Supercritical Fluids as Solvents and Reaction Media by Gerd H. Brunner
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Supercritical Fluids as Solvents and Reaction Media by Gerd H. Brunner
•
ISBN: 0444515747
•
Publisher: Elsevier Science & Technology Books
•
Pub. Date: July 2004
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v PREFACE Supercritical fluids are gaseous compounds or mixtures of compounds with properties in between of a typical gas and of a typical liquid. These properties can be smoothly changed by varying the pressure. The effect is that supercritical fluids behave either like a gas or a liquid, depending on the values of thermodynamic properties (p,V,T). This tuning of properties, and other advantageous properties of supercritical fluids like a very low viscosity, led to innovative technologies. More than 100 plants of production size are now in operation worldwide in the areas of process and production technology, environmental applications, and particle engineering. New processes are under research and development in various fields, including downstream processing in biotechnical processes and enzymatic catalysis. Actually, processes applying supercritical fluids are in operation for a long time and for huge amounts of substances. Examples are supercritical paraffins in mineral oil processing (e.g. the ROSE-process) and high pressure polymerization of ethylene to poly-ethylene. These important processes make use of the advantageous properties of supercritical fluids in singular cases. Application of these properties in processing technology has often been proposed since Hannay and Hogarth in 1879 first observed these phenomena. Yet these activities remained isolated. Only since about 1970, when Zosel proposed a great variety of processes with supercritical fluids, the topic began to be treated more systematically. In the 70ies of the 20th century it developed into a rapidly growing field of research, development, and technical application. All fields of process technology involving solvents are now under close investigation, and new applications will emerge soon. The scientific community may now comprise about 1500 researchers with about 500 researchers having chosen supercritical fluids as their main area of interest. World conferences on supercritical fluids, like the 6th International Symposium on Supercritical Fluids, April 2003 in Versailles, France, attract about 450 participants with about 350 scientific contributions. German scientific institutes and German industry still play an important role in the field of supercritical fluids and its application as sustainable and environmental benign technology. Knowledge and production plants have been created and exported. The perspective of this technology is bright, provided that research and development is continued on an appropriate scale. Therefore, the “Deutsche Forschungsgemeinschaft, DFG”, (the German National Council For Science) launched a research program on “Supercritical fluids as solvents and reaction media” on the initiative of the “GVC-Fachausschuß Hochdruckverfahrenstechnik” (i.e. the German working party on High Pressure Chemical Engineering of the Society of Chemical Engineers), and after a proposal of
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vi Prof. Dr. G. Brunner, Technische Universität Hamburg-Harburg, Prof. Dr. Buback, Universität Göttingen, Prof. Dr. H. Lentz, Universität-GHS Siegen, Prof. Dr. G. Luft, Technische Universität Darmstadt, Prof. Dr. G.M. Schneider, Ruhr-Universität Bochum, Prof. Dr. O. Tiltscher +, Technische Universität München. The cooperation between pure and applied scientists, as had been the case within the working group “Hochdruckverfahrenstechnik” for a long time, made it probable to achieve substantial results within the limited time of the program of 6 years. The goal was to achieve the scientific and engineering fundamentals for new innovative processes using supercritical fluids. Further applications of supercritical fluids should be made accessible. Research should concentrate on further investigation of physical and chemical properties of supercritical fluids, transport properties, separation processes (summarized under the term “extraction”), chemical reactions in and with supercritical fluids, making use of the tunable properties of supercritical fluids for engineering of particles and materials, and to further develop mechanical compounds for processing plants. The book contains results of most of the projects. The table of contents lists the contributions. They speak for themselves and are therefore not additionally commented here. Further results of projects sponsored within this program are published in various scientific journals. The content of this book provides an overview on the research activities in this field in Germany. Many of the groups involved have additional research activities in similar areas. Therefore, this book is by no means a report on all the activities in the field of supercritical fluids in Germany from 1996 to 2002. Nevertheless, the research program “Supercritical fluids as solvents and reaction media” provided an immensely valuable platform for exchange of knowledge and experience. More than 50 young researchers were involved contributing with their expertise, their new ideas, and the motivation of youth. Cooperation between the research groups was intensified during the research program. It will carry on, since there are still many things to be found out and to be developed in the field of supercritical fluids. Hamburg, June 2003
G. Brunner
Table of Contents
1
Phase equilibrium, solubility
1
Experimental determination of phase equilibria and comprehensive examination of the predictive capabilities of group contribution 1.1
3 equations of state with a view to the synthesis of supercritical extraction processes Influence of additional components on the solvent power of supercritical
1.2
39 ethylene High pressure phase equilibria of copolymer solutions - experiments and
1.3
61 correlation Fluid phase equilibria of binary mixtures with supercritical solvents with
1.4
85 in-situ concentration measurements by Raman spectroscopy High-pressure solubility measurement of solids in near- and supercritical
1.5
121 fluids Phase behaviour of organic solid solutes and supercritical fluids with
1.6
147 respect to particle formation processes Supercritical carbon dioxide as solvent for organic compounds present in
1.7
163 aqueous salt solutions
1.8
Correlation and prediction of high-pressure phase equilibria and related
185
thermodynamic properties of simple fluid mixtures Development of simplified equation of state for molecular fluids and 1.9
their applications for the investigation of supercritical chain molecule
211
solutions and mixtures Correlation of the solubility of low-volatile organic compounds in near1.10
241 and supercritical fluids based on an accurate equation of state Thermo- and fluiddynamic aspects of the hydrogenation of triglycerides
1.11
269 and esters in presence of supercritical fluids Perturbed-chain-SAFT : development of a new equation of state for
1.12
295 simple, associating, multipolar and polymeric compounds Extractability of As-chelates and solubility of different Rh, Pd-chelates
1.13
323 is supercritical fluid CO[subscript 2]
2
Properties
341
P,T-dependence of molecular mobility in supercritical fluids studied by 2.1
343 high pressure NMR Interfacial phenomena in countercurrent and spray processing using
2.2
363 supercritical fluids
3
Formulation
379
3.1
Synthesis of silica aerogels and their application as drug delivery system
381
3.2
Investigation and modelling of the gas-antisolvent process
429
3.3
Formation of nanoscale drugs by rapid expansion of supercritical
449
solutions (RESS): - experimental and theoretical investigations 4
Extraction
463
Separation efficiency and axial mixing in packed high pressure 4.1
465 extraction columns Separation of organic compounds from aqueous solutions by means of
4.2
489 supercritical carbon dioxide Supercritical SO[subscript 2] for preparation of sulfur dioxide
4.3
523 complexes and for recovery of precious metals from used catalysts
5
Reactions
531
Polymerizations in supercritical carbon dioxide : surfactants, micelle 5.1
533 formation, and heterophase polymerization The kinetics of the early stage of dispersion polymerization in
5.2
559 supercritical CO[subscript 2] Rate coefficients of free-radical polymerization in homogeneous fluid
5.3
573 mixtures with carbon dioxide
5.4
Ammonia as reagent or reaction medium for polymers Inorganic materials (metals, ceramics, glasses) under the influence of reactants in supercritical aqueous solutions as well as chemical reactions
5.5 (partial oxidations, hydrolysis, dehydrations) under the influence of inorganic materials in supercritical aqueous solutions
593
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Phase equilibria and group contribution equations of state
Gas Storage
Equilibrium Cell with Windows
Pressure Sensor
GC Carrier Gas Stream
Vacuum
Liquid Storage Stirrer
Microsampler
5
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6
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Adjustment
CompressedAir GC-CarrierGas
Steel Monel Capillar Heating Equilibrium
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Phase equilibria and group contribution equations of state
P
pressure controller
T Peltier-cooler
N2
T = const. HPLC-pumps
mixing-tube
calibration resistor
control heater
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16
S
log Pi [kPa]
H. Gardeler and J. Gmehling
3. 2.
Tm,phenanthrene
1. 0.
323.15 K
-1. -2. -3. -4.
Tm,anthracene
-5. -6. 0.0015
0.002
0.0025
0.003
1/T [1/K]
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Phase equilibria and group contribution equations of state
log y2 [ ]
VTPR, with Poynting factor
VTPR, without Poynting factor
(1) carbon dioxide + (2) phenanthrene T = 323.15 K ideal, with Poynting factor
ideal
P [bar]
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328.15 K 318.15 K 308.15 K
(1) carbon dioxide + (2) propylbenzene 313.15 K
log y2 [ ]
(1) carbon dioxide + (2) ethylbenzene
log y2 [ ]
log y2 [ ]
Phase equilibria and group contribution equations of state
(1) carbon dioxide + (2) hexylbenzene
318.15 K
PSRK
PSRK
PSRK
P [bar]
P [bar]
P [bar]
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Phase equilibria and group contribution equations of state
308.15 K
log y2 [–]
log y2 [–]
328.15 K
323.15 K 298.15 K
(1) carbon dioxide + (2) naphthalene
(1) ethylene + (2) naphthalene VTPR
PSRK
P [bar]
P [bar]
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26
H. Gardeler and J. Gmehling
-1. ] [
-1.
V T PR
][
P S R K 2
2
y
y -2. g o l
exp. data, 0 % MeOH 0 % MeOH 2 % MeOH 5 % MeOH
-3.
g o l
-3.
-5.
( 1 ) c a r b o n d io x id e ( 2 ) p h e n a n t h re n e
-4.
T = 308.15 K
( 2 ) a n t h ra c e n e
-7.
PSRK
-5.
0
90
180
270 P [b ar]
360
T
0
100
= 3 2 3 .1 5 K
200
300
400
P [b ar]
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G L I
F
H
J E
B A
C D K
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Supercritical CO2 as solvent for organic compounds
b
e
f
c
h
m
i
p
n
o
p
q
r
s
p
p p
T a
c d
e
f
c g k
j
l
n o
p
q
s
r
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1
0.35
0.32
0.31
0.3
0.29
m 0.4 0.25 0
a)
0.28 0.16
0.2
0.27
0.5 0.6
-1 -1
0.26
0.3 0.35 0.4 0.5
0.6
0
1
0.25 2
3
4
5
k
6
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257
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258
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Correlation of the solubility of low-volatile organic compounds
100
p / MPa
90
303.1 K
314.8 K
80 70
322.5 K
60 50
423.15 K
393.15 K
40 30 20 10 0
0
100
200
300
400
500
s / 10 mol dm -6
-3
600
700
800
259
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Th. Kraska et al.
