Alternative Energy

First Edition, 2011

ISBN 978-93-81157-39-8

© All rights reserved.

Published by: The English Press 4735/22 Prakashdeep Bldg, Ansari Road, Darya Ganj, Delhi - 110002 Email: [email protected] 

Table of Contents Chapter 1- Introduction to Alternative Energy Chapter 2 - Alternative Fuel Chapter 3 - Alcohol Fuel Chapter 4 - Butanol Fuel Chapter 5 - Ethanol Fuel Chapter 6 - Methanol Fuel Chapter 7 - Coalbed Methane Chapter 8 - Biomass Briquettes

Chapter- 1

Introduction to Alternative Energy

Offshore wind turbines near Copenhagen Alternative energy is an umbrella term that refers to any source of usable energy intended to replace fuel sources without the undesired consequences of the replaced fuels. The term "alternative" presupposes a set of undesirable energy technologies against which "alternative energies" are contrasted. As such, the list of energy technologies excluded is an indicator of what problems that the alternative technologies are intended to address. Controversies regarding dominant sources of energy and their alternatives have a long history. The nature of what was regarded alternative energy sources has changed considerably over time, and today, because of the variety of energy choices and differing goals of their advocates, defining some energy types as "alternative" is highly controversial. In a general sense in contemporary society, alternative energy is that which is produced without the undesirable consequences of the burning of fossil fuels, such as high carbon dioxide emissions, which is considered to be the major contributing factor of global warming according to the Intergovernmental Panel on Climate Change. Sometimes, this less comprehensive meaning of "alternative energy" excludes nuclear energy (e.g. as defined in the Michigan Next Energy Authority Act of 2002).

Definitions

Source

Definition energy fuelled in ways that do not use up Oxford natural resources or harm the Dictionary environment. energy derived from sources that do not Princeton use up natural resources or harm the WordNet environment. Responding to energy derived from nontraditional Climate Change sources (e.g., compressed natural gas, 2007 solar, hydroelectric, wind). Natural energy that is not popularly used and is Resources usually environmentally sound, such as Defense solar or wind energy (as opposed to fossil Council fuels). Fuel sources that are other than those Materials derived from fossil fuels. Typically used interchangeably for renewable energy. Management Examples A** include: wind, solar, Services biomass, wave and tidal energy. Torridge Energy generated from alternatives to District Council fossil fuel. Need not be renewable.

History Historians of economies have studied the key transitions to alternative energies and regard the transitions as pivotal in bringing about significant economic change. Prior to shift to an alternative energy, supplies of the dominant energy type became erratic, accompanied by rapid increases in energy prices.

Coal as an alternative to wood Historian Norman F. Cantor describes how in the late medieval period, coal was the new alternative fuel to save the society from overuse of the dominant fuel, wood: "Europeans had lived in the midst of vast forests throughout the earlier medieval centuries. After 1250 they became so skilled at deforestation that by 1500 AD they were running short of wood for heating and cooking... By 1500 Europe was on the edge of a fuel and nutritional disaster, [from] which it was saved in the sixteenth century only by the burning of soft coal and the cultivation of potatoes and maize."

Petroleum as an alternative to whale oil

Whale oil was the dominant form of lubrication and fuel for lamps in the early 19th century, but the depletion of the whale stocks by mid century caused whale oil prices to skyrocket setting the stage for the adoption of petroleum which was first commercialized in Pennsylvania in 1859.

Alcohol as an alternative to fossil fuels In 1917, Alexander Graham Bell advocated ethanol from corn and other foodstuffs as an alternative to coal and oil, stating that the world was in measurable distance of depleting these fuels. For Bell, the problem requiring an alternative was lack of renewability of orthodox energy sources. Since the 1970s, Brazil has had an ethanol fuel program which has allowed the country to become the world's second largest producer of ethanol (after the United States) and the world's largest exporter. Brazil’s ethanol fuel program uses modern equipment and cheap sugar cane as feedstock, and the residual cane-waste (bagasse) is used to process heat and power. There are no longer light vehicles in Brazil running on pure gasoline. By the end of 2008 there were 35,000 filling stations throughout Brazil with at least one ethanol pump. Cellulosic ethanol can be produced from a diverse array of feedstocks, and involves the use of the whole crop. This new approach should increase yields and reduce the carbon footprint because the amount of energy-intensive fertilizers and fungicides will remain the same, for a higher output of usable material. As of 2008, there are nine commercial cellulosic ethanol plants which are either operating, or under construction, in the United States.

Coal gasification as an alternative to petroleum In the 1970s, President Jimmy Carter's administration advocated coal gasification as an alternative to expensive imported oil. The program, including the Synthetic Fuels Corporation was scrapped when petroleum prices plummeted in the 1980s. The carbon footprint and environmental impact of coal gasification are both very high.

Renewable energy vs non-renewable energy Renewable energy is generated from natural resources—such as sunlight, wind, rain, tides and geothermal heat—which are renewable (naturally replenished). When comparing the processes for producing energy, there remain several fundamental differences between renewable energy and fossil fuels. The process of producing oil, coal, or natural gas fuel is a difficult and demanding process that requires a great deal of complex equipment, physical and chemical processes. On the other hand, alternative energy can be widely produced with basic equipment and naturally basic processes. Wood, the most renewable and available alternative energy, burns the same amount of carbon it would emit if it degraded naturally.

Ecologically friendly alternatives

Renewable energy sources such as biomass are sometimes regarded as an alternative to ecologically harmful fossil fuels. Renewables are not inherently alternative energies for this purpose. For example, the Netherlands, once leader in use of palm oil as a biofuel, has suspended all subsidies for palm oil due to the scientific evidence that their use "may sometimes create more environmental harm than fossil fuels". The Netherlands government and environmental groups are trying to trace the origins of imported palm oil, to certify which operations produce the oil in a responsible manner. Regarding biofuels from foodstuffs, the realization that converting the entire grain harvest of the US would only produce 16% of its auto fuel needs, and the decimation of Brazil's CO2 absorbing tropical rain forests to make way for biofuel production has made it clear that placing energy markets in competition with food markets results in higher food prices and insignificant or negative impact on energy issues such as global warming or dependence on foreign energy. Recently, alternatives to such undesirable sustainable fuels are being sought, such as commercially viable sources of cellulosic ethanol.

Relatively new concepts for alternative energy Algae fuel Algae fuel is a biofuel which is derived from algae. During photosynthesis, algae and other photosynthetic organisms capture carbon dioxide and sunlight and convert it into oxygen and biomass. The benefits of algal biofuel are that it can be produced industrially, thereby obviating the use of arable land and food crops (such as soy, palm, and canola), and that it has a very high oil yield as compared to all other sources of biofuel.

Biomass briquettes Biomass briquettes are being developed in the developing world as an alternative to charcoal. The technique involves the conversion of almost any plant matter into compressed briquettes that typically have about 70% the calorific value of charcoal. There are relatively few examples of large scale briquette production. One exception is in North Kivu, in eastern Democratic Republic of Congo, where forest clearance for charcoal production is considered to be the biggest threat to Mountain Gorilla habitat. The staff of Virunga National Park have successfully trained and equipped over 3500 people to produce biomass briquettes, thereby replacing charcoal produced illegally inside the national park, and creating significant employment for people living in extreme poverty in conflict affected areas. Biogas digestion Biogas digestion deals with harnessing the methane gas that is released when waste breaks down. This gas can be retrieved from garbage or sewage systems. Biogas digesters are used to process methane gas by having bacteria break down biomass in an anaerobic environment. The methane gas that is collected and refined can be used as an energy source for various products.

Biological Hydrogen Production Hydrogen gas is a completely clean burning fuel; its only by-product is water. It also contains relatively high amount of energy compared with other fuels due to its chemical structure. 2H2 + O2 → 2H2O + High Energy High Energy + 2H2O → 2H2 + O2 This requires a high-energy input, making commercial hydrogen very inefficient. Use of a biological vector as a means to split water, and therefore produce hydrogen gas, would allow for the only energy input to be solar radiation. Biological vectors can include bacteria or more commonly algae. This process is known as biological hydrogen production. It requires the use of single celled organisms to create hydrogen gas through fermentation. Without the presence of oxygen, also known as an anaerobic environment, regular cellular respiration cannot take place and a process known as fermentation takes over. A major by-product of this process is hydrogen gas. If we could implement this on a large scale, then we could take sunlight, nutrients and water and create hydrogen gas to be used as a dense source of energy. Large-scale production has proven difficult. It was not until 1999 that we were able to even induce these anaerobic conditions by sulfur deprivation. Since the fermentation process is an evolutionary back up, turned on during stress, the cells would die after a few days. In 2000, a two-stage process was developed to take the cells in and out of anaerobic conditions and therefore keep them alive. For the last ten years, finding a way to do this on a large-scale has been the main goal of research. Careful work is being done to ensure an efficient process before large-scale production, however once a mechanism is developed, this type of production could solve our energy needs.

Floating wind farms Floating wind farms are similar to a regular wind farm, but the difference is that they float in the middle of the ocean. Offshore wind farms can be placed in water up to 40 metres (130 ft) deep, whereas floating wind turbines can float in water up to 700 metres (2,300 ft) deep. The advantage of having a floating wind farm is to be able to harness the winds from the open ocean. Without any obstructions such as hills, trees and buildings, winds from the open ocean can reach up to speeds twice as fast as coastal areas. A Norwegian energy company, StatoilHydro, will launch the first test period for the floating wind farms in autumn 2009.

Investing in alternative energy Over the last three years publicly traded alternative energy have been very volatile, with some 2007 returns in excess of 100%, some 2008 returns down 90% or more, and peakto-trough returns in 2009 again over 100%. In general there are three subsegments of “alternative” energy investment: solar energy, wind energy and hybrid electric vehicles.

Alternative energy sources which are renewable, free and have lower carbon emissions than what we have now are wind energy, solar energy, geothermal energy, and bio fuels. Each of these four segments involve very different technologies and investment concerns. For example, photovoltaic solar energy is based on semiconductor processing and accordingly, benefits from steep cost reductions similar to those realized in the microprocessor industry (i.e., driven by larger scale, higher module efficiency, and improving processing technologies). PV solar energy is perhaps the only energy technology whose electricity generation cost could be reduced by half or more over the next 5 years. Better and more efficient manufacturing process and new technology such as advanced thin film solar cell is a good example of that helps to reduce industry cost. The economics of solar PV electricity are highly dependent on silicon pricing and even companies whose technologies are based on other materials (e.g., First Solar) are impacted by the balance of supply and demand in the silicon market. In addition, because some companies sell completed solar cells on the open market (e.g., Q-Cells), this creates a low barrier to entry for companies that want to manufacture solar modules, which in turn can create an irrational pricing environment. In contrast, because wind power has been harnessed for over 100 years, its underlying technology is relatively stable. Its economics are largely determined by siting (e.g., how hard the wind blows and the grid investment requirements) and the prices of steel (the largest component of a wind turbine) and select composites (used for the blades). Because current wind turbines are often in excess of 100 meters high, logistics and a global manufacturing platform are major sources of competitive advantage. These issues and others were explored in a research report by Sanford Bernstein. Some of its key conclusions are shown here.

Alternative energy in transportation Due to steadily rising gas prices in 2008 with the US national average price per gallon of regular unleaded gas rising above $4.00 at one point, there has been a steady movement towards developing higher fuel efficiency and more alternative fuel vehicles for consumers. In response, many smaller companies have rapidly increased research and development into radically different ways of powering consumer vehicles. Hybrid and battery electric vehicles are commercially available and are gaining wider industry and consumer acceptance worldwide. For example, Nissan USA introduced the world's first mass-production Electric Vehicle "Nissan Leaf".

Making Alternative Energy Mainstream Before alternative energy becomes main-stream there are a few crucial obstacles that it must overcome: First there must be increased understanding of how alternative energies

work and why they are beneficial; secondly the availability components for these systems must increase and lastly the pay-off time must be decreased. For example, electric vehicles (EV) and Plug-in Hybrid Electric Vehicles (PHEV) are on the rise. These vehicles depend heavily on an effective charging infrastructure such as a smart grid infrastructure to be able to implement electricity as mainstream alternative energy for future transportations.

Chapter- 2

Alternative Fuel

Typical Brazilian filling station with four alternative fuels for sale: biodiesel (B3), gasohol (E25), neat ethanol (E100), and compressed natural gas (CNG). Piracicaba, São Paulo, Brazil. Alternative fuels, also known as non-conventional or advanced fuels, are any materials or substances that can be used as fuels, other than conventional fuels. Conventional fuels include: fossil fuels (petroleum (oil), coal, propane, and natural gas), and nuclear materials such as uranium.

Some well known alternative fuels include biodiesel, bioalcohol (methanol, ethanol, butanol), chemically stored electricity (batteries and fuel cells), hydrogen, non-fossil methane, non-fossil natural gas, vegetable oil,and other biomass sources.

Background The main purpose of fuel is to store energy, which should be in a stable form and can be easily transported to the place of production. Almost all fuels are chemical fuels. We as a user use this fuel to perform mechanical work, such as powering an engine.

Biofuel

Information on pump regarding ethanol fuel blend up to 10%, California.

Bus run on biodiesel. Biofuels are a wide range of fuels which are in some way derived from biomass. The term covers solid biomass, liquid fuels and various biogases. Biofuels are gaining increased public and scientific attention, driven by factors such as oil price spikes, the need for increased energy security, and concern over greenhouse gas emissions from fossil fuels. Bioethanol is an alcohol made by fermenting the sugar components of plant materials and it is made mostly from sugar and starch crops. With advanced technology being developed, cellulosic biomass, such as trees and grasses, are also used as feedstocks for ethanol production. Ethanol can be used as a fuel for vehicles in its pure form, but it is usually used as a gasoline additive to increase octane and improve vehicle emissions. Bioethanol is widely used in the USA and in Brazil. Biodiesel is made from vegetable oils, animal fats or recycled greases. Biodiesel can be used as a fuel for vehicles in its pure form, but it is usually used as a diesel additive to reduce levels of particulates, carbon monoxide, and hydrocarbons from diesel-powered vehicles. Biodiesel is produced from oils or fats using transesterification and is the most common biofuel in Europe. Biofuels provided 1.8% of the world's transport fuel in 2008. Investment into biofuels production capacity exceeded $4 billion worldwide in 2007 and is growing.

Liquid fuels for transportation

Most transportation fuels are liquids, because vehicles usually require high energy density, as occurs in liquids and solids. High power density can be provided most inexpensively by an internal combustion engine; these engines require clean burning fuels, to keep the engine clean and minimize air pollution. The fuels that are easiest to burn cleanly are typically liquids and gases. Thus liquids (and gases that can be stored in liquid form) meet the requirements of being both portable and clean burning. Also, liquids and gases can be pumped, which means handling is easily mechanized, and thus less laborious.

First generation biofuels 'First-generation biofuels' are biofuels made from sugar, starch, and vegetable oil. Bioalcohols

Neat ethanol on the left (A), gasoline on the right (G) at a filling station in Brazil. Biologically produced alcohols, most commonly ethanol, and less commonly propanol and butanol, are produced by the action of microorganisms and enzymes through the fermentation of sugars or starches (easiest), or cellulose (which is more difficult). Biobutanol (also called biogasoline) is often claimed to provide a direct replacement for gasoline, because it can be used directly in a gasoline engine (in a similar way to biodiesel in diesel engines).

Ethanol fuel is the most common biofuel worldwide, particularly in Brazil. Alcohol fuels are produced by fermentation of sugars derived from wheat, corn, sugar beets, sugar cane, molasses and any sugar or starch that alcoholic beverages can be made from (like potato and fruit waste, etc.). The ethanol production methods used are enzyme digestion (to release sugars from stored starches), fermentation of the sugars, distillation and drying. The distillation process requires significant energy input for heat (often unsustainable natural gas fossil fuel, but cellulosic biomass such as bagasse, the waste left after sugar cane is pressed to extract its juice, can also be used more sustainably).

