 | Moulijn J. Chemical process technology / Moulijn J., Makkee M., van Diepen A. - Chichester: Wiley, 2001. - xii, 453 p.: ill. - ISBN 0-471-63062-4
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Preface ....................................................... xi
1. Introduction ................................................ 1
2. The Chemical Industry ....................................... 7
2.1. Introduction ........................................... 7
2.2. Structure of the chemical industry ..................... 7
2.3. Raw materials and energy .............................. 10
2.3.1. Fossil fuel consumption and reserves ........... 10
2.3.2. Energy and the chemical industry ............... 12
2.3.3. Composition of fossil fuels .................... 15
2.4. Base chemicals ........................................ 23
3. Processes in the Oil Refinery .............................. 27
3.1. Oil refinery - an overview ............................ 27
3.2. Physical processes .................................... 27
3.2.1. Desalting/dehydration .......................... 27
3.2.2. Crude distillation ............................. 29
3.2.3. Propane deasphalting ........................... 31
3.3. Thermal processes ..................................... 32
3.3.1. Visbreaking .................................... 32
3.3.2. Delayed coking ................................. 33
3.4. Catalytic processes ................................... 33
3.4.1. Catalytic cracking ............................. 36
3.4.2. Hydrotreating .................................. 49
3.4.3. Hydrocracking .................................. 54
3.4.4. Catalytic reforming ............................ 59
3.4.5. Alkylation ..................................... 65
3.5. Conversion of heavy residues .......................... 70
3.5.1. Flexicoking .................................... 71
3.5.2. Catalytic hydrogenation of residues ............ 73
3.6. Treatment of refinery gas streams ..................... 78
3.6.1. Removal of H2S from refinery exhaust gases ..... 78
3.6.2. Recovery of hydrogen from refinery gas
streams ........................................ 83
3.7. Current and future trends in oil refining ............. 88
3.7.1. Reformulated gasoline .......................... 88
3.7.2. Diesel ......................................... 89
3.7.3. The use of zeolites for shape selectivity
in the oil refinery ............................ 90
3.7.4. Alternative technology and fuels ............... 96
4. Steam Cracking: Production of Lower
Alkenes ................................................... 109
4.1. Introduction ......................................... 109
4.2. Cracking reactions ................................... 110
4.2.1. Thermodynamics ................................ 110
4.2.2. Mechanism ..................................... 111
4.2.3. Kinetics ...................................... 112
4.3. Industrial process ................................... 113
4.3.1. Influence of feedstock on steam cracker
operation and products ........................ 114
4.3.2. Cracking furnace .............................. 117
4.3.3. Heat exchanger ................................ 119
4.3.4. Coke .......................................... 120
4.4. Product processing ................................... 121
4.5. Current and future developments ...................... 123
4.5.1. Selective dehydrogenation ..................... 123
4.5.2. Other sources of lower alkenes ................ 126
5. Synthesis Gas ............................................. 131
5.1. Introduction ......................................... 131
5.2. Synthesis gas from natural gas ....................... 133
5.2.1. Reactions and thermodynamics .................. 133
5.2.2. Steam reforming process ....................... 135
5.2.3. Advances in steam reforming ................... 139
5.2.4. Autothermic reforming ......................... 140
5.2.5. Novel developments ............................ 142
5.3. Coal gasification .................................... 144
5.3.1. Gasification reactions ........................ 144
5.3.2. Thermodynamics ................................ 147
5.3.3. Current coal gasification processes ........... 149
5.3.4. Recent developments ........................... 153
5.3.5. Applications .................................. 154
5.4. Purification and adjustment of synthesis gas ......... 158
5.4.1. Conversion of carbon monoxide ................. 158
5.4.2. Gas purification .............................. 159
6. Bulk Chemicals and Synthetic Fuels Derived from
Synthesis Gas ............................................. 163
6.1. Ammonia .............................................. 163
