is useful for low to moderate power, with sizes ranging from 0.03 to 5 Ah. Finally, the third category (where the solid electrolyte LiI is formed in situ when Li is contacted by I2) is useful for very low power applications, with sizes of 3 to 500 mAh. The highest market share is for the Li/MnO2 system, mainly used for automatic cameras. The Li/FeS2 system, with an operating voltage of 1.5 V, is a direct replacement for alkaline batteries. In the growing area of batteries for medical use, Li primary batteries play a major role. Li/I2 is still very important for pacemakers, while Li/AgV205 has taken over many high-rate applications, e.g. defibrillators and neurostimulators.
Secondary batteries 9 Lead-Acid
After 150 years, the lead-acid accumulator is still the most successful one with about 50% of the sales of all batteries in the world and an annual growth of 5%. This is explained by considering that this accumulator is always the cheapest one in any application, while granting a good performance. It can be produced in a variety of sizes. Small individual cells can power electric appliances and electronic devices. Through a full range of intermediate capacities, an accumulator can reach the dimensions of the one used in Chino, California, for the electric grid: 40 MWhr, 10 MW, 2,000 V, 5,000 A. The lead-acid battery has high-surface area Pb as a negative electrode and PbO2 as a positive. In the concentrated (37%) H2SO4 electrolyte solution, the reactions occurring at the electrodes lead to the overall process: Pb + PbO2 + 2 H2804 ~ " ~ 2 PbSO4 + 2 H20
334 Details on the electrodes construction and on the technological evolution are given in chapter 8. 9 Sealed Lead-Acid
These are small, maintenance-free batteries which are sealed as the electrolyte is not depleted during operation. The electrolyte is absorbed in a porous separator or in a gel, so that the battery can be operated in different orientations without spilling. This allows the batteries to be used in portable devices. The chemistry of these batteries is that of conventional lead-acid batteries. However, they have a unique characteristics. The oxygen generated on overcharge is recombined in the cell and there is no water loss. Indeed, oxygen reacts at the negative electrode: Pb + HSO4- + I-I+ + 8902 ~ " ~ PbSO4 + H20 This reaction is possible insofar as there is a very limited amount of electrolyte in the cell, this allowing quick gas diffusion between the plates. Sealed lead-acid batteries are in both cylindrical and prismatic shapes. The cyclindrical ones (usually designed as SLA batteries) have excellent high-rate characteristics. Other than in portable devices, sealed batteries can be used in standby applications, e.g. telephone exchange stations, were they are kept in float charge. In this case too, oxygen recombination is possible. Small lead-acid batteries lag behind other systems in terms of electrochemical performance. However, they have a notably high shelf-life and an attractive price. .
Vented Industrial Ni-Cd
Industrial Ni-Cd batteries are rugged, long-life, cheap batteries capable of operating at high rates. The so-called pocket-plate battery can stand overcharge, polarity reversal and short-circuits. To better utilize the electrode materials, two other structures have been developed: the fiber plate and the plastic-bonded plate. The latter has afforded improved performance characteristics (e.g. an energy density of 110 Wh/1). The negative electrode is Cd, the positive NiOOH, and the electrolyte is a concentrated solution of KOH (with additions of LiOH). The overall reaction is:
335 Cd + 2 NiOOH + 2 H20 4[--) Cd(OH)2 + 2 Ni(OH)2 The discharge voltage is about 1.2 V. Under normal conditions, an industrial battery can reach 2,000 cycles and lifetimes of 8-25 years. This battery can practically be used in all industrial applications, with capacities ranging from 10 to 1,000 Ah. A recent development of the Ni-Cd system is the sintered-plate battery having an energy density higher (up to 50%) than that of the pocket-plate one. It is used in highpower applications,e.g, in turbine engines and many military uses. 9 Sealed Ni-Cd
These batteries, as the sealed lead-acid ones, allow oxygen recombination on overcharge, so that they can be sealed and need no maintenance. The electrodes reactions are those mentioned for conventional batteries. However, in this case, the negative electrode has a higher capacity than the positive. During charge, the latter is fully oxidized first and starts to evolve 02, which migrates to the negative electrode and reacts: Cd + 8902 + H20 ")' Cd(OH)2 As for the sealed lead-acid, a thin electrolyte layer is used to help oxygen transfer. The most common cells are cylindrical (0.05 to 35 Ah) or button-type (0.02 to 0.5 Ah). However, sealed Ni-Cd batteries of 200-400 Ah have been built for EV applications. 9 Ni-MeH
In these batteries, the cadmium used in Ni-Cd batteries is replaced by the hydrogen absorbed in a metal alloy. In comparison with Ni-Cd, the Ni-MeH battery has a higher capacity and is environmentally friendly. On the other hand, its rate capability is lower and overcharge may cause problems. In many portable devices, such as cellular phones and laptop computers, Ni-MeH batteries have replaced Ni-Cd also in view of the similar costs. Large batteries are now being developed for EV traction.
336 The negative electrode, in the charged state, is hydrogen in the form of metal hydride, the positive is nickel oxyhydroxide and the electrolyte is a KOH solution. The overall reaction is: MeH + NiOOH (""~ Me + Ni(OH)2 In the sealed cell, an oxygen recombination reaction occurs during charge. At the positive electrode, oxygen is evolved: 2 OH- -'-) H20 + 8902 + 2e Then, 02 migrates to the negative through the thin electrolyte layer and gives rise to the reaction: 02 + 4 MeH --)
H20 + 4 Me
Water is produced and no overpressure builds up. Two types of metallic alloys are used: a) rare-earth (misch metal) alloys, known as ABs, based on lanthanum and nickel (LaNi5 plus some substituents); b) alloys based on titanium and nickel, plus V, Zr, Cr, known as AB2. The first type is the most widely used. A hydrogen-absorbing alloy must allow quantitative absorption-desorption at relatively high rates and for hundreds of cycles. These batteries are built in cyclindrical, button
or prismatic configurations. The
capacities of portable cells vary from 35 to 2,400 mAh. Their discharge characteristics are similar to those of Ni-Cd batteries. The discharge voltage is around 1.2 V. 9 Li a n d L i - l o n
A traditional rechargeable lithium battery uses a Li anode, a solid cathode (e.g. thermally treated MnO2) and a non-aqueous solution based on a Li salt dissolved in aprotic solvents. Today, the only commercial batteries of this type are the small Li/MnO2 coin cells developed at Sanyo. Research on alternative batteries with sulphur cathodes (normally as organic sulphides) is in progress. However, the known rechargeability problems of the Li anode and the related safety concern have shifted the choice towards the Li-ion batteries. These have such anodes as
337 crystalline graphite or carbon, where Li can be reversibly intercalated. The cathodes are ternary oxides of the type: LiCoO2, LiCoxNil_xO2, LiMn204. The electrolyte can be liquid, e.g. LiPF6 in ethylenecarbonate-dimethylcarbonate, or polymeric. Since 1999, polymer Li-ion batteries have appeared in the market. Such cells, with an in-situ crosslinked polymer, are now used in cellular phones of thin profile. However, at present, the market is dominated by the liquid-electrolyte batteries. The proliferation of portable devices is favouring their rapid growth. Early batteries were of the cylindrical type, but now the prismatic design represents 50% of the production, because of the demand for small sizes. Li-ion cells have superior electrochemical performance, as shown in Table 1, while the initially high costs are slowly being reduced. Furthermore, this type of battery is becoming satisfactorily safe and environmentally benign. Typical voltages are around 3 V and typical capacities in the range 0.5-2 Ah. Large batteries for EV traction have been built and tested. The evolution of the market of portable rechargeable batteries in reported in Table 2.
338
Figure 1. The World Battery Market by Type (Courtesy: Avicenne)
339 Table 1;. Comparison of Portable Rechargeable Batteries
Specific Energy (Whkg "1) Energy Density (Wh1-1) OCV (V) Operating Voltage (V) Peak Charge/ Discharge Rate (C) Charging Time (h) Overcharge Permitted Cycle Life 30% DOD 80% DOD Calendar Life (years) Self Discharge (%/month, RT) Component Toxicity Cost (S/KWh)
Lead-Acid
Ni-Cd
Ni-MeH
Li-lon
30
50
60
100
50 2.1 2.0-1.8
100 1.3 1.2-1.0
180 1.3 1.2-1.0
200 4.1 3.8-3.0
6 2-20 Limited
10 1-3 Yes
5 2-5 No
1 3-20 No
500 200 3
2000 800 5
800 600 3
ca. 2000 800 3-5
3-5 High 0.25
15-20 High 0.40
20-30 Medium 0.45
8-15 Medium 1.25
Table 2. Worldwide Production of Portable Rechargeable Batteries (%)*
Battery
1997
2000
Ni-Cd NiMeH Li-Ion Li-Polymer Lead-Acid
55.7 25.0 7.6 11.7
39.0 34.7 17.3 0.3 8.7
* Adapted from Table 1 in Chapter 2 of this book
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APPENDIX B MAIN LEGISLATION ON BATTERY WASTE IN THE U.S.A. AND E.U.