The Koenigsegg CCXR Edition at the 2008 Geneva Motor Show. This is an "environmentally friendly" version of the CCX, which can use E85 and E100. Ethanol can be used in petrol engines as a replacement for gasoline; it can be mixed with gasoline to any percentage. Most existing car petrol engines can run on blends of up to 15% bioethanol with petroleum/gasoline. Ethanol has a smaller energy density than gasoline, which means it takes more fuel (volume and mass) to produce the same amount of work. An advantage of ethanol (CH3CH2OH) is that it has a higher octane rating than ethanol-free gasoline available at roadside gas stations which allows an increase of an engine's compression ratio for increased thermal efficiency. In high altitude (thin air) locations, some states mandate a mix of gasoline and ethanol as a winter oxidizer to reduce atmospheric pollution emissions. Ethanol is also used to fuel bioethanol fireplaces. As they do not require a chimney and are "flueless", bio ethanol fires are extremely useful for new build homes and apartments

without a flue. The downside to these fireplaces, is that the heat output is slightly less than electric and gas fires. In the current alcohol-from-corn production model in the United States, considering the total energy consumed by farm equipment, cultivation, planting, fertilizers, pesticides, herbicides, and fungicides made from petroleum, irrigation systems, harvesting, transport of feedstock to processing plants, fermentation, distillation, drying, transport to fuel terminals and retail pumps, and lower ethanol fuel energy content, the net energy content value added and delivered to consumers is very small. And, the net benefit (all things considered) does little to reduce un-sustainable imported oil and fossil fuels required to produce the ethanol. Although ethanol-from-corn and other food stocks has implications both in terms of world food prices and limited, yet positive energy yield (in terms of energy delivered to customer/fossil fuels used), the technology has led to the development of cellulosic ethanol. According to a joint research agenda conducted through the U.S. Department of Energy, the fossil energy ratios (FER) for cellulosic ethanol, corn ethanol, and gasoline are 10.3, 1.36, and 0.81, respectively. Many car manufacturers are now producing flexible-fuel vehicles (FFV's), which can safely run on any combination of bioethanol and petrol, up to 100% bioethanol. They dynamically sense exhaust oxygen content, and adjust the engine's computer systems, spark, and fuel injection accordingly. This adds initial cost and ongoing increased vehicle maintenance. As with all vehicles, efficiency falls and pollution emissions increase when FFV system maintenance is needed (regardless of the fuel mix being used), but is not performed. FFV internal combustion engines are becoming increasingly complex, as are multiple-propulsion-system FFV hybrid vehicles, which impacts cost, maintenance, reliability, and useful lifetime longevity. Even dry ethanol has roughly one-third lower energy content per unit of volume compared to gasoline, so larger / heavier fuel tanks are required to travel the same distance, or more fuel stops are required. With large current unsustainable, non-scalable subsidies, ethanol fuel still costs much more per distance traveled than current high gasoline prices in the United States. Methanol is currently produced from natural gas, a non-renewable fossil fuel. It can also be produced from biomass as biomethanol. The methanol economy is an interesting alternative to get to the hydrogen economy, compared to today's hydrogen production from natural gas. But this process is not the state-of-the-art clean solar thermal energy process, where hydrogen production is directly produced from water. Butanol is formed by ABE fermentation (acetone, butanol, ethanol) and experimental modifications of the process show potentially high net energy gains with butanol as the only liquid product. Butanol will produce more energy and allegedly can be burned "straight" in existing gasoline engines (without modification to the engine or car), and is less corrosive and less water soluble than ethanol, and could be distributed via existing

infrastructures. DuPont and BP are working together to help develop Butanol. E. coli have also been successfully engineered to produce Butanol by hijacking their amino acid metabolism. Fermentation is not the only route to forming biofuels or bioalcohols. One can obtain methanol, ethanol, butanol or mixed alcohol fuels through pyrolysis of biomass including agricultural waste or algal biomass. The most exciting of these pyrolysis alcoholic fuels is the pyrolysis biobutanol. The product can be made with limited water use and most places in the world. Green diesel Green diesel, also known as renewable diesel, is a form of diesel fuel which is derived from renewable feedstock rather than the fossil feedstock used in most diesel fuels. Green diesel feedstock can be sourced from a variety of oils including canola, algae, jatropha and salicornia in addition to tallow. Green diesel uses traditional fractional distillation to process the oils, not to be confused with biodiesel which is chemically quite different and processed using transesterification. “Green Diesel” as commonly known in Ireland should not be confused with dyed green diesel sold at a lower tax rate for agriculture purposes, using the dye allows custom officers to determine if a person is using the cheaper diesel in higher taxed applications such as commercial haulage or cars. Biodiesel

In some countries biodiesel is less expensive than conventional diesel. Biodiesel is the most common biofuel in Europe. It is produced from oils or fats using transesterification and is a liquid similar in composition to fossil/mineral diesel. Chemically, it consists mostly of fatty acid methyl (or ethyl) esters (FAMEs). Feedstocks for biodiesel include animal fats, vegetable oils, soy, rapeseed, jatropha, mahua, mustard, flax, sunflower, palm oil, hemp, field pennycress, pongamia pinnata and algae. Pure biodiesel (B100) is the lowest emission diesel fuel. Although liquefied petroleum gas and hydrogen have cleaner combustion, they are used to fuel much less efficient petrol engines and are not as widely available. Biodiesel can be used in any diesel engine when mixed with mineral diesel. In some countries manufacturers cover their diesel engines under warranty for B100 use, although

Volkswagen of Germany, for example, asks drivers to check by telephone with the VW environmental services department before switching to B100. B100 may become more viscous at lower temperatures, depending on the feedstock used. In most cases, biodiesel is compatible with diesel engines from 1994 onwards, which use 'Viton' (by DuPont) synthetic rubber in their mechanical fuel injection systems. Electronically controlled 'common rail' and 'unit injector' type systems from the late 1990s onwards may only use biodiesel blended with conventional diesel fuel. These engines have finely metered and atomized multi-stage injection systems that are very sensitive to the viscosity of the fuel. Many current generation diesel engines are made so that they can run on B100 without altering the engine itself, although this depends on the fuel rail design. Since biodiesel is an effective solvent and cleans residues deposited by mineral diesel, engine filters may need to be replaced more often, as the biofuel dissolves old deposits in the fuel tank and pipes. It also effectively cleans the engine combustion chamber of carbon deposits, helping to maintain efficiency. In many European countries, a 5% biodiesel blend is widely used and is available at thousands of gas stations. Biodiesel is also an oxygenated fuel, meaning that it contains a reduced amount of carbon and higher hydrogen and oxygen content than fossil diesel. This improves the combustion of fossil diesel and reduces the particulate emissions from un-burnt carbon. Biodiesel is also safe to handle and transport because it is as biodegradable as sugar, 10 times less toxic than table salt, and has a high flash point of about 300 F (148 C) compared to petroleum diesel fuel, which has a flash point of 125 F (52 C). In the USA, more than 80% of commercial trucks and city buses run on diesel. The emerging US biodiesel market is estimated to have grown 200% from 2004 to 2005. "By the end of 2006 biodiesel production was estimated to increase fourfold [from 2004] to more than 1 billion gallons". Vegetable oil

Filtered waste vegetable oil. Straight unmodified edible vegetable oil is generally not used as fuel, but lower quality oil can be used for this purpose. Used vegetable oil is increasingly being processed into biodiesel, or (more rarely) cleaned of water and particulates and used as a fuel. Also here, as with 100% biodiesel (B100), to ensure that the fuel injectors atomize the vegetable oil in the correct pattern for efficient combustion, vegetable oil fuel must be heated to reduce its viscosity to that of diesel, either by electric coils or heat exchangers. This is easier in warm or temperate climates. Big corporations like MAN B&W Diesel, Wärtsilä and Deutz AG as well as a number of smaller companies such as Elsbett offer engines that are compatible with straight vegetable oil, without the need for after-market modifications. Vegetable oil can also be used in many older diesel engines that do not use common rail or unit injection electronic diesel injection systems. Due to the design of the combustion chambers in indirect injection engines, these are the best engines for use with vegetable oil. This system allows the relatively larger oil molecules more time to burn. Some older engines, especially Mercedes are driven experimentally by enthusiasts without any conversion, a handful of drivers have experienced limited success with earlier pre"Pumpe Duse" VW TDI engines and other similar engines with direct injection. Several companies like Elsbett or Wolf have developed professional conversion kits and successfully installed hundreds of them over the last decades.

Oils and fats can be hydrogenated to give a diesel substitute. The resulting product is a straight chain hydrocarbon, high in cetane, low in aromatics and sulfur and does not contain oxygen. Hydrogenated oils can be blended with diesel in all proportions Hydrogenated oils have several advantages over biodiesel, including good performance at low temperatures, no storage stability problems and no susceptibility to microbial attack. Bioethers Bio ethers (also referred to as fuel ethers or oxygenated fuels) are cost-effective compounds that act as octane rating enhancers. They also enhance engine performance, whilst significantly reducing engine wear and toxic exhaust emissions. Greatly reducing the amount of ground-level ozone, they contribute to the quality of the air we breathe. Biogas

Pipes carrying biogas Biogas is methane produced by the process of anaerobic digestion of organic material by anaerobes. It can be produced either from biodegradable waste materials or by the use of energy crops fed into anaerobic digesters to supplement gas yields. The solid byproduct, digestate, can be used as a biofuel or a fertilizer. •

Biogas can be recovered from mechanical biological treatment waste processing systems. Note:Landfill gas is a less clean form of biogas which is produced in landfills through naturally occurring anaerobic digestion. If it escapes into the atmosphere it is a potential greenhouse gas.

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Farmers can produce biogas from manure from their cows by getting a anaerobic digester (AD).

Syngas Syngas, a mixture of carbon monoxide and hydrogen, is produced by partial combustion of biomass, that is, combustion with an amount of oxygen that is not sufficient to convert the biomass completely to carbon dioxide and water. Before partial combustion the biomass is dried, and sometimes pyrolysed. The resulting gas mixture, syngas, is more efficient than direct combustion of the original biofuel; more of the energy contained in the fuel is extracted. •

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Syngas may be burned directly in internal combustion engines or turbines. The wood gas generator is a wood-fueled gasification reactor mounted on an internal combustion engine. Syngas can be used to produce methanol and hydrogen, or converted via the Fischer-Tropsch process to produce a diesel substitute, or a mixture of alcohols that can be blended into gasoline. Gasification normally relies on temperatures >700°C. Lower temperature gasification is desirable when co-producing biochar but results in a Syngas polluted with tar.

Solid biofuels Examples include wood, sawdust, grass cuttings, domestic refuse, charcoal, agricultural waste, non-food energy crops (see picture), and dried manure. When raw biomass is already in a suitable form (such as firewood), it can burn directly in a stove or furnace to provide heat or raise steam. When raw biomass is in an inconvenient form (such as sawdust, wood chips, grass, urban waste wood, agricultural residues), the typical process is to densify the biomass. This process includes grinding the raw biomass to an appropriate particulate size (known as hogfuel), which depending on the densification type can be from 1 to 3 cm (1 in), which is then concentrated into a fuel product. The current types of processes are wood pellet, cube, or puck. The pellet process is most common in Europe and is typically a pure wood product. The other types of densification are larger in size compared to a pellet and are compatible with a broad range of input feedstocks. The resulting densified fuel is easier to transport and feed into thermal generation systems such as boilers. A problem with the combustion of raw biomass is that it emits considerable amounts of pollutants such as particulates and PAHs (polycyclic aromatic hydrocarbons). Even modern pellet boilers generate much more pollutants than oil or natural gas boilers. Pellets made from agricultural residues are usually worse than wood pellets, producing much larger emissions of dioxins and chlorophenols.

Notwithstanding the above noted study, numerous studies have shown that biomass fuels have significantly less impact on the environment than fossil based fuels. Of note is the U.S. Department of Energy Laboratory, Operated by Midwest Research Institute Biomass Power and Conventional Fossil Systems with and without CO2 Sequestration – Comparing the Energy Balance, Greenhouse Gas Emissions and Economics Study. Power generation emits significant amounts of greenhouse gases (GHGs), mainly carbon dioxide (CO2). Sequestering CO2 from the power plant flue gas can significantly reduce the GHGs from the power plant itself, but this is not the total picture. CO2 capture and sequestration consumes additional energy, thus lowering the plant's fuel-to-electricity efficiency. To compensate for this, more fossil fuel must be procured and consumed to make up for lost capacity. Taking this into consideration, the global warming potential (GWP), which is a combination of CO2, methane (CH4), and nitrous oxide (N2O) emissions, and energy balance of the system need to be examined using a life cycle assessment. This takes into account the upstream processes which remain constant after CO2 sequestration as well as the steps required for additional power generation. firing biomass instead of coal led to a 148% reduction in GWP. A derivative of solid biofuel is biochar, which is produced by biomass pyrolysis. Biochar made from agricultural waste can substitute for wood charcoal. As wood stock becomes scarce this alternative is gaining ground. In eastern Democratic Republic of Congo, for example, biomass briquettes are being marketed as an alternative to charcoal in order to protect Virunga National Park from deforestation associated with charcoal production.

Second generation biofuels Supporters of biofuels claim that a more viable solution is to increase political and industrial support for, and rapidity of, second-generation biofuel implementation from non-food crops. These include waste biomass, the stalks of wheat, corn, wood, and special-energy-or-biomass crops (e.g. Miscanthus). Second generation (2G) biofuels use biomass to liquid technology, including cellulosic biofuels. Many second generation biofuels are under development such as biohydrogen, biomethanol, DMF, Bio-DME, Fischer-Tropsch diesel, biohydrogen diesel, mixed alcohols and wood diesel. Cellulosic ethanol production uses non-food crops or inedible waste products and does not divert food away from the animal or human food chain. Lignocellulose is the "woody" structural material of plants. This feedstock is abundant and diverse, and in some cases (like citrus peels or sawdust) it is in itself a significant disposal problem. Producing ethanol from cellulose is a difficult technical problem to solve. In nature, ruminant livestock (like cattle) eat grass and then use slow enzymatic digestive processes to break it into glucose (sugar). In cellulosic ethanol laboratories, various experimental processes are being developed to do the same thing, and then the sugars released can be fermented to make ethanol fuel. In 2009 scientists reported developing, using "synthetic

biology", "15 new highly stable fungal enzyme catalysts that efficiently break down cellulose into sugars at high temperatures", adding to the 10 previously known. The use of high temperatures, has been identified as an important factor in improving the overall economic feasibility of the biofuel industry and the identification of enzymes that are stable and can operate efficiently at extreme temperatures is an area of active research. In addition, research conducted at TU Delft by Jack Pronk has shown that elephant yeast, when slightly modified can also create ethanol from non-edible ground sources (e.g. straw). The recent discovery of the fungus Gliocladium roseum points toward the production of so-called myco-diesel from cellulose. This organism was recently discovered in the rainforests of northern Patagonia and has the unique capability of converting cellulose into medium length hydrocarbons typically found in diesel fuel. Scientists also work on experimental recombinant DNA genetic engineering organisms that could increase biofuel potential. Scientists working in New Zealand have developed a technology to use industrial waste gases from steel mills as a feedstock for a microbial fermentation process to produce ethanol. Second, third, and fourth generation biofuels are also called advanced biofuels.

Third generation biofuels Algae fuel, also called oilgae or third generation biofuel, is a biofuel from algae. Algae are low-input, high-yield feedstocks to produce biofuels. Based on laboratory experiments, it is claimed that algae can produce up to 30 times more energy per acre than land crops such as soybeans, but these yields have yet to be produced commercially. With the higher prices of fossil fuels (petroleum), there is much interest in algaculture (farming algae). One advantage of many biofuels over most other fuel types is that they are biodegradable, and so relatively harmless to the environment if spilled. Algae fuel still has its difficulties though, for instance to produce algae fuels it must be mixed uniformly, which, if done by agitation, could affect biomass growth. The United States Department of Energy estimates that if algae fuel replaced all the petroleum fuel in the United States, it would require only 15,000 square miles (38,849 square kilometers), which is roughly the size of Maryland, or less than one seventh the amount of land devoted to corn in 2000. Algae, such as Botryococcus braunii and Chlorella vulgaris are relatively easy to grow, but the algal oil is hard to extract. There are several approaches, some of which work better than others. Macroalgae (seaweed) also have a great potential for bioethanol and biogas production. Ethanol from living algae

Most biofuel production comes from harvesting organic matter and then converting it to fuel but an alternative approach relies on the fact that some algae naturally produce ethanol and this can be collected without killing the algae. The ethanol evaporates and then can be condensed and collected. The company Algenol is trying to commercialize this process.

Fourth generation biofuels A number of companies are pursuing advanced "bio-chemical" and "thermo-chemical" processes that produce "drop in" fuels like "green gasoline," "green diesel," and "green aviation fuel." While there is no one established definition of "fourth-generation biofuels," some have referred to it as the biofuels created from processes other than first generation ethanol and biodiesel, second generation cellulosic ethanol, and third generation algae biofuel. Some fourth generation technology pathways include: pyrolysis, gasification, upgrading, solar-to-fuel, and genetic manipulation of organisms to secrete hydrocarbons. •

•

GreenFuel Technologies Corporation developed a patented bioreactor system that uses nontoxic photosynthetic algae to take in smokestacks flue gases and produce biofuels such as biodiesel, biogas and a dry fuel comparable to coal. With thermal depolymerization of biological waste one can extract methane and other oils similar to petroleum.

Hydrocarbon plants or petroleum plants are plants which produce terpenoids as secondary metabolites that can be converted to gasoline-like fuels. Latex producing members of the Euphorbiaceae such as Euphorbia lathyris and E. tirucalli and members of Apocynaceae have been studied for their potential energy uses. Green fuels However, if biocatalytic cracking and traditional fractional distillation are used to process properly prepared algal biomass i.e. biocrude, then as a result we receive the following distillates: jet fuel, gasoline, diesel, etc.. Hence, we may call them third generation or green fuels.

Biofuels by region Recognizing the importance of implementing bioenergy, there are international organizations such as IEA Bioenergy, established in 1978 by the OECD International Energy Agency (IEA), with the aim of improving cooperation and information exchange between countries that have national programs in bioenergy research, development and deployment. The U.N. International Biofuels Forum is formed by Brazil, China, India, South Africa, the United States and the European Commission. The world leaders in biofuel development and use are Brazil, United States, France, Sweden and Germany.

Issues with biofuel production and use There are various social, economic, environmental and technical issues with biofuel production and use, which have been discussed in the popular media and scientific journals. These include: the effect of moderating oil prices, the "food vs fuel" debate, poverty reduction potential, carbon emissions levels, sustainable biofuel production, deforestation and soil erosion, loss of biodiversity, impact on water resources, as well as energy balance and efficiency.

Alternative fuel dispensers at a regular gasoline station in Arlington, Virginia. B20 biodiesel at the left and E85 ethanol at the right. Biofuels are also considered a renewable source. Although renewable energy is used mostly to generate electricity, it is often assumed that some form of renewable energy or at least it is used to create alternative fuels.

Biomass Biomass in the energy production industry is living and recently dead biological material which can be used as fuel or for industrial production.

Algae based fuels

Algae based biofuels have been hyped in the media as a potential panacea to our Crude Oil based Transportation problems. Algae could yield more than 2000 gallons of fuel per acre per year of production. Algae based fuels are being successfully tested by the navy Algae based plastics show potential to reduce waste and the cost per pound of algae plastic is expected to be cheaper than traditional plastic prices.

Alcohol fuels Methanol and Ethanol fuel are typically primary sources of energy; they are convenient fuels for storing and transporting energy. These alcohols can be used in "internal combustion engine as alternative fuels", with butanol also having known advantages, such as being the only alcohol-based motor fuel that can be transported readily by existing petroleum-product pipeline networks, instead of only by tanker trucks and railroad cars.

Hydrogen Hydrogen as a fuel has been suggested to have the capability to create a hydrogen economy.

HCNG

HCNG -CNG emission HCNG (or H2CNG) is a mixture of compressed natural gas and 4-9 percent hydrogen by energy. It may be used as a fuel gas for internal combustion engines and home appliances. HCNG dispensers can be found at Hynor (Norway) Thousand palms and Barstow California Fort Collins Colorado, Dunkerque (France), Goteborg Sweden, Dwarka and Faridabad (Delhi), India and the BC hydrogen highway in Canada. HCNG for mobile use is premixed at the hydrogen station.

