CATALYST

HANDBOOK
SECOND EDITION

Edited by
Martyn V. Twigg
BSc, PhD, CChem., FRSC
Catalytic Systems Division
Johnson Mauhey PIc.
Formerly at the Catalysis Centre
ICI Chemicals & Polymers Ltd
CRC Press
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© 1989, 1996 by M.V. Twigg

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Contributo rs
G .W. Bridger BSe, MRSC
P.J.H. Carnell BSe, PhO
P. Oavies BSe
R.T. Donald
D.R. Goodman BA
N .H . Harbord BSe, PhD
J .R. Jennings BSe , PhD
L. Lloyd BSe, PhO
W.J. Lywood BSe, ACGI
B. B. Pearee BSe, PhD
D.E. Ridler BSe
M.S. Spencer MA, PhD, CChem, FRSC
M.V. TwiggBSe, PhO, CChem, FRSC
S.A. Ward BSe
C. Woodward BSe , PhD
Contents

Preface ... 16

Chapter 1.

Fundamental Principles
M.S. Spencer

1.1. Fundamentals of Heterogeneous Catalysis 17

1.1.1. Introduction 17
1.1.2. The Role of Catalysis 18
1.1.2.1. Ammonia Synthesis 18
1.1.2.2. Ammonia Oxidation .. 19
1.1.3. The Nature of the Catalytic Process 23
1.1.4. Catalyst Activity ... 24
1.1.5. Catalyst SeIectivity 26
1.1.6. Steps in the Catalytic Process 27
1.1.7. Adsorption and Desorption 29
1.1.8. Catalyst Design 32
1.2. Catalyst Manufacture. 34
1.2.1. Introduction 34
1.2.2. Unsupported Metals .. 34
1.2.3. Fused Catalysts 35
1.2.4. Wet Methods of Catalyst Manufacture 37
1.2.5. Fundamentals of Precipitation Processes 38
1.2.6. Catalyst Manufacture by Precipitation Processes 40
1.2.7. Impregnation Processes 41
1.2.8. Forming Stages 43
1.3. Catalyst Testing 48
1.3.1. I ntroduction 48
1.3.2. Chemical and Physical Properties 49
1.3.3. Bulk Chemical Properties 49
1.3.4. Surface Chemical Properties 50
1.3.5. Physical Properties 52
1.3.6. Catalyst Performance 55
1.3.7. Coarse Laboratory Screening 56
1.3.8. Fine Laboratory Screening 58
1.3.9. Semi-technical Catalyst Testing 60
1.3.10. Reaction Kinetics 61
1.3.11. Catalyst Ageing 65
1.3.12. Mechanism of the Catalytic Reaction 66
 Contents

1.3.12.1. Ammonia Synthesis .... ........... ... ......................... 67

1.3.12.2. Methanol Synthesis ........................................... 68
1.4. Catalyst in Use .. ........ .............. ............... .......... ................ .... ... 69
1.4.1. Introduction ....................... ............ ................ .......... ...... 69
1.4.2. Pretreatment and Activation. ........ ............. ..... ........... .... .... 69
1.4.3. Loss of Catalyst Performance ............................... .............. 73
1.4.4. Physical Causes of Decay .............. .... ...... ................ .......... 76
1.4.5. Poisoning by Impurities in Feeds or Catalysts ..... .......... ......... 77
1.4.6. Poisoning by Reactants or Products ......... ............ ................ 81
1.4.7. Interactions in Catalyst Deactivation ................................... 82

Chapter2.

Process Design, Rating and

Performance
W.J. Lywood

2.1. Design of Catalytic Reactors ............ ......... .................. ............... 85

2.1.1. Operating Temperature and Pressure ...... ............................ 87
2.1.1.1. Desulphurization Reactor ...................................... 87
2.1.1.2. Steam Reformers ................................................. 87
2.1.1.3. Water-gas Shift Reactors. ....................... ................ 88
2.1.1.4. Methanation Reactor ..... ...... ....................... .......... 89
2.1.1.5. Ammonia and Methanol Synthesis Reactors......... ...... 89
2.1.2. Converter Types............................................................. 90
2.1.2.1. Single Adiabatic Bed............................................. 90
2.1.2.2. Quench Converter ........................ ........ ................ 91
2.1.2.3. Inter-bed Coolin~ ......................... ..... ................... 91
2.1.2.4. ICI High-conversion Reactor ..... ............... .............. 96
2.1.2.5. Tube-cooled Reactor............................. ................ 96
2.1.2.6. Steam-raising Reactor ........................................... 96
2.1.3. Catalyst Life.. ............ ............. .............. ............ .............. 96
2.1.4. Optimum Catalyst Size and Shape..................................... 101
2.1.4.1. Voidage ........................................................... 101
2.1.4.2. Catalyst Particle Size.. ........ ............. .................... 103
2.1.5. Design Conversion of Reactor.......................................... 105
2.1.6. CaICulation of Catalyst Volume ........................................ 107
2.1.6.1. Catalyst Volume for Low concentration Reactant
Being Removed................................................. 107
2.1.6.2. Catalyst Volume for Low concentration Product Being
Formed ............................................................ 108
2.1.6.3. Equilibrium Concentrations. ............ ..................... 109
2.1.6.4. Rate Constants .................................................. 119
2.1.7. VesseIDimensions......................................................... 119
2.2. Reactor Rating...................................................................... 121
Contents