342 COUNCIL DIRECTIVE of 18 March 1991 on batteries and accumulators containing certain dangerous substances (91/157/EEC)
THE COUNCIL OF THE EUROPEAN COMMUNITIES, Having regard to the Treaty establishing the European Economic Community, and in particular Article 100a thereof, Having regard to the proposal from the Commission (1), In cooperation with the European Parliament (2), Having regard to the opinion of the Economic and Social Committee (3), Whereas any disparity between the laws or administrative measures adopted by the Member States on the disposal of batteries and accumulators could create barriers to trade and distort competition in the Community and may thereby have a direct impact on the establishment and functioning of the internal market; whereas it therefore appears necessary to approximate the laws in the field; Whereas Article 2 (2) of Council Directive 75/442/EEC of 15 July 1975 on waste (4), as amended by Directive 91/156/EEC (5), provides that specific rules for particular instances or supplementing those of the said Directive in order to regulate the management of particular categories of waste shall be laid down by means of individual Directives; Whereas the objectives and principles of the Community's environment policy, as set out in the European Community action programmes on the environment on the basis of the principles enshrined in Article 130r (1) and (2) of the EEC Treaty, aim in particular at preventing, reducing and as far as possible eliminating pollution and ensuring sound management of raw materials resources, on the basis also of the 'polluter pays' principle; Whereas, in order to achieve these objectives, the marketing of certain batteries and accumulators should be prohibited, in view of the amount of dangerous substances they contain; Whereas, to ensure that spent batteries and accumulators are recovered and disposed of in a controlled manner, Member States must take measures to ensure that they are marked and collected separately; Whereas collection and recycling of spent batteries and accumulators can help avoid unnecessary use of raw materials; Whereas appliances containing non-removable batteries or accumulators may represent an environmental hazard when they are disposed of; whereas Member States should therefore take appropriate measures; Whereas programmes should be set up in the Member States to achieve the various objectives set out above; whereas the Commission should be informed of these programmes and of the specific measures taken; Whereas recourse to economic instruments such as the setting up of a deposit system may encourage the separate collection and recycling of spent batteries and accumulators; Whereas provision should be made for consumer information in this field; Whereas provision should be made for appropriate procedures to implement the provisions of this Directive, particularly the making system, and to ensure that the
343 Directive can be easily adapted to scientific and technical progress; whereas the committee referred to in Article 18 of Directive 75/442/EEC should be instructed to assist the Commission in these tasks, HAS ADOPTED THIS DIRECTIVE: Article 1 The aim of this Directive is to approximate the laws of the Member States on the recovery and controlled disposal of those spent batteries and accumulators containing dangerous substances in accordance with Annex I. Article 2 For the purposes of this Directive: (a) 'battery or accumulator' means a source of electrical energy generated by direct conversion of chemical energy and consisting of one or more primary (nonrechargeable) batteries or secondary (rechargeable) cells, as listed in Annex I; (b) 'spent battery or accumulator' means a battery or accumulator which is not re-usable and is intended for recovery or disposal; (c) 'disposal' means any operation, provided that it is applicable to batteries and accumulators, included in Annex II A to Directive 75/442/EEC; (d) 'recovery' means any operation, provided that it is applicable to batteries and accumulators, included in Annex IIB to Directive 75/442/EEC; (e) 'collection' means the gathering, sorting and/or grouping together of spent batteries and accumulators; (f) 'deposit system' means a system under which the buyer, upon purchase of batteries or accumulators, pays the seller a sum of money which is refunded when the spent batteries or accumulators are returned. Article 3 1. Member States shall prohibit, as from 1 January 1993, the marketing of: alkaline manganese batteries for prolonged use in extreme conditions (e.g. temperatures below 0 ~ C or above 50 ~ C, exposed to shocks) containing more than 0,05 % of mercury by weight, - all other alkaline manganese batteries containing more than 0,025 % of mercury by weight. Alkaline manganese button cells and batteries composed of button cells shall be exempted from this prohibition. 2. Paragraph 1 shall be inserted in Annex I to Council Directive 76/769/EEC of 27 July 1976 on the approximation of the laws, regulations and administrative provisions of the Member States relating to restrictions on the marketing and use of certain dangerous substances and preparations (6), as last amended by Directive 85/610/EEC (7). Article 4 1. In the context of the programmes referred to in Article 6, Member States shall take appropriate steps to ensure that spent batteries and accumulators are collected separately with a view to their recovery or disposal. 2. To this end, Member States shall ensure that batteries and accumulators and, where appropriate, appliances into which they are incorporated are marked in the appropriate manner. The marking must include indications as to the following points: separate collection, where appropriate, recycling, the heavy-metal content. -
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344 3. The Commission shall draw up, in accordance with the procedure referred to in Article 10, the detailed arrangements for the marking system. These arrangements shall be published in the Official Journal of the European Communities. Article 5 Member States shall take measures to ensure that batteries and accumulators cannot be incorporated into appliances unless they can be readily removed, when spent, by the consumer. These measures shall enter into force on 1 January 1994. This Article shall not apply to the categories of appliance included in Annex II. Article 6 Member States shall draw up programmes in order to achieve the following objectives: reduction of the heavy-metal content of batteries and accumulators, promotion of marketing of batteries and accumulators containing smaller quantities of dangerous substances and/or less polluting substances, gradual reduction, in household waste, of spent batteries and accumulators covered by Annex I, promotion of research aimed at reducing the dangerous-substance content and favouring the use of less polluting substitute substances in batteries and accumulators, and research into methods of recycling, separate disposal of spent batteries and accumulators covered by Annex I. The first programmes shall cover a four-year period starting on 18 March 1993. They shall be communicated to the Commission by 17 September 1992 at the latest. The programmes shall be reviewed and updated regularly, at least every four years, in the light in particular of technical progress and of the economic and environmental situation. Amended programmes shall be communicated to the Commission in good time. Article 7 1. Member States shall ensure the efficient organization of separate collection and, where appropriate, the setting up of a deposit system. Furthermore, Member States may introduce measures such as economic instruments in order to encourage recycling. These measures must be introduced after consultation with the parties concerned, be based on valid ecological and economic criteria and avoid distortions of competition. 2. When notifying the programmes to which Article 6 refers, Member States shall inform the Commission of the measures they have taken pursuant to paragraph 1. Article 8 In the context of the programmes referred to in Article 6, Member States shall take the necessary steps to ensure that consumers are fully informed of: (a) the dangers of uncontrolled disposal of spent batteries and accumulators; (b) the marking of batteries, accumulators and appliances with permanently incorporated batteries and accumulators; (c) the method of removing batteries and accumulators which are permanently incorporated into appliances. Article 9 Member States may not impede, prohibit or restrict the marketing of batteries and accumulators covered by this Directive and conforming to the provisions laid down herein. Article 10 The Commission shall adapt Articles 3, 4 and 5 and Annexes I and II to technical -
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345 progress in accordance with the procedure laid down in Article 18 of Directive 75/442/EEC. Article 11 1. Member States shall take the measures necessary to comply with this Directive before 18 September 1992. They shall forthwith inform the Commission thereof. 2. Member States shall communicate to the Commission the texts of the provisions of national law which they adopt in the field governed by this Directive. The Commission shall inform the other Member States thereof. Article 12 This Directive is addressed to the Member States. ANNEX I BATTERIES AND ACCUMULATORS COVERED BY THE DIRECTIVE 1. Batteries and accumulators put on the market as from the date laid down in Article 11 (1) and containing: more than 25 mg mercury per cell, except alkaline manganese batteries, more than 0,025 % cadmium by weight, more than 0,4 % lead by weight. 2. Alkaline manganese batteries containing more than 0,025 % mercury by weight placed on the market as from the date laid down in Article 11 (1). ANNEX II LIST OF CATEGORIES OF APPLIANCE EXCLUDED FROM THE SCOPE OF ARTICLE 5 1. Those appliances whose batteries are soldered, welded or otherwise permanently attached to terminals to ensure continuity of power supply in demanding industrial usage and to preserve the memory and data functions of information technology and business equipment, where use of the batteries and accumulators referred to in Annex I is technically necessary. 2. Reference cells in scientific and professional equipment, and batteries and accumulators placed in medical devices designed to maintain vital functions and in heart pacemakers, where uninterrupted functioning is essential and the batteries and accumulators can be removed only by qualified personnel. 3. Portable appliances, where replacement of the batteries by unqualified personnel could present safety hazards to the user or could affect the operation of the appliance, and professional equipment intended for use in highly sensitive surroundings, for example in the presence of volatile substances. Those appliances the batteries and accumulators of which cannot be readily replaced by the user, in accordance with this Annex, shall be accompanied by instructions informing the user of the content of environmentally hazardous batteries and accumulators and showing how they can be removed safely. -