ln(p/MPa) Price and Hawkins 1998 McDowell 1973 Anselrode 1977
T fus
-10
Nishida et al. 1977
-15
-20
Sung and Shim 1999
-25 0.0018
0.0022
0.0026
T /K -1
-1
0.0030
0.0034
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Correlation of the solubility of low-volatile organic compounds
25
p / MPa
20 340 K
C N H C N H
15
10 305 K 5
0
100
200
300
400
500
s / 10 mol dm -6
-3
p / MPa
25
20
340.1 K 15 NC H HC N
10
5
310.1 K
0
50
100
150
200
250
s / 10 mol dm -6
-3
300
350
261
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263
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267
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269
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E. Weidner, C. Brake and D. Richter
gas
liquid oil cat
gas
liquid oil
cat
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Hydrogenation of triglycerides and esters
271
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272
E. Weidner, C. Brake and D. Richter
PICR spindle pumps M spindle pumps 1+2 3+4
liquid
gas
sampling devices
thermostat TICR TICR
density ρ calibrated capillary
pressure drop
C01S11.fm Page 273 Monday, May 3, 2004 12:01 PM
273
Hydrogenation of triglycerides and esters
24 20
a]
16
P [M
12
p 8 4
H2
20
24
20
CO2 / H2
0
soybean oil / H2
for T > T crit.(CO 2): CO2 and H2 are completely miscible
80 60
40
8
60
20
0
4
80 soybean oil 20
40
60
80
CO2
0
4 8 p [MPa]
12 10
16
40
binodal curve
10 12
T = 373 K T = 403 K
16 20 24
soybean oil / CO 2
p
[M P
a]
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274
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275
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276
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Hydrogenation of triglycerides and esters
277
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278
E. Weidner, C. Brake and D. Richter
H2 p = 4 MPa p = 10 MPa p = 14 MPa p = 18 MPa
90
10
80
20
70
30
mixing line
60
40 50
50 40
60 70
30
80
20
90 soybean oil 10
10 20
30
40
50
60
70
80
90
CO2
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279
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280
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a) gas
gas
liquid oil
cat
liquid oil cat
b) cat oil + H2 + SCF cat
oil + H 2 + SCF
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281
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282
E. Weidner, C. Brake and D. Richter
ester H2 SCF
reactor
FOH alcohol H2 SCF
separation 1
FOH
alcohol H2 SCF
recompression
(alcohol) H2 SCF
separation 2
alcohol (SCF)
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283
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284
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285
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286
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287
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288
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Hydrogenation of triglycerides and esters
Version 1
gas
V1 Temperature
Version 2
V2
Version 3 V3
H2
x [mol-%]
liquid
C3 H8
289
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290
E. Weidner, C. Brake and D. Richter
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291
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292
E. Weidner, C. Brake and D. Richter
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Hydrogenation of triglycerides and esters
293
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294
E. Weidner, C. Brake and D. Richter
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295
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296
J. Gross and G. Sadowski
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Perturbed-Chain-SAFT
297
C01S12.fm Page 298 Monday, May 3, 2004 12:24 PM
298
J. Gross and G. Sadowski
B
Attractive interactions [related pure comp. parameters] Disp ersion [εi/k]
A B B
A
A Association between two association sites A and B [ε iAiBi/k and κ iAiBi] Multipolar; electrostatic forces from permanent partial charges, e.g. dipole-dipole interaction [µIDD and xpDD]
C01S12.fm Page 299 Monday, May 3, 2004 12:24 PM
Perturbed-Chain-SAFT
299
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300
J. Gross and G. Sadowski
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Perturbed-Chain-SAFT
301
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302
J. Gross and G. Sadowski
C01S12.fm Page 303 Monday, May 3, 2004 12:24 PM
303
Perturbed-Chain-SAFT 20 T*=3 (Tavares et al., 1995) T*=3 (Yethiraj, Hall; 1991) T*=2 (Tavares et al., 1995) T*=2 (Yethiraj, Hall; 1991) T*=1.5 (Tavares et al., 1995) T*=1.5 (Yethiraj, Hall; 1991) this work
compressibility factor Z
15
10
5
0
-5 0
0.2
0.4
0.6
Packing Fraction η
0.8
1
C01S12.fm Page 304 Monday, May 3, 2004 12:24 PM
304
J. Gross and G. Sadowski
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Perturbed-Chain-SAFT
305
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306
J. Gross and G. Sadowski
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Perturbed-Chain-SAFT
307
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308
J. Gross and G. Sadowski 30
2,3-Dimethylbutan Benzol Isobutan n-Butylbenzol Cyclopentan Propylen
100 (Pexp – Pcalc) / Pexp
A: PC – SAFT
20
10
0
-10 0.2
0.4
0.6
T/T
0.8
1.0
Crit,exp
30
2,3-Dimethylbutan Benzol Isobutan n-Butylbenzol Cyclopentan Propylen
100 (Pexp – Pcalc) / Pexp
A: SAFT
20
10
0
-10 0.2
0.4
0.6
T/T
Crit,exp
0.8
1.0
C01S12.fm Page 309 Monday, May 3, 2004 12:24 PM
309
Perturbed-Chain-SAFT
400
h
LV
/ kJ/kg
600
Cyclopantane
200
23-Dimethylbutane PC-SAFT SAFT 0 0.2
0.4
0.6
0.8
1
crit,exp
T/T
L
cp / kJ/(kg K)
3
2
n-Octene
1
n-Butylbenzene PC-SAFT SAFT
0 150
250
350
T / K
450
C01S12.fm Page 310 Monday, May 3, 2004 12:24 PM
310
J. Gross and G. Sadowski
C01S12.fm Page 311 Monday, May 3, 2004 12:24 PM
311
Perturbed-Chain-SAFT
P / bar
10 3
10 2
10 1 10 1
10 2
Density / kg/m
10 3 3
C01S12.fm Page 312 Monday, May 3, 2004 12:24 PM
312
J. Gross and G. Sadowski
150
Exp. Data (T=121C ) Exp. Data (T=21C) PC-SAFT SAFT
P / bar
100
50
0 0.0
0.2
0.4
0.6
xMethane
0.8
1.0
150 Exp. Data (238C) Exp. Data (171C) PC-SAFT SAFT
P / bar
100
50
0 0.0
0.2
0.4
0.6
xEthane
0.8
1.0
C01S12.fm Page 313 Monday, May 3, 2004 12:24 PM
Perturbed-Chain-SAFT
313
C01S12.fm Page 314 Monday, May 3, 2004 12:24 PM
314
J. Gross and G. Sadowski 150
T / °C
125
100
75
Cho et al., 1984 Zhuravleva et al., 1970 PC-SAFT SAFT
50
25 0.0
0.2
0.4
0.6
xH O 2
0.8
1.0
C01S12.fm Page 315 Monday, May 3, 2004 12:24 PM
Perturbed-Chain-SAFT
315
C01S12.fm Page 316 Monday, May 3, 2004 12:24 PM
316
J. Gross and G. Sadowski
C01S12.fm Page 317 Monday, May 3, 2004 12:24 PM
317
Perturbed-Chain-SAFT
400
P / bar
42% CO2
300
34.9% CO2
200
21.3% CO2 17% CO2 13.1% CO2
100
0% CO2
0 75
125
175
T / °C
225
275
C01S12.fm Page 318 Monday, May 3, 2004 12:24 PM
318
J. Gross and G. Sadowski
C01S12.fm Page 319 Monday, May 3, 2004 12:24 PM
Perturbed-Chain-SAFT
319
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320
J. Gross and G. Sadowski
C01S12.fm Page 321 Monday, May 3, 2004 12:24 PM
Perturbed-Chain-SAFT
321
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322
J. Gross and G. Sadowski
C01S13.fm Page 323 Monday, May 3, 2004 12:30 PM
Supercritical Fluids as Solvents and Reaction Media G. Brunner (editor) © 2004 Elsevier B.V. All rights reserved
323
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324
B. W. Wenclawiak, A. Wolf and S. Wilnewski
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Extractability of As-Chelates and Solubility of Rh, Pd-Chelates
325
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326
B. W. Wenclawiak, A. Wolf and S. Wilnewski
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Extractability of As-Chelates and Solubility of Rh, Pd-Chelates
327
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328
B. W. Wenclawiak, A. Wolf and S. Wilnewski
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Extractability of As-Chelates and Solubility of Rh, Pd-Chelates
329
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330
B. W. Wenclawiak, A. Wolf and S. Wilnewski
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Extractability of As-Chelates and Solubility of Rh, Pd-Chelates
331
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332
B. W. Wenclawiak, A. Wolf and S. Wilnewski
C01S13.fm Page 333 Monday, May 3, 2004 12:30 PM
Extractability of As-Chelates and Solubility of Rh, Pd-Chelates
333
C01S13.fm Page 334 Monday, May 3, 2004 12:30 PM
334
B. W. Wenclawiak, A. Wolf and S. Wilnewski
C01S13.fm Page 335 Monday, May 3, 2004 12:30 PM
Extractability of As-Chelates and Solubility of Rh, Pd-Chelates
335