2.2.1. Optimum Operating Temperature 121

2.3. Catalyst Performance 123
2.3.1. Fall in Apparent Catalyst Activity 123
2.3.1.1. PoisoningiSintering 123
2.3.1.2. Poor Gas Distribution 124
2.3.1.3. Poor Mixing of Reactants 124
2.3.2. Increase in Pressure Drop 125
2.3.2.1. Breakage or Erosion of Catalyst ParticIes 125
2.3.2.2. Disintegration of Catalyst ParticIes 125
2.3.2.3. Deformation of Catalyst ParticIes 126
2.3.2.4. Carry-over onto Catalyst Bed 126
2.3.2.5. Collapse of Bed Support 126
2.3.3. Measurement of Performance 126
2.3.3.1. Analysis 126
2.3.3.2. Mass Balance 127
2.3.3.3. Catalyst-bed Temperature Rises 127
2.3.3.4. Catalyst-bed Temperature Profiles 127
2.3.3.5. Radioactive Tracing .. 127
2.3.3.6. Pressure Drop 127
2.3.4. Quantifying Catalyst Performance 127
2.3.4.1. Composition at the Exit from the Reactor 128
2.3.4.2. Approach to Equilibrium .............. . 128
2.3.4.3. Activity or Active Volume of Catalyst 128
2.3.5. Calculation of Catalyst Performance 128
2.3.5.1. Reactor Exit Composition 129
2.3.5.2. Calculation of Approach to Equilibrium 130
2.3.5.3. Calculation of Activity or Active Volume from
Composition 132
2.3.5.4. Calculation of Activity or Active Volume from
Temperature Profiles 133
2.3.6. Application of Methods to Ammonia and Methanol Catalysts 134
2.3.6.1. Desulphurizer 135
2.3.6.2. Primary and Secondary Reformer 135
2.3.6.3. High Temperature Shift 136
2.3.6.4. Low Temperature Shift 136
2.3.6.5. Methanator 136
2.3.6.6. Ammonia and Methanol Synthesis Converter 137
2.4. Computer Programs ...... 137
2.4.1. Reasons for Using Computer Calculations 137
2.4.1.1. Accurate Calculations 137
2.4.1.2. Non-isothermal Reactors 138
2.4.1.3. Multiple Reactions 138
2.4.1.4. Optimization 138
2.4.1.5. Simulation 138
2.4.2. Types of Computer Programs 138
 Contents

Chapter3.

Handling and Using Catalysts in the

Plant
D.R. Goodman

3.1. Introduction 140

3.2. Catalyst Storage 140
3.3. Drum Handling 141
3.4. Intermediate Bulk Containers and Socks 142
3.5. Sieving Catalyst 149
3.6. Catalyst Charging 150
3.6.1. Pre-charging Checks 150
3.6.2. Charging Vessels 151
3.6.3. Charging Ammonia Converters 155
3.6.4. Charging Reformer Tubes 156
3.7. Catalyst Red uction 161
3.7.1. Reduction of Reforming Catalyst.. 162
3.7.1.1. Typical Reduction with Steam and Natural Gas 163
3.7.1.2. Reduction with Gas Recirculation ... 164
3.7.2. Reduction of High-temperature Shift Catalyst 165
3.7.2.1. Typical Reduction of High-temperature Shift
Catalyst 166
3.7.3. Reduction of Low-temperature Shift Catalyst 166
3.7.3.1. Typical Reduction of Low-temperature Shift Catalyst 170
3.7.4. Reduction of Methanation Catalyst 171
3.7.5. Reduction of Ammonia Synthesis Catalyst.. 171
3.7.5.1. Typical Reduction of a Tube-cooled Ammonia
Converter 173
3.7.5.2. Typical Reduction of a Multibed Quench Converter 174
3.8. Catalyst Shutdown and Restarts 175
3.9. Catalyst Regeneration 176
3.9.1. Regeneration of Reformin~ Catalyst. 176
3.9.2. Regeneration of High-temperature Shift Catalyst 177
3.9.3. Regeneration of Low-temperature Shift Catalyst 177
3.9.4. Washing of Methanation Catalyst 177
3.9.5. Regeneration of Ammonia Synthesis Catalyst.. .. 178
3.10. Blanketing of Reduced Catalyst 178
3.11. Catalyst Stabilization 179
3.11.1. Stabilization of Reforming Catalyst.. 180
3.11.2. Stabilization of High-temperature Shift Catalyst 180
Contents

3.11.3. Stabilization of Low-temperature Shift Catalyst .................. 181

3.11.4. Stabilization of Methanation Catalyst............................... 182
3.11.5. Stabilization of Ammonia Synthesis Catalyst.. .................... 183
3.12. Catalyst Discharge ............ ................... ................. ................ 183
3.12.1. General..................................................................... 183
3.12.2. Discharge of Pyrophoric Catalyst ......... ........... ................ 184
3.12.3. Top Discharge............................................................. 185
3.12.4. Blanketing Pyrophoric Catalyst During Vacuum Extraction.. 186
3.12.5. Discharge of Ammonia Synthesis Catalyst .......... ............... 186
3.13. Re-use of Discharged Catalyst............... .................................. 187
3.14. DisposalofUsedCatalyst....................................................... 188
3.15. Safety Precautions ................................................................ 188

Chapter4.

Feedstock Purification
P.J.H. Carnell

4.1. Introduction ......................................................................... 191

4.2. Feedstocks for Ammonia, Methanol and Hydrogen Production ....... 192
4.2.1.NaturaIGas ................................................................. 192
4.2.2. Associated Gas, Natural Gas Condensates and LPG ............. 193
4.2.3. Naphtha................. ........................................... .......... 194
4.2.4. Refinery Off Gases and Electrolytic Hydrogen ............. ....... 194
4.2.5. Coal Gasification and Coke Oven Gas ............................... 194
4.2.6. Mixed Feeds................................................................. 195
4.3. Desulphurization ................................................................... 196
4.3.1. Processes for Single-stage Sulphur Removal................. ....... 196
4.3.2. Processes for Two-stage Sulphur Removal.......................... 198
4.4. Thermal Dissociation of Sulphur Compounds............. ........... ....... 199
4.5. Hydrogenolysis of Sulphur Compounds .. ................ ....... ........ ..... 200
4.6. Carbonyl Sulphide ........... .................. ............... ..................... 203
4.7. Cobalt Molybdate Catalysts ..................................................... 204
4.7.1. Presulphiding Cobalt Molybdate Catalyst ........................... 205
4.7.2. Other Reactions Over Cobalt Molybdate Catalyst ......... ....... 206
4.8. Nickel Molybdate Catalysts...................................................... 207
4.9. Physical Form ofCobalt and Nickel Molybdate Catalysts ................ 207
4.10. Replacement and Discharging of Cobalt and Nickel Molybdate
Catalysts... .................. ........................... ............................. 208
 Contents