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346 Commission Directive 93/86/EEC of 4 October 1993 adapting to technical progress Council Directive 91/157/EEC on batteries and accumulators containing certain dangerous substances
THE COMMISSION OF THE EUROPEAN COMMUNITIES, Having regard to the Treaty establishing the European Economic Community, Having regard to Council Directive 75/442/EEC of 15 July 1975 on waste (1), as last amended by Directive 91/692/EEC (2), and in particular Article 18 thereof, Having regard to Council Directive 91/157/EEC of 18 March 1991 on batteries and accumulators containing certain dangerous substances (~), and in particular Article 10 thereof, Whereas detailed arrangements should be established for the making system provided for in Article 4 of Directive 91/157/EEC; Whereas appliances need not be marked, since Annex II to Directive 91/157/EEC provides for a special information system for appliances from which the consumer cannot easily remove the battery or accumulator; Whereas there is a need for a symbol clearly showing that batteries or accumulators covered by Directive 91/157/EEC should be collected separately from other household waste; Whereas the use of this symbol for batteries and accumulators covered by Directive 91/157/EEC must be protected; Whereas the measures provided for in this Directive are in accordance with the opinion delivered by the Committee for the Adaptation to Scientific and Technical Progress of Community Legislation on Waste, HAS ADOPTED THIS DIRECTIVE: Article 1 1. This Directive establishes the detailed arrangements for the marking system envisaged in Article 4 of Directive 91/157/EEC on batteries and accumulators covered by that Direcctive and manufactured for sale in, imported into, the Community on or after 1 January 1994. 2. The batteries and accumulators referred to in paragraph 1 which are produced in, or imported into, the Community before 1 January 1994 may be marketed without the symbols provided for in Articles 2 and 3 until 31 December 1995. Article 2 The symbol indicating separate collection shall consist of one of the roll-out containers crossed through, as shown below: The decision on the choice of symbol to be used on batteries and accumulators covered by Directive 91/157/EEC shall be made by the person responsible for marking as described in Article 5 of this Directive. The use of the two symbols shall be considered equivalent throughout the Community. Member States shall inform the public of the meaning of both symbols and grant them equal status in their national provisions regarding batteries and accumulators covered by Directive 91/157/EEC. The use of either symbol shall not constitute a means of arbitrary discrimination or a disguised restriction on trade between Member States. Article 3 The symbol indicating the heavy-metal content shall consist of the chemical symbol for the metal concerned, Hg, Cd or Pb according to the type of battery or accumulator concerned, as described in Annex I to Directive 91/157/EEC.
347 Article 4 1. The symbol described in Article 2 shall cover 3 % of the area of the largest side of the battery or accumulator, up to a maximum size of 5 x 5 cm. For cylindrical cells the symbol shall cover 3 % of half the surface area of the battery or accumulator and shall have a maximum size of 5 x 5 cm. Where the size of the battery or accumulator is such that the symbol would be smaller than 0,5 x 0,5 cm, the battery or accumulator need not be marked but a symbol measuring 1 x 1 cm shall be printed on the packaging. 2. The symbol referred to in Article 3 shall be printed beneath the symbol referred to in Article 2. It shall cover an area of at least one quarter the size of the symbol described in paragraph 1 of this Article. 3. The symbols shall be printed visibly, legibly and indelibly. Article 5 Member States shall take the necessary steps to ensure that the marking complies with the provisions of this Directive and is carried out by the manufacturer or his authorized representative established in the Member State concemed or else by the person responsible for placing the batteries or accumulators on the national market. Article 6 Member States shall adopt appropriate measures to ensure full implementation of all the provisions of this Directive, in particular as regards observance of the symbols referred to in Articles 2 and 3. Member States shall lay down the penalties to be applied in the event of an infringement of the measures adopted to comply with this Directive; such penalties must be effective, proportionate and deterrent in their effect. Article 7 Member States shall take the measures necessary to comply with this Directive no later than 31 December 1993. They shall immediately inform the Commission thereof. When Member States adopt these provisions, these shall contain a reference to this Directive or shall be accompanied by such reference at the time of their official publication. The procedure for such reference shall be adopted by Member States. Article 8 This Directive is addressed to the Member States.
348 Commission Directive 98/101~C of 22 December 1998 adapting to technical progress Council Directive 91/157/EEC on batteries and accumulators containing certain dangerous substances (Text with EEA relevance)
THE COMMISSION OF THE EUROPEAN COMMUNITIES, Having regard to the Treaty establishing the European Community, Having regard to Council Directive 91/157/EEC of 18 March 1991 on batteries and accumulators containing certain dangerous substances (1), and in particular Article 10 thereof, Whereas within the framework of the Act of Accession of Austria, Finland and Sweden, in particular in Articles 69 and 112, it is foreseen that during a period of four years from the date of accession the provisions concerning the mercury containing batteries referred to in Article 3 of Directive 91/157/EEC should be reviewed in accordance with EC procedures; Whereas, in order to achieve a high level of environmental protection, the marketing of certain batteries should be prohibited, in view of the amount of mercury they contain; whereas that prohibition, in order to achieve its full effect for the environment, must cover appliances into which such batteries and accumulators are incorporated; whereas such prohibition may have a positive impact in facilitating the recovery of batteries; Whereas the technical development of alternative heavy-metal-free batteries should be taken into account; Whereas Directive 91/157/EEC should be adapted accordingly; Whereas the measures provided for in this Directive are in accordance with the opinion expressed by the Committee established pursuant to Article 18 of Council Directive 75/442/EEC of 15 July 1975 on waste (2), as last amended by Commission Decision 96/350/EC (3), HAS ADOPTED THIS DIRECTIVE: Article 1 Directive 91/157/EEC is amended as follows: 1. Article 3(1) is replaced by the following: '1. Member States shall prohibit, as from 1 January 2000 at the latest, the marketing of batteries and accumulators, containing more than 0,0005 % of mercury by weight, including in those cases where these batteries and accumulators are incorporated into appliances. Button cells and batteries composed of button cells with a mercury content of no more than 2 % by weight shall be exempted from this prohibition.'; 2. Annex I is replaced by the text in the Annex to this Directive. Article 2 Member States shall adopt and publish, before 1 January 2000, the provisions necessary to comply with this Directive. They shall forthwith inform the Commission thereof. When Member States adopt those provisions, they shall contain a reference to this Directive or be accompanied by such a reference on the occasion of their official publication. Member States shall determine how such reference is to be made. Article 3 This Directive shall enter into force on the 20th day following its publication in the Official Journal of the European Communities.
349 ArtMe 4 This Directive is addressed to the Member States. ANNEX 'ANNEX I The following batteries and accumulators are covered by this Directive: 1. Batteries and accumulators put on the market as from 1 January 1999 containing more than 0,0005 % of mercury by weight. 2. Batteries and accumulators put on the market as from 18 September 1992 and containing: more than 25 mg of mercury per cell, except alkaline manganese batteries, more than 0,025 % of cadmium by weight, more than 0,4 % of lead by weight. 3. Alkaline manganese batteries containing more than 0,025 % of mercury by weight placed on the market as from 18 September 1992." -
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350 Draft Proposal of a New Directive of the European Commission on Batteries and Accumulators (with a view to replacing Directives
91/157/EEC and 93/86/EEC) EUROPEAN PARLIAMENT AND COUNCIL DIRECTIVE ../.../EC of .............
on batteries and accumulators
THE EUROPEAN PARLIAMENT AND THE COUNCIL OF THE EUROPEAN UNION, . ........... HAVE ADOPTED THIS DIRECTIVE: Article 1 Objectives
1. The aim of this Directive is to harmonise national measures concerning batteries and accumulators and the management of their wastes in order, on the one hand, to prevent or reduce the negative impact thereof on the environment, thus providing a high level of environmental protection, and, on the other hand, to ensure the functioning of the internal market and to avoid obstacles to trade and distortion and restriction of competition within the Community. 2. To this end, this Directive lays down measures aiming at preventing or reducing the hazardous nature of waste from batteries and accumulators, at ensuring the separate collection of all types of spent batteries and accumulators with a view to recovering their content and at reducing the final disposal of such waste. Article 2 Scope
3. This Directive shall cover all types of batteries and accumulators, as well as the appliances into which they are incorporated as regards marketing, marking and battery removal requirements, whether new or spent, whether they are used for consumer, automotive or industrial purposes, regardless of their shape, volume, weight or material composition. 4. This Directive shall apply without prejudice to other Community legislation, in particular as regards health, quality and safety standards.