Research

Testing is underway in Ameland for a 3 year field testing until 2010 were 20 % hydrogen is added to the local CNG distribution net, the appliances involved are kitchen stoves, condensing boilers and micro-CHP boilers. To get the most out of a ICE in transportation if higher levels of hydrogen are added modifications have to be made in the corresponding engine and the control strategy.

Codes and Standards The National Fire Protection Association 52 presently covers CNG and hydrogen fueling stations. Blends with < 20% hydrogen by volume are treated identically to CNG HCNG (or H2CNG) is a mixture of compressed natural gas and 4-9 percent hydrogen by energy.

Liquid nitrogen Liquid nitrogen is another type of emissionless fuel.

Compressed air The air engine is an emission-free piston engine using compressed air as fuel. Unlike hydrogen, compressed air is about one-tenth as expensive as fossil oil, making it an economically attractive alternative fuel.

Alternative fossil fuels Compressed natural gas (CNG) is a cleaner burning alternative to conventional petroleum automobile fuels. The energy efficiency is generally equal to that of gasoline engines, but lower compared with modern diesel engines. CNG vehicles require a greater amount of space for fuel storage than conventional gasoline power vehicles because CNG takes up more space for each GGE (Gallon of Gas Equivalent). Almost any existing gasoline car can be turned into a bi-fuel (gasoline/CNG) car. However, natural gas is a finite resource like all fossil fuels, and production is expected to peak gas soon after .

Nuclear power Nuclear power is any nuclear technology designed to extract usable energy from atomic nuclei via controlled nuclear reactions. The most common method today is through nuclear fission, though other methods include nuclear fusion and radioactive decay. All current methods involve heating a working fluid such as water, which is then converted into mechanical work for the purpose of generating electricity or propulsion. Today, more than 15% of the world's electricity comes from nuclear power, over 150 nuclear-powered naval vessels have been built, and a few radioisotope rockets have been produced.

Chapter- 3

Alcohol Fuel

Although Fossil fuels have become the dominant energy resource for the modern world, alcohol has been used as a fuel throughout history. The first four aliphatic alcohols (methanol, ethanol, propanol, and butanol) are of interest as fuels because they can be synthesized biologically, and they have characteristics which allow them to be used in current engines. One advantage shared by all four alcohols is octane rating. Biobutanol has the advantage that its energy density is closer to gasoline than the other alcohols (while still retaining over 25% higher octane rating) - however, these advantages are outweighed by disadvantages (compared to ethanol and methanol) concerning production, for instance. Generally speaking, the chemical formula for alcohol fuel is CnH2n+1OH. Alcohol fuels are usually of biological rather than petroleum sources. When obtained from biological sources, they are known as bioalcohols (e.g. bioethanol). There is no chemical difference between biologically produced alcohols and those obtained from other sources. However, ethanol that is derived from petroleum should not be considered safe for consumption as this alcohol contains about 5% methanol and may cause blindness or death. This mixture may also not be purified by simple distillation, as it forms an azeotropic mixture.

Methanol and ethanol

Ethanol used as a fuel. Methanol and ethanol can both be derived from fossil fuels, biomass, or perhaps most simply, from carbon dioxide and water. Ethanol has most commonly been produced through fermentation of sugars, and methanol has most commonly been produced from synthesis gas, but there are more modern ways to obtain these fuels. Enzymes can be used instead of fermentation. Methanol is the simpler molecule, and ethanol can be made from methanol. Methanol can be produced from nearly any biomass, including animal waste, or from carbon dioxide and water using electrolysis or enzymes. As a fuel methanol and ethanol both have advantages and disadvantages over fuels such as petrol and diesel. In spark ignition engines both alcohols can run at a much higher Exhaust gas recirculation rates and with higher compression ratios. Both alcohols have a high octane rating, with ethanol at 109 RON, 90 MON, (which equates to 99.5 AKI) and methanol at 109 RON, 89 MON (which equates to 99 AKI). Ordinary European petrol is typically 95 RON, 85 MON, equal to 90 AKI. Note that AKI refers to 'Anti-Knock Index' which averages the RON and MON ratings (RON+MON)/2, and is used on U.S. gas station pumps. As a compression ignition engine fuel, both alcohols create very little particulates, but their low cetane number means that an ignition improver like glycol must be mixed into the fuel with approx. 5%.

When used in spark ignition engines alcohols have the potential to reduce NOx, CO, HC and particulates. A test with E85 fueled Chevrolet Luminas showed that NMHC went down by 20-22%, NOx by 25-32% and CO by 12-24% compared to reformulated gasoline. Toxic emissions of benzene and 1,3 Butadiene also decreased while aldehyde emissions increased (acetaldehyde in particular). Tailpipe emissions of CO2 also decrease due to the lower carbon-to-hydrogen ratio of these alcohols, and the improved engine efficiency. Methanol and ethanol contain soluble and insoluble contaminants. Halide ions, which are soluble contaminants, such as chloride ions, have a large effect on the corrosivity of alcohol fuels. Halide ions increase corrosion in two ways: they chemically attack passivating oxide films on several metals causing pitting corrosion, and they increase the conductivity of the fuel. Increased electrical conductivity promotes electrical, galvanic and ordinary corrosion in the fuel system. Soluble contaminants such as aluminum hydroxide, itself a product of corrosion by halide ions, clogs the fuel system over time. To prevent corrosion the fuel system must be made of suitable materials, electrical wires must be properly insulated and the fuel level sensor must be of pulse and hold type (or similar). In addition, high quality alcohol should have a low concentration of contaminants and have a suitable corrosion inhibitor added. Methanol and ethanol are also incompatible with some polymers. The alcohol reacts with the polymers causing swelling, and over time the oxygen breaks down the carbon-carbon bonds in the polymer causing a reduction in tensile strength. For the past few decades though, most cars have been designed to tolerate up to 10% ethanol (E10) without problem. This include both fuel system compatibility and lambda compensation of fuel delivery with fuel injection engines featuring closed loop lambda control. In some engines ethanol may degrade some compositions of plastic or rubber fuel delivery components designed for conventional petrol, and also be unable to lambda compensate the fuel properly. "FlexFuel" vehicles have upgraded fuel system and engine components which are designed for long life using E85 or M85, and the ECU can adapt to any fuel blend between gasoline and E85 or M85. Typical upgrades include modifications to: fuel tanks, fuel tank electrical wiring, fuel pumps, fuel filters, fuel lines, filler tubes, fuel level sensors, fuel injectors, seals, fuel rails, fuel pressure regulators, valve seats and inlet valves. "Total Flex" Autos destined for the Brazilian market can use E100 (100% Ethanol). One liter of ethanol contain 21.1 MJ, a liter of methanol 15.8 MJ and a liter of gasoline approximately 32.6 MJ. In other words, for the same energy content as one liter or one gallon of gasoline, one needs 1.6 liters/gallons of ethanol and 2.1 liters/gallons of methanol. Although actual fuel consumption doesn't increase as much as energy content numbers indicate.

Methanol has been proposed as a future biofuel. Methanol has a long history as a racing fuel. Early Grand Prix Racing used blended mixtures as well as pure methanol. The use of the fuel was primarily used in North America after the war. However, methanol for racing purposes has largely been based on methanol produced from natural gas and therefore this methanol would not be considered a biofuel. Methanol is a possible biofuel, however. Methanol might be produced from carbon dioxide and captive hydrogen derived using nuclear power or any renewable energy source. Compared to ethanol, the primary advantage of methanol biofuel is its much greater well-to-wheel efficiency when produced from syngas. Ethanol is already being used extensively as a fuel additive, and the use of ethanol fuel alone or as part of a mix with gasoline is increasing. Compared to methanol its primary advantage is that it is less corrosive and additionally the fuel is non-toxic, although the fuel will produce some toxic exhaust emissions. From 2007, the Indy Racing League will use ethanol as its exclusive fuel, after 40 years of using methanol. Since September 2007 petrol stations in NSW, Australia are mandated to supply all their petrol with 2% Ethanol content Methanol combustion is: 2CH3OH + 3O2 → 2CO2 + 4H2O + heat Ethanol combustion is: C2H5OH + 3O2 → 2CO2 + 3H2O + heat

Butanol and Propanol Propanol and butanol are considerably less toxic and less volatile than methanol. In particular, butanol has a high flashpoint of 35 °C, which is a benefit for fire safety, but may be a difficulty for starting engines in cold weather. The concept of flash point is however not directly applicable to engines as the compression of the air in the cylinder means that the temperature is several hundred degrees Celsius before ignition takes place. The fermentation processes to produce propanol and butanol from cellulose are fairly tricky to execute, and the Weizmann organism (Clostridium acetobutylicum) currently used to perform these conversions produces an extremely unpleasant smell, and this must be taken into consideration when designing and locating a fermentation plant. This organism also dies when the butanol content of whatever it is fermenting rises to 7%. For comparison, yeast dies when the ethanol content of its feedstock hits 14%. Specialized strains can tolerate even greater ethanol concentrations - so-called turbo yeast can withstand up to 16% ethanol . However, if ordinary Saccharomyces yeast can be modified to improve its ethanol resistance, scientists may yet one day produce a strain of the Weizmann organism with a butanol resistance higher than the natural boundary of 7%. This would be useful because butanol has a higher energy density than ethanol, and because waste fibre left over from sugar crops used to make ethanol could be made into butanol, raising the alcohol yield of fuel crops without there being a need for more crops to be planted.

Despite these drawbacks, DuPont and British Petroleum have recently announced that they are jointly to build a small scale butanol fuel demonstration plant alongside the large bioethanol plant they are jointly developing with Associated British Foods. Energy Environment International developed a method for producing butanol from biomass, which involves the use of two separate micro-organisms in sequence to minimize production of acetone and ethanol byproducts. The Swiss company Butalco GmbH uses a special technology to modify yeasts in order to produce butanol instead of ethanol. Yeasts as production organisms for butanol have decisive advantages compared to bacteria. Butanol combustion is: C4H9OH + 6O2 → 4CO2 + 5H2O + heat The 3-carbon alcohol, propanol (C3H7OH), is not used as a direct fuel source for petrol engines that often (unlike ethanol, methanol and butanol), with most being directed into use as a solvent. However, it is used as a source of hydrogen in some types of fuel cell; it can generate a higher voltage than methanol, which is the fuel of choice for most alcoholbased fuel cells. However, since propanol is harder to produce than methanol (biologically OR from oil), methanol fuel cells are still used a lot more often than those that utilise propanol.

By country Alcohol in Brazil Brazil was until recently the largest producer of alcohol fuel in the world, typically fermenting ethanol from sugarcane. The country produces a total of 18 billion liters (4.8 billion gallons) annually, of which 3.5 billion liters are exported, 2 billion of them to the U.S.. Alcohol cars debuted in the Brazilian market in 1978 and became quite popular because of heavy subsidy, but in the 80's prices rose and gasoline regained the leading market share. However, from 2003 on, alcohol is rapidly rising its market share once again because of new technologies involving flexible-fuel engines, called "Flex" by all major car manufacturers (Volkswagen, General Motors, Fiat, etc.). "Flex" engines work with gasoline, alcohol or any mixture of both fuels. As of May 2009, more than 88% of new vehicles sold in Brazil are flex fuel Because of the Brazilian leading production and technology, many countries became very interested in importing alcohol fuel and adopting the "Flex" vehicle concept. On March 7 of 2007, US president George W. Bush visited the city of São Paulo to sign agreements with Brazilian president Lula on importing alcohol and its technology as an alternative fuel.

Alcohol in China

China has reported with a 70% methanol use to conventional gasoline an independence from crude oil. National Committee of Planning and Action Coordination for Clean Automobile had listed key technologies related to alcohol/ether fuel and accelerated industrialization into its main agenda. Alcohol fuels had become part of five main alternative fuels: Two of which were alcohols; methanol and ethanol

Alcohol in Russia Russia has reduced its dependency on oil by using methanol made from the destructive pyrolysis of eucalyptus wood and fibre. However, this system is less likely to be emulated elsewhere, due to the disadvantages of methanol fuel.

Alcohol in the United States The United States at the end of 2007 was producing 7 billion gallons (26.9 billion liters) per year. E10 or Gasohol is commonly marketed in Delaware and E85 is found in many states, particularly in the Mid West where ethanol from corn is produced locally. Due to government subsidies, many new vehicles are sold each year that can use E85, although the majority are run solely on gasoline due to the limited availability of E85. Many states and municipalities have mandated that all gasoline fuel be blended with 10 percent alcohol (usually ethanol) during some or all of the year. This is to reduce pollution and allows these areas to comply with federal pollution limits. Because alcohol is partially oxygenated, it produces less overall pollution, including ozone. In some areas (California in particular) the regulations may also require other formulations or added chemicals that reduce pollution, but add complexity to the fuel distribution and increase the cost of the fuel.

Alcohol in the European Union Consumption of Bioethanol (GWh) # Country 2005 2006 2007 2008 871 1,719 3,164 4,693 1 France 2 Germany 1,682 3,544 3,448 4,675 3 Sweden 1,681 1,894 2,119 2,488 4 0 179 1,023 1,512 Netherlands 1,314 1,332 1,512 1,454 5 Spain 6 Poland 329 611 837 1,382 7 United Kingdom 502 563 906 1,223 8 Finland 0 10 20 858 0 0 199 633 9 Austria

10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 27

Hungary Czech Republic Ireland Lithuania Belgium Slovakia Bulgaria

28 136 314 454 0 13 1 378 0 13 59 207 10 64 134 182 0 0 0 145 0 4 140 76 0 0 72 0 42 60 50 Denmark Slovenia 0 2 9 28 Estonia 0 0 0 17 Latvia 5 12 0 0 Luxembourg 0 0 14 11 0 0 0 0 Portugal 59 0 0 0 Italy 0 0 0 0 Greece 0 0 0 Romania 0 0 0 0 Malta Cyprus 0 0 0 0 European Union 6,481 10,138 13,962 20,538

1 toe = 11,63 MWh, 0 = no data Alcohol consumption does not specify the traffic fuel use The 2008 data is not confirmed yet

Alcohol in Japan The first alcohol fuel in Japan started from GAIAX in 1999. GAIAX was developed in South Korea, and imported by Japan. The principal ingredient was a methanol. Because GAIAX was not gasoline, it was a tax-free object of the gas tax of Japan. However, the use of GAIAX came to be considered to be an act of smuggling from Japanese Government and the petroleum industry in Japan as a result. The retailer of GAIAX was done to evade the tax evasion criticism by independently paying the diesel fuel tax in the legal system regulations either. The fire accident from the vehicle where GAIAX was refueled began to be reported in around 2000 when the tax evasion discussion ended almost. The car industry in Japan criticized GAIAX , saying that "A fire broke out because high density alcohol had made them corrode the fuel pipe". And, GAIAX was named "High density alcoholic fuel", and the campaign from the market to exclude it was executed for a long term. Finally, the Ministry of Economy, Trade and Industry also joined this campaign.

The gasoline quality method was revised by the pretext from the reason on safety in 2003. This was a content that prohibited the manufacturing sales of "High density alcoholic fuel", and a substantial GAIAX sales ban. The thing that the fuel manufacturer provided by revising this law prohibits gasoline from adding of the alcohol of 3% or more. This law revision is grounds not to be able to sell the fuel alcohol more than the E3 fuel in Japan. GAIAX was excluded from the market by such details. The consumer came also to acknowledge that the fuel alcohol was dangerous widely by a negative campaign of the industrial-government complex cooperation. However, Japan sarcastically invited the result of leaving from the tendency to making of a worldwide vehicle fuel alcohol as a result. The petroleum industry in Japan is advancing the research and development of a fuel alcohol that differs from GAIAX and is original now. However, the above-mentioned law used to exclude GAIAX becomes a trouble on the market of their fuel alcohol. Moreover, the prospect of marketing doesn't stand because disgust to "High density alcoholic fuel" of the consumer in Japan strongly remains by a longtime campaign, too at all.

Chapter- 4

Butanol Fuel

Butanol may be used as a fuel in an internal combustion engine. Because its longer hydrocarbon chain causes it to be fairly non-polar, it is more similar to gasoline than it is to ethanol. Butanol has been demonstrated to work in vehicles designed for use with gasoline without modification. It can be produced from biomass (as "biobutanol") as well as fossil fuels (as "petrobutanol"); but biobutanol and petrobutanol have the same chemical properties.

Production of biobutanol Butanol from biomass is called biobutanol. It can be used in unmodified gasoline engines.

Technologies Biobutanol can be produced by fermentation of biomass by the A.B.E. process. The process uses the bacterium Clostridium acetobutylicum, also known as the Weizmann organism. It was Chaim Weizmann who first used this bacteria for the production of acetone from starch (with the main use of acetone being the making of Cordite) in 1916. The butanol was a by-product of this fermentation (twice as much butanol was produced). The process also creates a recoverable amount of H2 and a number of other by-products: acetic, lactic and propionic acids, acetone, isopropanol and ethanol. The difference from ethanol production is primarily in the fermentation of the feedstock and minor changes in distillation. The feedstocks are the same as for ethanol: energy crops such as sugar beets, sugar cane, corn grain, wheat and cassava, prospective nonfood energy crops such as switchgrass and even guayule in North America, as well as agricultural byproducts such as straw and corn stalks. According to DuPont, existing bioethanol plants can cost-effectively be retrofitted to biobutanol production.

Additionally, butanol production from biomass and agricultural byproducts could be more efficient (i.e. unit engine motive power delivered per unit solar energy consumed) than ethanol or methanol production. Algae butanol Biobutanol can be made entirely with solar energy, from algae (called Solalgal Fuel) or diatoms.

Producers ButylFuel, LLC used a U.S. Department of Energy Small Business Technology Transfer grant to develop a process aimed at making biobutanol production economically competitive with petrochemical production processes. DuPont and BP plan to make biobutanol the first product of their joint effort to develop, produce, and market next-generation biofuels. In Europe the Swiss company Butalco is developing genetically modified yeasts for the production of biobutanol from cellulosic materials. The number of biobutanol producers with commercial plants coming on line continues to grow monthly. At present, there are number of bioethanol plants which are being coverted to biobutanol plants. At last count, there are over 10 companies seeking to develop this promising fuel. Read more about BioButanol companies.

