Lloyd L. Handbook of Industrial Catalysts

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478

Index

industrial application, 75, 77

Ipatieff, 75–77

iso octane, 81

Kieselguhr supports, 75, 80–84,

92, 99, 101

nickel oxide, 73, 75, 79–85, 90,

99–101, 103, 105–106, 113

Paal/precious metals, 76, 77

platinum black, 74, 77

prereduction, 81

Raney nickel, 78–80, 90, 93

Sabatier/coworkers, 73–77, 80,

89, 90, 100

Willstatter, 76–78

Hydrogen production, 356, 390–391

Hydrotreating

catalyst development

activation, 222, 227–228

composition, 226, 227

handling, 225–227

operation, 222–225, 228, 229

production, 224–225

reactions, 223–225, 229, 230

regeneration, 222, 224, 225,

227, 229–231

Imperial chemical industries

Impregnation, 5, 8, 10, 11, 13, 236,

251, 322, 327, 329, 387, 419,

456, 462

Industrial catalysts

development (1740–1923), 1, 3,

4, 15, 17, 22, 52, 54, 140

importance, 4, 15

processes, 1–8, 10, 14–22, 51, 74

properties, 5, 10–12, 14, 15, 37

quality control, 78, 80

shapes, 4, 11, 16, 75

supports, 2, 5, 8, 10, 13

Intercooling

exothermic processes

acetylene hydrogenation, 108

ammonia synthesis, 352, 407,

410, 414

methanol synthesis, 421, 423,

433

Iridium, catalytic reforming, 247,

249

Iron catalysts

ammonia synthesis, 51, 52, 63,

65, 377, 404

Fischer Tropsch process, 63–65,

67, 69

Iron molybdate, 138

water gas shift catalysis, 42

Isomerization

aluminium chloride, 287

dualfunction catalysts, 257

isomerization catalysts, 256–257

limitations catalytic reforming,

246, 248

mordenite supports, 257

octane number C5/C6

hydrocarbons, 256

operating conditions, 94, 95,

197, 256, 257

reaction mechanism, 179,

257–258

recycle, 100, 256, 257, 306

Isopropanol/acetone

copperoxide/zinc oxide catalyst,

88, 265–266

isopropanol

dehydrogenation/acetone, 88

methylethyl ketone, 266

propylene hydration, 265

Isopropylbenzene. See Cumene

479

Index

Kieselguhr

catalyst support, 75, 80–84, 92,

99, 101

Lead chamber process, 1, 24–29,

121

Lean town gas, 390

Low pressure methanol processes

Lurgi, 426, 428

Topsoe, 426, 428

Low pressure polyethylene

Amoco medium pressure

process, 313

Aufbau reaction, 313

catalysts used, 313

high density polyethylene

(HDPE), 313

low density polyethylene

(LDPE), 313

Mulheim atmospheric

polyethylene, 313

Natta polypropylene process,

314

Phillips medium pressure

process, 313

process development, 313

Ziegler polyethylene process,

313, 314

Maleic anhydride

benzene feed, 144, 148

catalyst developments

recipe, 158

circulating fluidized bed,

149–150

fluid bed reactors, 148, 149

mixed oxide catalyst, 144–146

n-butane feed, 148–149

operating conditions, 146, 149,

150

reaction mechanism, 138, 140,

153–154, 157, 159–161

reactor types, 145, 146, 148, 149

selectivity, 146

state of catalyst

novel precipitation, 146

operation, 145, 146, 148

Mars and Van Krevelen, 140, 146,

149, 155–156

Metallocenes

ANSA metallocenes, 336

catalyst structure, 336–338

cationic complex, 335, 338, 340

early investigation, 335–338

effects of bridge, 334, 336–338

gradual introduction, 334

methyl aluminoxane, 334–336,

338

single site catalyst, 334–341

soluble/supported catalyst, 336,

337

stereospecificity, 336, 337, 340

Metallocenes/operation

catalyst activators, 338–339

molecular weight control,

339–340

new catalysts, 340–341

non-coordinating anions,

336–340

operating costs, 334, 338

Metathesis of olefins

catalyst development

regeneration, 305

catalysts

chromium, 304

480

Index

regeneration, 305

chromium polymerization, 304

feed purification, 305

olefin disproportionation

Phillips (1964), 304

process development, 304–305

propylene production, 305

triolefin process, 304