Article 3 Definitions
For the purposes of this Directive:
351 1. "battery" means any source of electrical energy generated by direct conversion of chemical energy and consisting of one or more primary battery cells (non-rechargeable); 2. "accumulator" means any source of electrical energy generated by direct conversion of chemical energy and consisting of one or more secondary battery cells (rechargeable); 3. "battery pack" means any set of batteries or accumulators encapsulated in an outer casing into one complete unit, not intended to be opened by the consumer; 4. "portable battery or accumulator" means any battery or accumulator being used in products for private or professional use; 5. "button batteries and accumulators" means small button-shaped cells, normally with a weight of less than 50 g, used for special purposes such as hearing aids, watches and small portable equipment; 6. "industrial and automotive batteries or accumulators" means any battery or accumulator used for industrial purposes, for instance as standby or traction power, or for automotive starter power for vehicles; 7. "spent battery or accumulator" means any battery or accumulator which is a waste within the meaning of Article 1(a) of Directive 75/442/EEC; 8. "separate collection" means the gathering, sorting and/or grouping together of spent batteries and accumulators, separately from any other waste stream; 9. "recovery" means any of the applicable operations provided for in Annex IIB of Directive 75/442/EEC; 10. "recycling" means the reprocessing in a production process of the waste materials for the original purpose or for other purposes but excluding energy recovery. Energy recovery means the use of combustible waste as a means to generate energy through direct incineration with or without other waste but with recovery of the heat; 11. "disposal" means any of the applicable operations provided for in Annex IIA of Directive 75/442/EEC.
Article 4
Prevention
1. Member States shall prohibit the marketing of all batteries and accumulators, with the exception of button batteries and accumulators, containing more than 0.0005% of mercury by weight as well as the appliances into which they are incorporated.
352 2. Member States shall prohibit the marketing of all button batteries and accumulators containing more than 2% of mercury by weight as well as the appliances into which they are incorporated. 3. a) Without prejudice to Article 4 (2) of Directive 2000/53/EC on end of life vehicles, Member States shall prohibit, as from 1 January 2008, the marketing of batteries and accumulators containing more than 0.002% of cadmium by weight as well as the appliances into which they are incorporated. b) Paragraph (a) shall not apply to applications listed in Annex III. d) Member States shall take the necessary measures to ensure that, without prejudice to the requirements contained in Article 8, producers of nickel/cadmium batteries used in applications listed in Annex III provide for the setting up and the financing of the registration, collection, treatment, recovery, safe disposal and monitoring of these spent batteries. Such measures shall ensure a closed loop system and shall be communicated to the Commission. 4. In accordance with the procedure laid down in Article 16, the Commission shall revise paragraph 2 of this Article and Annex III by the end of 2005, taking into account new scientific evidence and technical developments. This revision exercise shall be repeated every three years thereafter. Article 5
Removal of batteries and accumulators from appliances Member States shall ensure that batteries and accumulators cannot be incorporated into appliances unless they can be readily removed, when spent, by the consumer. This provision shall not apply to the categories of appliance included in Annex I. All appliances into which batteries and accumulators are incorporated shall be accompanied by instructions showing how they can be removed safely and, where appropriate, informing the user of the content of the incorporated batteries and accumulators. Article 6
Marking requirements Member States shall ensure that all batteries and accumulators and battery packs are appropriately marked with the symbol shown in Annex II according to the technical requirements laid down in that Annex. Annex II shall be adapted to technical progress in accordance to Article 16. Article 7
Freedom to place on the market
353 Member States may not impede, prohibit or restrict the marketing in their territory of batteries and accumulators conforming to the provisions laid down in this Directive. Article 8
Separate Collection 1. Member States shall ensure that systems are set up so that last holders can return spent batteries and accumulators. They shall take the necessary measures to ensure that portable batteries and accumulators can be returned free of charge. 2. Member States shall aim at achieving no later than 31 December 2004 the following targets for separate collection covering their whole territory: (a) a minimum of 75% by weight of all spent consumer batteries and accumulators; this target shall also apply as a minimum to batteries containing more than 5 ppm mercury and to accumulators containing lead or cadmium considered individually. (b) a minimum of 95% by weight of all spent industrial and automotive batteries and accumulators; this target shall also apply to accumulators containing cadmium considered individually. 3. In line with the information required under Article 14, the targets shall be based on the weight of batteries sold taking into account the lifetime of the batteries. The Commission shall establish, in accordance with the procedure referred to in Article 16 and no later than the date by which this Directive must be implemented in national law, the reference elements on the basis of which the above targets shall be calculated. 4. No later than 31 December 2008 the collection targets shall be reviewed in accordance with the procedure by which this Directive is adopted. Article 9
Recovery and disposal 1. Member States shall ensure that all spent batteries and accumulators collected according to the provisions laid down in Article 8 are recovered or disposed of in accordance with Article 4 of Directive 75/442/EEC. 2. Member States shall ensure that any establishment or undertaking carrying out treatment operations obtains a permit from the competent authorities, in compliance with Articles 9 and 10 of Directive 75/442/EEC. 3. Member States shall aim at achieving no later than 31 December 2004 a minimum recycling rate of 55% by weight of the materials contained in the collected spent batteries and accumulators. No later than 31 December 2008 this recycling target shall be reviewed in accordance with the procedure by which this Directive is adopted.
354 Article 10
Collection and recovery systems Collection and recovery systems shall be open to the participation of the economic operators of the sectors concerned and to the participation of the competent authorities. They shall also apply to imported products under non-discriminatory conditions, and shall be designed so as to avoid barriers to trade or distortions of competition. Article 11
Consumer information Member States shall ensure that consumers are fully informed of: (a) the possibilities to prevent and minimise the use of batteries and accumulators (b) the most environmentally friendly batteries and accumulators for the various applications (c) how to choose appliances operating with environmentally friendly batteries or accumulators (d) the risks of disposing of spent batteries, accumulators and appliances into which they are incorporated together with the ordinary household waste; (e) the collection and return systems available to them;
(f) the meaning of the symbol and the chemical signs (Hg, Cd and Pb) laid down in Annex II; (g) the method of removing batteries and accumulators which are incorporated into appliances. 2. The targets referred to in Article 8 shall be published by the Member States and shall be the subject of an information campaign for the general public and economic operators. Article 12
Programmes Member States shall draw up programmes in order to achieve the following objectives: -promotion of research on and marketing of batteries and accumulators substituting those containing mercury, cadmium and where possible those containing lead
355 -promotion and development of collection and, where appropriate, deposit systems in order to improve separate collection of batteries and accumulators including the reduction of spent batteries stored at home -promotion of research on environmentally friendly and cost-effective recycling methods for all types of batteries These programmes shall be communicated to the Commission at the same time and covering the same period as the reports requested in Article 15. The report which is to be drawn up under Article 15 shall refer to these programmes. Article 13
Economic instruments 1. Member States may, in accordance with the principles governing Community environmental policy, inter alia, the polluter-pays principle, adopt economic instruments to promote the achievement of the objectives of this Directive. Member States shall ensure that these instruments do not distort internal market and competition rules. 2. Member States shall communicate to the Commission the draft measures which they intend to adopt concerning the use of economic instruments to achieve the objectives of this Directive. Article 14
Data collection 1. Member States shall ensure that databases on the quantities of batteries and accumulators including those incorporated in appliances are established in order to allow monitoring of the implementation of the objectives of this Directive for every calendar year. The database shall contain the units and weight of each type of battery and accumulator marketed within the Member States, as well as collected, recycled and disposed of as spent battery or accumulator. 2. Member States shall ensure that the information required under paragraph 1 is provided in a format, which shall be established in accordance with the procedure referred to in Article 16 and no later than the date by which this Directive must be implemented in national law. Article 15
Reporting obligation At three year intervals Member States shall send a report to the Commission on the implementation of this Directive. The report shall be drawn up on the basis of a questionnaire or outline drafted by the Commission in accordance with the procedure
356 laid down in Article 6 of Council Directive 91/692/EEC 13 of 23 December 1991 standardising and rationalising reports on the implementation of certain Directives relating to the environment. The questionnaire or outline shall be sent to the Member States six months before the start of the period covered by the report. The report shall be made available to the Commission within nine months of the end of the three-year period covered by it. The first report shall cover the period of three full calendar years starting from [ 18 months after the date of entry into force of this Directive]. Article 16
Committee procedure 1. The Commission shall be assisted by the committee instituted by Article 18 of Directive 75/442/EEC 14. 2. Where reference is made to this Article, the regulatory procedure laid down in Article 5 of Decision 1999/468/EC 15 shall apply, in compliance with Article 7 and Article 8 thereof. 3. The period provided for in Article 5(6) of Decision 1999/468/EC shall be three months. Article 17
Transposition 1. Member States shall bring into force the law, regulations and administrative provisions necessary to comply with this Directive by ..... [18 months after the date of adoption] at the latest. They shall immediately inform the Commission thereof. 2. When Member States adopt those provisions, they shall contain a reference to this Directive or be accompanied by such a reference on the occasion of their official publication. Member States shall determine how such reference is to be made. 3. Member States shall communicate to the Commission the text of all existing laws, regulations and administrative provisions adopted in the field covered by this Directive. 4. Member States shall lay down the penalties to be applied in the event of an infringement of the measures adopted to comply with this Directive; such penalties must be effective, proportionate and deterrent in their effect.