4.11. Zinc Oxide.......................................................................... 209

4.11.1. Background to Zinc Oxide Absorbents .................. ....... .... 209
4.11.2. Thermodynamics and Reaction Kinetics ........................... 209
4.11.3. Formulation of Commercial Zinc Oxide............................ 211
4.11.4. Use of Test Rcactors to Assess Zinc Oxide Absorbents ........ 211
4.11.5. Effect of Tempcrature. Pressure and Space Velocity on
Efficiency of Zinc Oxide Absorbcnts................................ 213
4.11.6. Effect of Gas Composition ............................................. 216
4.11. 7. Effect of Reactor Design............................................... 217
4.11.8. Other Desulphurization Uses for Zinc Oxide ..... ................ 219
4.11.9. Impurities in Zinc Oxide................................................ 220
4.12. Dechlorination .................................................................... 220
4.12.1. Chloride Sources and Absorbents.................................... 220
4.12.2. Operating Conditions .. .......... ......... ................... ........... 222
4.13. Removal of Silica and Fluoride ...... ............... ......... .................. 223
4.14. Demetallization ................................................................... 223
4.15. Denitrification ................. .................................................... 224

Chapter 5.

Steam Reforming
D.E. Ridlcr. M.V. Twigg

5.1. History ..................... ........................................................... 225

5.2. Feedstock and Feedstock Pretreatment....................................... 226
5.2.1. Natural Gas.......... ...................................... ............ ..... 227
5.2.2. Naphthas..................................................................... 228
5.3. Chemistry of Steam Rcforming .................... .................. ........... 230
5.3.1. Thermodynamics............................ ........... .......... .......... 230
5.3.2. Kinetics...... ....... ...................... ...................... ... ........... 239
5.4. Design of Steam Rcforming Catalysts......................................... 244
5.4.1. Sclectivity ........ ................. ............. ..... ......................... 244
5.4.2. Thermal Stability........................................................... 244
5.4.3. Physical Properties ...... ................ ............ ............. ......... 244
5.4.4. Nickel as a Steam Reforming Catalyst ................................ 244
5.4.5. Supports for Nickel Steam Reforming Catalysts .. ................. 249
5.4.6. Carbon Formation on Rcforming Catalysts .................. ....... 250
5.5. Secondary Reforming ............................... ................... ........... 253
5.6. Catalyst Dimensions............................................................... 254
5.7. Uses of Catalytic Steam Rcforming............................................ 256
Contents

5.7. I. Ammonia Synthesis ....................................................... 256

5.7.2. Methanol Svnthesi.s........................................................ 258
5.7.3. Oxo Synthesis Gas .... ..................... .... ... ........ ................. 259
5.7.4. Reducing Gas............................................................... 260
5.7.5. Town Gas .................................................................... 261
5.7.6. Substitute Natural Gas (SNG) .......................................... 263
5.8. Practical Aspects of Steam Reformers ........................................ 264
5.8.1. Containing the Catalyst .............. .......... .... ...................... 267
5.8.2. Reactant Gas Distribution.......... .... ...... ... .................. ...... 269
5.8.3. Firing the Reformer ....................................................... 270
5.8.4. Expansion and Contraction of Reformer Tubes.................... 271
5.8.5. Facilities to Charge and Discharge Catalyst ... ....... ............... 273
5.8.6. Designing aReformer for Efficient Operation ................ ..... 274
5.8.7. Catalyst Reduction ........................................................ 274
5.8.7.1. Reduction with Hydrogen .................................... 275
5.8.7.2. Reduction with Ammonia .................................... 275
5.8.7.3. Reduction with Methanol..................................... 276
5.8.7.4. Reduction with NatlJral Gas.................................. 276
5.8.7.5. Reduction with Other Hydrocarbons ...................... 276
5.8.7.6. Reduction After Shutdown .................. ................. 277
5.9. Factors Affecting the Life of Reforming Catalyst........................... 277
5.10. Catalyst Poisons. ................................. ........................... ...... 278
5.10.1. Sulphur .. ... ... .... ... ................ .... ...... ..... ................. ...... 278
5.10.2. Arsenic...................................................................... 278
5.11. Hot Bands in Natural Gas Reformers.............. .......................... 280

Chapter6.

The Water-gas Shift Reaction

L. Lloyd, D.E. Ridler, M.V. Twigg

6.1. Introduction ......................................................................... 283

6.2. Thermodynamics ................................................................... 285
6.3. Kinetics and Mechanism ........ .... ... .... ........................ ...... ......... 288
6.3.1. Kinetics Over HT Shift Catalyst........................................ 288
6.3.2. Kinetics Over LT Shift Catalyst ........................................ 289
6.3.3. Mechanism of the Catalytic Water-gas Shift Reaction..... .... ... 290
6.4. Converter Design.................. ........................... ..... ................. 291
6.5. High-temperature Shift ........................................................... 293
6.5.1. High-temperature Shift Catalyst Formulation ...... ............... 293
6.5.2. Diffusion Effects and Pellet Slze . ...... ....... .... ............... ...... 295
 Contents

6.5.2.1. Effect of Pellet Size on Activity . 295

6.5.2.2. Effect of Pellet Size on Pressure Drop 296
6.5.3. Reduction of HT Shift Catalyst.. 298
6.5.4. Operation of HT Shift Catalyst 302
6.5.5. Poisoning and Deactivation 304
6.5.6. Reoxidation and Discharge 306
6.6. Low-temperature Shift 308
6.6.1. General. 308
6.6.2. Low Temperature Shift Catalyst formulation 309
6.6.3. Diffusion Effects and Pellet Size 312
6.6.4. Reduction of LT Shift Catalyst 314
6.6.4.1. General Considerations 314
6.6.4.2. Once-through Reductions 317
6.6.4.3. Recycle Reduction Systems. 318
6.6.4.4. Commissioning Reduced Catalyst 319
6.6.5. Operation and Monitoring Performance 320
6.6.6. Deactivation and Poisoning 324
6.6.6.1. Deactivation . 324
6.6.6.2. Sulphur Poisoning 326
6.6.6.3. Chloride and Other Poisons 328
6.6.7. Oxidation and Discharge 330
6.6.8. Guard Beds 331
6.6.9. Economics of Operation 335
6.7. Recent Developments 335
6.7.1. Sulphur-tolerant Shift Catalysts 335
6.7.2. Operation at Very Low Steam Ratios. 338

Chapter 7.