Methanation

catalyst composition

poisons, 387

operating conditions, 386–387

reduction, 387

synthesis loop protection, 385

Methanol oxidation

catalysts

iron molybdate, 120, 132

silver, 120, 136

formaldehyde, 3, 13, 19, 120,

131, 132

Methanol synthesis

copper oxide catalysts

ICI developments, 426

novel precipitation, 430

operating conditions, 426

poison free synthesis gas, 425

reaction mechanism, 432

reactor types, 433

high pressure process

BASF developments, 421, 422

byproduct formation, 430

catalyst preparation, 422

converter design, 433

operating conditions, 423–425

reduction of CrO

, 423

surface area, 422, 424, 425

Zno/CrO catalysts, 426

low pressure process

basic copper/zinc carbonate,

430

byproduct formation, 430

catalyst production, 426, 428,

430

converter design, 428, 429

reduction, 430, 431, 433–434

Methyl tertiary butyl ether (MTBE),

197, 207, 208, 212, 219, 258,

264, 305

Mobile sources, 451–465

Natta violet Ticl

commercial catalysts, 316

particle size/production, 316

precipitation/grinding, 315

stereospecific x-Ticl, 315, 316

titanium trichloride, 316–317

Nickel catalysts, 64, 75, 77–80, 83,

84, 86, 90, 91, 93, 96, 97, 100,

103, 105, 111, 114, 211, 223,

232, 237, 285, 291, 340, 353,

354, 365, 374

Nitric acid. See Ammonia oxidation

Nylon 6

benzoic acid hydrogenation, 291

butadiene to HMD, 292

ε–caprolactam, 289, 291, 292

catalysts, 289–291

cyclohexanol dehydrogenation,

289, 290

cyclohexanone oxime

conversion to lactam, 291–292

DSM process, 290–292

phenol hydrogenation, 289, 290

polycaprolactam/perlonL, 289

Schleck/Farben, I.G., 289

SNIA Viscosa process, 291

sulphate byproduct, 290

481

Index

toluene oxidation, 290, 291

Nylon 66

adipic acid, 285

adiponitrile, 286–288, 292

benzene/cyclohexane, 285, 286

carothers/DuPont, 284

catalysts, 285–288

cyclohexane oxidation, 284, 285

hexamethalene diamine, 284,

286–288

K/A oil, 285

nylon intermediates, 285

nylon polymer, 288–289

nylon salt, 287–289

phenol hydrogenation, 286

Octane boosting

M-forming, 254

selectoforming, 253–254

shape selective reactions, 253

Octane catalysts, 175, 187, 199, 206

catalyst inventory change, 197

catalyst use 1970s, 192

center cracking, 197

chemical dealumination, 195–196

clean air act (1970s), 192

defect sites, 195

higher olefin content, 196

hydrothermal dealumination,

193–195

increased aromatics, 196

increased octane, 192, 196, 197

metal impurities, 198

MTBE/TAME, 197

octane-barrel catalysts, 196

octane dip, 192

operating changes, 197

shape selective cracking, 197–198

silica/alumina ratio, 193, 195, 196

ultra stable Y-zeolite, 193–196

zeolite catalyst, 192, 193, 196

ZSM-co-catalyst, 197

Olefin metathesis, 304–306

Olefin polymerization

catalytic polymerization, 311

high pressure polymerization,

313, 329

polyolefin production, 311, 312,

331

world demand, 318

Oxchlorination (Deacon process), 3,

10, 39–41, 119, 270

Oxidation catalysts

active sites, 159–161, 447

development, 121, 128, 132,

139–141, 151, 155, 156

lattice oxygen, 140, 146, 149,

156, 160

Mars and Van Krevelen, 140,

146, 149, 155–156

mixed oxides, 123, 132,

136–137, 139, 140, 143, 144,

146, 155–159, 162

redox mechanism, 143, 149,

156, 163

Oxidative dehydrogenation

butadiene production, 277

Oxydative ammonolysis

ammoxidation, 120, 159–161,

287, 290

Palladium catalysts

acetylene hydrogenation, 103,

104, 106, 107

automobile exhaust emissions,

452

482

Index

Wacker process, 303

Paraxylene

from catalytic reformers, 293

m-xylene isomerization,

294

steam crackers, 304

isomerization catalysts, 293

terephthalic acid, 293

xylenes separation, 293

Partial oxidation of propane

acrylic acid, 161–162

isobutene oxidation, 162

