Lloyd L. Handbook of Industrial Catalysts
Подождите немного. Документ загружается.
468 Chapter 11
11.3.2 VOC Oxidation Catalysts
The active component when treating hydrocarbons is usually high activity
platinum or palladium, at a concentration of about 0.3-0.5wt%. In the presence
of poisons or when oxidizing chlorinated hydrocarbons, catalysts such as copper
chromite promoted with barium oxide, may be used although a higher tempera-
ture is required and the concentration of chlorine compound should be less than
one volume percent. Details are given in Table 11.17.
42
Other supports, such as ion exchange resins impregnated with chromia or titania
can be used for the oxidation of halogenated hydrocarbons at temperatures
around 250°C. Properly operated, precious metal catalysts can have lives ex-
ceeding fifteen years even if regenerated at intervals to remove carbon or dust
deposits. Base metal catalysts can only operate for shorter periods of a few years
before being replaced and can be deactivated at temperatures between 500°–
700°C.
TABLE 11.17. Volatile Organic Compound Oxidation Catalysts.
Catalyst
Platinum Impregnated 0.3–0.5wt%
Support Alumina shapes or cordierite/metal monolith
with alumina washcoat.
Regeneration
Thermal at 400°–500°C or physical removal
of dust.
Life Longer than 15 years in good conditions.
Operation
250°–350°C
Space velocity 40,000–100,000 h
-1
typical
Conversion Almost 100%
Copper chromite Precipitated
Promoter Barium oxide
Life ~2 years
Operation
Up to 450°C
The most active catalysts are derived from supported platinum group metals, or
copper chromite when the VOC contains chlorine. The catalyst supports are
produced as high surface area gamma-alumina spheres, extrudates or cylindrical
pellets that can be used in dust free conditions. Alternatively, when treating
large volumes of effluent gas, honeycomb monoliths made from cordierite or
metal sheets are coated with a surface washcoat of the same alumina are
particularly useful. The supports are selected to be stable at the operating
temperature of the reaction.
Environmental Catalysts 469
REFERENCES
1. Nebel and Wright, Environmental Science (7
th
edition), Prentice Hall, NJ,
2000.
2. L R Raber, Chem. Eng. News (April 14 1997) 12.
3. EPA Toxic Release Inventory: reported C & EN, (April 3 1995) 4; C & EN,
(July 15 1996) 29.
4. Worldwide Refining Survey, Oil Gas Journal, (Dec 18 2000).
5. Haldor Topsøe, SNOX Process Leaflet, 8.94; Topsøe Topics (July 1992).
6. Garten, Dalla Betta, Schlatter, Catalytic Combustion, Ed. by Ertl, p. 1668;
Millard & Bowman, Prog. Energy Combustion Science, 15 (1989) 287.
7. Stambler et al, Gas Turbine World, (1993) 32.
8. Power Generation, Hydrocarbon Processing, (Sept 2000) 27.
9. Inui et al., Catalysis Today, 10 (1991) 1.
10. Spitznagel et al., Environmental Catalysis, Ed. by Armor, ACS Symposium
Series 552, 250
th
National Meeting, Denver, Colorado, 1994, p. 172.
11. J N Armor, Appl Catal 1 (1992) 221; Chem. Mat. 6 (1994) 730; H. Bosch
and F. J. Janssen, Catal. Today 2 (1987) 369; F. J. Janssen, Catal Today 16
(1993) 155.
12. Norton Chemical Processes (St. Gobain NorPro. Chem. Corpn.) Literature
(1991); L. B. Sand, Chem. Ind. (1968) 71.
13. Heck et al., Environmental Catalysis, Ed. by Armor, ACS Symposium Se-
ries 552, 250
th
National Meeting, Denver, Colorado, 1994, p. 215.
14. Lowe and Ellison, Environmental Catalysis, Ed. by Armor, ACS Symposi-
um Series 552, 250
th
National Meeting, Denver, Colorado, 1994, p. 190.