Distribution Butanol better tolerates water contamination and is less corrosive than ethanol and more suitable for distribution through existing pipelines for gasoline. In blends with diesel or gasoline, butanol is less likely to separate from this fuel than ethanol if the fuel is contaminated with water. There is also a vapor pressure co-blend synergy with butanol and gasoline containing ethanol, which facilitates ethanol blending. This facilitates storage and distribution of blended fuels.

Properties of common fuels Fuel Gasoline and biogasoline Butanol fuel Ethanol fuel

Energy density

Airfuel ratio

32 MJ/L 14.6 29.2 MJ/L 19.6

11.1 9.0

Specific Heat of RON MON energy vaporization 2.9 MJ/kg air 3.2 MJ/kg air 3.0 MJ/kg

0.36 MJ/kg

91– 99

81– 89

0.43 MJ/kg

96

78

0.92 MJ/kg

107

89

MJ/L Methanol

16 MJ/L

6.4

air 3.1 MJ/kg air

1.2 MJ/kg

106

92

Energy content and effects on fuel economy Switching a gasoline engine over to butanol would in theory result in a fuel consumption penalty of about 10% but butanol's effect on mileage is yet to be determined by a scientific study. While the energy density for any mixture of gasoline and butanol can be calculated, tests with other alcohol fuels have demonstrated that the effect on fuel economy is not proportional to the change in energy density.

Octane rating The octane rating of n-butanol is similar to that of gasoline but lower than that of ethanol and methanol. n-Butanol has a RON (Research Octane number) of 96 and a MON (Motor octane number) of 78 while t-butanol has octane ratings of 105 RON and 89 MON. tButanol is used as an additive in gasoline but cannot be used as a fuel in its pure form because its relatively high melting point of 25.5 °C causes it to gel and freeze near room temperature. A fuel with a higher octane rating is less prone to knocking (extremely rapid and spontaneous combustion by compression) and the control system of any modern car engine can take advantage of this by adjusting the ignition timing. This will improve energy efficiency, leading to a better fuel economy than the comparisons of energy content different fuels indicate. By increasing the compression ratio, further gains in fuel economy, power and torque can be achieved. Conversely, a fuel with lower octane rating is more prone to knocking and will lower efficiency. Knocking can also cause engine damage.

Air-fuel ratio Alcohol fuels, including butanol and ethanol, are partially oxidized and therefore need to run at richer mixtures than gasoline. Standard gasoline engines in cars can adjust the airfuel ratio to accommodate variations in the fuel, but only within certain limits depending on model. If the limit is exceeded by running the engine on pure butanol or a gasoline blend with a high percentage of butanol, the engine will run lean, something which can critically damage components. Compared to ethanol, butanol can be mixed in higher ratios with gasoline for use in existing cars without the need for retrofit as the air-fuel ratio and energy content are closer to that of gasoline.

Specific energy Alcohol fuels have less energy per unit weight and unit volume than gasoline. To make it possible to compare the net energy released per cycle a measure called the fuels specific

energy is sometimes used. It is defined as the energy released per air fuel ratio. The net energy released per cycle is higher for butanol than ethanol or methanol and about 10% higher than for gasoline.

Viscosity Kinematic Substance viscosity at 20°C Butanol 3.64 cSt Ethanol 1.52 cSt Methanol 0.64 cSt Gasoline 0.4–0.8 cSt Diesel >3 cSt Water 1.0 cSt The viscosity of alcohols increase with longer carbon chains. For this reason, butanol is used as an alternative to shorter alcohols when a more viscous solvent is desired. The kinematic viscosity of butanol is several times higher than that of gasoline and about as viscous as high quality diesel fuel.

Heat of vaporization The fuel in an engine has to be vaporized before it will burn. Insufficient vaporization is a known problem with alcohol fuels during cold starts in cold weather. As the heat of vaporization of butanol is less than half of that of ethanol, an engine running on butanol should be easier to start in cold weather than one running on ethanol or methanol.

Potential problems with the use of butanol fuel The potential problems with the use of butanol are similar to those of ethanol: •

• • •

To match the combustion characteristics of gasoline, the utilization of butanol fuel as a substitute for gasoline requires fuel-flow increases (though butanol has only slightly less energy than gasoline, so the fuel-flow increase required is only minimal, maybe 10%, compared to 40% for ethanol.) Alcohol-based fuels are not compatible with some fuel system components. Alcohol fuels may cause erroneous gas gauge readings in vehicles with capacitance fuel level gauging. While ethanol and methanol have lower energy densities than butanol, their higher octane number allows for greater compression ratio and efficiency. Higher combustion engine efficiency allows for lesser greenhouse gas emissions per unit motive energy extracted.

•

Butanol is toxic at a rate of 20g per liter and may need to undergo Tier 1 and Tier 2 health effects testing before being permitted as a primary fuel by the EPA.

Possible butanol fuel mixtures Standards for the blending of ethanol and methanol in gasoline exist in many countries, including the EU, the US and Brazil. Approximate equivalent butanol blends can be calculated from the relations between the stochiometric fuel-air ratio of butanol, ethanol and gasoline. Common ethanol fuel mixtures for fuel sold as gasoline currently range from 5% to 10%. The share of butanol can be 60% greater than the equivalent ethanol share, which gives a range from 8% to 16%. "Equivalent" in this case refers only to the vehicle's ability to adjust to the fuel. Other properties such as energy density, viscosity and heat of vaporisation will vary and may further limit the percentage of butanol that can be blended with gasoline. Consumer acceptance may be limited due to the offensive smell of butanol. Plans are underway to market a fuel that is 85% Ethanol and 15% Butanol (E85B), so existing E85 internal combustion engines can run on a 100% renewable fuel that could be made without using any fossile fuels. Because its longer hydrocarbon chain causes it to be fairly non-polar, it is more similar to gasoline than it is to ethanol. Butanol has been demonstrated to work in vehicles designed for use with gasoline without modification. It can be produced from biomass (as "biobutanol") as well as fossil fuels (as "petrobutanol"); but biobutanol and petrobutanol have the same chemical properties.

Current use of butanol in vehicles Currently no production vehicle is known to be approved by the manufacturer for use with 100% butanol. As of early 2009, only few vehicles are approved for even using E85 fuel (i.e. 85% ethanol + 15% gasoline)in the USA. However, in Brazil all vehicle manufacturers (Fiat, Ford, VW, GM, Toyota, Honda, Peugeot, Citroen and others) produce flex fuel vehicles that can run on 100% ethanol or any mix of ethanol and gasoline. These flex fuel cars represent 90% of the sales of personal vehicles in Brazil, in 2009. BP and Dupont, engaged in a joint venture to produce and promote butanol fuel, claim that "biobutanol can be blended up to 10%v/v in European gasoline and 11.5%v/v in US gasoline". David Ramey drove from Blacklick, Ohio to San Diego, California using butanol in an unmodified 1992 Buick Park Avenue. In the 2009 Petit Le Mans race, the No. 16 Lola B09/86 - Mazda MZR-R of Dyson Racing ran on a mixture of biobutanol and ethanol developed by team technology partner BP.

Research

The Swiss company Butalco GmbH uses a special technology to modify yeasts in order to produce butanol instead of ethanol. Yeasts as production organisms for butanol have decisive advantages compared to bacteria. The company Gevo, Inc., in Englewood, Colorado, is developing a biotechnology process to mass-produce isobutanol from renewable resources.

Chapter- 5

Ethanol Fuel

Saab 9-3 SportCombi BioPower. The second E85 flexifuel model introduced by Saab in the Swedish market.

BEST program ED95 trial bus operating in São Paulo, Brazil. Ethanol fuel is ethanol (ethyl alcohol), the same type of alcohol found in alcoholic beverages. It is most often used as a motor fuel, mainly as a biofuel additive for gasoline. World ethanol production for transport fuel tripled between 2000 and 2007 from 17 billion to more than 52 billion litres. From 2007 to 2008, the share of ethanol in global gasoline type fuel use increased from 3.7% to 5.4%. In 2009 worldwide ethanol fuel production reached 19.5 billion gallons (73.9 billion liters). Ethanol is widely used in Brazil and in the United States, and together both countries were responsible for 86 percent of the world's ethanol fuel production in 2009. Most cars on the road today in the U.S. can run on blends of up to 10% ethanol, and the use of 10% ethanol gasoline is mandated in some U.S. states and cities. Since 1976 the Brazilian government has made it mandatory to blend ethanol with gasoline, and since 2007 the legal blend is around 25% ethanol and 75% gasoline (E25). In addition, by 2010 Brazil had a fleet of more than 10 million flexible-fuel vehicles regularly using neat ethanol fuel (known as E100). Bioethanol, unlike petroleum, is a form of renewable energy that can be produced from agricultural feedstocks. It can be made from very common crops such as sugar cane, potato, manioc and corn. However, there has been considerable debate about how useful bioethanol will be in replacing gasoline. Concerns about its production and use relate to increased food prices due to the large amount of arable land required for crops, as well as the energy and pollution balance of the whole cycle of ethanol production, especially from corn. Recent developments with cellulosic ethanol production and commercialization may allay some of these concerns. Cellulosic ethanol offers promise because cellulose fibers, a major and universal component in plant cells walls, can be used to produce ethanol. According to the

International Energy Agency, cellulosic ethanol could allow ethanol fuels to play a much bigger role in the future than previously thought.

Chemistry

Structure of ethanol molecule. All bonds are single bonds Glucose (a simple sugar) is created in the plant by photosynthesis. 6 CO2 + 6 H2O + light → C6H12O6 + 6 O2 During ethanol fermentation, glucose is decomposed into ethanol and carbon dioxide. C6H12O6 → 2 C2H5OH+ 2 CO2 + heat During combustion ethanol reacts with oxygen to produce carbon dioxide, water, and heat: C2H5OH + 3 O2 → 2 CO2 + 3 H2O + heat After doubling the combustion reaction because two molecules of ethanol are produced for each glucose molecule, and adding all three reactions together, there are equal numbers of each type of molecule on each side of the equation, and the net reaction for the overall production and consumption of ethanol is just: light → heat The heat of the combustion of ethanol is used to drive the piston in the engine by expanding heated gases. It can be said that sunlight is used to run the engine (as is the case with any renewable energy source, as sunlight is the only way energy enters the planet). Glucose itself is not the only substance in the plant that is fermented. The simple sugar fructose also undergoes fermentation. Three other compounds in the plant can be fermented after breaking them up by hydrolysis into the glucose or fructose molecules that compose them. Starch and cellulose are molecules that are strings of glucose

molecules, and sucrose (ordinary table sugar) is a molecule of glucose bonded to a molecule of fructose. The energy to create fructose in the plant ultimately comes from the metabolism of glucose created by photosynthesis, and so sunlight also provides the energy generated by the fermentation of these other molecules. Ethanol may also be produced industrially from ethene (ethylene). Addition of water to the double bond converts ethene to ethanol: C2H4 + H2O → CH3CH2OH This is done in the presence of an acid which catalyzes the reaction, but is not consumed. The ethene is produced from petroleum by steam cracking. When ethanol is burned in the atmosphere rather than in pure oxygen, other chemical reactions occur with different components of the atmosphere such as nitrogen (N2). This leads to the production of nitrous oxides, a major air pollutant.

Sources

Sugar cane harvest

Cornfield in South Africa

Switchgrass Ethanol is a renewable energy source because the energy is generated by using a resource, sunlight, which can't be depleted. Creation of ethanol starts with photosynthesis causing a feedstock, such as sugar cane or corn, to grow. These feedstocks are processed into ethanol. About 5% of the ethanol produced in the world in 2003 was actually a petroleum product. It is made by the catalytic hydration of ethylene with sulfuric acid as the catalyst. It can also be obtained via ethylene or acetylene, from calcium carbide, coal, oil gas, and other sources. Two million tons of petroleum-derived ethanol are produced annually. The principal suppliers are plants in the United States, Europe, and South Africa. Petroleum derived ethanol (synthetic ethanol) is chemically identical to bio-ethanol and can be differentiated only by radiocarbon dating. Bio-ethanol is usually obtained from the conversion of carbon based feedstock. Agricultural feedstocks are considered renewable because they get energy from the sun using photosynthesis, provided that all minerals required for growth (such as nitrogen and

phosphorus) are returned to the land. Ethanol can be produced from a variety of feedstocks such as sugar cane, bagasse, miscanthus, sugar beet, sorghum, grain sorghum, switchgrass, barley, hemp, kenaf, potatoes, sweet potatoes, cassava, sunflower, fruit, molasses, corn, stover, grain, wheat, straw, cotton, other biomass, as well as many types of cellulose waste and harvestings, whichever has the best well-to-wheel assessment. An alternative process to produce bio-ethanol from algae is being developed by the company Algenol. Rather than grow din mor algae and then harvest and ferment it the algae grow in sunlight and produce ethanol directly which is removed without killing the algae. It is claimed the process can produce 6000 gallons per acre per year compared with 400 gallons for corn production. Currently, the first generation processes for the production of ethanol from corn use only a small part of the corn plant: the corn kernels are taken from the corn plant and only the starch, which represents about 50% of the dry kernel mass, is transformed into ethanol. Two types of second generation processes are under development. The first type uses enzymes and yeast to convert the plant cellulose into ethanol while the second type uses pyrolysis to convert the whole plant to either a liquid bio-oil or a syngas. Second generation processes can also be used with plants such as grasses, wood or agricultural waste material such as straw. Production process The basic steps for large scale production of ethanol are: microbial (yeast) fermentation of sugars, distillation, dehydration, and denaturing (optional). Prior to fermentation, some crops require saccharification or hydrolysis of carbohydrates such as cellulose and starch into sugars. Saccharification of cellulose is called cellulolysis. Enzymes are used to convert starch into sugar. Fermentation Ethanol is produced by microbial fermentation of the sugar. Microbial fermentation will currently only work directly with sugars. Two major components of plants, starch and cellulose, are both made up of sugars, and can in principle be converted to sugars for fermentation. Currently, only the sugar (e.g. sugar cane) and starch (e.g. corn) portions can be economically converted. However, there is much activity in the area of cellulosic ethanol, where the cellulose part of a plant is broken down to sugars and subsequently converted to ethanol. Distillation

Ethanol plant in West Burlington, Iowa

Ethanol plant in Sertãozinho, Brazil.

For the ethanol to be usable as a fuel, water must be removed. Most of the water is removed by distillation, but the purity is limited to 95-96% due to the formation of a lowboiling water-ethanol azeotrope. The 95.6% m/m (96.5% v/v) ethanol, 4.4% m/m (3.5% v/v) water mixture may be used as a fuel alone, but unlike anhydrous ethanol, is immiscible in gasoline, so the water fraction is typically removed in further treatment in order to burn in combination with gasoline in gasoline engines. Dehydration There are basically five dehydration processes to remove the water from an azeotropic ethanol/water mixture. The first process, used in many early fuel ethanol plants, is called azeotropic distillation and consists of adding benzene or cyclohexane to the mixture. When these components are added to the mixture, it forms a heterogeneous azeotropic mixture in vapor-liquid-liquid equilibrium, which when distilled produces anhydrous ethanol in the column bottom, and a vapor mixture of water and cyclohexane/benzene. When condensed, this becomes a two-phase liquid mixture. Another early method, called extractive distillation, consists of adding a ternary component which will increase ethanol's relative volatility. When the ternary mixture is distilled, it will produce anhydrous ethanol on the top stream of the column. With increasing attention being paid to saving energy, many methods have been proposed that avoid distillation altogether for dehydration. Of these methods, a third method has emerged and has been adopted by the majority of modern ethanol plants. This new process uses molecular sieves to remove water from fuel ethanol. In this process, ethanol vapor under pressure passes through a bed of molecular sieve beads. The bead's pores are sized to allow absorption of water while excluding ethanol. After a period of time, the bed is regenerated under vacuum or in the flow of inert atmosphere (e.g. N2) to remove the absorbed water. Two beds are used so that one is available to absorb water while the other is being regenerated. This dehydration technology can account for energy saving of 3,000 btus/gallon (840 kJ/l) compared to earlier azeotropic distillation.

Technology Ethanol-based engines Ethanol is most commonly used to power automobiles, though it may be used to power other vehicles, such as farm tractors, boats and airplanes. Ethanol (E100) consumption in an engine is approximately 51% higher than for gasoline since the energy per unit volume of ethanol is 34% lower than for gasoline. However, the higher compression ratios in an ethanol-only engine allow for increased power output and better fuel economy than could be obtained with lower compression ratios. In general, ethanol-only engines are tuned to give slightly better power and torque output than gasoline-powered engines. In flexible fuel vehicles, the lower compression ratio requires tunings that give the same output when using either gasoline or hydrated ethanol. For maximum use of ethanol's benefits, a much higher compression ratio should be used, Current high compression neat ethanol

engine designs are approximately 20-30% less fuel efficient than their gasoline-only counterparts. A 2004 MIT study and an earlier paper published by the Society of Automotive Engineers identify a method to exploit the characteristics of fuel ethanol substantially better than mixing it with gasoline. The method presents the possibility of leveraging the use of alcohol to achieve definite improvement over the cost-effectiveness of hybrid electric. The improvement consists of using dual-fuel direct-injection of pure alcohol (or the azeotrope or E85) and gasoline, in any ratio up to 100% of either, in a turbocharged, high compression-ratio, small-displacement engine having performance similar to an engine having twice the displacement. Each fuel is carried separately, with a much smaller tank for alcohol. The high-compression (which increases efficiency) engine will run on ordinary gasoline under low-power cruise conditions. Alcohol is directly injected into the cylinders (and the gasoline injection simultaneously reduced) only when necessary to suppress ‘knock’ such as when significantly accelerating. Direct cylinder injection raises the already high octane rating of ethanol up to an effective 130. The calculated over-all reduction of gasoline use and CO2 emission is 30%. The consumer cost payback time shows a 4:1 improvement over turbo-diesel and a 5:1 improvement over hybrid. In addition, the problems of water absorption into pre-mixed gasoline (causing phase separation), supply issues of multiple mix ratios and cold-weather starting are avoided. Ethanol's higher octane rating allows an increase of an engine's compression ratio for increased thermal efficiency. In one study, complex engine controls and increased exhaust gas recirculation allowed a compression ratio of 19.5 with fuels ranging from neat ethanol to E50. Thermal efficiency up to approximately that for a diesel was achieved. This would result in the fuel economy of a neat ethanol vehicle to be about the same as one burning gasoline. Since 1989 there have also been ethanol engines based on the diesel principle operating in Sweden. They are used primarily in city buses, but also in distribution trucks and waste collectors. The engines, made by Scania, have a modified compression ratio, and the fuel (known as ED95) used is a mix of 93.6 % ethanol and 3.6 % ignition improver, and 2.8% denaturants. The ignition improver makes it possible for the fuel to ignite in the diesel combustion cycle. It is then also possible to use the energy efficiency of the diesel principle with ethanol. These engines have been used in the United Kingdom by Reading Transport but the use of bioethanol fuel is now being phased out.