Methanation
B.B. Pearce, M.V. Twigg, C. Woodward

7.1. Introduction 340

7.2. Methanation in Ammonia and Hydrogen Plants 341
7.2.1. Methanation Equlibria 344
7.2.2. Kinetics and Mechanisms 347
7.2.3. Catalyst Formulation 352
7.2.4. Physical Properties of Methanation Catalysts 358
7.2.5. Catalyst Reduction 359
7.2.6. Catalyst Poisons 360
7.2.7. Prediction of Catalyst Life 362
7.2.8. Operating Experience 365
7.3. Methanation in Hydrogen Streams for Olefin Plants 367
Contents

7.4. Substitute Natural Gas (SNG) .................................................. 368

7.4.1. Oil-based Routes to SNG ................................................ 368
7.4.2. Coal-based Routes to SNG .................. ..................... ....... 372
7.4.2.1. Lurgi Coal/SNG Process ...................................... 373
7.4.2.2. HICOM Coal/SNG Process .................................. 374
7.4.2.3. Other Developments. ......................... .... ...... ....... 376
7.5. Heat Transfer Applications 378
7.5.1. The EVA-ADAM Project 378

Chapter8.

Ammonia Synthesis
J.R. Jennings, S.A. Ward

8.1. Introduction ......................................................................... 384

8.2. Thermodynamics of Ammonia Synthesis..................................... 388
8.2.1. Theoretical Aspects ....................................................... 388
8.2.2. Process Consequences ..... ............... ..... ... ....... ....... .......... 390
8.2.3. The Synthesis Loop........................................................ 391
8.3. Ammonia Synthesis Catalysts ................................................... 393
8.3.1. The Iron Component ............................ .................. ....... 394
8.3.2. Promoters.................................................................... 395
8.3.2.1. Structural Promoters........ ............. ....... ......... ...... 395
8.3.2.2. Electronic Promoters .......................................... 398
8.4. Catalyst Reduction................................ ........... ........ .............. 400
8.4.1. Typical Plant Procedure. .................... ....... ....... ............... 400
8.4.2. Prereduced Catalysts...................................................... 402
8.4.3. Economics of Prereduced Catalyst ..... ........................ ....... 404
8.5. Poisoning and Deactivation ...................................................... 404
8.5.1. Introduction ......... .............................. .......................... 404
8.5.2. Temporary Poisoning in Ammonia Converters .. .................. 406
8.5.3. Permanent Poisoning in Ammonia Converters..................... 407
8.6. Kinetics and Mechanism........................................... .......... ..... 409
8.6.1. Temkin Kinetics..... .......................... ............................. 409
8.6.2. Effect of Catalyst Size .................................................... 411
8.6.3. Implications on Process Design. ................................. ...... 412
8.6.4. Reaction Mechanism...................................................... 413
8.7. Plant Operation..................................................................... 415
8.7.1. General Considerations .................................................. 415
8.7.2'. Circulation................................................................... 418
8.7.3. HydrogenINitrogen Ratio ............................................... 420
8.7.4. Influence of Inert Gas Concentration and Purge Rate............ 420
 Contents

8.8. Commercial Ammonia Converters.............. .............. .......... ....... 423

8.8.1. General Considerations . .... ... ............................ .............. 423
8.8.1.1.F1owType ......................................................... 424
8.8.1.2. Temperature Contral and Heat Recovery ............ .... 425
8.8.2. Quench Converter .. ...... ....... .... ....... ... ............ ............ .... 426
8.8.3. Indirectly Cooled Multi-bed Converter ... ... ... ..... .... .... .... .... 433
8.8.4. Tube-cooled Converter................................................... 433
8.9. Tbe Future ........................................................................... 439

Chapter9.

Methanol Synthesis
G.W. Bridger, M.S. Spencer

9.1. Introduction ......................................................................... 441

9.2. Thermodynamic Aspects ................... ....... ........ ...... ............ ..... 442
9.2.1. Methanol Formation ........ .... ......... ... .... ......... ........... ...... 442
9.2.2. Selectivity ........ ..... ... .... ...... ......... ................... .............. 444
9.3. Tbe Methanol Synthesis Process................................................ 446
9.3.1. Tbe Synthesis Loop .............. ................................. ........ 446
9.3.2. Make-up Gas Composition ....... ..... ......... ................. ........ 452
9.4. Methanol Synthesis Catalysts......... ............ ....... ................ ....... 453
9.4.1. High-pressure Catalysts ................................................. 453
9.4.2. Low-pressure Catalysts.................................................. 455
9.5. Selectivity and Poisons ............................................................ 460
9.6. Mechanisms and Kinetics......................................................... 462
9.6.1. Reaction Mechanism..................................... ................. 462
9.6.2. Kinetics...................................................... ................. 467
9.7. Recent Developments............................................................. 467

Chapter 10.