15. Janssen, Environmental Catalysts – Stationary Sources, in Handbook of
Heterogeneous Catalysis Vol. 4, Ed. by G. Ertl, H. Knozinger and J.
Weitkamp, VCH Weinheim, 1997, p. 1633.
16. G. Bond, J. Cat, 116 (1989) 531.
17. Haldor Topsøe, WSA Process Leaflet, 1.94.
18. Snyder et al., 85
th
Annual Meeting & Exhibition, Kansas City, Missouri
(June 21-26, 1992) 2.
19. KTI/Shell DeNOX, Gas Turbine World, (July/Aug 1997).
20.
Oil Gas Journal,
1998) 76.
21. Furuya et al., Proc 2
nd
Int Workshop on Catalytic Combustion, Tokyo, Ed.
by H. Arad, 1994, p. 162.
22. Rollbuhler, Paper A1AA-91-2463, 27
th
Jet Propulsion Conf., Sacramento,
California, 1991.
23. Catalytic
Combustion, p. 1668; Avai, Bull.
Chem. Soc. Japan 61 (1988) 3659.
24. Cohn, Steele, Anderson, USP 2975025 (1961).
25. CRI/KTI, Shell DeNOX System Literature (1999).
J C Solt and J C Schlatter, Xonon Catalytic Process,
M Machida, H Eguchi and H Arai, Garton, Dalla Betta, Schlatter,
(April 6,
470 Chapter 11
26. M Iwamoto in Future Opportunities in Catalytic and Separation Technolo-
gy, Ed. by M. Misono, Y. Moro-oka and S. Krinura, Elsevier, Amsterdam,
1990, p. 121; Environmental Catalysis, Ed. by J. N. Armor, ACS Symposi-
um Series 552,205
th
National Meeting, Denver, Colorado, 1994.
27. Manahan and Stanley, General & Applied Chemistry, 2
nd
Ed., William
Grant Press, Boston, 1982, p. 381.
28. Haagen-Smit and Fox, Ind. Eng. Chem., 48 (1956) 1484.
29. Acres and Cooper, Plat. Metals Rev., 16(3) (1972) 74; M. V. Twigg (Ibid),
43(4) (1999) 168.
30. Summers et al., Ind. Eng. Chem. Research & Development, 11 (1972) 2;
Barnes, Advances in Chemistry Series 143, Washington DC (1975).
31. Acres British Pat. 1390182 (1971); US Pat. 3951860 (1976).
32. M. V. Twigg, personal communication; E. S. J. Lox and B. T. Engler, in
Handbook of Heterogeneous Catalysis 4, 1559, Ed by G. Ertl, Knozinger
and Weitkamp, VCH Weinheim (1997).
33. (Jan 25, 1999) 36.
34. J. M. Thomas and W. J. Thomas, Principles and Practice of Heterogeneous
Catalysis, VCH Publishers Inc, NY and Weinheim, Germany, 1997, p. 578.
35.
36. University of Texas, SW Research Inst., New Scientist, (Feb 3, 2001) 19.
37. H C Kung et al., J. Catal. 181 (1999) 1.
38. Hawker, Platinum Metals Review, 39 (1995) 2; Cook and Roth, Plat. Metal
Rev. 39 (1995) 178; US Pat. 4902478.
39. Spivey, Ind. Eng. Chem. Research, 26 (1987) 2165; Jennings et al., Catalyt-
ic Incineration for Control of VOC Emissions, Noyes, N.Y., 1985.
40. Catalytic Control of VOC Emissions, Manufacturers of Emissions Control
Association (MECA), 1707 L Street NW, Washington DC, Suite 5701,
1992.