Engine cold start during the winter

The Brazilian 2008 Honda Civic flex-fuel has outside direct access to the secondary reservoir gasoline tank in the front right side, the corresponding fuel filler door is shown by the arrow. High ethanol blends present a problem to achieve enough vapor pressure for the fuel to evaporate and spark the ignition during cold weather (since ethanol tends to increase fuel enthalpy of vaporization ). When vapor pressure is below 45 kPa starting a cold engine becomes difficult. In order to avoid this problem at temperatures below 11 ° Celsius (59 °F), and to reduce ethanol higher emissions during cold weather, both the US and the European markets adopted E85 as the maximum blend to be used in their flexible fuel vehicles, and they are optimized to run at such a blend. At places with harsh cold weather, the ethanol blend in the US has a seasonal reduction to E70 for these very cold regions, though it is still sold as E85. At places where temperatures fall below -12 °C (10 °F) during the winter, it is recommended to install an engine heater system, both for gasoline and E85 vehicles. Sweden has a similar seasonal reduction, but the ethanol content in the blend is reduced to E75 during the winter months. Brazilian flex fuel vehicles can operate with ethanol mixtures up to E100, which is hydrous ethanol (with up to 4% water), which causes vapor pressure to drop faster as compared to E85 vehicles. As a result, Brazilian flex vehicles are built with a small secondary gasoline reservoir located near the engine. During a cold start pure gasoline is injected to avoid starting problems at low temperatures. This provision is particularly necessary for users of Brazil's southern and central regions, where temperatures normally drop below 15 ° Celsius (59 °F) during the winter. An improved flex engine generation was launched in 2009 that eliminates the need for the secondary gas storage tank. In

March 2009 Volkswagen do Brasil launched the Polo E-Flex, the first Brazilian flex fuel model without an auxiliary tank for cold start.

Ethanol fuel mixtures

Hydrated ethanol × gasoline type C price table for use in Brazil To avoid engine stall due to "slugs" of water in the fuel lines interrupting fuel flow, the fuel must exist as a single phase. The fraction of water that an ethanol-gasoline fuel can contain without phase separation increases with the percentage of ethanol. This shows, for example, that E30 can have up to about 2% water. If there is more than about 71% ethanol, the remainder can be any proportion of water or gasoline and phase separation will not occur. However, the fuel mileage declines with increased water content. The increased solubility of water with higher ethanol content permits E30 and hydrated ethanol to be put in the same tank since any combination of them always results in a single phase. Somewhat less water is tolerated at lower temperatures. For E10 it is about 0.5% v/v at 70 F and decreases to about 0.23% v/v at -30 F.

In many countries cars are mandated to run on mixtures of ethanol. Brazil requires cars be suitable for a 25% ethanol blend, and has required various mixtures between 22% and 25% ethanol, as of July 2007 25% is required. The United States allows up to 15% blends, and some states require this (or a smaller amount) in all gasoline sold. Other countries have adopted their own requirements. Beginning with the model year 1999, an increasing number of vehicles in the world are manufactured with engines which can run on any fuel from 0% ethanol up to 100% ethanol without modification. Many cars and light trucks (a class containing minivans, SUVs and pickup trucks) are designed to be flexible-fuel vehicles (also called dual-fuel vehicles). In older model years, their engine systems contained alcohol sensors in the fuel and/or oxygen sensors in the exhaust that provide input to the engine control computer to adjust the fuel injection to achieve stochiometric (no residual fuel or free oxygen in the exhaust) air-to-fuel ratio for any fuel mix. In newer models, the alcohol sensors have been removed, with the computer using only oxygen and airflow sensor feedback to estimate alcohol content. The engine control computer can also adjust (advance) the ignition timing to achieve a higher output without pre-ignition when it predicts that higher alcohol percentages are present in the fuel being burned. This method is backed up by advanced knock sensors - used in most high performance gasoline engines regardless of whether they're designed to use ethanol or not - that detect pre-ignition and detonation.

Fuel economy In theory, all fuel-driven vehicles have a fuel economy (measured as miles per US gallon, or liters per 100 km) that is directly proportional to the fuel's energy content. In reality, there are many other variables that come into play that affect the performance of a particular fuel in a particular engine. Ethanol contains approx. 34% less energy per unit volume than gasoline, and therefore in theory, burning pure ethanol in a vehicle will result in a 34% reduction in miles per US gallon , given the same fuel economy, compared to burning pure gasoline. Since ethanol has a higher octane rating, the engine can be made more efficient by raising its compression ratio. In fact using a variable turbocharger, the compression ratio can be optimized for the fuel being used, making fuel economy almost constant for any blend. . For E10 (10% ethanol and 90% gasoline), the effect is small (~3%) when compared to conventional gasoline, and even smaller (1-2%) when compared to oxygenated and reformulated blends. However, for E85 (85% ethanol), the effect becomes significant. E85 will produce lower mileage than gasoline, and will require more frequent refueling. Actual performance may vary depending on the vehicle. Based on EPA tests for all 2006 E85 models, the average fuel economy for E85 vehicles resulted 25.56% lower than unleaded gasoline. The EPA-rated mileage of current USA flex-fuel vehicles should be considered when making price comparisons, but it must be noted that E85 is a high performance fuel, with an octane rating of about 104, and should be compared to premium. In one estimate the US retail price for E85 ethanol is 2.62 US dollar per gallon or 3.71 dollar corrected for energy equivalency compared to a gallon of gasoline priced at 3.03 dollar. Brazilian cane ethanol (100%) is priced at 3.88 dollar against 4.91 dollar for E25 (as July 2007).

Consumer production systems

While biodiesel production systems have been marketed to home and business users for many years, commercialized ethanol production systems designed for end-consumer use have lagged in the marketplace. In 2008, two different companies announced home-scale ethanol production systems. The AFS125 Advanced Fuel System from Allard Research and Development is capable of producing both ethanol and biodiesel in one machine, while the E-100 MicroFueler from E-Fuel Corporation is dedicated to ethanol only.

Experience by country The world's top ethanol fuel producers in 2009 were the United States with 10.75 billion U.S. liquid gallons (bg) and Brazil (6.58 bg), accounting for 89% of world production of 19.53 billion US gallons (73.9 billion liters or 58.3 million metric tonnes). Strong incentives, coupled with other industry development initiatives, are giving rise to fledgling ethanol industries in countries such as Germany, Spain, France, Sweden, China, Thailand, Canada, Colombia, India, Australia, and some Central American countries.

Annual Fuel Ethanol Production by Country (2007–2009) Top 10 countries/regional blocks (Millions of U.S. liquid gallons per year)

World rank

Country/Region

1

United States

10,750.00 9,000.00 6,498.60

2

Brazil

6,577.89 6,472.20 5,019.20

3

European Union 1,039.52

4

China

5 6

2009

2008

2007

733.60

570.30

541.55

501.90

486.00

Thailand

435.20

89.80

79.20

Canada

290.59

237.70

211.30

7

India

91.67

66.00

52.80

8

Colombia

83.21

79.30

74.90

9

Australia

56.80

26.40

26.40

10

Other World Total

247.27 19,534.99 17,335.29 13,101.70

Brazil

Brazil has ethanol fuel available throughout the country. A typical Petrobras filling station at São Paulo with dual fuel service, marked A for alcohol (ethanol) and G for gasoline.

Typical Brazilian "flex" models from several carmakers, that run on any blend of ethanol and gasoline, from E20-E25 gasohol to E100 ethanol fuel.

The Honda CG 150 Titan Mix was launched in the Brazilian market in 2009 and became the first flex-fuel motorcycle sold in the world. Brazil has the largest and most successful bio-fuel programs in the world, involving production of ethanol fuel from sugarcane, and it is considered to have the world's first sustainable biofuels economy. In 2006 Brazilian ethanol provided 18% of the country's road transport sector fuel consumption needs, and by April 2008, more than 50% of fuel consumption for the gasoline market. As a result of the increasing use of ethanol, together with the exploitation of domestic deep water oil sources, Brazil reached in 2006 a volumetric self-sufficiency in oil supply, but is not effectively self-sufficient, since most of its locally extracted oil is heavy. Together, Brazil and the United States lead the industrial world in global ethanol fuel production, accounting together for 89% of worldwide production. In 2009 Brazil produced 24.9 billion liters (6.57 billion U.S. liquid gallons), representing 33.7% of the world's total ethanol used as fuel. Sugar cane plantations cover 3.6 million hectares of land for ethanol production, representing just 1% of Brazil's arable land, with a productivity of 7,500 liters of ethanol per hectare, as compared with the U.S. maize ethanol productivity of 3,000 liters per hectare. The ethanol industry in Brazil is more than 30 year-old and even though it is no longer subsidized, production and use of ethanol was stimulated through: • • • •

Low-interest loans for the construction of ethanol distilleries Guaranteed purchase of ethanol by the state-owned oil company at a reasonable price Retail pricing of neat ethanol so it is competitive if not slightly favorable to the gasoline-ethanol blend Tax incentives provided during the 1980s to stimulate the purchase of neat ethanol vehicles.

Guaranteed purchase and price regulation were ended some years ago, with relatively positive results. In addition to these other policies, ethanol producers in the state of São Paulo established a research and technology transfer center that has been effective in improving sugar cane and ethanol yields. There are no longer light vehicles in Brazil running on pure gasoline. Since 1977 the government made mandatory to blend 20% of ethanol (E20) with gasoline (gasohol), requiring just a minor adjustment on regular gasoline motors. Today the mandatory blend is allowed to vary nationwide between 20% to 25% ethanol (E25) and it is used by all regular gasoline vehicles and flexible-fuel vehicles. The Brazilian car manufacturing industry developed flexible-fuel vehicles that can run on any proportion of gasoline and ethanol. Introduced in the market in 2003, these vehicles became a commercial success. By December 2009 the fleet of "flex" cars and light commercial vehicles had reached 9.35 million vehicles, and 183.3 thousand flex-fuel motorcycles. The cumulative production of flex-fuel cars and light commercial vehicles since 2003 reached the milestone of 10 million units produced in March 2010. The ethanol-powered "flex" vehicles, as they are popularly known, are manufactured to tolerate hydrated ethanol (E100), an azeotrope composed of 95.6% ethanol and 4.4% water. The latest innovation within the Brazilian flexible-fuel technology is the development of flex-fuel motorcycles. The first flex motorcycle was launched to the market by Honda in March 2009. Produced by its Brazilian subsidiary Moto Honda da Amazônia, the CG 150 Titan Mix is sold for around US$2,700. During the first eight months after its market launch the CG 150 Titan Mix has sold 139,059 motorcycles, capturing a 10.6% market share, and ranking second in sales of new motorcycles in the Brazilian market by October 2009.

United States United States fuel ethanol production and imports (2001–2009) (Millions of U.S. liquid gallons)

Year Production Imports Demand 2001 1,770 n/a n/a 2002 2,130 46 2,085 2003 2,800 61 2,900 2004 3,400 161 3,530 2005 3,904 135 4,049 2006 4,855 653 5,377 2007 6,500 450 6,847 2008 9,000 556 9,637 2009 10,600 190 10,940 Note: Demand figures includes stocks change

and small exports in 2005

The United States produces and consumes more ethanol fuel than any other country in the world. Ethanol use as fuel dates back to Henry Ford, who in 1896 designed his first car, the "Quadricycle" to run on pure ethanol. Then in 1908, he produced the famous Ford Model T capable of running on gasoline, ethanol or a combination of both. Ford continued to advocate for ethanol as fuel even during Prohibition. Most cars on the road today in the U.S. can run on blends of up to 10% ethanol, and motor vehicle manufacturers already produce vehicles designed to run on much higher ethanol blends. In 2007 Portland, Oregon, became the first city in the United States to require all gasoline sold within city limits to contain at least 10% ethanol. As of January 2008, three states — Missouri, Minnesota, and Hawaii — require ethanol to be blended with gasoline motor fuel. Many cities also require ethanol blends due to non-attainment of federal air quality goals.

E85 FlexFuel Chevrolet Impala LT 2009, Miami, Florida. Several motor vehicle manufacturers, including Ford, Chrysler, and GM, sell flexible-fuel vehicles that can use gasoline and ethanol blends ranging from pure gasoline all the way up to 85% ethanol (E85). By December 2009 it was estimated there were 8.4 million E85-compatible vehicles on U.S. roads, though actual used of E85 fuel is limited, not only because the ethanol fueling infrastructures is limited, but also because many owners are not aware their vehicle is flex-fuel capable.

In the USA there are currently about 1,900 stations distributing ethanol, although most stations are in the corn belt area. One of the debated methods for distribution in the US is using existing oil pipelines, which raises concerns over corrosion. In any case, some companies proposed building a 1,700-mile (2,700 km) pipeline to carry ethanol from the Midwest through Central Pennsylvania to New York. The production of fuel ethanol from corn in the United States is controversial for a few reasons. Production of ethanol from corn is 5 to 6 times less efficient than producing it from sugarcane. Ethanol production from corn is highly dependent upon subsidies and it consumes a food crop to produce fuel. The subsidies paid to fuel blenders and ethanol refineries have often been cited as the reason for driving up the price of corn, and in farmers planting more corn and the conversion of considerable land to corn (maize) production which generally consumes more fertilizers and pesticides than many other land uses. This is at odds with the subsidies actually paid directly to farmers that are designed to take corn land out of production and pay farmers to plant grass and idle the land, often in conjunction with soil conservation programs, in an attempt to boost corn prices. Recent developments with cellulosic ethanol production and commercialization may allay some of these concerns. A theoretically much more efficient way of ethanol production has been suggested to use sugar beets which make about the same amount of ethanol as corn without using the corn food crop especially since sugar beets can grow in less tropical conditions than sugar cane.

Most of the ethanol consumed in the US is in the form of low blends with gasoline up to 10%. Shown a fuel pump in Maryland selling mandatory E10.

On October 2008 the first "biofuels corridor" was officially opened along I-65, a major interstate highway in the central United States. Stretching from northern Indiana to southern Alabama, this corridor consisting of more than 200 individual fueling stations makes it possible to drive a flex-fueled vehicle from Lake Michigan to the Gulf of Mexico without being further than a quarter tank worth of fuel from an E85 pump. On April 23, 2009, the California Air Resources Board approved the specific rules and carbon intensity reference values for the California Low-Carbon Fuel Standard (LCFS) that will go into effect in January 1, 2011. During the consultation process there was controversy regarding the inclusion and modeling of indirect land use change effects. After the CARB's ruling, among other criticisms, representatives of the US ethanol industry complained that this standard overstates the environmental effects of corn ethanol, and also criticized the inclusion of indirect effects of land-use changes as an unfair penalty to domestically produced corn ethanol because deforestation in the developing world is being tied to US ethanol production. The initial reference value set for 2011 for LCFS means that Mid-west corn ethanol will not meet the California standard unless current carbon intensity is reduced. A similar controversy arose after the U.S. Environmental Protection Agency (EPA) published on May 5, 2009, its notice of proposed rulemaking for the new Renewable Fuel Standard (RFS). The draft of the regulations was released for public comment during a 60-day period. EPA's proposed regulations also included the carbon footprint from indirect land-use changes. On the same day, President Barack Obama signed a Presidential Directive with the aim to advance biofuels research and improve their commercialization. The Directive established a Biofuels Interagency Working Group comprising of three agencies, the Department of Agriculture, the Environmental Protection Agency, and the Department of Energy. This group will develop a plan to increase flexible fuel vehicle use and assist in retail marketing efforts. Also they will coordinate infrastructure policies impacting the supply, secure transport, and distribution of biofuels. The group will also come up with policy ideas for increasing investment in next-generation fuels, such as cellulosic ethanol, and for reducing the environmental footprint of growing biofuels crops, particularly corn-based ethanol. In 2010, Growth Energy, an industry lobbist group, claimed that increasing the percentage of ethanol in gasoline to 15% would create 136,000 jobs. The Environmental Working Group said that 27,000 might be created, each costing the taxpayers $446,000 per year (in 2010 constant dollars). In October 2010 the E.P.A. granted a waiver to allow the E15 blend to be sold only for cars and trucks with a model year of 2007 or later, representing about 15% of vehicles on the U.S. roads. As stations are not required to offer E15, a practical barrier to the commercialization of E15 is the lack of infrastructure, similar to the limitations suffered by sales of E85.