C01S13.fm Page 336 Monday, May 3, 2004 12:30 PM
336
B. W. Wenclawiak, A. Wolf and S. Wilnewski
C01S13.fm Page 337 Monday, May 3, 2004 12:30 PM
337
Extractability of As-Chelates and Solubility of Rh, Pd-Chelates
2 ,5 0 E -0 3
2 ,0 0 E -0 3
P d ( 3 0 0 b a r /5 0 °C ) R h (3 0 0 b a r/6 0 °C )
1 ,5 0 E -0 3
1 ,0 0 E -0 3
5 ,0 0 E -0 4
0 ,0 0 E + 0 0
R h (3 0 0 b a r /6 0 ° C )
D E D TC
D iP D T C
P d (3 0 0 b a r/5 0 ° C )
D B D TC
D iB D T C
D P D TC
D H D TC
DO DTC
C01S13.fm Page 338 Monday, May 3, 2004 12:30 PM
338
B. W. Wenclawiak, A. Wolf and S. Wilnewski
C01S13.fm Page 339 Monday, May 3, 2004 12:30 PM
Extractability of As-Chelates and Solubility of Rh, Pd-Chelates
339
C01S13.fm Page 340 Monday, May 3, 2004 12:30 PM
340
B. W. Wenclawiak, A. Wolf and S. Wilnewski
C02S01.fm Page 343 Monday, May 3, 2004 12:34 PM
Supercritical Fluids as Solvents and Reaction Media G. Brunner (editor) © 2004 Elsevier B.V. All rights reserved
343
C02S01.fm Page 344 Monday, May 3, 2004 12:34 PM
344
T. Groß, Liuping Chen, and H.-D. Lüdemann
C02S01.fm Page 345 Monday, May 3, 2004 12:34 PM
p, T- dependence of molecular mobility
345
C02S01.fm Page 346 Monday, May 3, 2004 12:34 PM
346
T. Groß, Liuping Chen, and H.-D. Lüdemann
C02S01.fm Page 347 Monday, May 3, 2004 12:34 PM
p, T- dependence of molecular mobility
347
C02S01.fm Page 348 Monday, May 3, 2004 12:34 PM
348
T. Groß, Liuping Chen, and H.-D. Lüdemann
C02S01.fm Page 349 Monday, May 3, 2004 12:34 PM
p, T- dependence of molecular mobility
349
C02S01.fm Page 350 Monday, May 3, 2004 12:34 PM
350
T. Groß, Liuping Chen, and H.-D. Lüdemann
C02S01.fm Page 351 Monday, May 3, 2004 12:34 PM
p, T- dependence of molecular mobility
351
C02S01.fm Page 352 Monday, May 3, 2004 12:34 PM
352
T. Groß, Liuping Chen, and H.-D. Lüdemann
C02S01.fm Page 353 Monday, May 3, 2004 12:34 PM
p, T- dependence of molecular mobility
353
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354
T. Groß, Liuping Chen, and H.-D. Lüdemann
C02S01.fm Page 355 Monday, May 3, 2004 12:34 PM
p, T- dependence of molecular mobility
355
C02S01.fm Page 356 Monday, May 3, 2004 12:34 PM
356
T. Groß, Liuping Chen, and H.-D. Lüdemann
C02S01.fm Page 357 Monday, May 3, 2004 12:34 PM
p, T- dependence of molecular mobility
357
C02S01.fm Page 358 Monday, May 3, 2004 12:34 PM
358
T. Groß, Liuping Chen, and H.-D. Lüdemann
C02S01.fm Page 359 Monday, May 3, 2004 12:34 PM
p, T- dependence of molecular mobility
359
C02S01.fm Page 360 Monday, May 3, 2004 12:34 PM
360
T. Groß, Liuping Chen, and H.-D. Lüdemann
C02S01.fm Page 361 Monday, May 3, 2004 12:34 PM
p, T- dependence of molecular mobility
361
C02S01.fm Page 362 Monday, May 3, 2004 12:34 PM
362
T. Groß, Liuping Chen, and H.-D. Lüdemann
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Supercritical Fluids as Solvents and Reaction Media G. Brunner (editor) © 2004 Elsevier B.V. All rights reserved
363
C02S02.fm Page 364 Monday, May 3, 2004 12:35 PM
364
R. Eggers, P. Jaeger
C02S02.fm Page 365 Monday, May 3, 2004 12:35 PM
Interfacial Phenomena in Countercurrent and Spray Processing
365
C02S02.fm Page 366 Monday, May 3, 2004 12:35 PM
366
R. Eggers, P. Jaeger
C02S02.fm Page 367 Monday, May 3, 2004 12:35 PM
Interfacial Phenomena in Countercurrent and Spray Processing
367
C02S02.fm Page 368 Monday, May 3, 2004 12:35 PM
368
R. Eggers, P. Jaeger
C02S02.fm Page 369 Monday, May 3, 2004 12:35 PM
Interfacial Phenomena in Countercurrent and Spray Processing
369
C02S02.fm Page 370 Monday, May 3, 2004 12:35 PM
370
R. Eggers, P. Jaeger
C02S02.fm Page 371 Monday, May 3, 2004 12:35 PM
Interfacial Phenomena in Countercurrent and Spray Processing
140 water, 40°C triglycerides, 40°C coffee solution (5 % DS), 40,5°C (30 % DS), 40,5°C (40 % DS), 40,5°C
θ 120 100 80 60 40 20 0 0
5
10
15 P [MPa]
20
25
30
371
C02S02.fm Page 372 Monday, May 3, 2004 12:35 PM
372
R. Eggers, P. Jaeger
Xraffinate / X Feed [ppm/ppm]
100 %
10 %
water-caffeine-CO2: Mellapak 500.X, L=5.28 m, 80°C Mellapak 500.X, L=5.28 m, 50°C coffee-extract-caffeine-CO 2: wire mesh l = 6.0 m, 80°C Mellapak 500.X, L=5.28 m, 80°C
1% 20
40
60
80
100
solvent ratio [kg H2O / kg CO2]
120
C02S02.fm Page 373 Monday, May 3, 2004 12:35 PM
Interfacial Phenomena in Countercurrent and Spray Processing
373
C02S02.fm Page 374 Monday, May 3, 2004 12:35 PM
374
R. Eggers, P. Jaeger
C02S02.fm Page 375 Monday, May 3, 2004 12:35 PM
375
Interfacial Phenomena in Countercurrent and Spray Processing
Water in CO2;
cw of solid spheres
3
=800 kg/m
g
veg. Oil in CO2;
3
=800 kg/m
g
DRAG COEFFICIENT cw [-]
Water/TritonX in CO2; Water in Air [12];
1 0.9 0.8 0.7 0.6
3
=800 kg/m
g
3
=1.16 kg/m
g
σ H O-TritonX/CO = 13 mN/m 2
2
0.5 0.4 σ Oil/CO = 2 mN/m
0.3
2
σ Water/CO = 24 mN/m 2
100
1000
DROP REYNOLDS NUMBER ReD [-]
10000
C02S02.fm Page 376 Monday, May 3, 2004 12:35 PM
376
R. Eggers, P. Jaeger
C02S02.fm Page 377 Monday, May 3, 2004 12:35 PM
Interfacial Phenomena in Countercurrent and Spray Processing
377
C03S01.fm Page 381 Monday, May 3, 2004 12:36 PM
Supercritical Fluids as Solvents and Reaction Media G. Brunner (editor) © 2004 Elsevier B.V. All rights reserved
381
C03S01.fm Page 382 Monday, May 3, 2004 12:36 PM
382
I. Smirnova and W. Arlt
C03S01.fm Page 383 Monday, May 3, 2004 12:36 PM
Synthesis of silica aerogels and their application
383
C03S01.fm Page 384 Monday, May 3, 2004 12:36 PM
384
I. Smirnova and W. Arlt
C03S01.fm Page 385 Monday, May 3, 2004 12:36 PM
Synthesis of silica aerogels and their application
385
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386
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C03S01.fm Page 387 Monday, May 3, 2004 12:36 PM
Synthesis of silica aerogels and their application
387
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388
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C03S01.fm Page 389 Monday, May 3, 2004 12:36 PM
Synthesis of silica aerogels and their application
389
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390
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C03S01.fm Page 391 Monday, May 3, 2004 12:36 PM
Synthesis of silica aerogels and their application
391
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392
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C03S01.fm Page 393 Monday, May 3, 2004 12:36 PM
Synthesis of silica aerogels and their application
393
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394
I. Smirnova and W. Arlt
C03S01.fm Page 395 Monday, May 3, 2004 12:36 PM
395
Synthesis of silica aerogels and their application
Gelation time, min
250
-1.2021
y = 1217.1x
200 150 100 50 0 0
5
10
15
20
25
Total concentration of CO2, wt%
30
35
C03S01.fm Page 396 Monday, May 3, 2004 12:36 PM
396
I. Smirnova and W. Arlt
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Synthesis of silica aerogels and their application
397
C03S01.fm Page 398 Monday, May 3, 2004 12:36 PM
398
I. Smirnova and W. Arlt
60
This work, reacting mixture, 40˚C
50
Kordikowski et al., Acetonitrile - Carbon dioxide, 40˚C
P,bar
40 30 20 10 0 0
5
10
15
20
25
30
35
40
45
50
55
60
Concentration of CO 2 in the liquid phase, wt %
250 Gelation time, min
y = 765.56x-1.0986
200 150 100 50 0 0
5
10
15
20
CO2 concentration in liquid phase, wt%
25
30
C03S01.fm Page 399 Monday, May 3, 2004 12:36 PM
399
Optimal CO2 concentration in the liquid phase, wt%
Synthesis of silica aerogels and their application
70 60 50 40 30 20 10 0 0.01
0.02
0.03
0.04
0.05
Target density, g/cm3
0.06
0.07
0.08
C03S01.fm Page 400 Monday, May 3, 2004 12:36 PM
400
I. Smirnova and W. Arlt
50 29°C
Optimal CO2 concentration in the liquid phase, wt %
45
40°C
40
70°C
35 30 25 20
y = 2.2127x -0.8301
15 y = 0.9143x -1.0591
10
y = 0.1083x -1.5758
5 0 0.025
0.035
0.045
0.055
0.065 3
Target density, g/cm
0.075
0.085
C03S01.fm Page 401 Monday, May 3, 2004 12:36 PM
Synthesis of silica aerogels and their application
401
C03S01.fm Page 402 Monday, May 3, 2004 12:36 PM
402
I. Smirnova and W. Arlt
C03S01.fm Page 403 Monday, May 3, 2004 12:36 PM
403
Synthesis of silica aerogels and their application
A1 A5
A2
Transmittance
A4
A3
3950
3450
2950
2450
1950 -1
Wave numbers, cm
1450
950
450
C03S01.fm Page 404 Monday, May 3, 2004 12:36 PM
404
I. Smirnova and W. Arlt
C03S01.fm Page 405 Monday, May 3, 2004 12:36 PM
Synthesis of silica aerogels and their application
405
C03S01.fm Page 406 Monday, May 3, 2004 12:36 PM
406
I. Smirnova and W. Arlt
C03S01.fm Page 407 Monday, May 3, 2004 12:36 PM
407
Synthesis of silica aerogels and their application
Transmittance
MeOH
3950
EtOH
3450
2950
2450
1950
1450 -1
Wavenumber, cm
950
450
C03S01.fm Page 408 Monday, May 3, 2004 12:36 PM
408
I. Smirnova and W. Arlt