41. Johnson Matthey and Haldor Topsøe catalyst literature.
42. C & EN, (Sept 7 1992) 34; Drago et al., Environmental Catalysis, Ed. by
Armor, ACS Symposium Series 552, 250
th
National Meeting, Denver, Colo-
rado, 1994, p. 341; Gervasini et al., Environmental Catalysis, Ed. by Armor
ed., ACS Symposium Series 552, 250
th
National Meeting, Denver, Colora-
do, 1994, p. 353; Haldor Topsøe, Catalytic Combustion Technology for Air
Purification, (10/96) and Regenox Process (9/90).
M Jacoby, C and EN
E S J Lox and B T Engler, Environmental Catalysis - Mobile Sources, p 1559
in Handbook of Heterogeneous Catalysis 4, eds G Ertl, H Knozinger and
J Weitkamp, VCH Weinheim (1997).
INDEX
L. Lloyd, Handbook of Industrial Catalysts, Fundamental and Applied Catalysis,
DOI 10.1007/978-0-387-49962-8, © Springer Science+Business Media, LLC 2011
471
A
Acetaldehyde
catalytica process, 303
Hoechst process, 303
palladium/copper catalysts,
303
Wacker process, 303
Acetic acid
acetaldehyde oxidation, 301
catalysts, 285, 294
methanol carbonylation, 302
operating conditions, 301
Acetone
Hock and Lang process, 266
isopropanol, 265
Acetylene, selective hydrogenation,
102–114
Acid catalysts
acid resins, 265
acid sites, 221
phosphoric acid/silica, 267
silica alumina, 267
zeolites, 267
Acid sites. See Fluid catalytic
cracking (FCC); Zeolite catalysts
Acrolein/acrylonitrile
acrylonitrile, 156–157
bismuth phosphomolybdate,
157, 158
catalyst life
structure, 158, 161
fluid bed process, 157
multi component catalyst, 157
propylene oxidation, 157
reaction mechanism, 159–161
Sohio process, 157–159, 161
Acrylic acid, mixed oxide catalysts,
161–162
Acrylonitrile, 4, 155, 157–160, 264,
466, 467
Active sites, 6, 7, 12, 48, 159–161,
189–190, 221, 225, 251, 252,
315, 320, 325–327, 339, 341,
344, 412, 418, 431, 432, 447,
448
Activity testing, 15–18
Adkins catalyst, 12
Air/fuel ratio
basic catalyst systems, 454
catalyst cycles, 453
exhaust gas composition, 453, 454
impurity removal, 454
photochemical smog, 452
precious metal catalysts, 452
three way catalysts, 453, 454
λ value, 453
Alkylation
liquid acid processes, 219
operating conditions, 220
production in USA, 218
reaction mechanism, 219–220
solid acid processes, 221
Alumina, 3, 45, 78, 142, 170, 215,
270, 313, 360, 397, 456
Ammonia oxidation
catalyst operation, 128–130
Kuhlmann discovery, 3, 120
modern process, 51
non platinum catalysts, 120
Ostwald process, 121
platinum catalysts, 120
platinum recovery, 131
Index
472
platinum/rhodium gauge, 128,
131
Sir William Crookes, 49–50
Ammonia synthesis (1905–50)
Carl Bosch/Alwin Mittasch, 52
catalyst development, 180–184
catalyst types, 355, 356
commercial application, 52
early investigation, 52
Haber/Bosch reactor, 53–54
Haber process, 412
nitrogen problem, 49
operating conditions, 52
process development, 353–354
Sir William Crookes, 49–50
Ammonia synthesis (1960–2000)
catalysts
iron/cobalt, 418
loading/discharge, 408
pre 1950, 397, 398
production, 426–430
promoters, 52, 397
properties, 251
reduction mechanism,
409–412
ruthenium, 419–421
low pressure process, 426
new catalyst development,
417–421
processes
converters, 414–416
loop design, 412–414
Swedish magnetite, 398, 401