Europe Production of Bioethanol in the European Union (GWh)

No 1 2 3 4 5 6 7 8 9 10 11 12 27

Country

2005 2006 2,55 Germany 978 4 2,38 1,796 Spain 2 1,48 853 France 2 Sweden 907 830 47 759 Italy Poland 379 711 Hungary 207 201 Lithuania 47 107 47 89 Netherlands 89 Czech Republic 0 Latvia 71 71 Finland 77 0 9,27 Total 5,411 4

n.a. = not available

Consumption of Bioethanol in the European Union (GWh) No Country 2005 2006 Germany 1,682 3,544 1 2 871 1,719 France Sweden 1,681 1,894 3 4 1,314 1,332 Spain 5 Poland 329 611 United Kingdom 502 563 6 7 Bulgaria 0 8 0 0 Austria 0 4 9 Slovakia 10 Lithuania 10 64 11 Hungary 28 136 12 0 179 Netherlands 42 13 Denmark 14 Ireland 0 13 15 Latvia 5 12 Luxembourg 0 0 16 17 Slovenia 0 2

2007 3,408 3,174 2,113 1,310 991 907 769 254 154 135 107 101 70 54 20 10 9

18 19 20 27

Czech Republic Italy Finland EU

0 13 2 59 0 0 0 10 n.a. 6,481 10,138 13,563

The consumption of bioethanol in Europe is largest in Germany, Sweden, France and Spain. Europe produces equivalent to 90% of its consumption (2006). Germany produced ca 70% of its consumption, Spain 60% and Sweden 50% (2006). In Sweden there are 792 E85 filling stations and in France 131 E85 service stations with 550 more under construction. On Monday, September 17, 2007 the first ethanol fuel pump was opened in Reykjavik, Iceland. This pump is the only one of its kind in Iceland. The fuel is imported by Brimborg, a Volvo dealer, as a pilot to see how ethanol fueled cars work in Iceland. In the Netherlands regular petrol with no bio-additives is slowly being outphased, since EU-legislation has been passed that requires the fraction of nonmineral origin to become minimum 5.75% of the total fuel consumption volume in 2010. This can be realised by substitutions in diesel or in petrol of any biological source; or fuel sold in the form of pure biofuel. (2007) There are only a few gas stations where E85 is sold, which is an 85% ethanol, 15% petrol mix. Directly neighbouring country Germany is reported to have a much better biofuel infrastructure and offers both E85 and E50. Biofuel is taxed equally as regular fuel. However, fuel tanked abroad cannot be taxed and a recent payment receipt will in most cases suffice to prevent fines if customs check tank contents. (Authorities are aware of high taxation on fuels and cross-border fuel refilling is a wellknown practice.)

An example of an ethanol powered bus. This is a Scania OmniCity which has been touring the United Kingdom, which does not use the fuel widely. A larger fleet of similar buses will enter service in Stockholm in 2008. Sweden Sweden is the leading country in Europe regarding the use of ethanol as fuel, though it has to import most of the ethanol. All Swedish gas stations are required by an act of parliament to offer at least one alternative fuel, and every fifth car in Stockholm now drives at least partially on alternative fuels, mostly ethanol. The number of bioethanol stations in Europe is highest in Sweden, with 1,200 stations and a fleet of 116 thousand flexi-fuel vehicles as of July 2008. Stockholm will introduce a fleet of Swedish-made electric hybrid buses in its public transport system on a trial basis in 2008. These buses will use ethanol-powered internalcombustion engines and electric motors. The vehicles’ diesel engines will use ethanol. In order to achieve a broader use of biofuels several government incentives were implemented. Ethanol, as the other biofuels, were exempted of both, the CO2 and energy taxes until 2009, resulting in a 30% price reduction at the pump of E85 fuel over gasoline. Furthermore, other demand side incentives for flexifuel vehicle owners include

a USD 1,800 bonus to buyers of FFVs, exemption from the Stockholm congestion tax, up to 20% discount on auto insurance, free parking spaces in most of the largest cities, lower annual registration taxes, and a 20% tax reduction for flexifuel company cars. Also, a part of the program, the Swedish Government ruled that 25% of their vehicle purchases (excluding police, fire and ambulance vehicles) must be alternative fuel vehicles. ; By the first months of 2008, this package of incentives resulted in sales of flexible-fuel cars representing 25% of new car sales. Bioethanol stations European Union Country Sweden France Germany

Stations

1,200 211 193 40 Switzerland Ireland 29 United Kingdom 22

No/106 persons 131.26 3.27 2.35 5.27 6.84 0.36

Asia China China is promoting ethanol-based fuel on a pilot basis in five cities in its central and northeastern region, a move designed to create a new market for its surplus grain and reduce consumption of petroleum. The cities include Zhengzhou, Luoyang and Nanyang in central China's Henan province, and Harbin and Zhaodong in Heilongjiang province, northeast China. Under the program, Henan will promote ethanol-based fuel across the province by the end of this year. Officials say the move is of great importance in helping to stabilize grain prices, raise farmers' income and reducing petrol- induced air pollution. Thailand Thailand already use 10% ethanol (E10) widely on big scale on the local market. Beginning in 2008 Thailand started with the sale of E20 and by late 2008 E85 flexible fuel vehicles were introduced with only two gas stations selling E85. Thailand is now converting some of the cassava stock hold by the government into fuel ethanol. Cassava-based ethanol productions are being ramped up to help manage the agricultural outputs of both cassava and sugar cane. With its abundant biomass resources, it is believed that the fuel ethanol program will be a new means of job creation in the rural areas while enhancing the balance sheet of fuel imports.

Australia

Legislation in Australia imposes a 10% cap on the concentration of fuel ethanol blends. Blends of 90% unleaded petrol and 10% fuel ethanol are commonly referred to as E10. E10 is available through service stations operating under the BP, Caltex, Shell and United brands as well as those of a number of smaller independents. Not surprisingly, E10 is most widely available closer to the sources of production in Queensland and New South Wales where Sugar Cane is grown. E10 is most commonly blended with 91 RON "regular unleaded" fuel. There is a requirement that retailers label blends containing fuel ethanol on the dispenser. Due to ethanol's greater stability under pressure it is used by Shell in their 100 octane fuel. Similarly IFS add 10% ethanol to their 91 octane fuel, label it premium fuel and sell it more cheaply than regular unleaded. This is converse to the general practice of adding ethanol to a lesser quality fuel to bring its octane rating up to 91. Some concern was raised over the use of ethanol blend fuels in petrol vehicles in 2003, yet manufacturers widely claimed that their vehicles were engined for such fuels. Since then there have been no reports of adverse affects to vehicles running on ethanol blended fuels.

Caribbean Basin United States fuel ethanol imports by country (2002–2007) (Millions of U.S. liquid gallons)

Country 2007 2006 2005 2004 2003 2002 188.8 433.7 31.2 90.3 0 0 Brazil Jamaica 75.2 66.8 36.3 36.6 39.3 29.0 El Salvador 73.3 38.5 23.7 5.7 6.9 4.5 Trinidad and Tobago 42.7 24.8 10.0 0 0 0 Costa Rica 39.3 35.9 33.4 25.4 14.7 12.0 All countries in Central America, northern South America and the Caribbean are located in a tropical zone with suitable climate for growing sugar cane. In fact, most of these countries have a long tradition of growing sugar cane mainly for producing sugar and alcoholic beverages. As a result of the guerilla movements in Central America, in 1983 the United States unilateral and temporarily approved the Caribbean Basin Initiative, allowing most countries in the region to benefit from several tariff and trade benefits. These benefits were made permanent in 1990 and more recently, these benefits were replaced by the Caribbean Basin Trade and Partnership Act, approved in 2000, and the Dominican Republic–Central America Free Trade Agreement that went to effect in 2008. All these agreements have allowed several countries in the region to export ethanol to the U.S free of tariffs. Until 2004, the countries that benefited the most were Jamaica and Costa Rica,

but as the U.S. began demanding more fuel ethanol, the two countries increased their exports and two others began exporting. In 2007, Jamaica, El Salvador, Trinidad & Tobago and Costa Rica exported together to the U.S. a total of 230.5 million gallons of ethanol, representing 54.1% of U.S. fuel ethanol imports. Brasil began exporting ethanol to the U.S. in 2004 and exported 188.8 million gallons representing 44.3% of U.S. ethanol imports in 2007. The remaining 1.6% imports that year came from Canada and China. In March 2007, "ethanol diplomacy" was the focus of President George W. Bush's Latin American tour, in which he and Brazil's president, Luiz Inacio Lula da Silva, were seeking to promote the production and use of sugar cane based ethanol throughout Latin America and the Caribbean. The two countries also agreed to share technology and set international standards for biofuels. The Brazilian sugar cane technology transfer would allow several Central American, Caribbean and Andean countries to take advantage of their tariff-free trade agreements to increase or become exporters to the United States in the short-term. Also, in August 2007, Brazil's President toured Mexico and several countries in Central America and the Caribbean to promote Brazilian ethanol technology. The ethanol alliance between the U.S. and Brazil generated some negative reactions from Venezuela's President Hugo Chavez, and by then Cuba's President, Fidel Castro, who wrote that "you will see how many people among the hungry masses of our planet will no longer consume corn." "Or even worse," he continued, "by offering financing to poor countries to produce ethanol from corn or any other kind of food, no tree will be left to defend humanity from climate change."' Daniel Ortega, Nicaragua's President, and one of the preferencial recipients of Brazilian technical aid also voiced critics to the Bush plan, but he vowed support for sugar cane based ethanol during Lula's visit to Nicaragua. Colombia Colombia's ethanol program began in 2002, based on a law approved in 2001 mandating a mix of 10% ethanol with regular gasoline, and the plan is to gradually reach a 25% blend in twenty-years. Sugar cane-based ethanol production began in 2005, when the law went into effect, and as local production was not enough to supply enough ethanol to the entire country's fleet, the program was implemented only on cities with more than 500,000 inhabitants, such as Cali, Pereira, and the capital city of Bogotá. All of the ethanol production comes from the Department of Valle del Cauca, Colombia's traditional sugar cane region. Cassava is the second source of ethanol, and potatoes and castor oil are also being studied. On March 2009 the Colombian government enacted a mandate to introduce E85 flexiblefuel cars. The executive decree applies to all gasoline-powered vehicles with engines smaller than 2.0 liters manufactured, imported, and commercialized in the country beginning in 2012, mandating that 60% of such vehicles must have flex-fuel engines capable of running with gasoline or E85, or any blend of both. By 2014 the mandatory quota is 80% and it will reach 100% by 2016. All vehicles with engines bigger than 2.0 liters must be E85 capable starting in 2013. The decree also mandates that by 2011 all

gasoline stations must provide infrastructure to guarantee availability of E85 throughout the country. The mandatory introduction of E85 flex-fuels has been controversial. Costa Rica The government, based on the National Biofuel Program, established the mandatory use of all gasoline sold in Costa Rica with a blend of around 7.5% ethanol, starting in October 2008. The implementation phase follows a two year trial that took place in the provinces of Guanacaste and Puntarenas. The government expects to increase the percentage of ethanol mixed with gasoline to 12% in the next 4 to 5 years. The Costa Rican government is pursuing this policy to lower the country's dependency of foreign oil and to reduce the amount of greenhouse gases produced. The plan also calls for an increase in ethanol producing crops and tax breaks for flex-fuel vehicles and other alternative fuel vehicles. However, the introduction of the blend of 7% ethanol was postponed in September 2008 until the beginning of 2009. This delay was due to a request by the national association of fuel retailers to have more time available to adapt their fueling infrastructure. Additional delays caused another postponement, as fueling stations were not ready yet for handling ethanol fuel, and now implementation is expected for November 2009. Despite the official postponement, during the months of February and March 2009, ethanol in different blends was sold without warning to consumers, which was cause for complains. The national distribution company, RECOPE, explained that it had already bought 50,000 barrels (7,900 m3) of ethanol stored and ready for distribution, so it decided to used as an oxygenate in substitution of MTBE. Nevertheless, retail sales of E7 continue uninterrupted in the trial regions of Guanacaste and the Central Pacific for three years now. El Salvador As a result of the cooperation agreement between the United States and Brazil, El Salvador was chosen in 2007 to lead a pilot experience to introduce state-of-the-art technology for growing sugar cane for production of ethanol fuel in Central America, as this technical bilateral cooperation is looking for helping Central American countries to reduce their dependence on foreign oil.

Comparison of Brazil and the U.S.

Evolution of the ethanol productivity per hectare of sugarcane planted in Brazil between 1975 and 2004. Brazil's sugar cane-based industry is far more efficient than the U.S. corn-based industry. Brazilian distillers are able to produce ethanol for 22 cents per liter, compared with the 30 cents per liter for corn-based ethanol. Sugarcane cultivation requires a tropical or subtropical climate, with a minimum of 600 mm (24 in) of annual rainfall. Sugarcane is one of the most efficient photosynthesizers in the plant kingdom, able to convert up to 2% of incident solar energy into biomass. Ethanol is produced by yeast fermentation of the sugar extracted from sugar cane. Sugarcane production in the United States occurs in Florida, Louisiana, Hawaii, and Texas. In prime growing regions, such as Hawaii, sugarcane can produce 20 kg for each square meter exposed to the sun. The first three plants to produce sugar cane-based ethanol are expected to go online in Louisiana by mid 2009. Sugar mill plants in Lacassine, St. James and Bunkie were converted to sugar cane-based ethanol production using Colombian technology in order to make possible a profitable ethanol production. These three plants will produce 100 million gallons of ethanol within five years. U.S. corn-derived ethanol costs 30% more because the corn starch must first be converted to sugar before being distilled into alcohol. Despite this cost differential in production, in contrast to Japan and Sweden, the U.S. does not import much of Brazilian ethanol because of U.S. trade barriers corresponding to a tariff of 54-cent per gallon – a levy designed to offset the 45-cent per gallon blender's federal tax credit that is applied to

ethanol no matter its country of origin. One advantage U.S. corn-derived ethanol offers is the ability to return 1/3 of the feedstock back into the market as a replacement for the corn used in the form of Distillers Dried Grain.

Comparison of key characteristics between the ethanol industries in the United States and Brazil

Characteristic

Brazil

U.S.

Units/comments

Sugar cane

Maize

Main cash crop for ethanol production, the US has less than 2% from other crops.

Total ethanol fuel production (2009)

6,578

10,750

Million U.S. liquid gallons

Total arable land

355

270(1)

Million hectares.

Feedstock

Total area used for ethanol crop (2006)

Productivity per hectare

Energy balance (input energy productivity)

3.6 (1%)

6,8008,000

10 (3.7%) Million hectares (% total arable)

Liters of ethanol per hectare. Brazil

3,800-4,000 is 727 to 870 gal/acre (2006), US is 321 to 424 gal/acre (2003)

Ratio of the energy obtained from

8.3 to 10.2 1.3 to 1.6 ethanol/energy expended in its production

% GHGs avoided by using ethanol

Estimated GHG 86-90%(2) emissions reduction

10-30%(2) instead of gasoline, using existing

Full life-cycle carbon intensity

105.10(3) per MJ of energy produced,

73.40

crop land (No ILUC).

Grams of CO2 equivalent released includes indirect land use changes.

Estimated payback time for GHG emissions

17 years

(4)

(4)

93 years

Brazilian cerrado for sugarcane and US grassland for corn. Land use change scenarios by Fargione

Flexible-fuel vehicles produced (autos and light trucks)

10.6 million

Brazil as of June 2010 (FFVs use any blend up to E100). 9.3 million U.S. as of December 2009 (FFVs use E85).

Ethanol fueling stations in the country

35,017

2,326(1%) country. Brazil by December 2007.

Ethanol's share in the gasoline market

50%(5)

8%

As % of total consumption on a volumetric basis. Brazil as of April 2008. U.S. as of December 2009.

Cost of production (USD/gallon)

0.83

1.14

2006/2007 for Brazil (22¢/liter), 2004 for U.S. (35¢/liter)

Government subsidy (in USD)

0 (6)

Import tariffs (in USD)

(100%)

0

(7)

As % of total gas stations in the

U.S. by July 2010. (170,000 total. )

U.S. since 2009-01-01 as a tax

0.45/gallon credit. Brazilian ethanol production is no longer subsidized.(6)

Brazil does not import 0.54/gallon ethanol fuel since 2002. The U.S. does in a regular basis.

Notes: (1) Only contiguous U.S., excludes Alaska. (2) Assuming no land use change. (3) CARB estimate for Midwest corn ethanol. California's gasoline carbon intensity is 95.86 blended with 10% ethanol. (4) Assuming direct land use change. (5) If diesel-powered vehicles are included and due to ethanol's lower energy content by volume, bioethanol represented 16.9% of the road sector energy consumption in 2007. (6) Brazilian ethanol production is no longer subsidized, but gasoline is heavily taxed favoring ethanol fuel consumption (~54% tax). By the end of July 2008, when oil prices were close to its latest peak and the Brazilian Real exchange rate to the US dollar was close to its most recent minimum, the average gasoline retail price at the pump in Brazil was USD 6.00 per gallon, while the average US price was USD 3.98 per gallon. The latest gas retail price increase in Brazil occurred in late 2005, when oil price was at USD 60 per barrel. (7) Brazilian import tax is 20% (FOB) but in early 2010 it was temporarily cut to zero until 2011.

Environment Energy balance Energy balance Country Type Energy balance United States Corn ethanol 1.3 Sugarcane ethanol 8 Brazil Germany Biodiesel 2.5 † United States Cellulosic ethanol 2–36†† † experimental, not in commercial production †† depending on production method All biomass goes through at least some of these steps: it needs to be grown, collected, dried, fermented, and burned. All of these steps require resources and an infrastructure. The total amount of energy input into the process compared to the energy released by burning the resulting ethanol fuel is known as the energy balance (or "Net energy gain"). Figures compiled in a 2007 by National Geographic Magazine point to modest results for corn ethanol produced in the US: one unit of fossil-fuel energy is required to create 1.3 energy units from the resulting ethanol. The energy balance for sugarcane ethanol produced in Brazil is more favorable, 1:8. Energy balance estimates are not easily produced, thus numerous such reports have been generated that are contradictory. For instance, a separate survey reports that production of ethanol from sugarcane, which requires a tropical climate to grow productively, returns from 8 to 9 units of energy for each unit expended, as compared to corn which only returns about 1.34 units of fuel energy for each unit of energy expended. Carbon dioxide, a greenhouse gas, is emitted during fermentation and combustion. However, this is canceled out by the greater uptake of carbon dioxide by the plants as they grow to produce the biomass. When compared to gasoline, depending on the production method, ethanol releases less greenhouse gases.

Air pollution Compared with conventional unleaded gasoline, ethanol is a particulate-free burning fuel source that combusts with oxygen to form carbon dioxide, water and aldehydes. 3rd paragraph from the last. Since ethanol contains 2/3 of the energy per volume as gasoline, ethanol produces 19% more CO2 than gasoline for the same energy. The Clean Air Act requires the addition of oxygenates to reduce carbon monoxide emissions in the United States. The additive MTBE is currently being phased out due to ground water contamination, hence ethanol becomes an attractive alternative additive. Current

production methods include air pollution from the manufacturer of macronutrient fertilizers such as ammonia. A study by atmospheric scientists at Stanford University found that E85 fuel would increase the risk of air pollution deaths relative to gasoline by 9% in Los Angeles, USA: a very large, urban, car-based metropolis that is a worst case scenario. Ozone levels are significantly increased, thereby increasing photochemical smog and aggravating medical problems such as asthma.