Catalytic Oxidations
P. Davies, R.T. Donald, N.H. Harbord

10.1. Introduction ................. ................. ......................... .... ......... 469

Contents

10.2. Ammonia Oxidation. ... ... ..... ... .... ... ... ... ...... ... .... ... ... ...... .... .... 470
10.2.1. History of Nitric Acid Production ... ...... ... .... ... ... ...... .... .... 470
10.2.1.1. Routes from Atmospheric Nitrogen...................... 470
10.2.1.2. Ammonia Oxidation.......................................... 471
10.2.2. Chemistry of the Modern Process .................................... 477
10.2.3. Tbe Chemistry of Absorption............ ... .... .... ... ...... .... ..... 477
10.2.4. Nitric Oxide Oxidation Chemistry ... ...... ... .... ......... .... ...... 478
10.2.5. Ammonia Oxidation Chemistry ...................................... 479
10.2.6. Modern Plants............................................................. 482
10.2.7. The Burner Gauze-Platinum/Rhodium Catalyst ............... 484
10.2.7.1. Gauze Activation.............................................. 484
10.2.7.2. Gauze Deactivation and Cleaning......................... 488
10.2.7.3. Metal Recovery ................................................ 489
10.3. Methanol Oxidation.............................................................. 490
10.3.1. Introduction ............................................................... 490
10.3.2. Tbe Silver-catalysed Process........................................... 490
10.3.2.1. Silver-catalysed Reactions ..... .......... .... ......... ...... 493
10.3.2.2. Selectivity .. ..... ... ... ....... ......... ... .... ......... .... ...... 494
10.3.2.3. Poisoning ........ ... ... .... ... ..... .... ... ....... ...... .......... 494
10.3.2.4. Composition of Reaction Gases .... ....... ................ 497
10.3.3. Tbe Metal Oxide-catalysed Process.................................. 499
10.3.3.1. Metal Oxide-catalysed Reactions .... .... ... ...... .... .... 501
10.3.3.2. Composition of Reaction Gases ... ....... ......... ........ 502
10.3.4. Future Process Developments ...... ......... .......... ...... ......... 502
10.4. Sulphur Dioxide Oxidation..... ............. ...... ................... ..... ..... 503
10.4.1. Introduction .... ...... ............ ...... ..... ....... .... ......... .... ...... 503
10.4.2. Tbermodynamics... ...... ... ... ....... ... ...... ... ....... ..... ........... 503
10.4.2.1. Equilibrium Calculations .................................... 503
10.4.2.2. Application to the Contact Process ...... ............. .... 506
10.4.3. Tbe Contact Process............. ... .... ..... .... .... ... ... .............. 507
10.4.3.1. Vanadium Catalysts........................................... 508
10.4.3.2. Tbe Modern Sulphuric Acid Plant ........................ 510
10.4.4. Mechanisms and Kinetics............................................... 511
10.4.5. Catalyst Poisoning ....................................................... 514
10.4.6. Disposal ofUsed Vanadium Catalysts .............................. 517
10.4.7. Possible Further Developments ...................................... 517

Appendices
1. Further Reading .................................................................... 519
2. Numerical Examples of the Use of Equations Derived in Chapter 2... 525
3. ICI Catalysts for the Production of Hydrogen. Ammonia and
Methanol ............................................................................. 528
4. Pigtail Nipping....................................................................... 530
5., ICI Technical Publications.. ..... ... ....... ... ...... .......... .... ...... .... ...... 532
6. Equilibrium Constants: for the Methane-Steam Reaction at Various
Temperatures........................................................................ 537
7. Equilibrium Constants: for the CO Conversion Reaction (Shift) at
Various Temperatures... ........................................................ 543
 Contents

8. Nomograph of Selectcd Properties of Ammonia 549

9. Thermodynamic Properties of Elements and Compounds at 298.15K 550
10. Physical Properties of Methanol 553
11. Approximatc Boiling Ranges of Hydrocarbon Feedstocks 554
12. Monitoring Steam Reformer Tube Wall Temperature 555
13. Heat Released Ouring Catalyst Reduction 557
14. Heat Released Ouring Catalyst Oxidation 558
15. Temperature Conversions 559
16. Specific Heats of Catalysts 561
17. Atomic Weights of the Common Elements 562
18. Measurement of Pressure Drop Across Steam Reformer Tubes 565
19. Charging Primary Steam Reformer Catalyst-a Case Study 568
20. Equilibrium Constants far the Reaction for Zinc Oxide
with Hydrogen Sulphide 572
21. Temperature Measurements in Catalyst Bed 574

References 576
Index 591
Preface
The first edition of Catalyst Handbook was published twenty years ago.
It contained fundamental information on heterogeneous catalysis and
practical details about the catalysts and processes employed in the
production of hydrogen and ammonia via the steam reforming of
hydrocarbons. It was used extensively by industrialists, and also by
those working in research and teaching institutions, who found it
valuable because it was one of the very few easily accessible
authoritative sources of information about industrial catalysis and the
operation of catalytic processes.
Since the publication of the first edition, there have been significant
advances in areas of catalysis and the technologies it covered, many of
which originated from ICI's operations at Billingham, in the North East
of England. As a result there have been numerous requests for an
updated edition incorporating the new developments.
This second edition is very different from the first edition. Tbe
sections concerned with the catalysts and catalytic processes employed
in the production of synthesis gas for making ammonia and hydrogen
have been completely rewritten. In addition to these broadened main
sections, there is a chapter on methanol synthesis as the technology is in
many ways similar to that used in ammonia and hydrogen plants, having
as it does the same initial steps for the production of synthesis gas from
hydrocarbons. Conversion of methanol to formaldehyde is the largest
outlet for methanol, and as it is often operated with methanol synthesis
on the same site it is appropriate for it to be covered here. Similarly,
sulphuric acid and nitric acid plants have long been associated with
ammonia for the manufacture of nitrogen and compound fertilizers, and
so brief sections dealing with them are included.
Tbe production of this book was truly multi-disciplinary involving
specialists with extensive experience of catalyst development, catalyst
manufacture, plant design, and plant operation. Tbis brought together a
team of research workers and technologists comprising chemists,
physicists, metallurgists. chemical engineers and others. Tbe result is a
handbook that is intended primarily for people working in the chemical
industry. However, it has been written with other readers in mind, so
that it can be used as a reference source for research and teaching
purposes in universities.
In addition to the named contributors, many other people at ICI both
at Billingham and at Chicago, USA, helped in compiling this book, and
the editor would like to extend his sincere thanks to them.