357 Article 18
Existing Community legislation on batteries and accumulators Directive 91/157/EEC and 93/86/EEC are hereby repealed with effect from the date referred to in Article 17.
ANNEX I LIST OF CATEGORIES OF APPLIANCE EXCLUDED F R O M THE SCOPE OF ARTICLE 5 1. Reference cells in scientific and professional equipment, and batteries and accumulators placed in medical devices designed to maintain vital functions and in heart pacemakers, where uninterrupted functioning is essential and the batteries and accumulators can be removed only by qualified personnel; 2. Portable appliances with an intended lifetime exceeding that of the original set of batteries or accumulators, where their replacement by unqualified personnel could present safety hazards to the user or could affect the operation of the appliance; 3. Appliances in respect of which legal safety standards require the use of tools for battery removal or which are designed and sold as waterproof; 4. Batteries and accumulators incorporated into professional equipment intended for use in highly sensitive surroundings, for example, in the presence of volatile substances.
ANNEX II
SYMBOLS AND TECHNICAL ASPECTS FOR THE MARKING OF BATTERIES AND ACCUMULATORS, BATTERY PACKS AND APPLIANCES WITH A VIEW TO SEPARATE COLLECTION 1. The symbol indicating separate collection for all batteries and accumulators shall consist of the crossed out wheeled bin, as shown below:
358 2. As regards batteries and accumulators as well as button batteries and accumulators containing cadmium or mercury above the levels indicated in Article 4.1 and 4.3 or lead above 0,1% of the weight of the battery, the chemical symbol for the metal concerned, Cd, Hg, Pb, shall be indicated. The symbol indicating the heavy metal content shall be printed beneath the symbol referred to in paragraph 1 of this Annex. 3. The symbol referred to in paragraph 1 of this Annex shall cover 3% of the area of the largest side of the battery, accumulator or battery pack, up to a maximum size of 5 x 5 cm. For cylindrical cells the symbol shall cover 1.5% of the surface area of the battery or accumulator and shall have a maximum size of 5 x 5 cm. Where the size of the battery, accumulator or battery pack is such that the symbol would be smaller than 0.4 x 0.4 cm, the battery, accumulator or battery pack need not to be marked but a symbol measuring 1 x 1 cm shall be printed on the packaging. 4. The symbol referred to in paragraph 1 of this Annex shall cover 3% of the area of the largest side of appliances which are required to be marked pursuant to Article 6 of this Directive, up to a maximum size of 5 x 5 cm. Where the size of the appliance is such that the symbol would be smaller than 0.4 x 0.4 cm, the appliance need not to be marked but a symbol measuring 1 x 1 cm shall be printed on the packaging. Where batteries, accumulators or battery packs are incorporated into appliances in such a way that the symbol referred to in paragraph 1of this Annex is fully visible without having to remove the batteries, accumulators or battery packs from the appliance, the appliance need not to be marked. 5. The symbols shall be printed visibly, legibly and indelibly.
ANNEX IH
NICD BATTERY APPLICATIONS, WHICH ARE EXEMPTED FROM THE REQUIREMENT OF ARTICLE 4(3)(A) -Railway and metro (locomotive starting and braking, lighting, signalling) -Aviation (airports, starting, emergency power for aircraft controls) -Stationary (uninterrupted power supply for hospitals, utilities, telecom))
359
The Mercury-Containing and Rechargeable Battery Management Act (The "Battery Act") Public Law 104-142 104th Congress An Act To phase out the use of mercury in batteries and provide for the efficient and cost-effective collection and recycling or proper disposal of used nickel cadmium batteries, small sealed lead-acid batteries, and certain other batteries, and for other purposes. SECTION 1. SHOT TITLE. This Act may be cited as the "'Mercury-Containing and Rechargeable Battery Management Act". SEC. 2. FINDINGS. The Congress f'mds that-- (1) it is in the public interest to-- (A) phase out the use of mercury in batteries and provide for the efficient and cost-effective collection and recycling or proper disposal of used nickel cadmium batteries, small sealed lead-acid batteries, and other regulated batteries; and (B) educate the public concerning the collection, recycling, and proper disposal of such batteries; (2) uniform national labeling requirements for regulated batteries, rechargeable consumer products, and product packaging will significantly benefit programs for regulated battery collection and recycling or proper disposal; and (3) it is in the public interest to encourage persons who use rechargeable batteries to participate in collection for recycling of used nickel-cadmium, small sealed lead-acid, and other regulated batteries. SEC. 3. DEFINITIONS. For purposes of this Act: (1) Administrator.--The term "'Administrator" means the Administrator of the Environmental Protection Agency. (2) Button cell.--The term "'button cell" means a button- or coin-shaped battery. (3) Easily removable.--The term "'easily removable", with respect to a battery, means detachable or removable at the end of the life of the battery-- (A) from a consumer product by a consumer with the use of common household tools; or (B) by a retailer of replacements for a battery used as the principal electrical power source for a vehicle. (4) Mercuricoxide battery.--The term "'mercuric-oxide battery" means a battery that uses a mercuric-oxide electrode. (5) Rechargeable battery.--The term "'rechargeable battery"-(A) means 1 or more voltaic or galvanic cells, electrically connected to produce electric energy, that is designed to be recharged for repeated uses; and (B) includes any type of enclosed device or sealed container consisting of 1 or more such cells, including what is commonly called a battery pack (and in the case of a battery pack, for the purposes of the requirements of easy removability and labeling under section 103, means the battery pack as a whole rather than each component individually); but (C) does not include-- (i) a lead-acid battery used to start an internal combustion engine or as the principal electrical power source for a vehicle, such as an automobile, a truck, construction equipment, a motorcycle, a garden tractor, a golf cart, a wheelchair, or a boat; (ii) a lead-acid battery used for load leveling or for storage of electricity generated by an alternative energy source, such as a solar cell or wind-driven generator; (iii) a battery used as a backup power source for memory or program instruction storage, timekeeping, or any similar purpose that requires uninterrupted electrical power in order to function if the primary energy supply fails or fluctuates momentarily; or (iv) a rechargeable alkaline battery. (6) Rechargeable consumer product.--The term "'rechargeable consumer product"-- (A) means a product that, when sold at retail, includes a regulated battery as a primary energy supply, and that is primarily intended
360 for personal or household use; but (B) does not include a product that only uses a battery solely as a source of backup power for memory or program instruction storage, timekeeping, or any similar purpose that requires uninterrupted electrical power in order to function if the primary energy supply fails or fluctuates momentarily. (7) Regulated battery.--The term "'regulated battery" means a rechargeable battery that-(A) contains a cadmium or a lead electrode or any combination of cadmium and lead electrodes; or (B) contains other electrode chemistries and is the subject of a determination by the Administrator under section 103(d). (8) Remanufactured product.-The term "'remanufactured product" means a rechargeable consumer product that has been altered by the replacement of parts, repackaged, or repaired after initial sale by the original manufacturer. SEC. 4. INFORMATION DISSEMINATION. The Administrator shall, in consultation with representatives of rechargeable battery manufacturers, rechargeable consumer product manufacturers, and retailers, establish a program to provide information to the public concerning the proper handling and disposal of used regulated batteries and rechargeable consumer products with nonremovable batteries. SEC. 5. ENFORCEMENT. (a) Civil Penalty.--When on the basis of any information the Administrator determines that a person has violated, or is in violation of, any requirement of this Act (except a requirement of section 104) the Administrator-- (1) in the case of any violation, may issue an order assessing a civil penalty of not more than $10,000 for each violation, or requiring compliance immediately or within a reasonable specified time period, or both; or (2) in the case of any violation or failure to comply with an order issued under this section, may commence a civil action in the United States district court in the district in which the violation occurred or in the district in which the violator resides for appropriate relief, including a temporary or permanent injunction. (b) Contents of Order.--An order under subsection (a)(1) shall state with reasonable specificity the nature of the violation. (c) Considerations.--In assessing a civil penalty under subsection (a)(1), the Administrator shall take into account the seriousness of the violation and any good faith efforts to comply with applicable requirements. (d) Finality of Order; Request for Hearing.--An order under subsection (a)(1) shall become final unless, not later than 30 days after the order is served, a person named in the order requests a hearing on the record. (e) Hearing.--On receiving a request under subsection (d), the Administrator shall promptly conduct a hearing on the record. (f) Subpoena Power.--In connection with any hearing on the record under this section, the Administrator may issue subpoenas for the attendance and testimony of witnesses and for the production of relevant papers, books, and documents. (g) Continued Violation After Expiration of Period for Compliance.-- If a violator fails to take corrective action within the time specified in an order under subsection (a)(1), the Administrator may assess a civil penalty of not more than $10,000 for the continued noncompliance with the order. (h) Savings Provision.--The Administrator may not take any enforcement action against a person for selling, offering for sale, or offering for promotional purposes to the ultimate consumer a battery or product covered by this Act that was-- (1) purchased ready for sale to the ultimate consumer; and (2) sold, offered for sale, or offered for promotional purposes without modification. The preceding sentence shall not apply to a person-- (A) who is the importer of a battery covered by this Act, and (B) who has knowledge of the chemical contents of the battery when such chemical contents make the sale, offering for sale, or offering for promotional purposes of such battery unlawful under title II of this Act.