Manufacture In 2002, monitoring the process of ethanol production from corn revealed that they released VOCs (volatile organic compounds) at a higher rate than had previously been disclosed. The Environmental Protection Agency (EPA) subsequently reached settlement with Archer Daniels Midland and Cargill, two of the largest producers of ethanol, to reduce emission of these VOCs. VOCs are produced when fermented corn mash is dried for sale as a supplement for livestock feed. Devices known as thermal oxidizers or catalytic oxidizers can be attached to the plants to burn off the hazardous gases.

Carbon dioxide

UK government calculation of carbon intensity of corn bioethanol grown in the US and burnt in the UK.

Graph of UK figures for the carbon intensity of bioethanol and fossil fuels. This graph assumes that all bioethanols are burnt in their country of origin and that previously existing cropland is used to grow the feedstock. The calculation of exactly how much carbon dioxide is produced in the manufacture of bioethanol is a complex and inexact process, and is highly dependent on the method by which the ethanol is produced and the assumptions made in the calculation. A calculation should include: • • •

The cost of growing the feedstock The cost of transporting the feedstock to the factory The cost of processing the feedstock into bioethanol

Such a calculation may or may not consider the following effects: • • • • •

The cost of the change in land use of the area where the fuel feedstock is grown. The cost of transportation of the bioethanol from the factory to its point of use The efficiency of the bioethanol compared with standard gasoline The amount of Carbon Dioxide produced at the tail pipe. The benefits due to the production of useful bi-products, such as cattle feed or electricity.

The graph on the right shows figures calculated by the UK government for the purposes of the Renewable transport fuel obligation.

The January 2006 Science article from UC Berkeley's ERG, estimated reduction from corn ethanol in GHG to be 13% after reviewing a large number of studies. However, in a correction to that article released shortly after publication, they reduce the estimated value to 7.4%. A National Geographic Magazine overview article (2007) puts the figures at 22% less CO2 emissions in production and use for corn ethanol compared to gasoline and a 56% reduction for cane ethanol. Carmaker Ford reports a 70% reduction in CO2 emissions with bioethanol compared to petrol for one of their flexible-fuel vehicles. An additional complication is that production requires tilling new soil which produces a one-off release of GHG that it can take decades or centuries of production reductions in GHG emissions to equalize. As an example, converting grass lands to corn production for ethanol takes about a century of annual savings to make up for the GHG released from the initial tilling.

Change in land use Large-scale farming is necessary to produce agricultural alcohol and this requires substantial amounts of cultivated land. University of Minnesota researchers report that if all corn grown in the U.S. were used to make ethanol it would displace 12% of current U.S. gasoline consumption. There are claims that land for ethanol production is acquired through deforestation, while others have observed that areas currently supporting forests are usually not suitable for growing crops. In any case, farming may involve a decline in soil fertility due to reduction of organic matter, a decrease in water availability and quality, an increase in the use of pesticides and fertilizers, and potential dislocation of local communities. However, new technology enables farmers and processors to increasingly produce the same output using less inputs. Cellulosic ethanol production is a new approach which may alleviate land use and related concerns. Cellulosic ethanol can be produced from any plant material, potentially doubling yields, in an effort to minimize conflict between food needs vs. fuel needs. Instead of utilizing only the starch by-products from grinding wheat and other crops, cellulosic ethanol production maximizes the use of all plant materials, including gluten. This approach would have a smaller carbon footprint because the amount of energyintensive fertilisers and fungicides remain the same for higher output of usable material. The technology for producing cellulosic ethanol is currently in the commercialization stage. Many analysts suggest that, whichever ethanol fuel production strategy is used, fuel conservation efforts are also needed to make a large impact on reducing petroleum fuel use. Using Ethanol for Electricity Converting biomass to electricity for charging electric vehicles may be a more "climatefriendly" transportation option than using biomass to produce ethanol fuel, according to an analysis published in Science in May. "You make more efficient use of the land and

more efficient use of the plant biomass by making electricity rather than ethanol," said Elliott Campbell, an environmental scientist at the University of California at Merced, who led the research. "It's another reason that, rather than race to liquid biofuels, we should consider other uses of bio-resources." For bioenergy to become a widespread climate solution, however, technological breakthroughs are necessary, analysts say. Researchers continue to search for more costeffective developments in both cellulosic ethanol and advanced vehicle batteries. Health Costs of Ethanol Emissions For each billion ethanol-equivalent gallons of fuel produced and combusted in the US, the combined climate-change and health costs are $469 million for gasoline, $472–952 million for corn ethanol depending on biorefinery heat source (natural gas, corn stover, or coal) and technology, but only $123–208 million for cellulosic ethanol depending on feedstock (prairie biomass, Miscanthus, corn stover, or switchgrass).

Efficiency of common crops As ethanol yields improve or different feedstocks are introduced, ethanol production may become more economically feasible in the US. Currently, research on improving ethanol yields from each unit of corn is underway using biotechnology. Also, as long as oil prices remain high, the economical use of other feedstocks, such as cellulose, become viable. By-products such as straw or wood chips can be converted to ethanol. Fast growing species like switchgrass can be grown on land not suitable for other cash crops and yield high levels of ethanol per unit area.

Crop

Annual yield Greenhouse(Liters/hectare, gas savings vs. petrol[a] US gal/acre)

Miscanthus

7300 L/ha, 780 g/acre

Switchgrass

3100–7600 L/ha, 37%–73% 330–810 g/acre

37%–73%

Comments

Low-input perennial grass. Ethanol production depends on development of cellulosic technology. Low-input perennial grass. Ethanol production depends on development of cellulosic technology. Breeding efforts underway to increase yields. Higher biomass production possible with mixed species of perennial grasses.

Fast-growing tree. Ethanol production depends on development of cellulosic 3700–6000 L/ha, Poplar 51%–100% technology. Completion of 400–640 g/acre genomic sequencing project will aid breeding efforts to increase yields. Long-season annual grass. Used as feedstock for most bioethanol produced in Brazil. Newer 6800–8000 L/ha, Sugar cane 87%–96% processing plants burn residues 727–870 g/acre not used for ethanol to generate electricity. Only grows in tropical and subtropical climates. Low-input annual grass. Ethanol production possible using existing technology. Grows in tropical and Sweet 2500–7000 L/ha, temperate climates, but highest No data sorghum 270–750 g/acre ethanol yield estimates assume multiple crops per year (only possible in tropical climates). Does not store well. High-input annual grass. Used as feedstock for most bioethanol produced in USA. Only kernels can be processed using available 3100–4000 L/ha, Corn 10%–20% technology; development of 330–424 g/acre commercial cellulosic technology would allow stover to be used and increase ethanol yield by 1,100 2,000 litres/ha. Source (except those indicated): Nature 444 (December 7, 2006): 673-676. [a] - Savings of GHG emissions assuming no land use change (using existing crop lands).

Reduced petroleum imports and costs One rationale given for extensive ethanol production in the U.S. is its benefit to energy security, by shifting the need for some foreign-produced oil to domestically produced energy sources. Production of ethanol requires significant energy, but current U.S. production derives most of that energy from coal, natural gas and other sources, rather than oil. Because 66% of oil consumed in the U.S. is imported, compared to a net surplus of coal and just 16% of natural gas (2006 figures), the displacement of oil-based fuels to ethanol produces a net shift from foreign to domestic U.S. energy sources.

According to a 2008 analysis by Iowa State University, the growth in US ethanol production has caused retail gasoline prices to be US $0.29 to US $0.40 per gallon lower than would otherwise have been the case.

Criticism There are various social, economic, environmental and technical issues with biofuel production and use, which have been discussed in the popular media and scientific journals. These include: the effect of moderating oil prices, the "food vs fuel" debate, poverty reduction potential, carbon emissions levels, sustainable biofuel production, deforestation and soil erosion, loss of biodiversity, impact on water resources, as well as energy balance and efficiency.

Fuel system problems Fuels with more than 10% ethanol are not compatible with non E85-ready fuel system components and may cause corrosion of iron components. Ethanol fuel can negatively affect electric fuel pumps by increasing internal wear, cause undesirable spark generation, and is not compatible with capacitance fuel level gauging indicators and may cause erroneous fuel quantity indications in vehicles that employ that system. It is also not always compatible with marine craft, especially those that use fiberglass fuel tanks. Ethanol is also not used in aircraft for these same reasons. Using 100% ethanol fuel decreases fuel-economy by 15-30% over using 100% gasoline; this can be avoided using certain modifications that would, however, render the engine inoperable on regular gasoline without the addition of an adjustable ECU. Tough materials are needed to accommodate a higher compression ratio to make an ethanol engine as efficient as it would be on gasoline; these would be similar to those used in diesel engines which typically run at a CR of 20:1, vs. about 8-12:1 for gasoline engines. In April 2008 the German environmental minister cancelled a proposed 10% ethanol fuel scheme citing technical problems: too many older cars in Germany are unequipped to handle this fuel. Ethanol levels in fuel will remain at 5%.

Other non-transport uses There is still extensive use of kerosene for lighting and cooking in less developed countries, and ethanol can have a role in reducing petroleum dependency in this use too. A non profit named Project Gaia seeks to spread the use of ethanol stoves to replace wood, charcoal and kerosene. There is also potential for bioethanol replacing some kerosene use in domestic lighting from feedstocks grown locally. A 50% ethanol water mixture has been tested in specially designed stoves and lanterns for rural areas.

Chapter- 6

Methanol Fuel

Methanol is an alternate fuel for internal combustion and other engines, either in combination with gasoline or directly ("neat"). It is used in racing cars and in China. Methanol fuel has received less attention than ethanol fuel as an alternative to petroleum based fuels. It may be made from fossil or renewable resources.

History and production Historically, methanol was first produced by destructive distillation (pyrolysis) of wood, resulting in its common English name of wood alcohol. Presently, methanol is usually produced using methane (the chief constituent of natural gas) as a raw material. Methanol is made from coal in China for fuel. "Biomethanol" may be produced by gasification of organic materials to synthesis gas followed by conventional methanol synthesis. Production of methanol from synthesis gas using Biomass-To-Liquid can offer methanol production from biomass at efficiencies up to 75%. Widespread production by this route has a postulated potential to offer methanol fuel at a low cost and with benefits to the environment. These production methods, however, are not suitable for small scale production.

Major fuel use During the OPEC 1973 oil crisis, Reed and Lerner (1973) proposed methanol from coal as a proven fuel with well established manufacturing technology and sufficient resources to replace gasoline. Hagen (1976) reviewed prospects for synthesizing methanol from renewable resources and its use as a fuel. Then in 1986, the Swedish Motor Fuel Technology Co. (SBAD) extensively reviewed the use of alcohols and alcohol blends as motor fuels. It reviewed the potential for methanol production from natural gas, very heavy oils, bituminous shales, coals, peat and biomass. In 2005, 2006 Nobel prize winner George A. Olah and colleagues advocated an entire methanol economy based on energy storage in synthetically produced methanol. The Methanol Institute, the methanol trade

industry organization, posts reports and presentations on methanol. Director Gregory Dolan presented the 2008 global methanol fuel industry in China.

Uses Internal combustion engine fuel Both methanol and ethanol burn at lower temperatures than gasoline, and both are less volatile, making engine starting in cold weather more difficult. Using methanol as a fuel in spark ignition engines can offer an increased thermal efficiency and increased power output (as compared to gasoline) due to its high octane rating (114) and high heat of vaporisation. However, its low energy content of 19.7 MJ/kg and stoichiometric air fuel ratio of 6.42:1 mean that fuel consumption (on volume or mass basis) will be higher than hydrocarbon fuels. The extra water produced also makes the charge rather wet (similar to hydrogen/oxygen combustion engines)and combined with the formation of acidic products during combustion, the wearing of valves, valveseats and cylinder might be higher than with hydrocarbon burning. Certain additives may be added to the fuel in order to neutralize these acids. Methanol, just like ethanol, contains soluble and insoluble contaminants . These soluble contaminants, halide ions such as chloride ions, have a large effect on the corrosivity of alcohol fuels. Halide ions increase corrosion in two ways; they chemically attack passivating oxide films on several metals causing pitting corrosion, and they increase the conductivity of the fuel. Increased electrical conductivity promotes electric, galvanic, and ordinary corrosion in the fuel system. Soluble contaminents, such as aluminum hydroxide, itself a product of corrosion by halide ions, clog the fuel system over time. Methanol is hygroscopic, meaning it will absorb water vapor directly from the atmosphere. Because absorbed water dilutes the fuel value of the methanol (although, it suppresses engine knock), and may cause phase separation of methanol-gasoline blends, containers of methanol fuels must be kept tightly sealed.

Racing Beginning in 1965, pure methanol was used widespread in USAC Indy car competition, which at the time included the Indianapolis 500. A seven-car crash on the second lap of the 1964 Indianapolis 500 resulted in USAC's decision to encourage, and later mandate, the use of methanol. Eddie Sachs and Dave MacDonald died in the crash when their gasoline-fueled cars exploded. The gasolinetriggered fire created a dangerous cloud of thick black smoke, which completely blocked the view of the track for oncoming cars. Johnny Rutherford, one of the other drivers involved, drove a methanol-fueled car which also leaked following the crash. While this car burned from the impact of the first fireball, it formed a much lesser inferno than the gasoline cars, and one that burned invisibly. That testimony, and pressure from Indianapolis Star writer George Moore, led to the switch to alcohol fuel in 1965.

Methanol was used by the CART circuit during its entire campaign (1979–2007). It is also used by and many short track organizations, especially midget, sprint cars and speedway bikes. Pure methanol was used by the IRL from 1996-2006. In 2006, in partnership with the ethanol industry, the IRL used a mixture of 10% ethanol and 90% methanol as its fuel. Starting in 2007, the IRL switched to "pure" ethanol, E100. Methanol fuel is also used extensively in drag racing, primarily in the Top Alcohol category. Formula One racing continues to use gasoline as its fuel, but in pre war grand prix racing methanol was often used in the fuel. Methanol is also used in Monster Truck racing.

Toxicity Methanol occurs naturally in the human body and in some fruits, however it is poisonous in sufficient concentration. Ingestion of 10 ml can cause blindness and 60-100 ml can be fatal if the condition is untreated.. Like many volatile chemicals, methanol does not have to be swallowed to be dangerous since the liquid can be absorbed through the skin, and the vapors through the lungs. Methanol is safer when blended with ethanol. US maximum allowed exposure in air (40 h/week) is 1900 mg/m³ for ethanol, 900 mg/m³ for gasoline, and 1260 mg/m³ for methanol. However, it is less volatile than gasoline, and therefore has lower evaporative emissions. Use of methanol, like ethanol, significantly reduces the emissions of certain hydrocarbon-related toxins such as benzene and 1,3 butadiene. But as gasoline and ethanol are already quite toxic, safety protocol is the same.

Safety Since methanol vapour is heavier than air, it will linger close to the ground or in a pit unless there is good ventilation, and if the concentration of methanol is above 6.7% in air it can be lit by a spark, and will explode above 54 F / 12 C. Once ablaze, the flames give out very little light making it very hard to see the fire or even estimate its size, especially in bright daylight. If you are unlucky enough to be exposed to the poisonous substance through your respiratory system, its pungent odor should give you some warning of its presence. However, it is difficult to smell methanol in the air at less than 2,000 ppm (0.2%), and it can be dangerous at lower concentrations than that.

Use United States The State of California ran an experimental program from 1980 to 1990 which allowed anyone to convert a gasoline vehicle to 85% methanol with 15% additives of choice.

Over 500 vehicles were converted to high compression and dedicated use of the 85/15 methanol and ethanol, with great results. Detroit was not willing to produce any methanol or ethanol vehicles without government subsidy. In 1982 the big three were each given $5,000,000 for design and contracts for 5,000 vehicles to be bought by the State. That was the beginning of the low compression flexible-fuel vehicles which we can still buy today. In 2005, California's Governor, Arnold Schwarzenegger, stopped the use of methanol after 25 years and 200,000,000 miles of success, to join the expanding use of ethanol driven by producers of corn. In spite of this, he was optimistic about the future of the program, claiming "it will be back." Ethanol is currently (as of 2007) priced at 3 to 4 dollars per gallon, while methanol made from natural gas remains at 47 cents per gallon. Presently there are over 60 operating gas stations in California supplying methanol in their pumps. Rep. Eliot Engel [D-NY17] has introduced "An Open Fuel Standard" Act in Congress: "To require automobile manufacturers to ensure that not less than 80 percent of the automobiles manufactured or sold in the United States by each such manufacturer to operate on fuel mixtures containing 85 percent ethanol, 85 percent methanol, or biodiesel."

Brazil A drive to add a significant percentage of methanol to gasoline got very close to implementation in Brazil, following a pilot test set up by a group of scientists involving blending gasoline with methanol between 1989 and 1992. The larger-scale pilot experiment that was to be conducted in São Paulo was vetoed at the last minute by the city's mayor, out of concern for the health of gas station workers (who are mostly illiterate and could not be expected to follow safety precautions). As of 2006, the idea has not resurfaced.

Chapter- 7

Coalbed Methane

Coalbed methane (CBM) or Coal Bed Methane or coalbed gas is a form of natural gas extracted from coal beds. In recent decades it has become an important source of energy in United States, Canada, and other countries. Australia has rich deposits where it is known as coal seam gas (abbreviated "CSG"). The term refers to methane adsorbed into the solid matrix of the coal. It is called 'sweet gas' because of its lack of hydrogen sulfide. The presence of this gas is well known from its occurrence in underground coal mining, where it presents a serious safety risk. Coalbed methane, often referred to as CBM, is distinct from a typical sandstone or other conventional gas reservoir, as the methane is stored within the coal by a process called adsorption. The methane is in a near-liquid state, lining the inside of pores within the coal (called the matrix). The open fractures in the coal (called the cleats) can also contain free gas or can be saturated with water. Unlike much natural gas from conventional reservoirs, coalbed methane contains very little heavier hydrocarbons such as propane or butane, and no natural gas condensate. It often contains up to a few percent carbon dioxide. Some coal seams, such as those in certain areas of the Illawarra Coal Measures in NSW, Australia, contain little methane, with the predominant coal seam gas being carbon dioxide.