16
Chapter 1

Fundamental Principles

I ,.,.
Fundamentals of
Heterogeneous Catalysis

1.1.1. Introduction
The word "catalysis" is used to describc many phenomena but in all
instances an agent (the catalyst) excrts a more-than-proportional
influence over some change. Indecd, thc word catalysis, coined by
Berzelius in 1836 to describe some cnhanced chemical reactions,' is now
used popularly in a non-technical way. In this book we shall restriet use
of the term "catalysis" to the heterogeneous catalysis of gas-phase
reactions; that is, the promotion of reactions between gases by the use
of solid catalysts. We shall be concerned mainly with a few reactions of
great importance in thc heavy inorganic chemicals industry. The
simplicity of the overall chemistry of these reactions usually hides a
bewildering complexity of separate reaction steps on the catalyst
surface. The discussion in this chapter is limited to a few general
principles, which are illustrated by examples from the processes
described in later chapters. Further study, essential for any full
understanding of heterogeneous catalysis, can be undertaken using the
books listed in Appendix 1. All of the topics of this chapter are treated
comprehensively in arecent book by Richardson 1a.
Catalysts are frequently defined as materials which accelerate
chemical reactions without themselves undergoing change. As the
manager of any plant using a catalytic process knows, this is too
optimistic a definition: the properties of all real catalysts do change with
use. The definition is also unsatisfactory in a more general way, for it
implies that the acceleration is brought about without direct
involvement of the catalyst in the process. Rather than attempting to
produce an alternative succinct definition, we can list the essential
features of the heterogenous catalysis of gas-phase reactions.
1. The presence of a solid material (the heterogeneous catalyst)
changes the rate of an overall chemical reaction. The term "solid" is
subject to some qualification, as the sulphuric acid catalyst (see
Chapter 10) is a melt held in a porous solid and some other catalysts
also contain mobile phases, e.g. some potassium salts in steam
reforming catalysts (see Chapter 5). The overall chemical reaction

17
Chapter ,. Fundamental Principles

concerns the gas-phase species only, but this does not preelude the
involvement of the solid in the formation of intermediate
species--indeed, this is essential for heterogeneous catalysis.
2. Tbe products of the catalysed re action can, at least in principle, be
obtained from an uncatalysed re action under the same conditions.
Tbere is, therefore, no way of using catalysis to "cheat" equilibrium.
In practice, however, the uncatalysed reaction may be immeasurably
slow or may give very different products.
3. Any useful catalyst must have a high productivity. Tbus, we expect 1
tonne of catalyst to "make" many tonnes of product. Altematively,
to look at catalysis on the atomic scale, the catalysed reaction steps
must occur many times at the re action site on the catalyst surface
before catalytic activity is lost.
4. Tbe catalysed reaction steps take place very elose to the solid
surface. These steps may be between gas moleeules adsorbed on thc
catalyst surface, or extensive re action can take place involving the
topmost atomic layers of the catalysts. Tbe influence of the solid does
not effectively extend more than an atomic diameter into the gas
phase, and the direet involvement of atoms below the topmost layers
is not usually possible.

1.1.2. The Role ofCatalysis

The synthesis of ammonia and its subsequent oxidation to nitrie oxide
give illustrations of two ways in whieh catalysts are essential to the
chemical industry.

1.1.2.1. Ammonia synthesis

Ammonia synthesis from nitrogen and hydrogen occurs by the overall
re action shown in equation (1).
N 2 + 3H2 ~ 2NH 3 (1)
No reaction takes place with the reactants at ambient temperatures, and
even with an active catalyst a temperature of some 400°C is needed to
obtain commercially useful rates of reaction. Nothing happens in the
system without a catalyst as the temperature is raised until, at
temperatures higher than l000°C, a significant proportion of the
hydrogen molecules are dissociated into atoms, as shown in equation
(2). For example, at 1430°C, with apressure of molecular hydrogen of
150 bar, the partial pressure of atomic hydrogen would be 0.1 % of the
H 2 pressure, i.e. 0.15 bar. Even this does not provide a mechanism for
fixing nitrogen, for the re action of hydrogen atoms with nitrogen

18
 1.1. Fundamentals of Heterogeneous Catalysis

molecules is very slow. 2 Only above 3000°C, where thc even more
strongly-bound nitrogen molecules start dissociating to atoms, equation
(3), does nitrogen fixation become possible.
H2 H+H (2)
N2 N+N (3)
If each nitrogen atom formcd in this way gave a molecule of ammonia
by subsequent reactions with hydrogen molecules or atoms, then the
rate of ammonia formation can be calculated from the rate of re action
(3).2 A 100 m3 reactor containing a 3:1 hydrogen/nitrogen mixture at a
total pressure of 200 bar and a temperature of 3150°C would give 1300
tonnes of ammonia per day.
However, this simple analysis ignores the reverse re action . Reaction
(1) is an equilibrium reaction, and ammonia synthesis is favoured by low
temperatures and high pressures. Thermodynamic data 3 can be used to
show that the partial pressure of ammonia under the conditions above
cannot exceed 0.07 bar, so with agas space veJocity of 104 h- 1 , the make
rate of ammonia would be only 6 tonnes day-l .
The role of the catalyst in ammonia synthesis is therefore that of
making the reaction go sufficiently fast (by facilitating the dissociation
of molecular nitrogen) so that significant rates are obtained under
conditions where the equilibrium conversion is large enough to be useful
(Figure 1. 1).