wartime developments, 353
Ammonia synthesis gas
active carbon, 357
catalysts used, 354, 356
chlorine compounds, 375
hydrocarbon impurities, 357
hydrodesulphurization, 358–360
hydrogen sulphide, 356–358,
360–362, 377, 378
sulphur absorbent, 356, 363
zinc oxide, 354, 357, 358,
360–363
Ammoxidation. See Acrylonitrile
Amoco polyethylene process, 292,
313
Andrussov process
catalyst supports, 139
methane ammoxidation, 138
methylmethacrylate, 137
platinum/rhodium catalysts,
138–139
Aromatics
aromatics process, 254–255
cyclar process, 255
M2-forming process, 255
Automobile emission catalysts
bead catalysts, 456
catalyst combinations
formulations, 458
operation, 460–462
poisons, 459
diesel engines, 464–465
exhaust purification, 453
honeycomb washcoat, 457–458
mobile sources, 452–465
monoliths, 456–457
NO
x
level/leanburn engines,
463–464
operating temperature, 457, 458
oxide traps, 463
platinum group metals, 458–459
position of catalyst, 461
possible improvement, 457–458
precious metal demand, 452
reducing NOX emission, 453
473
Index
Automobile emission standards
emission control, 452
Autothermal reforming, 69, 393–395
B
Benzene
hydrogenation, 100–101
maleic anhydride, 144–150
oxidation, 119, 144, 145
styrene, 279
Benzene toluene xylene (BTX), 112
Bimetallic catalyst
catalytic reforming, 245, 248
Bismuth molybdate
SOHIO process, 157, 161
Bisphenol-A
ion exchange resins, 266
BrunauerEmmett-Teller (BET)
method
Butadiene
dehydrogenation catalysts, 105
Lebedev process, 274
oxidative dehydrogenation,
162–163, 277
synthetic rubber, 273–283
Butane/butene
maleic anhydride production,
144–146
C
Carbon
Conradson, 179, 198–200, 206,
208, 224, 229
deposition, 19, 20, 99, 138, 170,
222, 248, 275, 276, 278, 282,
283, 293, 354, 362, 370, 372,
391
fluid catalytic cracking, 149
steam reforming, 363
supports, 10, 357, 419
Carbonylation, 161, 286, 297–303
Catalysts
activation, 420
activity, 6, 11, 17, 34, 35, 48,
60, 87, 90, 106, 108, 137,
139, 140, 156, 173, 177, 184,
201, 214, 225, 229, 237, 242,
253, 256, 283, 314, 317, 323,
325, 330, 373, 399, 407, 419,
420, 422, 430, 431
analysis, 11, 15, 83, 405
composition, 16, 37, 85, 86,
92, 105, 137, 154, 158,
190, 247, 269, 272, 279,
355, 370, 371, 384, 423,
446, 447
definition, 5
development
acid treated bentonites, 181
Augene Houdry, 170, 175,
180
clay catalysts, 170
FCC catalysts, 190, 197,
201–203
kaolin-insitu catalysts, 175
need forgasoline, 180
silica alumina production,
180
synthetic silica alumina, 182
matrix
binders, 191
diluents/heat sink, 191
matrix evolution, 191–192
modifiers
alumina/zirconia, 327
cocatalysts, 327–328
fluorides, 327
organo chromium catalysts,
474
Index
328–329
polymer molecular weight,
325
titania, 326
operation
commissioning, 18
life, 18
problems, 18
processes/development, 19–20
reactor design, 18
pioneers, 21, 304
poisons, 41, 52, 54, 96, 177,
233, 272, 381, 387, 440, 444,
459, 460
preparation, 14, 36–37, 41, 63,
64, 76, 86, 107, 236–237,
315, 319, 320, 322, 419–420,
431
production
application, 8
fusion, 8
impregnation, 13
metals, 8
precipitation, 12
preparation, 8, 10
specification, 10, 11
supports, 10
promoters, 52, 145, 397, 406
properties, 5, 132, 178, 247, 251