361 SEC. 6. INFORMATION GATHERING AND ACCESS. (a) Records and Reports.--A person who is required to carry out the objectives of this Act, including-- (1) a regulated battery manufacturer; (2) a rechargeable consumer product manufacturer; (3) a mercury-containing battery manufacturer; and (4) an authorized agent of a person described in paragraph (1), (2), or (3), shall establish and maintain such records and report such information as the Administrator may by regulation reasonably require to carry out the objectives of this Act. (b) Access and Copying.--The Administrator or the Administrator's authorized representative, on presentation of credentials of the Administrator, may at reasonable times have access to and copy any records required to be maintained under subsection (a). (c) Confidentiality.--The Administrator shall maintain the confidentiality of documents and records that contain proprietary information. SEC. 7. STATE AUTHORITY. Nothing in this Act shall be construed to prohibit a State from enacting and enforcing a standard or requirement that is identical to a standard or requirement established or promulgated under this Act. Except as provided in sections 103(e) and 104, nothing in this Act shall be construed to prohibit a State from enacting and enforcing a standard or requirement that is more stringent than a standard or requirement established or promulgated under this Act. SEC. 8. AUTHORIZATION OF APPROPRIATIONS. There are authorized to be appropriated such sums as are necessary to carry out this Act. TITLE I--RECHARGEABLE BATTERY RECYCLING ACT SEC. 101. SHORT TITLE. This title may be cited as the "'Rechargeable Battery Recycling Act". SEC. 102. PURPOSE. The purpose of this title is to facilitate the efficient recycling or proper disposal of used nickel-cadmium rechargeable batteries, used small sealed leadacid rechargeable batteries, other regulated batteries, and such rechargeable batteries in used consumer products, by-- (1) providing for uniform labeling requirements and streamlined regulatory requirements for regulated battery collection programs; and (2) encouraging voluntary industry programs by eliminating barriers to funding the collection and recycling or proper disposal of used rechargeable batteries. SEC. 103. RECHARGEABLE CONSUMER PRODUCTS AND LABELING. (a) Prohibition.-- (1) In general.--No person shall sell for use in the United States a regulated battery that is ready for retail sale or a rechargeable consumer product that is ready for retail sale, if such battery or product was manufactured on or after the date 12 months after the date of enactment of this Act, unless the labeling requirements of subsection (b) are met and, in the case of a regulated battery, the regulated battery-- (A) is easily removable from the rechargeable consumer product; or (B) is sold separately. (2) Application.--Paragraph (1) does not apply to any of the following: (A) The sale of a remanufactured product unit unless paragraph (1) applied to the sale of the unit when originally manufactured. (B) The sale of a product unit intended for export purposes only. (b) Labeling.--Each regulated battery or rechargeable consumer product without an easily removable battery manufactured on or after the date that is 1 year after the date of enactment of this Act, whether produced domestically or imported shall bear the following labels: (1) 3 chasing arrows or a comparable recycling symbol. (2)(A) On each regulated battery which is a nickel-cadmium battery, the chemical name or the abbreviation "'Ni-Cd" and the phrase "'BATTERY MUST BE RECYCLED OR DISPOSED OF PROPERLY.". (B) On each regulated battery which is a lead-acid battery, "'Pb" or the words "'LEAD", "'RETURN", and "'RECYCLE" and if the
362 regulated battery is sealed, the phrase "'BATTERY MUST BE RECYCLED.". (3) On each rechargeable consumer product containing a regulated battery that is not easily removable, the phrase "'CONTAINS NICKEL-CADMIUM BATTERY. BATTERY MUST BE RECYCLED OR DISPOSED OF PROPERLY." or "'CONTAINS SEALED LEAD BATTERY. BATTERY MUST BE RECYCLED.", as applicable. (4) On the packaging of each rechargeable consumer product, and the packaging of each regulated battery sold separately from such a product, unless the required label is clearly visible through the packaging, the phrase "'CONTAINS NICKEL-CADMIUM BATTERY. BATTERY MUST BE RECYCLED OR DISPOSED OF PROPERLY." or "'CONTAINS SEALED LEAD BATTERY. BATTERY MUST BE RECYCLED.", as applicable. (c) Existing or Alternative Labeling.-- (1) Initial period.--For a period of 2 years after the date of enactment of this Act, regulated batteries, rechargeable consumer products containing regulated batteries, and rechargeable consumer product packages that are labeled in substantial compliance with subsection (b) shall be deemed to comply with the labeling requirements of subsection (b). (2) Certification.-- (A) In general.--On application by persons subject to the labeling requirements of subsection (b) or the labeling requirements promulgated by the Administrator under subsection (d), the Administrator shall certify that a different label meets the requirements of subsection (b) or (d), respectively, if the different label-- (i) conveys the same information as the label required under subsection (b) or (d), respectively; or (ii) conforms with a recognized intemational standard that is consistent with the overall purposes of this title. (B) Constructive certification.--Failure of the Administrator to object to an application under subparagraph (A) on the ground that a different label does not meet either of the conditions described in subparagraph (A) (i) or (ii) within 120 days after the date on which the application is made shall constitute certification for the purposes of this Act. (d) Rulemaking Authority of the Administrator.-- (1) In general.--If the Administrator determines that other rechargeable batteries having electrode chemistries different from regulated batteries are toxic and may cause substantial harm to human health and the environment if discarded into the solid waste stream for land disposal or incineration, the Administrator may, with the advice and counsel of State regulatory authorities and manufacturers of rechargeable batteries and rechargeable consumer products, and after public comment-- (A) promulgate labeling requirements for the batteries with different electrode chemistries, rechargeable consumer products containing such batteries that are not easily removable batteries, and packaging for the batteries and products; and (B) promulgate requirements for easy removability of regulated batteries from rechargeable consumer products designed to contain such batteries. (2) Substantial similarity.--The regulations promulgated under paragraph (1) shall be substantially similar to the requirements set forth in subsections (a) and (b). (e) Uniformity.--After the effective dates of a requirement set forth in subsection (a), (b), or (c) or a regulation promulgated by the Administrator under subsection (d), no Federal agency, State, or political subdivision of a State may enforce any easy removability or environmental labeling requirement for a rechargeable battery or rechargeable consumer product that is not identical to the requirement or regulation. (f) Exemptions.-- (1) In general.--With respect to any rechargeable consumer product, any person may submit an application to the Administrator for an exemption from the requirements of subsection (a) in accordance with the procedures under paragraph (2). The application shall include the following information: (A) A statement of the specific basis for the request for the exemption. (B) The name, business address, and telephone
363 number of the applicant. (2) Granting of exemption.--Not later than 60 days after receipt of an application under paragraph (1), the Administrator shall approve or deny the application. On approval of the application the Administrator shall grant an exemption to the applicant. The exemption shall be issued for a period of time that the Administrator determines to be appropriate, except that the period shall not exceed 2 years. The Administrator shall grant an exemption on the basis of evidence supplied to the Administrator that the manufacturer has been unable to commence manufacturing the rechargeable consumer product in compliance with the requirements of this section and with an equivalent level of product performance without the product-- (A) posing a threat to human health, safety, or the environment; or (B) violating requirements for approvals from governmental agencies or widely recognized private standard-setting organizations (including Underwriters Laboratories). (3) Renewal of exemption.--A person granted an exemption under paragraph (2) may apply for a renewal of the exemption in accordance with the requirements and procedures described in paragraphs (1) and (2). The Administrator may grant a renewal of such an exemption for a period of not more than 2 years after the date of the granting of the renewal. SEC. 104. REQUIREMENTS. (a) Batteries Subject to Certain Regulations.--The collection, storage, or transportation of used rechargeable batteries, batteries described in section 3(5)(C) or in title II, and used rechargeable consumer products containing rechargeable batteries that are not easily removable rechargeable batteries, shall, notwithstanding any law of a State or political subdivision thereof governing such collection, storage, or transportation, be regulated under applicable provisions of the regulations promulgated by the Environmental Protection Agency at 60 Fed. Reg. 25492 (May 11, 1995), as effective on May 11, 1995, except as provided in paragraph (2) of subsection (b) and except that-- (1) the requirements of 40 CFR 260.20, 260.40, and 260.41 and the equivalent requirements of an approved State program shall not apply, and (2) this section shall not apply to any lead acid battery managed under 40 CFR 266 subpart G or the equivalent requirements of an approved State program. (b) Enforcement Under Solid Waste Disposal Act.--(1) Any person who fails to comply with the requirements imposed by subsection (a) of this section may be subject to enforcement under applicable provisions of the Solid Waste Disposal Act. (2) States may implement and enforce the requirements of subsection (a) if the Administrator finds that-- (A) the State has adopted requirements that are identical to those referred to in subsection (a) governing the collection, storage, or transportation of batteries referred to in subsection (a); and (B) the State provides for enforcement of such requirements. TITLE II--MERCURY-CONTAINING BATTERY MANAGEMENT ACT SEC. 201. SHORT TITLE. This title may be cited as the "'Mercury-Containing Battery Management Act". SEC. 202. PURPOSE. The purpose of this title is to phase out the use of batteries containing mercury. SEC. 203. LIMITATIONS ON THE SALE OF ALKALINE- MANGANESE BATTERIES CONTAINING MERCURY. No person shall sell, offer for sale, or offer for promotional purposes any alkaline-manganese battery manufactured on or after the date of enactment of this Act, with a mercury content that was intentionally introduced (as distinguished from mercury that may be incidentally present in other materials), except that the limitation on mercury content in alkaline-manganese button cells shall be 25 milligrams of mercury per button cell.