1.1.2.2. Amm.onia oxidation

The question of selectivity does not arise in ammonia synthesis, because
there is only one stable product that can be made from nitrogen and
hydrogen. Ammonia oxidation, by contrast, can give various products
depending on rcaction conditions. These include molecular nitrogen
(N 2 ), nitric oxide (NO), nitrogen dioxide (N0 2 ), nitrous oxide (NzO),
hydrazine (N zH 4 ), nitrous acid (HNO z) and nitric acid (HNO J ). For
nitric acid manufacture, thc selective formation of nitric oxide as an
intermediate is essential (see Chapter 10). The catalyst in this process is
required, not to accelerate ammonia eonversion (the simplest way of
oxidizing ammonia is to buro it in a flame), but to give selectivity in the
oxidation to thc wanted product, nitrie oxide (Figure 1.2):
2NH J + 5/20 2 - 2NO + 3H zO (4)
2NH J + 3/2 0 2 - N2 + 3H 20 (5)

This se!ectivity is gained by an increase in the rate of reaction (4),

relative to the unselective reaetion (5). The difficulty of achieving this
aim by means other than the subtleties of catalysis becomes apparent

19
Chapter 1. Fundamental Principles

In the gas phase

Nitrogen Ammoma

Hydrogen

Ammonia~
On the catalyst surface

®® N;',ogoo

Hydrogen

Figure 1.1. Comparison of the reaction steps in the synthesis of ammonia by

homogeneous and heterogenous (catalytic) routes. Suitable catalysts make the
heterogeneous route fast enough to be useful.

when it is realized that reaction (5), giving the more stable products,
nitrogen and water, has the stronger thermodynamic driving force.
Moreover, it can be seen from the stoichiometries of the reactions that
reaction (4) requires more oxygen than the unselective reaction.
Selectivity cannot therefore be achieved by limiting the extent of
oxidation.
Despite the wide range of chemical processes in use wh ich would not
be possible without catalysis, catalysts are not quite the modem
equivalents of the philosophers' stone. There are a number of
transformations which would be desirable industrial processes if only
one could get them to go, or, in some cases, get them to go faster or give
different products. This can be demonstrated by three examples, all
related to nitric acid manufacture (Figure 1.2).
The direct oxidation of ammonia to nitric acid is theoretically
possible, since re action (6) lies weil on the right-hand side. In practice,
NH 3 + 202 HN0 3 + H 20 (6)

20
 ,. ,. Fundamentals of Heterogeneous Catalysis

Uncatalysed, e.g. flame

N;trio ,,;d .'.0''''

Uncatalysed, Uncatalysed,

Single-step reactions theoretically

possible, but no catalysts known

Figure 1.2. Various process routes, all theoretically possible, to make nitric acid
from ammonia or molecular nitrogen. Suitable catalysts achieve the necessary
selectivity in the conversion of ammonia but none has yet been found for the
nitrogen-based reactions.

no suitable catalyst has been found for re action (6), which would need
to be operated at low temperatures to avoid decomposition of nitric
acid. The principles of the nitric acid process are described in detail in
Chapter 10. The commercialization of reaction (6) awaits the discovery
of a new ammonia oxidation catalyst which is much more active than
currently available ones.
The conventional nitric acid process provides the second example of
the "limits" of catalysis. It is interesting that in the se ries of process steps
by which natural gas is converted first to ammonia and then to nitric
acid, a catalyst is used to bring about each chemical change up to and
including nitric oxide formation (Table 1.1). The subsequent reactions,
which also involve simultaneous absorption in water, consist of the
oxidation to N0 2 and the re action with water and oxygen to give nitrous
acid and, finally, nitric acid. No catalysts are used in these stages
(Chapter 10). Reaction (7) is agas-phase process and requires no energy
of activation: 2 its slowness is due to the infrequent occurrence at
ambient temperatures of the three-body (i.e. NO + NO + O 2) collisions
which are necessary for the reaction. Here there is no energy barrier to
be decreased.

2NO + O 2 - 2N02 (7)

21
Chapter ,. Fundamental Principles

Table 1.1. Process steps in the manufacture of ammonia and nitric acid from
natural gas

Process step Heterogeneous Catalytic properties

ADIyst requlred

Hydrodesulphurization Sulphided Co/Mo/AI 2 0 3 Activity,life

+ZnO
CH 3 SH + H2 (lCI Catalysts 41-6 and
-+ CH.. + H2S 61-1)
Primary steam Ni/AI 2 0 3 Activity,life
reforming
CH.. + H 2 0 (lCI Catalysts 46-1, 46-4,
-> CO, CO 2 + H2 46-9 and 57-3)

Secondary steam Ni/AI 2 0 3 Activity,life

reforming
CH.. + O2 + H2 0 (lCI Catalysts 54-3 and
-- CO, CO2 + H2 54-4)

High temperature Fe 3 0JCr2 0 3 Activity, selectivity,

water-gas shift life
CO + H2 0 (lCI Catalysts 15-4 and
-- CO 2 + H2 15-5)

Low temperature CulZnO/AI 2 0 3 Activity, selectivity,life

water-gas shift
CO+ H2 0 (lCI Catalyst 53-1)
-> CO 2 + H2
CO 2 removal None

Methanation Ni/AI 2 0 3 Activity,life

CO,C0 2 + H2 (lCI Catalyst 11-3)
-+ CH 4 + H2 0

Ammonia synthesis Fe, promoted by K, Ca, Activity,life

AI 20 3
N 2 + 3H 2 (lCI Catalysts 35-4 and
-- 2NH 3 35-8)

Ammonia oxidation PtlRh Activity, selectivity, life

2NH 3 + 5/2 0 2
-+2NO+ 3H 2 0

Nitric acid formation None

2NO + H2 0 + 3/2 0 2
-> 2HN0 3

22
 ,. ,. Fundamentals of Heterogeneous Catalysis

Sometimes. however. the failure to achieve any catalysis is a result of

the lack of reactivity of the raw materials, and then the possibility of
achieving a new process persists as a gleam in the catalyst researcher's
eye. In 1923. Lewis and Randall 4 calculated from the energetics of
reaction (8) that starting with water and air it should be possible to form
H 20 + N 2 + 5120 2 - 2HN0 3 (8)
nitric acid until it reaches a concentration of about 0.1 mol 1-1 . Clearly,
this re action could form the basis of the cheapest nitric acid process
possible. However, nitrogen is unreactive, and those few catalysts which
can activate nitrogen are poisoned by water and oxygen, so it is hardly
surprising that no-one in the past 60 years has succeeded in making any
nitric acid by reaction (8). Finally "it is to be hoped that nature will not
discover a catalyst for this reaction, which would permit all the oxygen
and part of the nitrogen of the air to turn the oceans into dilute nitric
acid".4

1.1.3. The Nature ofthe Catalytic Process

The good catalyst has three cardinal virtues; those of activity, selectivity
and life. While the general meaning of these terms is obvious, it is useful
to define them a little more closely, especially with respect to plant
performance (Table 1.2).