reduction, 15, 55, 64, 150, 163,
253, 324, 378, 387, 407,
409–412, 433–434, 445–449
selectivity regeneration, 7, 17,
93–94, 104, 107, 112, 114,
257, 281, 283, 445
shapes, 4, 35, 63, 93, 226, 227,
355, 356, 367, 370, 371, 373,
445
specification, 214, 225, 316
stability, 7
strength, 8
supports, 11, 14, 29, 31, 55, 63,
92, 105, 157, 161, 222, 232,
236, 238, 257, 268, 269, 273,
275, 278, 304, 325, 422, 447,
449, 468
testing, 14–18, 52, 426
activity, 15–18
composition, 14–15
physical properties, 14
structural analysis, 16–17
typical, 225
Catalytic coke (FCC), 200
Catalytic cracking (Fluid)
catalyst replacement, 177, 201
catalysts/regeneration, 175–176
deactivation/regeneration, 173
equilibrium catalyst, 177–178
fixed bed operation (1935), 170
fluidized beds (1942), 171–174
importance, 193
moving beds (1941), 169
operating cycle, 204
pevamping units, 174
zeolite catalysts (1961), 184–192
Catalytic dewaxing, 255–256
Catalytic oxidation processes, 119,
120, 440, 465
Catalytic reforming
bimetallic catalysts, 248–250
carbon burn, 252
catalyst life, 253
catalyst preparation
reduction, 253
regeneration, 251–252
chlorine infeed, 246
coke formation, 246–247
continuous catalyst
475
Index
regeneration, 245
cyclic reforming/fixed beds, 242
early catalyst, 240
effect of sulphur, 238
hydrogen production, 246
oxychlorination, 252
Catalytic rich gas process
coal gasification, 388
operating conditions, 389
substitute natural gas, 388
Chrome–alumina catalysts
butadiene, 275
butane/butenes, 275–277
dehydrogenation, 277
Coal hydrogenation
Bergius process/IGfarben,
55–56
creosote, 57
ICI, 56–57
Cobalt catalysts
Fischer Tropsch, 297
hydrodesulphurization,
297, 298
Conradson carbon, 179, 198–200,
206, 208, 224, 229
Contact process, 3, 10, 23, 27,
29–35, 37, 120, 402, 440, 448
Cumene
acetone/phenol, 266
benzene alkylation, 266
high octane aviation fuel,
266–267
Hock and Lang process, 266
operating conditions, 267
production, 266–267
strong acid catalyst, 267
Cyclar process
hydrodecyclisation, 255
LPG to aromatics, 255
D
Deacon process
catalyst preparation, 41
cyclic reaction, 40
feed purification, 43
liquid catalyst, 41
process/catalyst design, 40
vinyl chloride, 270
Deactivation, 5, 7, 10, 14, 19, 20,
22, 37, 43, 45, 48, 64, 83, 87,
88, 99, 101, 128, 154, 173, 176,
177, 180, 198, 199, 201–203,
205, 224, 230, 234, 236, 238,
246, 248, 251, 267, 281, 293,
305, 318, 330, 339, 367, 372,
381, 385, 387, 424
Dehydrogenation, 5, 6, 87, 88, 98,
131, 132, 136, 145, 162–163,
179, 199, 202, 203, 214, 215,
232, 238, 240, 243, 246, 255,
257, 262, 263, 265, 266, 273–
283, 290, 421
Diatomaceous earth. See Kieselguhr
Differential thermal analysis (DTA),
14, 16, 202
Direct iron ore reduction, 391
E
Edible oils, 89, 90
Electron microscope, 16, 130, 148,
321
Electron probe analysis, 14
Environmental catalysts
atmospheric pollution, 439
catalytic combustion
nitric acid effluent, 449–450
nitric oxide removal, 450–451
catalytic converters/exhaust
system, 439, 440, 454, 463
476
Index
chemical emissions (1993), 441
clean air acts (1956/75/90), 439,
440, 445, 465
emission control, 452–459
gaseous emissions (1995), 440
gas turbine emissions, 449–450
operating conditions, 446