6.1.1. Background information ........................ 163
6.1.2. Thermodynamic s ............................... 165
6.1.3. Commercial ammonia synthesis reactors ......... 166
6.1.4. Ammonia synthesis loop ........................ 169
6.1.5. Integrated ammonia plant ...................... 169
6.1.6. Applications of ammonia ....................... 173
6.2. Methanol ............................................. 180
6.2.1. Background information ........................ 180
6.2.2. Thermodynamics ................................ 180
6.2.3. Synthesis gas for methanol production ......... 183
6.2.4. Methanol synthesis ............................ 184
6.2.5. Applications of methanol ...................... 187
6.3. Fischer-Tropsch process .............................. 193
6.3.1. Reactions and thermodynamics .................. 194
6.3.2. Reactors used in Fischer-Tropsch synthesis .... 196
6.3.3. Carbon removal ................................ 197
6.3.4. Processes ..................................... 198
6.3.5. Future developments ........................... 201
7. Inorganic Bulk Chemicals .................................. 205
7.1. Sulfuric acid ........................................ 205
7.1.1. Reactions and thermodynamics .................. 206
7.1.2. S02 conversion reactor ........................ 207
7.1.3. Modern sulfuric acid production process ....... 208
7.1.4. Catalyst deactivation ......................... 210
7.2. Nitric acid .......................................... 210
7.2.1. Reactions and thermodynamics .................. 210
7.2.2. Processes ..................................... 212
7.2.3. NOx abatement ................................. 215
8. Homogeneous Catalysis ..................................... 219
8.1. Introduction ......................................... 219
8.2. Wacker oxidation ..................................... 221
8.2.1. Background information ........................ 222
8.2.2. Processes ..................................... 224
8.3. Acetic acid production ............................... 228
8.3.1. Background information ........................ 228
8.3.2. Methanol carbonylation process ................ 230
8.3.3. Process economics ............................. 235
8.4. Hydroformylation ..................................... 235
8.4.1. Background information ........................ 236
8.4.2. Thermodynamics ................................ 237
8.4.3. Catalyst development .......................... 237
8.4.4. Processes ..................................... 239
8.5. Dimethyl terephthalate and terephthalic acid
production ........................................... 244
8.5.1. Background information ........................ 245
8.5.2. Conversion of p-toluic acid intermediate ...... 246
8.5.3. Processes ..................................... 247
8.5.4. Process comparison ............................ 249
8.6. Review of reactors used in homogeneous catalysis ..... 250
8.6.1. Choice of reactor ............................. 250
8.6.2. Exchanging heat ............................... 252
8.7. Review of catalyst/product separation methods ........ 252
8.7.1. Current separation techniques ................. 253
8.7.2. Future developments ........................... 254
9. Heterogeneous Catalysis - Concepts and Examples ........... 257
9.1. Introduction ......................................... 257
9.2. Catalyst design ...................................... 258
9.2.1. Catalyst size and shape ....................... 258
9.2.2. Mechanical properties of catalyst particles ... 260
9.3. Reactor types and their characteristics .............. 260
9.3.1. Reactor types ................................. 261
9.3.2. Exchanging heat ............................... 263
9.3.3. Role of catalyst deactivation ................. 265
9.3.4. Other issues .................................. 267
9.4. Novel developments in reactor technology ............. 268
9.4.1. Adiabatic reactor with periodic flow
reversal ...................................... 269
9.4.2. Structured catalytic reactors ................. 270
9.4.3. Hybrid systems ................................ 272
9.5. Selected examples of heterogeneous catalysis ......... 277
9.5.1. Ethylbenzene and styrene production ........... 277
9.5.2. Selective oxidations .......................... 286
9.5.3. Monolith applications ......................... 294
10.Fine Chemistry ............................................ 307
10.1.Introduction ......................................... 307
10.2.Plants for the production of fine chemicals .......... 312
10.3.Batch reactor design ................................. 316
10.3.1.Mechanically stirred batch reactors ........... 316
10.3.2.Batch reactors for gas-liquid-solid systems ... 318