364 SEC. 204. LIMITATIONS ON THE SALE OF ZINC- CARBON BATTERIES CONTAINING MERCURY. No person shall sell, offer for sale, or offer for promotional purposes any zinc-carbon battery manufactured on or after the date of enactment of this Act, that contains mercury that was intentionally introduced as described in section 203. SEC. 205. LIMITATIONS ON THE SALE OF BUTTON CELL MERCURIC-OXIDE BATTERIES. No person shall sell, offer for sale, or offer for promotional purposes any button cell mercuric-oxide battery for use in the United States on or after the date of enactment of this Act. SEC. 206. LIMITATIONS ON THE SALE OF OTHER MERCURIC-OXIDE BATTERIES. (a) Prohibition.--On or after the date of enactment of this Act, no person shall sell, offer for sale, or offer for promotional purposes a mercuric-oxide battery for use in the United States unless the battery manufacturer, or the importer of such a battery-- (1) identifies a collection site in the United States that has all required Federal, State, and local government approvals, to which persons may send used mercuric-oxide batteries for recycling or proper disposal; (2) informs each of its purchasers of mercuric-oxide batteries of the collection site identified under paragraph (1); and (3) informs each of its purchasers of mercuric-oxide batteries of a telephone number that the purchaser may call to get information about sending mercuric-oxide batteries for recycling or proper disposal. (b) Application of Section.--This section does not apply to a sale or offer of a mercuric-oxide button cell battery. SEC. 207. NEW PRODUCT OR USE. On petition of a person that proposes a new use for a battery technology described in this title or the use of a battery described in this title in a new product, the Administrator may exempt from this title the new use of the technology or the use of such a battery in the new product on the condition, if appropriate, that there exist reasonable safeguards to ensure that the resulting battery or product without an easily removable battery will not be disposed of in an incinerator, composting facility, or landfill (other than a facility regulated under subtitle C of the Solid Waste Disposal Act (42 U.S.C. 6921 et seq.)). Approved May 13, 1996.
365 EPA's Document on the States Adopting Advanced Legislation for Battery Management (December 14, 2000) State Legislation Affecting Rechargeable Batteries The 1996 Battery Act eased the burden on battery recycling programs by mandating national, uniform labeling requirements for Ni-Cd and certain small sealed lead-acid batteries and by making the Universal Waste Rule effective in all 50 states. The Battery Act preempts state labeling requirements for these battery types and state legislative and regulatory authority for the collection, storage, and transportation of Ni-Cd and other covered batteries. States can, however, adopt standards for battery recycling and disposal that are more stringent than existing Federal standards. States can also adopt more stringent requirements concerning the allowable mercury content in batteries. Several states have passed legislation mandating additional reductions in mercury beyond those in the Battery Act and prohibiting or restricting the disposal in MSW of batteries with the highest heavy metal content (i.e., Ni-Cd, small sealed lead-acid, and mercuric-oxide batteries). A handful of states have gone further, placing collection and management requirements on battery manufacturers and retailers to ensure that certain types of batteries are recycled or disposed of properly. Among the states and regional organizations that have developed far-reaching legislation for battery management--beyond the scope of Federal law--are: Florida A Florida law, effective April 1998, requires manufacturers, importers, and marketers (excluding retail marketers) of Ni-Cd, small sealed lead-acid, and certain mercuric oxide batteries to develop and implement management programs for collecting and taking back spent batteries. Under the law, manufacturers have the sole responsibility for reclaiming or disposing of the batteries returned to them. Manufacturers are also required to accept brands other than their own, as long as the retumed battery is of the same general type. The same law includes labeling requirements for rechargeable batteries and bans their disposal in the mixed solid waste stream. The law also bans the sale of mercury button cell batteries and limits the mercury content in other nonrechargeable batteries sold in the state. Iowa
Iowa has a comprehensive collection, transportation, and recycling or disposal program for Ni-Cd, household small sealed lead-acid, and mercuric-oxide batteries. Each of these battery types is banned from disposal in MSW. Manufacturers must provide a telephone number to consumers, offering information on returning batteries for recycling or proper disposal. Costs of the program may be built into the original cost of the battery.
Minnesota Minnesota law requires manufacturers of rechargeable Ni-Cd batteries or products containing those batteries to take responsibility for the costs of collecting and managing waste batteries to ensure that they do not enter the waste stream. Consumers are responsible for returning spent batteries to the collection points, which include retail
366 stores and Minnesota's household hazardous waste facilities. New Jersey New Jersey legislation passed in 1992 bans rechargeable batteries from the municipal waste stream and requires that manufacturers take back these batteries for recycling or proper disposal. The legislation also requires that rechargeable batteries be easily removable from products and labeled as to their content and proper disposal. For batteries that aren't currently being recycled, such as alkaline batteries containing mercury, the legislation limits the content of heavy metals. Rhode Island Rhode Island law prohibits the disposal of Ni-Cd, mercuric-oxide, and small sealed lead-acid batteries in municipal or commercial solid waste. Manufacturers of these battery types must ensure that a system exists for the proper collection, transportation, and processing of waste batteries (this requirement pertains only to manufacturers whose batteries are used by a government agency or an industrial, communications, or medical facility). Manufacturers must accept waste batteries returned to their facilities for proper processing. Vermont Vermont law bans the disposal of Ni-Cd, non-consumer mercuric-oxide, and small sealed lead-acid batteries in any district or municipality where an ongoing program exists for treating these wastes. Govemment agencies and industrial, communications, and medical facilities may not dispose of these battery types in MSW. Battery manufacturers must implement a system for the proper collection, transportation, and processing of these battery types and include the cost of collection in the sales transaction. Manufacturers must accept waste batteries retumed to their facilities. Northeast Waste Management Officials' Association The Northeast Waste Management Officials' Association (NEWMOA), a coalition of state waste program directors from New England and New York, has developed draft model legislation meant to reduce mercury in waste. The model legislation proposes a variety of approaches that states can use to manage mercury-containing products (such as batteries, thermometers, and certain electronic products) and wastes, with a goal of instituting consistent controls throughout the region. The proposed approaches focus on notification; product phase-outs and exemptions; product labeling; disposal bans; collection and recycling programs; and a mechanism for interstate cooperation. Bills based on the model legislation have been under consideration by legislators in New Hampshire and Maine. In April 2000, NEWMOA released a revised version of the model legislation following a series of public meetings and the collection of comments from stakeholders. New England Governors' Conference The New England Governors' Conference passed a resolution in September 2000 recommending, among other things, that each New England state work with its legislature to adopt mercury legislation based on the NEWMOA model (see above). The NEWMOA model legislation is meant to reduce the amount of mercury in waste
367 through strategies such as product phase-outs, product labeling, disposal bans, and collection and recycling programs. Certain types of mercury-containing batteries are among the products targeted by the model legislation. State Legislation Affecting Lead-Acid Batteries Most states have passed legislation prohibiting the disposal of lead-acid batteries (which are primarily automotive batteries) in landfills and incinerators and requiring retailers to accept used batteries for recycling when consumers purchase new batteries. For example, Maine has adopted legislation that requires retailers to either: l) accept a used battery upon sale of a new battery, or 2) collect a $10 deposit upon sale of a new battery, with the provision that the deposit shall be returned to the customer if he or she delivers a used lead-acid battery within 30 days of the date of sale. This legislation is based on a model developed by the lead-acid battery industry. Lead-acid batteries are collected for recycling through a reverse distribution system. Spent lead batteries are returned by consumers to retailers, picked up by wholesalers or battery manufacturers, and finally taken to secondary smelters for reclamation. These recycling programs have been highly successful: the nationwide recycling rate for leadacid batteries stands at roughly 95 percent, making them one of the most widely recycled consumer products.