Perspex, 137, 138

Petrochemical catalysts

coal/refinery off gas, 261

cracking processes, 180, 262

development, 261–273

ethylene production, 262, 268,

269, 271, 279, 281

Mellon institute/gulfoil, 262

miracle decade, 262–263

petrochemicals from naphtha,

263, 264

Shell chemical company, 262

Union Carbide/Linde, 262

Universal oil products, 262

wartime developments (1939–

45), 273

Phillips polyethylene catalysts

active centres, 323–324

catalyst activation

composition, 325

development, 325

discovery, 322

formulation, 323

operation, 324–325

chain growth/termination, 325

effect of activation, 324

fragmentation of support, 325

gas phase processes, 323, 333

physical properties, 333

prereduction, 324

silyl chromates, 326

solution/slurry processes, 324

Phthalic anhydride

catalyst developments, 140

operating conditions, 141

redox mechanism, 143

titania supports, 143

tubular reactors, 141

US developments, 141

catalysts, 143

o-xylene oxidation, 142–143

Platinum

ammonia oxidation, 120, 132

Andrussov/HCN, 137–139

automobile catalysts, 455,

458–459

catalytic reforming, 238–239

Platinum dispersal, 252

Poisoning

auto catalysts, 458

catalytic reforming, 238

HT/LT shift catalysts, 370

steam reforming, 354

Polyesters

catalysts/operations, 293

ethylene glycol, 292

first production, 292

para xylene, use of aromatics

air oxidation, 293–294

terephthalic acid methylester,

294–296

Whinfield and Dickson, 292

Polyethylene

catalysts development, 314

ICI low density polyethylene,

313

483

Index

Karl Ziegler, 314–322

low pressure, 312–314

Phillips petroleum, 322–329

Standard oil Indiana, 313

supported catalysts, 313, 319–

320

Polymer gasoline

butane dehydrogenation, 214,

215

butylbenzene/cumene, 216

highoctane gasoline, 213

isobutylene polymerization, 215,

216

phosphoric acid/kieselguhr, 214

polymer gasoline process, 214,

215

Polymerization processes

autoclares/stirring, 332

commercial processes, 329

comonomer (LLDPE), 329, 330,

332

feed introduction-bottom, 330,

333

fluidized bed, 330, 333

gas phase processes, 333

high pressure (LDPE), 329

loop reactor/circulation, 332

low pressure (HDPE), 329

operating conditions, 332

polymer grades, 332, 333

polymer production, 332

reactor design, 330

residence time, 330, 332, 333

slurry processes, 330, 332, 333

solution processes, 330, 332–333

Polyolefin molecular structure

cocatalyst, 341

commercial polyolefins, 345

Cossee–Ariman mechanism, 341

formation of polypropylene

chains

polymer chain termination,

342–344

β-hydrogen abstraction, 342–344

metal alkyls, 343

molecular hydrogen, 343, 344

polymer chain length

structures defined, 344

proton donors, 344

single site catalysts, 341

uniform active sites, 341

vacant sites/γ complexes, 342

Polypropylene

development, 277, 314

Guilio Natta, 314

supported catalysts, 320

α-titanium trichloride, 314, 318

Precipitation, 5, 8–14, 63, 65,

76, 81, 84, 92, 93, 99, 137,

205, 266, 321, 322, 329, 354,

384, 387, 399, 418, 422, 423, 430

Prereduction ammonium synthesis

catalyst, 13, 55, 357, 398, 406–

408, 410

Process/catalyst development

carbon monoxide combustion,

175–176

catalyst

age distribution, 177

deactivation, 7, 180, 181, 201,

344

inventory, 173, 177, 178, 197,

198, 203

regeneration, 175–176, 221

replacement, 177, 197

cracking reactions, 170, 175,

178–179, 186

equilibrium catalyst testing,

484

Index

177–178, 201–203, 208

operating conditions, 170, 173,

176, 178, 179, 182

reaction mechanism, 178–179

trouble shooting, 178

Propylene

acrolein, 120, 155–158, 160, 162

acrylic acid, 120, 162, 466

acrylonitrile, 120, 157, 159–161,

264, 287

derivatives

acrylic acid, 120, 162

acrylonitrile, 120, 157–161,