reaction mechanism, 447–448
SCR catalysts
development, 445–446
reactions, 447–448
sulphur dioxide removal,
448–449
selective catalytic reduction
catalyst operation, poison, 447
stationary sources
formation/sources of NOX,
441
industrial NOX/SOX,
441–443
Ethyl benzene
dehydrogenation to styrene, 280,
283
styrene/shell, 281
Ethylene derivatives
acetaldehyde, 303
ethylene dichloride, 268, 269
ethylene oxide, 150–155
high density polyethylene, 313
linear low density polyethylene,
319, 322, 327, 329
low density polyethylene, 313,
329
styrene, 278–283
vinyl chloride, 267–273
Ethylene oxide
air oxygen process, 151
catalyst, 152–153
direct oxidation, 150
operation/reaction mechanism,
153–154
tubular reactors, 151
EVA process, 389
F
Fat hardening catalysts
catalyst operation
poisons, 92, 96
prereduction, 12, 55, 67, 81
producers, 92
production, 20, 92, 93, 95
selectivity, 19, 93–96
composition, 92, 93, 95
selective poisoning, 96
Fat hydrogenation processes
catalyst supports, 92
fatty acids, 90, 91, 93, 94, 96
hydrogenation process, 92, 93
nickel oxide catalysts, 90
oil hydrogenation, 90, 91
Raney nickel, 90, 93
vegetable oils, 90, 91, 94–96
Fatty acid hydrogenation
natural fatty alcohols, 97–98
synthetic fatty alcohols, 97
Faujacite structure
X and Y zeolites, 185
Feitknecht compounds, 84, 85,
431
First generation, 317
Fischer Tropsch process
catalysts, 13, 63–69, 297, 380,
421
gas to liquids, 68–69
process operation, 64, 66–68
Roelen catalysts, 64, 297
Sasol processes, 63, 65–69, 149
synthol process, 63, 65–69, 149
477
Index
wartime plants, 65, 66
Fluid catalytic cracking (FCC). See
Catalytic cracking
Formaldehyde
Adkin’s mixed oxide catalyst,
132
commercial development, 131,
132
copper/silver catalysts, 132, 136
ignition pellet, 132
methanol flameless combustion,
131
modern catalyst, 137
platinum catalyst, 131, 132, 138,
139
Fourth generation
catalysts, 321–322
controlled size/shape, 321
electron donors
external, 321
internal, 321
high isotactic index, 321
polymer particle size, 321, 322
Friedel Craft. See Alkylation
G
Gasoline fractions/catalytic
processes, 222
Gradient temperature profile, 367
Guard/spare reactors, 21, 96,
104–106, 108, 111, 275
H
Hock and Lang process
cumene production, 266–267
Hopcalite catalysts
carbon monoxide oxidation,
139–140
multicomponent catalysts, 140
use in gas masks, 139
Hydrocracking
acid catalyst supports, 232,
235–236
catalysts, 231–237
regeneration, 224, 231, 237
development, 231
heavy gas oil conversion, 231,
233
processes, single/double stage,
233–234
Hydroformylation/oxosynthesis
catalyst recovery, 298
cobalt carbonyl catalyst, 297–298
cobalt catalyst ligands, 299
commercial operation, 301
development/Roelen, 297
high pressure operation, 297, 301
low pressure operation, 300–301
phosphine modification,
298–299
reaction mechanism, 298, 302
rhodium catalyst operation, 299
rhodium catalysts/ligands,
300–302
two phase process, 300
Hydrogenation catalysts
Adams catalyst
development, 78
coal/creosote
early work, 59
wartime operation, 62
copper catalysts
Adkin, 80
copper chromite, 85, 86
copper/zinc oxides, 86–88
Feitknecht compound, 84, 85
food production, 90, 93
green rusts, 84