C03S01.fm Page 409 Monday, May 3, 2004 12:36 PM
Synthesis of silica aerogels and their application
409
C03S01.fm Page 410 Monday, May 3, 2004 12:36 PM
410
I. Smirnova and W. Arlt
C03S01.fm Page 411 Monday, May 3, 2004 12:36 PM
Synthesis of silica aerogels and their application
411
C03S01.fm Page 412 Monday, May 3, 2004 12:36 PM
412
I. Smirnova and W. Arlt
C03S01.fm Page 413 Monday, May 3, 2004 12:36 PM
Synthesis of silica aerogels and their application
413
C03S01.fm Page 414 Monday, May 3, 2004 12:36 PM
414
I. Smirnova and W. Arlt
C03S01.fm Page 415 Monday, May 3, 2004 12:36 PM
Synthesis of silica aerogels and their application
415
C03S01.fm Page 416 Monday, May 3, 2004 12:36 PM
416
I. Smirnova and W. Arlt
Aerogel
0.04
g Naphthalene / g
0.05
0.03 0.02 70°C 0.01
Langmuir, 70°C 40°C
0.00 0
0.1
0.2
0.3
0.4
C Naphthalene in CO2, wt%
0.5
0.6
C03S01.fm Page 417 Monday, May 3, 2004 12:36 PM
417
Synthesis of silica aerogels and their application
g Ketoprofen /g Aerogel
0.3 0.25 0.2 0.15 0.1
70°C Langmuir
0.05 0 0
0.1
0.2
0.3
C Ketoprofen in CO2 (%)
0.4
0.5
C03S01.fm Page 418 Monday, May 3, 2004 12:36 PM
418
I. Smirnova and W. Arlt
C03S01.fm Page 419 Monday, May 3, 2004 12:36 PM
Synthesis of silica aerogels and their application
419
C03S01.fm Page 420 Monday, May 3, 2004 12:36 PM
420
I. Smirnova and W. Arlt
C03S01.fm Page 421 Monday, May 3, 2004 12:36 PM
Synthesis of silica aerogels and their application
421
C03S01.fm Page 422 Monday, May 3, 2004 12:36 PM
422
I. Smirnova and W. Arlt 120
% Dissolved
100 80 60 40
Ketoprofen in aerogel
Fitting
20
Crystalline ketoprofen 0 0
50
100
150 t, min
200
250
C03S01.fm Page 423 Monday, May 3, 2004 12:36 PM
423
Synthesis of silica aerogels and their application
120
% Dissolved
100 80 60 40 Crystalline griseofulvin
20
Griseofulvin in aerogel First order fitting
0 0
50
100
150
200
250
300
350
t, min
100
% Dissolved
80 60 40
C rystalline M iconazole
M iconazole in aerogel
20
Fitting 0 0
40
80
120 t, m in
160
200
C03S01.fm Page 424 Monday, May 3, 2004 12:36 PM
424
I. Smirnova and W. Arlt
C03S01.fm Page 425 Monday, May 3, 2004 12:36 PM
Synthesis of silica aerogels and their application
425
C03S01.fm Page 426 Monday, May 3, 2004 12:36 PM
426
I. Smirnova and W. Arlt
C03S01.fm Page 427 Monday, May 3, 2004 12:36 PM
Synthesis of silica aerogels and their application
427
C03S02.fm Page 429 Monday, May 3, 2004 12:39 PM
Supercritical Fluids as Solvents and Reaction Media G. Brunner (editor) © 2004 Elsevier B.V. All rights reserved
429
C03S02.fm Page 430 Monday, May 3, 2004 12:39 PM
430
A. Weber, R. Kümmel and T. Kraska
C03S02.fm Page 431 Monday, May 3, 2004 12:39 PM
431
Investigation and Modelling of the Gas-Antisolvent Process
PIC primary solution nozzle secondary P2 flow
Lcrit
S1
A1
two phase flow supercritical fluid
P1
D1
C03S02.fm Page 432 Monday, May 3, 2004 12:39 PM
432
A. Weber, R. Kümmel and T. Kraska
L+S
ML MG
G
C03S02.fm Page 433 Monday, May 3, 2004 12:39 PM
Investigation and Modelling of the Gas-Antisolvent Process
433
C03S02.fm Page 434 Monday, May 3, 2004 12:39 PM
434
A. Weber, R. Kümmel and T. Kraska
t>0
t=0
R0+∆R
R0
Antisolvent a)
b) C
A (antisolvent)
B (primary solvent) C (solute)
R
P1 P2 P3 P4 P5 Particle Populations
C03S02.fm Page 435 Monday, May 3, 2004 12:39 PM
Investigation and Modelling of the Gas-Antisolvent Process
435
C03S02.fm Page 436 Monday, May 3, 2004 12:39 PM
436
A. Weber, R. Kümmel and T. Kraska
C03S02.fm Page 437 Monday, May 3, 2004 12:39 PM
Investigation and Modelling of the Gas-Antisolvent Process
437
C03S02.fm Page 438 Monday, May 3, 2004 12:39 PM
438
A. Weber, R. Kümmel and T. Kraska
C03S02.fm Page 439 Monday, May 3, 2004 12:39 PM
Investigation and Modelling of the Gas-Antisolvent Process
439
C03S02.fm Page 440 Monday, May 3, 2004 12:39 PM
440
A. Weber, R. Kümmel and T. Kraska
C03S02.fm Page 441 Monday, May 3, 2004 12:39 PM
Investigation and Modelling of the Gas-Antisolvent Process
441
C03S02.fm Page 442 Monday, May 3, 2004 12:39 PM
442
A. Weber, R. Kümmel and T. Kraska
C03S02.fm Page 443 Monday, May 3, 2004 12:39 PM
Investigation and Modelling of the Gas-Antisolvent Process
443
C03S02.fm Page 444 Monday, May 3, 2004 12:39 PM
444
A. Weber, R. Kümmel and T. Kraska
C03S02.fm Page 445 Monday, May 3, 2004 12:39 PM
Investigation and Modelling of the Gas-Antisolvent Process
445
C03S02.fm Page 446 Monday, May 3, 2004 12:39 PM
446
A. Weber, R. Kümmel and T. Kraska
C03S02.fm Page 447 Monday, May 3, 2004 12:39 PM
Investigation and Modelling of the Gas-Antisolvent Process
447
C03S02.fm Page 448 Monday, May 3, 2004 12:39 PM
448
A. Weber, R. Kümmel and T. Kraska
C03S03.fm Page 449 Monday, May 3, 2004 3:58 PM
Supercritical Fluids as Solvents and Reaction Media G. Brunner (editor) © 2004 Elsevier B.V. All rights reserved
449
C03S03.fm Page 450 Monday, May 3, 2004 3:58 PM
450
M. Türk et al.
C03S03.fm Page 451 Monday, May 3, 2004 3:58 PM
451
Formation of nanoscale drugs by RESS
M A
J
D H
G
I L
F B
C
3-WEM E
K
C03S03.fm Page 452 Monday, May 3, 2004 3:58 PM
452
M. Türk et al.
C03S03.fm Page 453 Monday, May 3, 2004 3:58 PM
Formation of nanoscale drugs by RESS
453
C03S03.fm Page 454 Monday, May 3, 2004 3:58 PM
454
M. Türk et al.
C03S03.fm Page 455 Monday, May 3, 2004 3:58 PM
Formation of nanoscale drugs by RESS
455
C03S03.fm Page 456 Monday, May 3, 2004 3:58 PM
456
M. Türk et al.
C03S03.fm Page 457 Monday, May 3, 2004 3:58 PM
Formation of nanoscale drugs by RESS
457
C03S03.fm Page 458 Monday, May 3, 2004 3:58 PM
458
M. Türk et al.
M A
D
J
H
G F B
C E
I
K
L
C03S03.fm Page 459 Monday, May 3, 2004 3:58 PM
Formation of nanoscale drugs by RESS
459
C03S03.fm Page 460 Monday, May 3, 2004 3:58 PM
460
M. Türk et al.
C03S03.fm Page 461 Monday, May 3, 2004 3:58 PM
Formation of nanoscale drugs by RESS
461
C03S03.fm Page 462 Monday, May 3, 2004 3:58 PM
462
M. Türk et al.
C04S01.fm Page 465 Wednesday, May 5, 2004 4:52 PM
Supercritical Fluids as Solvents and Reaction Media G. Brunner (editor) © 2004 Elsevier B.V. All rights reserved
465
C04S01.fm Page 466 Wednesday, May 5, 2004 4:52 PM
466
O. Becker and G. Heydrich
C04S01.fm Page 467 Wednesday, May 5, 2004 4:52 PM
Separation efficiency and axial mixing
467
C04S01.fm Page 468 Wednesday, May 5, 2004 4:52 PM
468
O. Becker and G. Heydrich
C04S01.fm Page 469 Wednesday, May 5, 2004 4:52 PM
469
Separation efficiency and axial mixing
38,6 bar 57,9 bar 100 bar 122 bar 185 bar
C04S01.fm Page 470 Wednesday, May 5, 2004 4:52 PM
470
O. Becker and G. Heydrich
C04S01.fm Page 471 Wednesday, May 5, 2004 4:52 PM
Separation efficiency and axial mixing
471
C04S01.fm Page 472 Wednesday, May 5, 2004 4:52 PM
472
O. Becker and G. Heydrich
1,4 1,2 v=5
1
HETS [m]
v = 10 0,8 v = 20 kgCO2/kgF 0,6 0,4
Sulzer-BX DN67 Water(d)/EtOH/CO2(c)
0,2 0 0
2
4
8
6
10
Total column load Bges [kg/m²s]
1,4 1,2
Bges=4,5 kg/m²s
HETS [m]
1 0,8
Bges=8,6 kg/m²s
0,6
Sulzer-BX DN67 Water(d)/EtOH/CO2(c)
0,4 0,2 0 0
5
10
15
Solvent ratio v [kgCO2/kgF]
20
C04S01.fm Page 473 Wednesday, May 5, 2004 4:52 PM
473
Separation efficiency and axial mixing
4 3,5
v = 20
v=5
HETS [m]
3 2,5
v = 10 kgCO2/kgF
2 1,5 Wiremesh Packing DN67 Water(d)/EtOH/CO2(c)
1 0,5 0 0
2
10
4 6 8 Total column load Bges [kg/(m² s)]
4 3,5
Bges = 4,5 kg/m²s
HETS [m]
3 2,5
Bges = 8,6 kg/m²s
2 1,5 Wiremesh Packing DN67 Water(d)/EtOH/CO2(c)
1 0,5 0 0
5
10
15
Solvent ratio v [kgCO2/kgF]
20
C04S01.fm Page 474 Wednesday, May 5, 2004 4:52 PM
474
O. Becker and G. Heydrich
0,35 0,3 Fraction
0,25 Bges~ 8,5 kg/(m²s) v= 10 kgCO2/kgF
0,2 0,15
Sulzer-BX
0,1
Wiremesh
0,05 0 0,5
1,5
2,5 3,5 4,5 dtr [mm]
5,5
6,5
C04S01.fm Page 475 Wednesday, May 5, 2004 4:52 PM
475
Separation efficiency and axial mixing
3
3
Sulzer BX DN67 Water(d)/EtOH/CO2(c)
[Vol%]
2
1,5 v = 10 1
v = 20 kgCO2/kgF
0,5
Wiremesh Packing DN67 Water(d)/EtOH/CO2(c)
2,5
Hold up
Hold up [Vol%]
2,5
v=5
v=5
2
1,5 v = 10
1
0,5 v = 20 kgCO2/kgF
0
0 0
2
4
6
Total column load Bges
8
10
[kg/(m²s)]
12
0
2
4
6
8
10
Total column load Bges [kg/(m2s)]
12
C04S01.fm Page 476 Wednesday, May 5, 2004 4:52 PM
476
O. Becker and G. Heydrich
Calculated mean Sauter diameter d32 [mm]
8 7
+15%
6 -15% 5 4 3 2
Wiremesh Sulzer BX
1
η=2,3 η=2,0
0 0
1
2
3
4
5
6
Measured mean Sauter diameter d32 [mm]
7
8
C04S01.fm Page 477 Wednesday, May 5, 2004 4:52 PM
Separation efficiency and axial mixing 4,0
Calculated hold up [Vol%]
3,5
Wiremesh Sulzer BX
+15%
3,0 2,5
-15%
2,0 1,5 1,0 0,5 0,0 0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 Measured hold up [Vol%]
477
C04S01.fm Page 478 Wednesday, May 5, 2004 4:52 PM
478
Optimized phase velocity Uc,opt [cm/s]
O. Becker and G. Heydrich
3
Wiremesh Packing
Uc,opt ~ 2U ic v= ∞
2,5
2
v=20 kgCO2/kgF v=10
1,5
v=5