10.4.Batch reactor scale-up ............................... 320
10.4.1.Temperature control ........................... 322
10.4.2.Heat transfer ................................. 322
10.4.3.Example of the scale-up of a batch and semi-
batch reactor ................................. 323
10.5.Safety aspects of fine chemicals ..................... 327
10.5.1.Thermal risks in the production of
chemicals ..................................... 328
10.5.2.Safety and process development ................ 328
10.5.3.Summary of scale-up of batch reactors ......... 330
11.Polymerization Processes .................................. 333
11.1.Introduction ......................................... 333
11.2.Polymerization reactions ............................. 334
11.2.1.Types of polymerization ....................... 334
11.2.2.Mechanisms of chain-growth polymerization ..... 336
11.3.Polyethenes - background information ................. 339
11.3.1.Catalyst development .......................... 339
11.3.2.Classification and properties ................. 339
11.3.3.Applications .................................. 341
11.4.Processes for the production of polyethenes .......... 341
11.4.1.Monomer production and purification ........... 342
11.4.2.Polymerization - exothermicity ................ 342
11.4.3.Production of LDPE ............................ 343
11.4.4.Production of HDPE and LLDPE .................. 348
11.4.5.Economics of polyethene production
processes ..................................... 350
12.Biotechnology ............................................. 353
12.1.Introduction ......................................... 353
12.2.Conversion Processes ................................. 355
12.2.1.Introduction .................................. 355
12.2.2.Mode of operation ............................. 356
12.2.3.Type of reactor ............................... 357
12.2.4.Sterilization ................................. 362
12.3.Fermentation technology - cell biomass (bakers'
yeast production) .................................... 363
12.3.1.Process layout ................................ 364
12.3.2.Cultivation equipment ......................... 365
12.3.3.Downstream processing ......................... 365
12.4.Fermentation technology - metabolic products
(biomass as renewable energy source) ................. 366
12.4.1.Ethanol ....................................... 366
12.4.2.Biogas ........................................ 367
12.5.Environmental application - wastewater treatment ..... 368
12.5.1.Introduction .................................. 368
12.5.2.Process layout ................................ 369
12.5.3.Biological treatment processes ................ 370
12.6.Enzyme technology - biocatalysts for
transformations ...................................... 376
12.6.1.General aspects ............................... 376
12.6.2.Production of L-amino acids ................... 378
12.6.3.Production of artificial sweeteners ........... 379
13.Process Development ....................................... 387
13.1.Dependence of strategy on product type and raw
materials ............................................ 387
13.2.The course of process development .................... 389
13.3.Development of individual steps ...................... 391
13.3.1.Exploratory phase ............................. 392
13.3.2.From process concept to preliminary flow
sheet ......................................... 392
13.3.3.Pilot plants/miniplants ....................... 395
13.4.Scale-up ............................................. 401
13.4.1.Reactors with a single fluid phase ............ 402
13.4.2.Fixed-bed catalytic reactors .................. 404
13.4.3.Catalyst stability and accumulation of
impurities .................................... 408
13.5.Safety and loss prevention ........................... 408
13.5.1.Introduction .................................. 408
13.5.2.Safety issues ................................. 409
13.5.3.Reactivity hazards ............................ 415
13.5.4.Design approaches to safety ................... 417
13.6.Process evaluation ................................... 419
13.6.1.Introduction .................................. 419
13.6.2.Capital cost estimation ....................... 420
13.6.3.Operating costs and earnings .................. 426
13.6.4.Profitability measures ........................ 430
13.7.Current and future trends ............................ 431
Appendix A: Chemical industry - Figures ...................... 437
Appendix B: Main Symbols used in Flow Schemes ................ 441
Index ........................................................ 445
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