287

polypropylene, 264, 277, 311,

314, 316, 336, 341–343

Pyrolysis gasoline

catalyst

composition, 112

operation, 114

types, 113

selective hydrogenation, 112–114

Quench cooling

ammonia synthesis, 400, 414

methanol synthesis, 424, 433

Raney nickel, 5, 6, 13, 78–80, 90,

93, 266, 285

Reactors

adiabatic, 20, 66, 88, 104, 141,

215, 275, 276, 279, 282, 373,

374, 392

fixed bed, 14, 65–67, 162, 170,

215, 271, 279, 285

fluid bed, 20, 66–68, 148, 149,

158, 159, 272

tubular, 14, 19, 32, 65–68, 88,

99, 100, 108, 141–143, 145,

146, 151, 162, 215, 271, 275,

276, 279, 282, 330, 371, 389,

428

Redox oxidation, 155–156

Reduction, 11, 15, 16, 20, 21, 32,

36, 39, 40, 55, 64, 67, 77,

81–83, 85, 87, 90, 92, 93,

99–101, 130, 150, 163, 184,

198, 202, 205–207, 223, 229,

237, 238, 249–253, 273, 282,

283, 290, 293, 295, 302, 315,

317, 318, 324–326, 329, 338,

339, 371, 376, 378, 381, 382,

387, 391, 398, 399, 403, 406,

407, 409–412, 418, 420–422,

424, 430, 431, 433, 440–444,

447–451, 453, 455, 458, 462,

463, 466

Refinery catalysts

alkylation, 212–214, 216–221,

254, 258

distillate conversion, 236

gasoline pool, 211, 212

octane number, 211, 212, 215,

238, 248, 253, 254, 256

polymerization, 212–216, 246,

257

thermal cracking, 211, 212, 214,

222, 255

treatment of crude oil, 211, 212,

222

Reformer operation, 240–246,

371–374

Reforming

catalysts

reactions, 243, 363

severity, 242, 246

485

Index

catalytic, 4, 19, 58, 69, 212,

221–223, 238–254, 256, 305,

354, 356, 362–364, 369–371,

374, 375, 387

steam, 3, 4, 58, 64, 68, 69, 85,

222, 223, 353–358, 360,

362–375, 379, 389–395, 412,

425–427

Residue additives

antimony, 202

bottoms cracking, 206

Clean Air Act (1970), 206

effect of sodium, 201

external demetallizing, 201, 203

FCC unit upgrading, 206

heavy cycle oil cracking, 204,

206

improved gasoline, 206

MTBE, 208

nickel additives, 201–202

nickel dehydrogenation, 202

rare earth oxides, 203, 206

reformulated gasoline, 204

Sox limits, 204

sulphur additives, 201, 203–206

sulphur in products, 201, 204

sulphur oxides (SOX), 203–206

vanadium dehydrogenation, 202,

203

vanadium traps, 201, 203, 206

zeolite deactivation, 202, 203,

205

Residue catalysts

catalyst/oil coke, 200

catalytic coke, 200

coke distribution, 200

coke yield, 199, 200

conradson carbon, 198–200

contaminant coke, 199, 200

delta coke, 200

feed coke, 200

increased zeolite content, 199,

200

use of additives, 198, 199

Rhenium

bimetallic catalysts, 239, 248,

249, 251

catalytic reforming, 247–249, 251

Rhodium

ammonia oxidation, 13, 123, 124

automobile exhaust treatment,

453, 458

Second generation

commercial catalysts, 317

electron donors, 317, 318

Lewis base addition, 317

linear low density PE, 319

magnesium supports, 319

nodular catalyst, 319

spherical particles, 318

supported catalysts

polyethylene, 318, 319

polypropylene, 318

σ, δ-TiCl

(3Ticl

.AlCl

), 317

Ticl

preparation, 317

Selective acetylene hydrogenation

catalyst development

modern catalysts, 106–107

operation, 102, 103, 105,

107–112, 114

production, 102

early catalysts, 102, 103,

105–106

ethylene loss, 103–108, 111

front end/tail end reactors,

104–112

486

Index

sources of ethylene, 102

use in steam crackers, 113

Selectivity, 5, 7, 12, 17, 19, 20, 65,

67, 74, 86, 93–96, 99–102, 104,

105, 107, 108, 111, 112, 114,

124, 131, 136–138, 140–144,

146, 151–154, 158, 159,

161–163, 176, 182, 196, 200,

208, 216, 236, 248, 255, 257,

262, 265–267, 271, 272,

275–278, 280–283, 285, 286,

288, 290, 291, 293, 295, 302,

303, 325, 424, 432–433, 445,

447

Semi-regenerative reforming

Shape selective catalysts

Mobil selectoforming, 253

Shell higher olefin process (SHOP)