1 Uc,opt = U ic
0,5
0 0
0,2
0,4
0,6
0,8
1
1,2
1,4
Interstitial phase velocity Uic [cm/s]
1,6
C04S01.fm Page 479 Wednesday, May 5, 2004 4:52 PM
479
Separation efficiency and axial mixing
Velocity profile at low liquid load Velocity profile at increased liquid load
Axial dispersion coefficient Dax,c [cm²/s]
600
Wiremesh Packing 500
v= ∞
400 v=20 kgCO 2/kgF 300
200 v=10 v=5
100
0 0
0,2
0,4
0,6
0,8
1
Interstitial phase velocity Uic
1,2
[cm/s]
1,4
1,6
C04S01.fm Page 480 Wednesday, May 5, 2004 4:52 PM
480
O. Becker and G. Heydrich 1,6 Uc,opt = U ic
Optimized phase velocity Uc,opt [cm/s]
1,4 1,2 1 0,8
Sulzer BX
0,6
Single phase 0,4
v=5 kg/kg v=10 kg/kg
0,2
v=20 kg/kg 0 0
0,2
0,4
0,6
0,8
1
1,2
Interstitial phase velocity Uic [cm/s]
1,4
1,6
C04S01.fm Page 481 Wednesday, May 5, 2004 4:52 PM
481
Separation efficiency and axial mixing
Axial dispersion coefficient Dax,c
[cm²/s]
70 60 50
Sulzer BX 40
Single phase v=5 kg/kg v=10 kg/kg v=20 kg/kg
30 20 10 0 0
0,2
0,4
0,6
0,8
Interstitial phase velocity Uic
1
1,2 [cm/s]
1,4
1,6
C04S01.fm Page 482 Wednesday, May 5, 2004 4:52 PM
482
Optimized disperse phase velocity Ud,opt [cm/s]
O. Becker and G. Heydrich
10 9 8 7 6 5
Wiremesh Sulzer BX
4 3
CO 2(c)/Water(d) DN67
2 1 0 0,00
0,05
0,10
0,15
0,20
0,25
0,30
Superficial disperse phase velocity Ud [cm/s]
0,35
0,40
C04S01.fm Page 483 Wednesday, May 5, 2004 4:52 PM
483
Separation efficiency and axial mixing
Axial dispersion coefficient Dax,d
[cm²/s]
160 140 120 100 80
Uc [cm/s]
60 40
0,00 0,52 1,03 1,55
Wiremesh Packing DN67 Water(d)/CO2(c)
20
0,26 0,77 1,29
0 0
0,05
0,1
0,15
0,2
0,25
Superficial disperse phase velocity Ud
0,3
0,35
[cm/s]
Axial dispersion coefficient Dax,d [cm/s]
120
100
80
60 Uc[cm/s] 40
Sulzer BX DN67 Water(d)/CO2(c)
20
0,06
0,32
0,64
0,96
1,28
0 0,00
0,05
0,10
0,15
Superficial disperse phase velocity Ud [cm/s]
0,20
C04S01.fm Page 484 Wednesday, May 5, 2004 4:52 PM
484
O. Becker and G. Heydrich
Axial dispersion coefficient D ax,c [cm²/s]
100,0
Supercritical Carbon Dioxide
CO2, Single Phase CO2, v=5 CO2, v=10 CO2, v=20 C3H8, v=5 C3H8, v=10 C3H8, v=20
10,0
Sulzer BX CO2(c)/Water(d) Propane(c)/Water(d)
Liquid Propane
1,0 0
0,5
1
1,5
Interstitial phase velocity Uic [cm/s]
2
C04S01.fm Page 485 Wednesday, May 5, 2004 4:52 PM
485
Separation efficiency and axial mixing
Optimized phase velocity Ud,opt [cm/s]
5,0 4,5 4,0 3,5 3,0 2,5 2,0 1,5
Sulzer BX
1,0
Carbon dioxide Propane
0,5 0,0 0,00
0,05
0,10
0,15
Superficial disperse phase velocity Ud [cm]
0,20
C04S01.fm Page 486 Wednesday, May 5, 2004 4:52 PM
486
O. Becker and G. Heydrich
C04S01.fm Page 487 Wednesday, May 5, 2004 4:52 PM
Separation efficiency and axial mixing
487
C04S01.fm Page 488 Wednesday, May 5, 2004 4:52 PM
488
O. Becker and G. Heydrich
C04S02.fm Page 489 Monday, May 3, 2004 12:48 PM
Supercritical Fluids as Solvents and Reaction Media G. Brunner (editor) © 2004 Elsevier B.V. All rights reserved
489
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490
G. Brunner, M. Budich
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Separation of organic compounds from aqueous solutions
491
C04S02.fm Page 492 Monday, May 3, 2004 12:48 PM
492
G. Brunner, M. Budich
C04S02.fm Page 493 Monday, May 3, 2004 12:48 PM
Separation of organic compounds from aqueous solutions
493
C04S02.fm Page 494 Monday, May 3, 2004 12:48 PM
494
G. Brunner, M. Budich
C04S02.fm Page 495 Monday, May 3, 2004 12:48 PM
Separation of organic compounds from aqueous solutions
495
C04S02.fm Page 496 Monday, May 3, 2004 12:48 PM
496
G. Brunner, M. Budich
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Separation of organic compounds from aqueous solutions
497
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498
G. Brunner, M. Budich
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Separation of organic compounds from aqueous solutions
499
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500
G. Brunner, M. Budich
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Separation of organic compounds from aqueous solutions
501
C04S02.fm Page 502 Monday, May 3, 2004 12:48 PM
502
G. Brunner, M. Budich
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Separation of organic compounds from aqueous solutions
503
C04S02.fm Page 504 Monday, May 3, 2004 12:48 PM
504
G. Brunner, M. Budich
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Separation of organic compounds from aqueous solutions
505
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506
G. Brunner, M. Budich
C04S02.fm Page 507 Monday, May 3, 2004 12:48 PM
Separation of organic compounds from aqueous solutions
507
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508
G. Brunner, M. Budich
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Separation of organic compounds from aqueous solutions
509
C04S02.fm Page 510 Monday, May 3, 2004 12:48 PM
510
G. Brunner, M. Budich
C04S02.fm Page 511 Monday, May 3, 2004 12:48 PM
Separation of organic compounds from aqueous solutions
511
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512
G. Brunner, M. Budich
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Separation of organic compounds from aqueous solutions
513
C04S02.fm Page 514 Monday, May 3, 2004 12:48 PM
514
G. Brunner, M. Budich
C04S02.fm Page 515 Monday, May 3, 2004 12:48 PM
Separation of organic compounds from aqueous solutions
515
C04S02.fm Page 516 Monday, May 3, 2004 12:48 PM
516
G. Brunner, M. Budich
C04S02.fm Page 517 Monday, May 3, 2004 12:48 PM
Separation of organic compounds from aqueous solutions
517
C04S02.fm Page 518 Monday, May 3, 2004 12:48 PM
518
G. Brunner, M. Budich
C04S02.fm Page 519 Monday, May 3, 2004 12:48 PM
Separation of organic compounds from aqueous solutions
519
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520
G. Brunner, M. Budich
C04S02.fm Page 521 Monday, May 3, 2004 12:48 PM
Separation of organic compounds from aqueous solutions
521
C04S02.fm Page 522 Monday, May 3, 2004 12:48 PM
522
G. Brunner, M. Budich
C04S03.fm Page 523 Monday, May 3, 2004 5:09 PM
Supercritical Fluids as Solvents and Reaction Media G. Brunner (editor) © 2004 Elsevier B.V. All rights reserved
523
C04S03.fm Page 524 Monday, May 3, 2004 5:09 PM
524
D.K. Breitinger et al.
C04S03.fm Page 525 Monday, May 3, 2004 5:09 PM
Preparation of SO2 complexes and recovery of Precious metals
525
C04S03.fm Page 526 Monday, May 3, 2004 5:09 PM
526
D.K. Breitinger et al.
C04S03.fm Page 527 Monday, May 3, 2004 5:09 PM
Preparation of SO2 complexes and recovery of Precious metals
527
C04S03.fm Page 528 Monday, May 3, 2004 5:09 PM
528
D.K. Breitinger et al.
C04S03.fm Page 529 Monday, May 3, 2004 5:09 PM
Preparation of SO2 complexes and recovery of Precious metals
529
C04S03.fm Page 530 Monday, May 3, 2004 5:09 PM
530
D.K. Breitinger et al.
C05S01.fm Page 533 Monday, May 3, 2004 4:15 PM
Supercritical Fluids as Solvents and Reaction Media G. Brunner (editor) © 2004 Elsevier B.V. All rights reserved
533
C05S01.fm Page 534 Monday, May 3, 2004 4:15 PM
534
W. Steffen et al.
C05S01.fm Page 535 Monday, May 3, 2004 4:15 PM
Polymerization in supercritical CO2
535
C05S01.fm Page 536 Monday, May 3, 2004 4:15 PM
536
W. Steffen et al.
C05S01.fm Page 537 Monday, May 3, 2004 4:15 PM
Polymerization in supercritical CO2
537
C05S01.fm Page 538 Monday, May 3, 2004 4:15 PM
538
W. Steffen et al.
C05S01.fm Page 539 Monday, May 3, 2004 4:15 PM
Polymerization in supercritical CO2
539
C05S01.fm Page 540 Monday, May 3, 2004 4:15 PM
540
W. Steffen et al.
C05S01.fm Page 541 Monday, May 3, 2004 4:15 PM
Polymerization in supercritical CO2
541
C05S01.fm Page 542 Monday, May 3, 2004 4:15 PM
542
W. Steffen et al.
C05S01.fm Page 543 Monday, May 3, 2004 4:15 PM
543
Polymerization in supercritical CO2
1 2 A
3 4 5 6
7 8 9 10 A 11 12 13
C05S01.fm Page 544 Monday, May 3, 2004 4:15 PM
544
W. Steffen et al.
C05S01.fm Page 545 Monday, May 3, 2004 4:15 PM
Polymerization in supercritical CO2
δ prism Laser beam
sapphire windows
545
C05S01.fm Page 546 Monday, May 3, 2004 4:15 PM
546
W. Steffen et al.
1.25
nλ=632,8 nm
1.20
reflectivity
1.0
0.5
0.0 20
1.15
ϑ/˚
30
40
50
1.10 1.05 1.00 0.0
0.2
0.4
0.6
ρ[kg / l]
0.8
1.0
C05S01.fm Page 547 Monday, May 3, 2004 4:15 PM
Polymerization in supercritical CO2
547
C05S01.fm Page 548 Monday, May 3, 2004 4:15 PM
548
W. Steffen et al.
C05S01.fm Page 549 Monday, May 3, 2004 4:15 PM
Polymerization in supercritical CO2
549
C05S01.fm Page 550 Monday, May 3, 2004 4:15 PM
550
W. Steffen et al.
C05S01.fm Page 551 Monday, May 3, 2004 4:15 PM
551
Polymerization in supercritical CO2
< Γ> [104 s]
6
1.00
4
2
(2)
g (q,t)-1
0.75
0
0.50
0
4
2 2
6 14
-2
q [10 m ] 0.25
0.00 10
-4
10
-3
10
-2
10
time [s]