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369 SUBJECT INDEX
ACCUREC GmbH, 163 Advanced battery systems recycling, 315 Advanced Lead Acid Battery Consortium (ALABC), 233,295 Accelerated Reduction and Elimination of Toxics (ARET), 9 Australian Mobile Telecommunications Association (AMTA), 127 Battery Act, 133 Battery Association of Japan (BAJ), 12, 87 Batteries annual acquisition rate, 56 collection efficiency, 55 and recycling rate, 76 collection methods, 184 collection, future options, 190 effect on human health, 307 and environment, 9 european legislation, 178 national legislation, 179, 181 emissions, 11-14 from MSW incinerators, 64 life cycle analysis, 2, 26 in MSW, 61-64 nominal compositions, 7 production in Japan, 88 raw materials production, 3, 5 rechargeable, european market, 39, 42 worldwide production, 41 recycling hydrometallurgical processes, 192 pyrometallurgical processes, 194 recycling score, 311 systems, use and maintenance, 15 sorting, 199 stages in, 202 UV sensing, 203 Efficiency, 205 systems, manufacture, 10 Big River Zinc, 149 British ECTEL, 125
Cadmium concentration in air, 14 in water, 13 in MSW, 37 daily intake levels, 19 emissions during production of NiCd, 22 for EV, 14 emissions during recycling, 22, 65 emissions from landfills, 66 hydrometallurgical separation, 150 partitioning in NiCd battery, 11 pyrometallurgical separation, 154 sources of human exposure, 8 COBAT (Italy), 235 institution, 235 collection network, 236 spent battery assignment to the recycling companies, 237 CollectNiCad, 37 Compositions of battery families, 7 Department of Energy (DOE), 296 Department of Transportation (DOT), 132 Disposal os spent batteries, 17 Dry cells and mercury, 88, 178, 183 composition, 90 recycling techniques, 90 Energizer, 149 Energy consumed in primary metal production, 9 Electric and electronic equipment, 36, 57-61 penetration rate, 46 timeframe for aquisition, 48 Electric arc furnaces, 209 recycling in, 215 Electric vehicle (EV) batteries for, 298 market, 297 general recycling issues, 308 pack characteristics, 298
370 Ecological and environmental impacts, 1,225 Energy to produce primary metals, 9 Environmental Protection Agency (EPA), 132, 305 Environmental impact values for battery metals, 26 for AA NiCd batteries, 30 Euro-Bat-Tri, 207 European Battery Directive EEC 91/57, 178, 234 European Portable Battery Association (EPBA), 182 European Union legislation on waste, 77 EV batteries environment/safety/ health issues, 305 recycling, 304 methods for, 308 Federal Resource Conservation and Recovery (RCRA), 130 GRS Batterien, 150
H2SO4 environmental impact, 227 health impact, 226 Human health impacts of battery components, 307 Heavy metal waste from AA NiCd batteries, 28 Hg in dry cells, 88, 179 Hoarding rate, 50 Hybrid Electric Vehicle (HEV) batteries, 297 International Cadmium Association, 11 International Metals Reclamation Company (INMETCO) NiCd battery recycling, 113, 171, Impact assessment evaluation methods, 24 KOBAR, 162 Lead-acid batteries collection in the European Union consortia-based, 246 non consortia-based, 239 rates, 248 costs, 249 collection in Japan, 92
components, 230 economical aspects, 228 environmental and health impact, 225 European Union regulations, 234 evolution of the market, 229 in EV, 310 recycling costs in Italy, 238 in the European Union, 239 recycling in Japan, 92 industrial, 93 small-size sealed, 94 recycling technologies, 252 comparison of, 260 fusion/reduction, 256 rotary kilns, 256 physical treatments, 253 "sink and float" separation, 253 hydrodynamic separation, 254 carbonatation, 255 flowchart, 257 Pb refining, 259 shipments (from Japan), 91 slag disposal costs, 250 transport to the recycling plants, 252 technological evolution in car accumulators, 231 in industrial accumulators, 233 VRLA, 233
Li2CO3from Li batteries, 289, 316 Lithium batteries Co recovering from, 277 components, 266 current recycling technologies, 277 wet methods, 278 pyrometaUurgical methods, 277 Toxco's cryoscopic technique, 279 economics of recycling, 277 environmental concerns, 272 hazards in recycling, 267, 270 primary batteries, 267 rechargeable batteries, 269 Li/SO2 analysis, 282 air emissions during recycling, 286 battery constituents, 284 chemical reactions, 286 recycling process, 284 Li/MnO2 analysis, 287
371 air emissions during recycling, 290 battery constituents, 287 biological effects, 290 recycling process, 288 safety measures during recycling, 271 sorting/packaging/transporting, 274 types, 266 Lithium-ion batteries, 7 in EV, 315 toxicity, 307 Lithium-polymer batteries, 267, 319 Manufacture of battery systems, 10 Mitsui Mining, 149 NiCd batteries, "Charge Up to Recycle Program", 109 collection of industrial, 68 closed processes, 160 hydrometallurgical process, 150 INMETCO HTMR process, 114 labeling, 111 market for industrial, 43 open processes, 157 performance parameters, 16 pyrometallurgical process, 154 recycling in Europe, 80, 148, 162, 163, 175, 176 Australia, 127 Mexico, 128 U.S.A., 105, 129 Canada, 105, 133 recycling rate formula, 80 sales in Europe, 42 sorting, 67 specific processes, 155 mechanical, 155 hydrometallurgical, 156 thermal, 157 transboundary movement within the OECD, 135, 139 transportation costs, 138 NiMH batteries in EV, 315 recycling, 317, toxicity, 306 Nippon Recycle Center, 148, 172 Optimized battery recycling processes
for NiMH, 317 for Li-ion, 319 for Li-polymer, 319 Organization for Economic Cooperation and Development (OECD), 10, 119 Members, 145 Partnership for a new Generation of Vehicles (PNVG), 295 Pb applications, 230 health impact, 225 mass in EV batteries, 312 reference dose, 226 Portable rechargeable batteries collection and recycling in Japan, 94 collection rates corrected with hoarding, 103 collection results in Japan, 100 collection schemes in Europe, 71 collection volumes in Europe, 68 color coding, 98 elimination modes, 51 hoarding issue, 43, 100 definitions, 45 hoarding rate, 50 in EEE: collection, 73 list of japanese recyclers, 99 market trends (Europe), 42 market trends (Japan), 95 metal contents, 97 quantity available for collection, 53 discarded in MSW, 54 Primary batteries additions to a steel melt, 211 definitions, 177 collection, 177 industry, 180 mercury in, 178, 183 recycling in the metals industry, 209 in the EAF, 210, 215 treatment os spent, in Japan, 88 waste stream analysis, 195 Rechargeable Battery Recycling Corporation (RBRC) in U.S.A. and Canada, 134 Charge Up to Recycle Program, 109, 112
372 Replacement batteries, 46 SAFT AB, 164 SNAM, 167 SORTBAT battery sorting, 204 Spent batteries, collection programs in Europe, 69 Starting, Lighting, Ignition (SLI) batteries, 35 Soci6t6 de Collecte et Recyclage du Mat6riel Electrique (SCRELEC), 74-76 Sources of human Cd exposures, 8 Toho Zinc, 149 Total life cycle analysis (LCA), 2 Toxco-Kinsbursky partnership, 304 Toxco-Nissan partnership, 305 Toxicity Characteristic Leaching Procedure (TCLP), 129, 307 UN environmental indicators, 77 Union Mini~re, 149 Universal Waste Rule, 132 United States Advanced Battery Consortium (USABC), 295 Valdi process, 219 Waelz kilns, 221 Waste from electric and electronic Equipment, 37 World Health Organization (WHO), 18, 226 Zero Emission Vehicle (ZEV) programs in California, 295