Permeability of coal bed methane reservoirs Permeability is key factor for CBM. Coal itself is a low permeability reservoir. Almost all the permeability of a coal bed is usually considered to be due to fractures, which in coal are in the form of cleats and joints. The permeability of the coal matrix is negligible by comparison. Coal cleats are of two types: butt cleats and face cleats, which occur at nearly right angles. The face cleats are continuous and provide paths of higher permeability while butt cleats are non-continuous and end at face cleats. Joints are larger fractures through the coal that may cross lithological boundaries. Hence, on a small scale, fluid flow through coal bed methane reservoirs usually follows rectangular paths. The ratio of permeabilities in the face cleat direction over the butt cleat direction may range

from 1:1 to 17:1. Because of this anisotropic permeability, drainage areas around coal bed methane wells are often elliptical in shape.

Intrinsic properties affecting gas production Gas contained in coal bed methane is mainly methane and trace quantities of ethane, nitrogen, carbon dioxide and few other gases. Intrinsic properties of coal as found in nature determine the amount of gas that can be recovered.

Porosity The porosity of coal bed reservoirs is usually very small, ranging from 0.1 to 10%.

Adsorption capacity Adsorption capacity of coal is defined as the volume of gas adsorbed per unit mass of coal usually expressed in SCF (standard cubic feet, the volume at standard pressure and temperature conditions) gas/ton of coal. The capacity to adsorb depends on the rank and quality of coal. The range is usually between 100 to 800 SCF/ton for most coal seams found in the US. Most of the gas in coal beds is in the adsorbed form. When the reservoir is put into production, water in the fracture spaces is pumped off first. This leads to a reduction of pressure enhancing desorption of gas from the matrix.

Fracture permeability As discussed before, the fracture permeability acts as the major channel for the gas to flow. The higher the permeability, higher is the gas production. For most coal seams found in the US, the permeability lies in the range of 0.1 to 50 milliDarcies. The permeability of fractured reservoirs changes with the stress applied to them. Coal displays a stress-sensitive permeability and this process plays an important role during stimulation and production operations.

Thickness of formation and initial reservoir pressure The thickness of the formation may not be directly proportional to the volume of gas produced in some areas. For Example: It has been observed in the Cherokee Basin in Southeast Kansas that a well with a single zone of 1–2 ft of pay can produce excellent gas rates, whereas an alternative formation with twice the thickness can produce next to nothing. Some coal (and shale) formations may have high gas concentrations regardless of the formation's thickness, probably due to other factors of the area's geology. The pressure difference between the well block and the sand face should be as high as possible as is the case with any producing reservoir in general.

Other properties Other affecting parameters include coal density, initial gas phase concentration, critical gas saturation, irreducible water saturation, relative permeability to water and gas at conditions of Sw = 1.0 and Sg = 1-Swirreducible respectively.

Extraction To extract the gas, a steel-encased hole is drilled into the coal seam (100 – 1500 meters below ground). As the pressure within the coal seam declines due to natural production or the pumping of water from the coalbed, both gas and 'produced water' come to the surface through tubing. Then the gas is sent to a compressor station and into natural gas pipelines. The 'produced water' is either reinjected into isolated formations, released into streams, used for irrigation, or sent to evaporation ponds. The water typically contains dissolved solids such as sodium bicarbonate and chloride. Coalbed methane wells often produce at lower gas rates than conventional reservoirs, typically peaking at near 300,000 cubic feet (8,500 m3) per day (about 0.100 m³/s), and can have large initial costs. The production profiles of CBM wells are typically characterized by a "negative decline" in which the gas production rate initially increases as the water is pumped off and gas begins to desorb and flow. A dry CBM well is similar to a standard gas well. The methane desorption process follows a curve (of gas content vs. reservoir pressure) called a Langmuir isotherm. The isotherm can be analytically described by a maximum gas content (at infinite pressure), and the pressure at which half that gas exists within the coal. These parameters (called the Langmuir volume and Langmuir pressure, respectively) are properties of the coal, and vary widely. A coal in Alabama and a coal in Colorado may have radically different Langmuir parameters, despite otherwise similar coal properties. As production occurs from a coal reservoir, the changes in pressure are believed to cause changes in the porosity and permeability of the coal. This is commonly known as matrix shrinkage/swelling. As the gas is desorbed, the pressure exerted by the gas inside the pores decreases, causing them to shrink in size and restricting gas flow through the coal. As the pores shrink, the overall matrix shrinks as well, which may eventually increase the space the gas can travel through (the cleats), increasing gas flow. The potential of a particular coalbed as a CBM source depends on the following criteria. Cleat density/intensity: cleats are joints confined within coal sheets. They impart permeability to the coal seam. A high cleat density is required for profitable exploitation of CBM. Also important is the maceral composition: maceral is a microscopic, homogeneous, petrographic entity of a corresponding sedimentary rock. A high vitrinite composition is ideal for CBM extraction, while inertinite hampers the same.

The rank of coal has also been linked to CBM content: a vitrinite reflectance of 0.8-1.5% has been found to imply higher productivity of the coalbed. The gas composition must be considered, because natural gas appliances are designed for gas with a heating value of about 1000 BTU (British thermal units) per cubic foot, or nearly pure methane. If the gas contains more than a few percent non-flammable gasses such as nitrogen or carbon dioxide, either these will have to be removed or it will have to be blended with higher-BTU gas to achieve pipeline quality. If the methane composition of the coalbed gas is less than 92%, it may not be commercially marketable.

Environmental impacts CBM wells are connected by a network of roads, pipelines, and compressor stations. These structures can compromise the scenic quality of the landscape, fragment wildlife habitat, and displace local wildlife populations. Over time, wells may be spaced more closely in order to extract the remaining methane. Additionally, the produced water may contain undesirable concentrations of dissolved substances. Water withdrawal may depress aquifers over a large area and affect groundwater flows. In Australia, produced water is typically evaporated in large ponds due to the high salinity of the water. When these ponds fail (e.g. Chinchilla) the salinity content has destroyed contiguous soil quality and vegetation. Recently a number of gas companies have commenced operating or developing plant to treat the product water for use as domestic supply, cooling water for power stations or discharge to streams. These plant typically use reverse osmosis to treat the product water. The environmental impacts of CBM development are considered by various governmental bodies during the permitting process and operation, which provide opportunities for public comment and intervention. Operators are required to obtain building permits for roads, pipelines and structures, obtain wastewater (produced water) discharge permits, and prepare Environmental Impact Statements. As with other natural resource utilization activities, the application and effectiveness of environmental laws, regulation, and enforcement vary with location. Violations of applicable laws and regulations are addressed through regulatory bodies and criminal and civil judicial proceedings. Several environmental and conservation organizations work specifically on advocating for responsible coal bed methane development. Northern Plains Resource Council has been leading this fight in Montana since 1999, and the Citizens Concerned About Coalbed Methane has worked out of Fernie, BC since 1998.

Reserves Coalbed methane reserve estimates vary; however a 1997 estimate from the U.S. Geological Survey predicts more than 700 trillion cubic feet (20 Tm³) of methane within

the US. At a natural gas price of US$6.05 per million Btu (US$5.73/GJ), that volume is worth US$4.37 trillion. At least 100 trillion cubic feet (2.8 Tm³) of it is economically viable to produce. In Canada, British Columbia is estimated to have approximately 90 trillion cubic feet (2,500 km3) of coalbed gas. Alberta, to date the only province with commercial coalbed methane wells, is estimated to have approximately 170 trillion cubic feet (4,800 km3) of economically recoverable coalbed methane. High natural gas prices are making CBM economically viable where it previously may not have been. Currently considered a non-renewable resource, there is evidence by the Alberta Research Council, Alberta Geological Survey and others showing coalbed methane is a renewable resource, because the bacterial action that formed the methane is ongoing. The assertion of being renewable, however, has itself become one of debate since it has also been shown that the dewatering that accompanies CBM production destroys the conditions needed for the bacteria to produce methane. In addition, the rate of formation of additional methane is undetermined. This debate is currently causing a right of ownership issue in the Canadian province of Alberta, as only non-renewable resources can legally be owned by the province.

Areas with coalbed methane Australia • •

Bowen Basin, (Fairview, Scotia, Spring Gully), Queensland, Australia Surat Basin, Berwyndale, Windibri, Kogan, Daandine, Tipton West, Queensland, Australia

Canada • •

Telkwa coalfield, British Columbia Western Canadian Sedimentary Basin, Alberta

South Africa •

Molteno Coal Field, Eastern Cape

United Kingdom • • •

Cheshire Lancashire Staffordshire

United States • • • • • • • •

Appalachian Basin, Alabama, Pennsylvania, Ohio, Virginia, West Virginia, Kentucky and Tennessee Black Warrior Basin, Alabama Cahaba Basin, Alabama Cherokee Basin, Kansas Slater Dome Basin, Wyoming and Colorado Powder River Basin, Wyoming and Montana Raton Basin, Colorado and New Mexico San Juan Basin, Colorado and New Mexico

Chapter- 8

Biomass Briquettes

Biomass briquettes are a biofuel substitute to coal and charcoal. They are used to heat industrial boilers in order to produce electricity from steam. The most common use of the briquettes are in the developing world, where energy sources are not as widely available. There has been a move to the use of briquettes in the developed world through the use of cofiring, when the briquettes are combined with coal in order to create the heat supplied to the boiler. This reduces carbon dioxide emissions by partially replacing coal used in power plants with materials that are already contained in the carbon cycle. Manufacturers mainly use three types of ways to create the briquettes, each depending on the way the biomass is dried out. Although biomass briquettes are usually manufactured, biomass has been used throughout history all over the world from simply starting campfires to the mass generation of electricity.

Briquette made by a Ruf briquetter out of hay

Composition and production

Straw or hay briquettes

Biomass briquettes are mostly made of green waste and other organic materials. They are commonly used for electricity generation, for heat and as cooking fuel. These compressed compounds contain various sorts of organic materials, including rice husk, bagasse, ground nut shells, municipal solid waste, agricultural waste, or anything that contains a high nitrogen content. The actual composition of the briquettes varies by area due to the availability of raw materials. The raw materials are gathered and compressed into briquette in order to burn longer and make transportation of the goods easier . These briquettes are very different from charcoal because they do not have large concentrations of carbonaceous substances and added materials. Compared to fossil fuels, the briquettes produce low greenhouse gas emissions because the material used is already a part of the carbon cycle. One of the most common variables of the biomass briquette production process is the way the biomass is dried out. Manufacturers can use torrefaction, carbonization, or varying degrees of pyrolysis. Researchers concluded that torrefaction and carbonization are the most efficient forms of drying out biomass, but the use of the briquette determines which method should be used. Compaction is another factor which has a profound effect on production. Some materials burn more efficiently if compacted at low pressures, such as corn stover grind. Other materials such as wheat and barley-straw require high amounts of pressure to produce heat. There are also different press technologies that can be used. A piston press is used to create solid briquettes for a wide array of purposes. Screw extrusion is used to compact biomass into loose, homogeneous briquettes that are substituted for coal in cofiring. This technology crates a doughnut-like briquette. The hole in the center of the briquette allows for a larger surface area, creating a higher combustion rate.

History People have been using biomass briquettes in Nepal since before recorded history. Though inefficient, the burning of loose biomass created enough heat for cooking purposes and keeping warm. The first commercial production plant was created in 1982 and produced almost 900 metric tons of biomass. In 1984, factories were constructed that incorporated vast improvements on efficiency and the quality of briquettes. They used a combination of rice husks and molasses. The King Mahendra Trust for Nature Conservation (KMTNC) along with the Institute for Himalayan Conservation (IHC) created a mixture of coal and biomass in 2000 using a unique rolling machine. In 1945, Japan independently started developing technology to harness the energy from sawdust briquettes, known as Ogalite. Between 1964 and 1969, Japan increased production fourfold by incorporating screw press and piston press technology. The new compaction techniques incorporated in these machines made briquettes of higher quality than those in Europe. As a result, European countries bought the licensing agreements and now manufacture Japanese designed machines.

Cofiring Cofiring relates to the combustion of two different types of materials. The process is primarily used to decrease CO2 emissions despite the resulting lower energy efficiency and higher variable cost. The combination of materials usually contains a high carbon emitting substance such as coal and a lesser CO2 emitting material such as biomass. Even though CO2 will still be emitted through the combustion of biomass, the net carbon emitted is nearly negligible. This is due to the fact that the material gathered for the composition of the briquettes are still contained in the carbon cycle whereas fossil fuel combustion releases CO2 that has been sequestered for millenniums. Boilers in power plants are traditionally heated by the combustion of coal, but if cofiring were to be implemented, then the CO2 emissions would decrease while still maintaining the heat inputted to the boiler. Implementing cofiring would require few modifications to the current characteristics to power plants, as only the fuel for the boiler would be altered. A moderate investment would be required for implementing biomass briquettes into the combustion process. Cofiring is considered the most cost-efficient means of biomass. A higher combustion rate will occur when cofiring is implemented in a boiler when compared to burning only biomass. The compressed biomass is also much easier to transport since it is more dense, therefore allowing more biomass to be transported per shipment when compared to loose biomass. Some sources agree that a near-term solution for the greenhouse gas emission problem may lie in cofiring.

Compared to coal The use of biomass briquettes has been steadily increasing as industries realize the benefits of decreasing pollution through the use of biomass briquettes. Briquettes provide higher calorific value per dollar than coal when used for firing industrial boilers. Along with higher calorific value, biomass briquettes on average saved 30-40% of boiler fuel cost. But other sources suggest that cofiring is more expensive due to the widespread availability of coal and its low cost. However, in the long run, briquettes can only limit the use of coal to a small extent, but it is increasingly being pursued by industries and factories all over the world. Both raw materials can be produced or mined domestically in the United States, creating a fuel source that is free from foreign dependence and less polluting than raw fossil fuel incineration. Environmentally, the use of biomass briquettes produces much fewer greenhouse gases, specifically, 13.8% to 41.7% CO2 and NOX. There was also a reduction from 11.1% to 38.5% in SO2 emissions when compared to coal from three different leading producers, EKCC Coal, Decanter Coal, and Alden Coal. Biomass briquettes are also fairly resistant to water degradation, an improvement over the difficulties encountered with the burning of wet coal. However, the briquettes are best used only as a supplement to coal. The use of cofiring creates an energy that is not as high as pure coal, but emits fewer pollutants and cuts down on the release of previously sequestered carbon. The continuous release of

carbon and other greenhouse gasses into the atmosphere leads to an increase in global temperatures. The use of cofiring does not stop this process but decreases the relative emissions of coal power plants.

Use In Developing world The Legacy Foundation has developed a set of techniques to produce biomass briquettes through artisanal production in rural villages that can be used for heating and cooking. These techniques were recently pioneered by Virunga National Park in eastern Democratic Republic of Congo, following the massive destruction of the Mountain Gorilla habitat for charcoal. Pangani, Africa, is an area covered in coconut groves. After harvesting the meat of the coconut, the indigenous people would litter the ground with the husks, believing them to be useless. The husks later became a profit center after it was discovered that coconut husks are well suited to be the main ingredient in bio briquettes. This alternative fuel mixture burns incredibly efficiently and leaves little residue, making it a reliable source for cooking in the undeveloped country. The developing world has always relied on the burning biomass due it its low cost and availability anywhere there is organic material. The briquette production only improves upon the ancient practice by increasing the efficiency of pyrolysis. Two major components of the developing world are China and India. The economies are rapidly increasing due to cheap ways of harnessing electricity and emitting large amounts of carbon dioxide. The Kyoto Protocol attempted to regulate the emissions of the three different worlds, but there were disagreements as to which country should be penalized for emissions based on its previous and future emissions. The United States has been the largest emitter but China has recently become the largest per capita. The United States had emitted a rigorous amount of carbon dioxide during its development and the developing nations argue that they should not be forced to meet the requirements. At the lower end, the undeveloped nations believe that they have little responsibility for what has been done to the carbon dioxide levels. The use of biomass briquettes is strongly encouraged by issuing Carbon Credits. One Carbon Credit is equal to one free ton of carbon dioxide to be emitted into the atmosphere. India has started to replace charcoal with biomass briquettes in regards to boiler fuel, especially in the southern parts of the country because the biomass briquettes can be created domestically, depending on the availability of land. Therefore, constantly rising fuel prices will be less influential in an economy if sources of fuel can be easily produced domestically.

Use in developed world Coal is the largest carbon dioxide emitter per unit area when it comes to electricity generation. It is also the most common ingredient in charcoal. There has been a recent

push to replace the burning of fossil fuels with biomass. The replacement of this nonrenewable resource with biological waste would lower the carbon footprint of grill owners and lower the overall pollution of the world. Citizens are also starting to manufacture briquettes at home. The first machines would create briquettes for homeowners out of compressed sawdust, however, current machines allow for briquette production out of any sort of dried biomass. Arizona has also taken initiative to turn waste biomass into a source of energy. Waste cotton and pecan material used to provide a nesting ground for bugs that would destroy the new crops in the spring. To stop this problem farmers buried the biomass, which quickly led to soil degradation. These materials were discovered to be a very efficient source of energy and took care of issues that had plagued farms. The United States Department of Energy has financed several projects to test the viability of biomass briquettes on a national scale. The scope of the projects is to increase the efficiency of gasifiers as well as produce plans for production facilities.

Criticism Biomass is composed of organic materials, therefore, large amounts of land are required to produce the fuel. Critics argue that the use of this land should be utilized for food distribution rather than crop degradation. Also, climate changes may cause a harsh season, where the material extracted will need to be swapped for food rather than energy. The assumption is that the production of biomass decreases the food supply, causing an increase in world hunger by extracting the organic materials such as corn and soybeans for fuel rather than food. The cost of implementing a new technology such as biomass into the current infrastructure is also high. The fixed costs with the production of biomass briquettes are high due to the new undeveloped technologies that revolve around the extraction, production and storage of the biomass. Technologies regarding extraction of oil and coal have been developing for decades, becoming more efficient with each year. A new undeveloped technology regarding fuel utilization that has no infrastructure built around makes it nearly impossible to compete in the current market.