-1
10
0
10
1
8
C05S01.fm Page 552 Monday, May 3, 2004 4:15 PM
552
W. Steffen et al.
C05S01.fm Page 553 Monday, May 3, 2004 4:15 PM
Polymerization in supercritical CO2
553
C05S01.fm Page 554 Monday, May 3, 2004 4:15 PM
554
W. Steffen et al.
C05S01.fm Page 555 Monday, May 3, 2004 4:15 PM
Polymerization in supercritical CO2
555
C05S01.fm Page 556 Monday, May 3, 2004 4:15 PM
556
W. Steffen et al.
C05S01.fm Page 557 Monday, May 3, 2004 4:15 PM
Polymerization in supercritical CO2
557
C05S01.fm Page 558 Monday, May 3, 2004 4:15 PM
558
W. Steffen et al.
C05S02.fm Page 559 Monday, May 3, 2004 4:17 PM
Supercritical Fluids as Solvents and Reaction Media G. Brunner (editor) © 2004 Elsevier B.V. All rights reserved
559
C05S02.fm Page 560 Monday, May 3, 2004 4:17 PM
560
U. Fehrenbacher and M. Ballauff
C05S02.fm Page 561 Monday, May 3, 2004 4:17 PM
Early stage of dispersion polymerization in supercritical CO2
561
C05S02.fm Page 562 Monday, May 3, 2004 4:17 PM
562
U. Fehrenbacher and M. Ballauff
C05S02.fm Page 563 Monday, May 3, 2004 4:17 PM
Early stage of dispersion polymerization in supercritical CO2
563
C05S02.fm Page 564 Monday, May 3, 2004 4:17 PM
564
U. Fehrenbacher and M. Ballauff
C05S02.fm Page 565 Monday, May 3, 2004 4:17 PM
Early stage of dispersion polymerization in supercritical CO2
565
C05S02.fm Page 566 Monday, May 3, 2004 4:17 PM
566
U. Fehrenbacher and M. Ballauff
C05S02.fm Page 567 Monday, May 3, 2004 4:17 PM
Early stage of dispersion polymerization in supercritical CO2
567
C05S02.fm Page 568 Monday, May 3, 2004 4:17 PM
568
U. Fehrenbacher and M. Ballauff
C05S02.fm Page 569 Monday, May 3, 2004 4:17 PM
Early stage of dispersion polymerization in supercritical CO2
569
C05S02.fm Page 570 Monday, May 3, 2004 4:17 PM
570
U. Fehrenbacher and M. Ballauff
C05S02.fm Page 571 Monday, May 3, 2004 4:17 PM
Early stage of dispersion polymerization in supercritical CO2
571
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Supercritical Fluids as Solvents and Reaction Media G. Brunner (editor) © 2004 Elsevier B.V. All rights reserved
573
C05S03.fm Page 574 Wednesday, May 5, 2004 4:03 PM
574
S. Beuermann and M. Buback
C05S03.fm Page 575 Wednesday, May 5, 2004 4:03 PM
Rate coefficients of free-radical polymerization
575
C05S03.fm Page 576 Wednesday, May 5, 2004 4:03 PM
576
S. Beuermann and M. Buback
C05S03.fm Page 577 Wednesday, May 5, 2004 4:03 PM
Rate coefficients of free-radical polymerization
577
C05S03.fm Page 578 Wednesday, May 5, 2004 4:03 PM
578
S. Beuermann and M. Buback
C05S03.fm Page 579 Wednesday, May 5, 2004 4:03 PM
Rate coefficients of free-radical polymerization
579
C05S03.fm Page 580 Wednesday, May 5, 2004 4:03 PM
580
S. Beuermann and M. Buback
C05S03.fm Page 581 Wednesday, May 5, 2004 4:03 PM
581
Rate coefficients of free-radical polymerization
PMA
probability
PVAc
-80
-60
-40
-20
interaction energy / kJ·mol–1
0
-60
-40
-20
interaction energy /
0 kJ·mol–1
C05S03.fm Page 582 Wednesday, May 5, 2004 4:03 PM
582
S. Beuermann and M. Buback
C05S03.fm Page 583 Wednesday, May 5, 2004 4:03 PM
Rate coefficients of free-radical polymerization
583
C05S03.fm Page 584 Wednesday, May 5, 2004 4:03 PM
584
S. Beuermann and M. Buback
C05S03.fm Page 585 Wednesday, May 5, 2004 4:03 PM
Rate coefficients of free-radical polymerization
585
C05S03.fm Page 586 Wednesday, May 5, 2004 4:03 PM
586
S. Beuermann and M. Buback
C05S03.fm Page 587 Wednesday, May 5, 2004 4:03 PM
Rate coefficients of free-radical polymerization
587
C05S03.fm Page 588 Wednesday, May 5, 2004 4:03 PM
588
S. Beuermann and M. Buback
C05S03.fm Page 589 Wednesday, May 5, 2004 4:03 PM
Rate coefficients of free-radical polymerization
589
C05S03.fm Page 590 Wednesday, May 5, 2004 4:03 PM
590
S. Beuermann and M. Buback
C05S03.fm Page 591 Wednesday, May 5, 2004 4:03 PM
Rate coefficients of free-radical polymerization
591
C05S04.fm Page 593 Monday, May 3, 2004 4:18 PM
Supercritical Fluids as Solvents and Reaction Media G. Brunner (editor) © 2004 Elsevier B.V. All rights reserved
593
C05S04.fm Page 594 Monday, May 3, 2004 4:18 PM
594
W. Mormann, H. Jung and D. Spitzer
C05S04.fm Page 595 Monday, May 3, 2004 4:18 PM
Ammonia as reagent or reaction medium for polymers
595
C05S04.fm Page 596 Monday, May 3, 2004 4:18 PM
596
W. Mormann, H. Jung and D. Spitzer
Temperature control
T Reactor
Filter Filter
T
T
T p Filter NH3
p
Sampling
C05S04.fm Page 597 Monday, May 3, 2004 4:18 PM
Ammonia as reagent or reaction medium for polymers
597
C05S04.fm Page 598 Monday, May 3, 2004 4:18 PM
598
W. Mormann, H. Jung and D. Spitzer
C05S04.fm Page 599 Monday, May 3, 2004 4:18 PM
Ammonia as reagent or reaction medium for polymers
599
C05S04.fm Page 600 Monday, May 3, 2004 4:18 PM
600
W. Mormann, H. Jung and D. Spitzer
C05S04.fm Page 601 Monday, May 3, 2004 4:18 PM
Ammonia as reagent or reaction medium for polymers
601
C05S04.fm Page 602 Monday, May 3, 2004 4:18 PM
602
W. Mormann, H. Jung and D. Spitzer
m /%
100
100 ¡C 120 ¡C
80
144¡C 80 ¡C
60
153 ¡C 60 ¡C 180 ¡C
40
35 ¡C 20 0
0
20
40
60
80
100 t /min
120
C05S04.fm Page 603 Monday, May 3, 2004 4:18 PM
Ammonia as reagent or reaction medium for polymers
603
C05S04.fm Page 604 Monday, May 3, 2004 4:18 PM
604
W. Mormann, H. Jung and D. Spitzer
C05S04.fm Page 605 Monday, May 3, 2004 4:18 PM
Ammonia as reagent or reaction medium for polymers
605
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606
W. Mormann, H. Jung and D. Spitzer
C05S04.fm Page 607 Monday, May 3, 2004 4:18 PM
Ammonia as reagent or reaction medium for polymers
607
C05S04.fm Page 608 Monday, May 3, 2004 4:18 PM
608
W. Mormann, H. Jung and D. Spitzer
C05S04.fm Page 609 Monday, May 3, 2004 4:18 PM
Ammonia as reagent or reaction medium for polymers
609
C05S04.fm Page 610 Monday, May 3, 2004 4:18 PM
610
W. Mormann, H. Jung and D. Spitzer
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Ammonia as reagent or reaction medium for polymers
611
C05S04.fm Page 612 Monday, May 3, 2004 4:18 PM
612
W. Mormann, H. Jung and D. Spitzer
C05S04.fm Page 613 Monday, May 3, 2004 4:18 PM
Ammonia as reagent or reaction medium for polymers
613
C05S04.fm Page 614 Monday, May 3, 2004 4:18 PM
614
W. Mormann, H. Jung and D. Spitzer
C05S04.fm Page 615 Monday, May 3, 2004 4:18 PM
Ammonia as reagent or reaction medium for polymers
615
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616
W. Mormann, H. Jung and D. Spitzer
C05S05.fm Page 617 Monday, May 3, 2004 4:19 PM
Supercritical Fluids as Solvents and Reaction Media G. Brunner (editor) © 2004 Elsevier B.V. All rights reserved
617
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618
H. Vogel et al.
C05S05.fm Page 619 Monday, May 3, 2004 4:19 PM
Inorganic materials and Chemical reactions
619
C05S05.fm Page 620 Monday, May 3, 2004 4:19 PM
620
H. Vogel et al.
PI
PIR
TIC
TIRC PIRC
PI
PI TIC
TIRC WIR
H2O2 decomposer aqueous educts
N2
PI
WIR
N2
organic educts
TIC
phase separator
C05S05.fm Page 621 Monday, May 3, 2004 4:19 PM
Inorganic materials and Chemical reactions
621
C05S05.fm Page 622 Monday, May 3, 2004 4:19 PM
622
H. Vogel et al.
C05S05.fm Page 623 Monday, May 3, 2004 4:19 PM
Inorganic materials and Chemical reactions
623
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624
H. Vogel et al.
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Inorganic materials and Chemical reactions