aldehydes to alcohols, 306

catalysts, 306, 340

ethylene oligomer, 306, 340

hydroformylation, 306

isomerization, 306

metathesis, 305, 306

Silica alumina, 5, 6, 10, 92, 103,

105, 170, 173, 175, 180–182,

184–191, 193–196, 199, 207,

232, 233, 235–238, 247, 254,

281, 293

Sintering/stability, 5, 20, 47, 64, 82,

83, 86, 88, 177, 249, 324, 422,

424, 449, 457

Sohio processes

acrylic acid, 157, 158

acrylonitrile, 157, 158, 161

Stationary sources

Nox removal catalysts, 441,

443–446, 449–451

Steam cracking, 104, 112, 113, 145,

154, 163, 263, 264, 273, 274, 277,

281

Steam hydrocarbon reforming

autothermal reforming, 379,

393–395

catalysts

composition, 355, 363, 370,

371

development, 353, 355, 356,

370, 373

early formulation, 370

improved shapes, 4, 355,

364, 367, 370, 371, 373

raschig rings, 64, 354, 356,

364, 370, 371, 375

hot bands, 370, 372, 373

naphtha, 223, 357, 358, 364,

373, 374, 389, 390, 392,

426

natural gas, 68, 354, 356, 357,

364, 368, 370, 374, 377,

390–393, 426, 427

operation, 353–354

prereformer, 373, 374

reformed gas, 372, 375

reformer design, 366–368, 374

secondary reforming

catalysts, 356, 374, 375, 390

development, 374, 375

modern process, 374

operating problems, 374–375

steam reforming

reformer, 363–368, 371–375

steam ratio, 367, 368,

372–374, 390–392, 395

tubular design, 354, 373

US reformers 1940, 364

Structural analysis, 15, 16

Styrene

487

Index

catalysts

development, 279

ethylbenzene, 279–281, 283

properties, 283

dehydrogenation, 273, 279–283

ethylbenzene production,

279–281

production post, 281–282

Rubber reserve company, 279

styrene production, 281–282

Styrene development

catalyst development, 279

catalyst properties, 283

dehydrogenation, 273, 279–283

ethylbenzene catalysts, 283

ethylbenzene production,

279–281

post war developments, 279, 280

Rubber Reserve Company, 279

Styrene process, 279, 282

Wartime, 279, 280

Substitute natural gas (SNG), 388,

391–393

Sulphuric acid

alkali promoters

cesium, 36, 38, 39

potassium, 38

catalyst production, 323

chemistry, 26–27

Clement and Desormes, 24, 25,

contact process, 3, 24, 27, 29–35,

37, 402, 440

early developments, 31

economics, 32–34

Gay Lussac, 25

Glover, 25–27

lead chamber process

operation to 1960s, 27

process improvement, 34

plant design

adiabatic beds, 37

double absorption, 33, 38, 39

operation

catalyst life, 34, 37, 39

interbed heat exchange, 33,

37–39

quench cooling, 37

screening catalyst, 39

platinum catalyst, 23, 29, 31, 32,

34, 120

shapes, 4, 35, 37, 39

silica support, 29, 32, 35, 36

sulphur

Claus process, 29, 41, 45, 440

Frasch, 29

Sicilian, 28, 31

vanadium pentoxide

development

Boreskov, 36

Frazer and Kirkpatrick, 34, 35

Grillo, 32, 34

Knietsch, 31

Mannheim process, 29, 31, 32

modern process, 35, 36

Phillips, 29, 30, 213

redox mechanism, 36

Slama and Wolff, 34, 35

Squire and Messel, 30, 31

Winkler, 31

Sulphur recovery, 44

Summary 3rd/4th generation, 322

Supercage (FCC), 185–187, 189,

194, 237

Surface area, 5, 7, 11, 12, 15, 37, 45,

47, 67, 75, 82, 83, 87, 92, 98, 107,

128, 137, 142–144, 152, 177, 181,

182, 185, 193, 206, 224, 227, 235,