625
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626
H. Vogel et al.
C05S05.fm Page 627 Monday, May 3, 2004 4:19 PM
Inorganic materials and Chemical reactions
627
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628
H. Vogel et al.
C05S05.fm Page 629 Monday, May 3, 2004 4:19 PM
Inorganic materials and Chemical reactions
629
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630
H. Vogel et al.
C05S05.fm Page 631 Monday, May 3, 2004 4:19 PM
Inorganic materials and Chemical reactions
631
C05S05.fm Page 632 Monday, May 3, 2004 4:19 PM
632
H. Vogel et al.
C05S05.fm Page 633 Monday, May 3, 2004 4:19 PM
Inorganic materials and Chemical reactions
633
635
Index acentric factor, 221 acetaldehyde, 489-519 acetic acid - carbon dioxide (hydrogen bonding), 354 acetic acid, 164-183 acetylacetone, 325 acrylate polymerization, 575,583,584 acrylic acid, 66 activation energies (diffusion), 360 activation volumes (diffusion), 360 adamantane, 245,250- 253,254, 255,265 adsorption (of drugs on aerogels), 382, 389, 391-393,414-425 aerogel - drug formulation, 314, 421,424 aerogel, 381-427 aerogel properties, 391 aerosol supercritical extraction system (ASES), 148, 431,449 aggregation of amphiphilic molecules, 538 alkoxysilane, 384 alkyl acrylate, 65, 75, 76 alkylbenzenes, 21 alpha function, 18, 19, 23 ammonia - acetonitrile (diffusion coefficients), 356 ammonia - benzene (diffuson coefficients), 356 ammonia - methanol (diffusion coefficients), 357 ammonia as reaction medium, 593-616 ammonia, intradiffusion coefficient, 343 ammonia, self diffusion coefficient, 343 ammonolysis of bisphenol-Apolycarbonate, 604 ammonolysis ofpolyamides, 594, 597, 598, 609, 610 ammonolysis of polyesters, 594-600, 616 ammonolysis of polymers, 593,594 ammonolytic cleavage of polyurethanes, 594 ammonolytic reactions, 594 anthracene, 16, 24 anthraquinone, 122-143,250-252, 258, 260, 262, 264-266 anti-solvent, 43, 44, 47-51, 54-57, 60, 225, 229-231, 431-447 aqueous flavor concentrates, 497 aqueous salt solutions, 163 aqueous solutions, 489-522
aqueous solutions (wetting), 366, 372 aroma components, 491 aroma recovery, 490 arsenic, 326 As-chelate, 323 ascorbic acid, 433 Aspen Plus ®, 283 associating compound, 295 asymmetric binary mixture, 148 attraction term, 211,214-223 attractive interactions, 297 autoclave for visual observation, 595 axial dispersion coefficient, 465-486 axial mixing, 465,485,486 azeotrope, 180 back mixing, 465 Barker-Henderson perturbation theory, 221 batch gas-anti-solvent crystallization, 429 benzoic acid - carbon dioxide, 451-457 benzoic acid - trifluoromethane, 451 binary critical line, 124 binary interaction parameter, 283 binodal curve, 180 biphenyl, 155 BQ75 term, 222
1,4-bis-(alkylamino)-9,10-anthraquinone, 128 Carbamate, 317 carbon dioxide - [3-carotene, 133 carbon dioxide - 2-propanol, 85-120 carbon dioxide - acetic acid, 167, 178 carbon dioxide - adamantane, 245,250, 254 carbon dioxide - benzene (diffusion coefficient), 352 carbon dioxide - diphenylmethane, 24, 25 carbon dioxide - ethanol - water, 489-522 carbon dioxide - ethanol, 85-120 carbon dioxide - ethylbenzene, 21 carbon d i o x i d e - hexadecane, 21, 22 carbon dioxide - hexylbenzene, 21 carbon dioxide - hydrogen (diffusion coefficients), 353 carbon dioxide - m-xylene, 26 carbon dioxide - naphthalene, 25, 152 carbon dioxide - n-heptane, 24 carbon dioxide - orange water-phase, 508 carbon dioxide - phenanthrene, 17 carbon dioxide - propylbenzene, 21 carbon dioxide - water - acetic acid sodium acetate, 177
636
carbon dioxide - water - acetic acid sodium chloride, 169 carbon dioxide - water - acetic acid, 163 carbon d i o x i d e - water, 167, 169, 170, 178-183 carbon dioxide - 13-carotene, 241-268 carbon dioxide + 1-decanol, 10, 12, 29, 32 carbon dioxide + dodecane, 6, 11, 13, 30, 31 carbon dioxide- benzene, 23 carbon dioxide, 42-44 carbon dioxide, intradiffusion coefficient, 343-362 carbon dioxide, self diffusion coefficient, 343 carbon dioxide-1-octanol, 21, 22 carbon dioxide-squalane, 78 Carnahan-Starling equation, 215 Carnahan-Starling-van der Waals EoS, 245 carotene (13-), 121-145,241-268 catalysis in supercritical water, 630 catalytic activity of inorganic materials in supercritical aqueous solutions, 624 catalytic converters (used), 528 ceramics in supercritical aqueous solutions, 617 chain molecule solutions, 211 chain molecules, 299 chain-transfer agent, 586 chain-transfer rate coefficient, 574, 585, 588 chain-transfer reaction, 585,590 chelate, 323 chelator, 324 CHF3/naphthalene, 153 chlorotrifluoromethane (CC1F3), 128 cholesterol - carbon dioxide, 451 Chrastil method, 142,244, 256, 259, 260 cloud-point, 39-55, 63, 61-84 cluster energy, 580 co-solvent, 225, 231 coexistence curve, 48 cohesion energy, 580 colloidal stability (interfacial tension), 376 column packing, 468-486 compressibility factor, 214, 215, 218, 220 construction materials for sulfur dioxide, 523 contact angle, 364, 366, 370, 371,376 continuous GAS, 431
copolymer systems (PC SAFT), 319 copolymer, 43, 66, 73,295,306 copolyrnerization, 574, 578,588-590 correlation of the solubility, 241-268 corresponding states principle, 221 corrosion of ceramic materials, 623 corrosion of metals and metal oxides (SCW), 621 corrosion reactor, 619 co-solvent (polymerization), 573 co-solvent, 26, 39, 46, 49, 54-57, 60, 64, 70, 82 countercurrent extraction processes, 465 countercurrent extraction, 369, 489-522 countercurrent processing, 363,370 countercurrent SFE, 489-522 critical behaviour, 243,244 critical compressibility factor, 219 critical curve, 147 critical exponent, 242, 243,246 critical isotherm, 242, 247, 248 critical micelle concentration (cmc), 539 critical phenomena in polymer systems, 214 critical phenomena, 224 critical point, 124 critical temperature minimum (CTM), 234 critical volume fraction, 234 crystallization from supercritical solutions, 323 cubic equations of state, 151 cyclohexyl methacrylate, 576 Debye-Ht~ckel, 174, 183 dehydrations in supercritical aqueous solutions, 617, 618,626-633 density distribution function, 245,246 density ratios for recompression, 300 density-dependent mixing rules, 185-209 deuterium, self diffusion coefficient, 343 dialkyldithiocarbamate, 325 diblock copolymer, 533,541,542,548 dielectric constant, 175 diglycerides, (interfacial tension), 376 diketonate ([3-), 325 dimerization, 164, 176, 178 dimethyl ether, 269-294 dipolar interaction, 295 Disperse Red 11 (1,4-diamino-2methoxyanthraquinone), 128 Disperse Red 60 (1-amino-4-methoxy-2phenoxy-9,10-anthraquinone), 128
637 dispersion, 298 dispersion dye, 250, 251 dispersion dyestuff, 122, 124, 128, 137 dispersion polymerization in carbon dioxide, 559-571 distribution coefficients, 490, 498,499, 510-512, 520 Dortmund Data Bank, 17 drag coefficient, 376 drop shape analysis, 365 drug delivery, 381,382, 425 drug release, 393,413 dynamic light scattering, 458 dynamic light scattering, 534, 547, 549, 552 dynamic solubility investigation, 128 dynamic viscosities, 368 dynamic viscosities of coexisting phases, 269 electrolytes, 164, 169, 174, 176, 179 enriching section, 514 equations of state, EOS, 1, 16, 17, 22 equation of state for the critical region, 242 equilibrium cell, 5 equilibrium solubility, 124, 129, 136 essence oil, 490 ethane - 1-decanol, 5, 8, 28 ethane - decane, 6, 7, 28 ethane - dodecane, 12 ethane - octacosane, 23, 24 ethane, 42-45 ethanol - hydrogen - dimethyl ether, 276 ethanol - hydrogen- propane, 275 ethanol - water - carbon dioxide, 468-486 ethanol (EOH), 61, 64, 70, 71, 82 ethyl acetate, 61, 64, 69-71, 82, 83,489519 ethyl butyrate, 489-519 ethyl oleate, 274 ethylene - 1-decanol, 6, 11, 12, 30, 34 ethylene - dodecane, 31 ethylene - naphthalene, 25 ethylene- vinyl acetic acid, 85-120 ethylene + diphenylmethane, 23, 24 ethylene, 39, 44-47, 53, 55-60, 66, 67 ethylene/LDPE, 72 ethylene/PEA, 72 ethylene/poly(ethylene-co-acrylicacid) (EAA), 63-65, 83 ethylene/-poly(ethylene-co-vinylacetate) (EVA), 63-65
ethylene/-polyethylene, 63, 64, 83 extractability (of chelates), 323-340 falling film, 371 fatty acid ester (hydrogenation), 281 fatty alcohols, 269 flavor concentrates, 497 flooding point, 489, 494, 514, 519 Flory-Huggins theory, 234 flow behavior of coexisting phases, 271 flow calorimeter, 3-7, 27 flow regime, 465 flow type apparatus (for equilibrium), 164 fluid-fluid phase diagram, 185-209 fluorinated dithiocarbamate, 343 fluoroform (CHF3), 128 free-radical polymerization in carbon dioxide, 573-590 Free-Volume-Theory, 65 fugacity approach, 242, 245,249 fugacity coefficient, 16 GAS (Gas Anti-Solvent), 148, 315, 429447,449 gas-gas equilibria, 185-209 gel permeation chromatography, 67 gel permeation chromatography, GPC, 42, 66 gelation, 381-426 gE-mixing rules, 19 glass cell (high pressure), 344 glasses in supercritical aqueous solutions, 617 global phase diagram method, 213 griseofulvin - trifluoromethane, 451-460 griseofulvin, 393,394, 317-425 group contribution equations of state, 18, 20 gyromagnetic ratio, 348 hard sphere model, 343,345,351,361 hard-sphere fluid, 214, 295,299 hard-sphere repulsion term, 214 helium, 42-45 Helmholtz energy, 277-299 Henry activity coefficient, 125 heterogeneous catalysis, 270, 281 heterogeneous polymerization of PVP, 534 heterophase (heterogeneous) polymerization, 533,534, 540, 548, 549, 552 HETS evaluation, 514-516, 519 Hexanal, 489-519 hexene (1-), 42
638 high pressure cell used for refractive index, 545 high pressure extraction process, 465-486 high pressure light scattering cell, 543 high pressure NMR, 343 high-pressure phase equilibria correlation, 185-209 high-pressure solubility correlation, 242 hold up (column), 467, 472, 475-479, 486 homopolymer PDMS, 534 homopolymers, 295,306, 322 hydrodynamics (column), 470-486 hydrogen bond formation, 355 hydrogen bonding, 347, 354 hydrogen, self diffusion coefficient, 343 hydrogenation of cyclohexene, 631 hydrogenation of fats in a supercritical fluid, 269-294 hydrogen-bonding, 295,297, 321, hydrolysis in supercritical aqueous solutions, 617, 618, 629-632 hydrolysis of ethyl acetate, 629 hydrolysis reaction, 384 hydrophilic aerogels, 382 hydrophobic aerogels, 382 hydroxyl proton chemical shift, 354 hydroxypropyl methacrylate (HPMA), 578 ibuprofen - carbon dioxide, 451-460 ibuprofen, 159, 160 inert gas, 43, 47-51, 55-57, 60 influence of inorganic materials in supercritical aqueous solutions, 617 inorganic materials in supercritical aqueous solutions, 617-632 interaction energy, 581 interaction parameter, 164, 173-183 interfacial phenomena, 363-376 intradiffusion coefficient, 343-361 lomc interaction parameters, 179, 180 ionic species, 164, 173, 174, 176, 183 isomerization, 122, 123, 132, 134, 136, 143 jet loop reactor, 620 ketoprofen, 393,394, 416-425 kinetics of dispersion polymerization, 559, 567, 568 kinetics of silylation, 613 LCST, 236 Lennard-Jones fluid, 297 Linalool, 489-419 living anionic polymerization, 541
loading of silica aerogels, 392 low density polyethylene (LDPE), 66 lower critical endpoint (LCEP), 124, 147, 148 lower critical solution temperature, LCST, 52 low-volatile organic compounds, 241-244, 249-251,265 magnetic coupled balance, 367 mapping approach, 213 Margules term, 175, 183 mass transfer (GAS), 433 mass transfer resistance (interfacial tension), 372, 376 Mathias-Copeman (alpha function), 18 MD-simulation, 343-35 I, 361 mean field equation of state, 243,245 Melhem modification, 163, 172, 183 melting point, 148-160, membranes ~br SFE, 499 metal chelates, 323-340 metal ions in carbon dioxide, 323-340 metals in supercritical aqueous solutions, 617 methacrylate polymerization, 573,575, 584 methane, 42-44 methanol - carbon dioxide (diffusion coefficients), 355 methanol - carbon dioxide (hydrogen bonding), 354 methanol - hydrogen - dimethyl ether, 288 methanol - hydrogen - propane, 287 methyl acrylate, 62, 64, 72, methyl oleate, 274 methylmethacrylate, MMA, 559 - 570 micelle formation, 533,534, 538,540, 549, 552, 554, 556 micellization of amphiphilic molecules, 539 Miconasol, 393,394 micro-emulsion, 538,539 mlcronization, 449 mlcroporosity, 381 micro-sampler, 5 miscibility windows, 231 mixing rules, 19 mixing theories, 185-209 mixtures of non-associating components (PC SAFT), 301
639 mixtures with associating components (PC SAFT), 3O3 mixtures with multipolar components (PC SAFT), 305 modeling (RESS), 455 molality, 169 molecular based equations of state, 212 molecular fluids, 211 molecular mobility in supercritical fluids, 343-361 molecular perturbation theory, 212 molecular weight distribution, 52, 574, 575,586, 587 monochlorotrifluoromethane - 13-carotene, 254, 256, 257, 258, 259, 265 monoglycerides, (interfacial tension), 376 Monte-Carlo integration, 215 multicomponent liquid mixtures, 489-519 multicomponent phase equilibria, 180 multipolar compound, 295 nanoscale drugs, 449 naphthalene- carbon dioxide, 451 naphthalene, 153 n-butane, 42-46 near critical region, 213 neon-krypton, 185-209 nitrogen, 39, 41-43, 47-49, 51, 55, 60 nitrous oxide - 13-carotene, 254, 255, 257, 258 nitrous oxide (N20), 128 nuclear magnetic resonance, NMR, 42 nucleation (GAS), 435 octadecyl (AQ 18), 128 octanoic acid (OA), 61, 64, 70, 71, 82 optical cell (SCW), 630 orange peel oil, 490 orange water-phase, 500 organic solid solutes, 147 organo phosphorous compounds, 328 osmotic coefficient, 179, 180 Ostwald ripening, 539 packed column, 369 packed column, 465 packing fraction, 214-219, 300 palmitic acid methyl ester - carbon dioxide (diffusion coefficient), 352 Panagiotopoulos - Reid mixing rule, 153, 173-183 Paracetamol, 415,420, 421,427, 428 partial molar volume, 158, 160
partial oxidation in supercritical aqueous solutions, 617, 618,624-632 particle formation, 147, 160, 560 particle growth (GAS), 435 particle size distribution, 431,436, 445449, 459, 461 particle size, 149, 159, 160, Patel-Teja-EoS, 151 PBT, 595,597, 599 PC-SAFT, 80 Pd-chelate, 315 pendant drop method, 364-366 Peng-Robinson (EOS), 17, 151-161,163, 164, 171, 172, 178-183,211,218,219, 220, 283 Peng-Robinson-attraction term, 218 peutane-2,4-dione, 317 perturbation term, 245-248 perturbation theory, 295-302, 321 perturbed-chain-SAFT EoS, 65,295-322 PET, 595,597, 599 PGSS (particle generation from gas saturated solution), 148, 149, 431 phase behaviour, 147, 149, 159-161 phase diagrams, 185-209, 225 phase equilibria, 1-340 phase equilibrium (in situ), 85-120 phase equilibrium criteria, 185-210 phospholipids, (interfacial tension), 376 Pitzer model, 174, 179, PMMA - 3-octanone, 235 poly(butyl acrylate) (PBA), 65 poly(dimethylsiloxane)monomethylacrylate, PDMS-MA, 559, 570 poly(ethylene terephthalate, 594 poly(ethylene-co-1-hexene), EH, 42, 43, 48 poly(ethylene-co-butyl acrylate) (EBA), 64 poly(ethylene-co-methyl acrylate) in ammonia, 594 poly(ethylene-co-vinyl acetate) copolymers (EVA), 39, 42, 43, 48 poly(glycidyl methacrylate), 578 poly(hexamethylene carbonate) (ammonolysis, solubility), 600, 601 poly(methyl acrylate) (PMA), 64, poly(styrene-b-dimethylsiloxane) (PS-bPDMS), 532 polyamide (ammonolysis), 594, 597, 598, 607-616
640 polybutylene terephthalate (ammonolysis), 598 polycarbonate, 594, 595,600, 601,604606, 616 polydimethylsiloxane/polyhexylmethylsiloxane (PDMS/PHMS), 233 polydispers blends, 231 polyester (ammonolysis), 594-600, 616 polyethylene terephthalate (ammonolysis), 598 polymer solutions, 225 polymer systems (PC SAFT), 316 polymeric compound, 295 polymerization in a micro-emulsion, 538 polymerization in homogeneous fluid mixtures, 573-590 polymerization in supercritical carbon dioxide, 533-556 polymerization of poly(vinylpyrrolidone) (PVP), 533,548 polyoxyethylene sorbitan monooleate (Tween-80), 458 population balance, 437 power law (equation of state), 242, 243 Poynting-factor, 15, 16 precipitation by compressed antisolvents, PCA, 150, 431,449 Predictive Soave-Redlich Kwong (PSRK), 6, 283 Prigogine's rule, 47, 60 propagation rate coefficient, 574, 589 propane + 1-decanol, 6, 29 propane + dodecane, 6, 9, 28 propane, 42-46 pulsed laser initiated polymerization (PLP), 574 quadrupolar interaction, 295 radial distribution function, 299 Raman spectroscopy, 85-120 rapid expansion of supercritical solutions (RESS), 449-460 rate coefficients of polymerization, 573590 reaction rates in presence of SCF, 280 reactivity ratios for copolymerization, 574, 588-590 recovery of precious metals, 523-529 recycling of car windows, 606 Redlich-Kwong EoS, 211,219-221 Redlich-Kwong term, 218 Redlich-Kwong-Aspen EoS, 283
Redlich-Kwong-Soave EoS, 17, 151 - 161, 211,271 reference equations of state, 213,298 removal of impurities from ethanol+water mixtures, 495 repulsion term, 211,214-219 repulsive interactions, 297 residence time distribution (column), 477 response factors of flavor components, 503 RESS (rapid expansion of supercritical solutions), 148, 149, 159, 160, 323,373, 432, 449-460 retrograde solubility, 127, 140 Rh-chelate, 323 SAFT EoS, 39, 55-57, 65,285 SAFT-VR attraction term, 220 salicylic acid, 433 salting-out, 169 Schwarzentruber-Renon EoS, 283, Scott equation, 216 selectivity of carbon dioxide for flavor components, 511 self diffusion coefficient, 343-361 separation efficiency, 465-486 separation factor, 494-518 separation factors of alcohols to ethanol, 496, 497 SFC-apparatus, 128 silica aerogel, 381-426 silicidic acid, 384 silylation of starch, 609 silylation reaction, 608 simple fluid mixtures, 185-209 simplified equation of state, 211 single-droplet model (GAS), 432 sitosterol ([3-)- carbon dioxide, 451-460 size distribution, 565 size-exclusion chromatography, 574 sodium acetate, 163-171, 179-182 sodium chloride, 163-171,177, 179-183 sodiumdodecylsulfate (SDS), 458 sol-gel process, 413 solid solubilities (GAS), 438 solid-fluid phase diagram, 185-209 solubility correlations, 249, 253,260, 264 solubility isotherm, 127, 129, 139, 141, 143 solubility of ammonolysis products in ammonia, 597 solubility of chelates in carbon dioxide, 323 -340
641 solubility of polymers in ammonia, 597 solubility of solids, 121,122 solubility of solids, 15 solution enhanced dispersion by supercritical fluid, SEDS, 148, 431,449 solvation ~br PMA and PVAc in CO2, 579 solvatochromism, 122, 123,132, 135, 143, solvent power, 39 solvent regeneration, 506 soybean oil - hydrogen - carbon dioxide, 271-273,278 soybean oil - hydrogen - dimethyl ether, 271,276 soybean oil - hydrogen - propane, 271, 274-276 soybean oil, 271-279 spectrophotometric analysis, 128 spray extraction, 373 spray processin, 363,373,376 stabilization of nanoparticles, 457 standard fugacity, 16 static equilibrium apparatus, 149 static principle (for equilibrium measurement), 128 stripping section, 514 styrene, 573 sublimation, 127, 185-209 sulfur dioxide (supercritical), 523-529 sulfur dioxide preparation of complexes, 523-529 sulfur hexafluoride (SF6), 128 sulfur-dioxide ruthenium complexes, 524 Sulzer BX packing, 470 Sulzer CY packing, 489, 490, Sulzer EX packing, 489 supercritical anti-solvent (SAS), 148, 431, 449 supercritical aqueous solutions, 617-632 supercritical drying, 382, 386, 387, 391 supercritical fluid extraction (SFE), 489519 supercritical fluid reaction, 323 supercritical water (SCW), 617-632 surface tension, 489 surfactant, 375,376, 533 synthesis of silica aerogel, 390 termination rate coefficient, 574, 582, 585, 588 termination reaction, 574, 582, 590 terpenes, 491 tetraethylorthosilicate (TEOS), 384
tetrafnnctional siliconalkoxide precursor, 384 textile colorant, 128 textile dyeing, 122 thermodynamic fundamentals of fluids and solids, 185-209 thermogravimetric analyses (TGA), 525 TMOS, 390, 425 topnote fraction, 491 TPT1 approach, 223 translational molecular mobility, 351 Trebble-Bishnoi-Salim-EoS, 151 Tributylphosphate, 326 triglyceride ester, 269 triglycerides, 269 trimethylsilylation of starch in ammonia, 594 triple point, 124 tubular reactor (SCW), 619 turbidimetry, 559, 560, 564, 567, 570 UCST, 236 upper critical endpoint (UCEP), 124, 147, 148 upper critical solution temperature, UCST, 52 used catalyst, 523 UV/VIS, 128 van der Waals EoS, 211-240 van der Waals mixing rules, 151 van der Waals repulsion term, 214 van Konynenburg and Scott types of phase diagrams, 225 vapor pressure of the solid phase, 15, 16 variable volume cell, 66 view cell, 40, 41,152 vinyl acetate, 39, 42, 52-54, 59, 60, 63, 72 virial coefficient, 212-222 virial equation, 215 viscosity, 368,369, 376 VLE measurements, 1-340 volatile (non-electrolyte) organic component, 489-519 volume translated Peng-Robinson, 17 volume translation, 217 water - carbon dioxide (interfacial tension), 366, 376, 377 water + acetic acid, 177 water-phase, 490 wetting behaviour, 364, 366, 370-372, 376 wiremesh packing, 470-486