Table 1.2. Essential catalyst properties

Property Definition

Activity Ability of the catalyst to convert feedstock to (various)

products, e.g.
kg reactant converted kg , (or 1-') catalyst h"
percentage change in reactant (conversion)
number of molecules reacting s-'/active site
(turnover number, TON, or turnover frequency, TOF)
NB: All measurements referred to standard conditions
Selectivity Ability of the catalyst to give the desired product, out of all
possible products, e.g. product as percentage of reactant
converted (yield)
Life Time for which the catalyst keeps a sufficient level of
activity and/or selectivity

23
Chapter 1. Fundamental Principles

1.1.4. Catalyst Activity

The "space" available for heterogeneous catalysis is sma11er than the
total volume of the reactor. Alhough catalysts are designed with a large
surface area, sometimes as high as 300 m 2 g-I of catalyst, the influence
of the catalytic surface extends only about one atom diameter from the
surface. For example, a 100 m 3 reactor containing a typical catalyst with
surface area of 50 m 2 g-I will contain, in a minutely convoluted form,
some 5000 km 2 of catalyst surface. That is equivalent to the areas of
Oxfordshire and Cambridgeshire combined, or of the State of
Delaware. If the reaction space is a11 within 0.5 nm of this surface, then
the volume of this space is only 2.5 m 3 , or 2.5% of the reactor volume.
Tbe available reaction space in the ga uze catalysts used for ammonia
oxidation is some orders of magnitude sma11er.
Although some concentration of reactants takes place in the adsorbed
phase on the catalyst surface, the increase in reaction rate which this
brings about rarely does much more than compensate for the decrease
in reaction space. The large increases in the re action rate given by active
catalysts are almost entirely due to the reduction of energy barriers. The
rates of catalysed reactions, like those of other chemical reactions, are
exponential functions of the energy barriers.
This effect can be demonstrated for ammonia synthesis. First of a11,
we show how effective the catalyst is from a comparison of the catalysed
and uncatalysed rates under comparable conditions. The rate of
ammonia synthesis over the face of a single iron crystal has been
carefu11y measured 5 with a 1:3 N 2/H 2 mixture at 20 bar and 525°C. If we
assurne (Chapter 8) that the reactor is filled with a typical ammonia
synthesis catalyst that has about 5 m 2 of active catalyst surface per cubic
centimetre of reactor space, then the rate of formation of ammonia is
about 5 X 10-3 mol NH 3 cm- 3 S-I. The uncatalysed reaction requires
the dissociation of nitrogen molecules, and the rate of uncatalysed
ammonia synthesis can then be shown to be about 10-52 mol NH 3 cm- 3
S-I, Le. some 5 X 10-49 times slower than the catalysed reaction. The
extreme slowness of uncatalysed ammonia synthesis can be shown in the
fo11owing way. A typical reactor in an ammonia plant with a volume of
about 100 m 3 will make some 1500 tonnes of NH 3 per day. If we imagine
a reactor of the size of the solar system (assumed to be a sphere of radius
equal to the mean distance of Pluto from the Sun) in which ammonia is
being made by the uncatalysed re action , under typical synthesis
conditions of 200 bar and 500°C, the rate of uncatalysed synthesis would
be only about 0.1 g NH 3 day-I.
Tbe reaction profiles for the reaction and the uncatalysed gas reaction
are shown in Figure 1.3, largely derived from the fundamental studies of

24
 1.1. Fundamentals of Heterogeneous Catalysis

Figure 1.3. Energy profiles tor the series ot reaction steps to make ammonia trom
nitrogen and hydrogen by both homogeneous gas-phase and iron-catalysed reac-
tions. The role ot the catalyst in decreasing the energy barrier to reaction can be
seen (numerical values are kJ mol I).

Ertl and his co-workers.6-9 The energy barrier for reaction is reduced by
the catalyst from 942 kJ mol-I. the energy required to dissociate the N2
moleeule in the gas phase, to about 13 kJ mol-I. This dccrease should
give an increase in reaction rate of about 1060 times, from the
exponential dependence of reaction rate on activation energy. This
factor is larger than the ratio of catalysed to uncatalysed reaction rates,
and thc explanation is that the ammonia synthesis catalyst has a "built-in
inefficiency": only about one N2 molecule in 106 with sufficient energy
to dissociate on the iran surface actually does so. In this comparison of
the ratio of catalysed and uncatalysed ammonia synthesis we have taken

25
Chapter ,. Fundamental Principles

a very simple approach, using single reactions. A computer model lO of

the catalysed reaction under working conditions, derived from the
kinetics of the individual reaction steps, agrees weil with plant
observations.
1.1.5. Catalyst Selectivity
Catalyst selectivity is of equal importance to activity in most catalytic
reactions (not ammonia synthesis, of course), and smaller changes in
energy barriers than those found in ammonia synthesis are sufficient to
give large changes in selectivity. As an oversimplication (Chapter 10) we
can write two processes in which methanol is oxidized:
CH 30H + 1/202 - HCHO + H 20 (9a)
CH30H - HCHO + H 2 (9b)
CH 30H + 3/202 _ CO 2 + 2H 2 0 (10)
The uncatalysed combustion of methanol with air at about 500°C
corresponds broadly with reaction (10), although some CO, together
with traces of formaldehyde, is formed. The silver catalyst used in the
formaldehyde process (Chapter 10) gives formaldehyde, by reactions
(9a) and (9b). The presence of the catalyst increases the formaldehyde
yield from, say, 0.1 % to 95%. To achieve this the rate ofreactions (9)
have to be increased relative to re action (10) by a factor of about
2 X 104 • This requires a change in the energy barrier to reaction of about
60 kJ mol-I-wen within the range of decreases in energy barriers
brought about by catalysts. A catalyst may change the rate of the
undesired reaction as weil as the rate of production of the wanted
product, but as long as the necessary change in relative rates is achieved,
then the catalyst will be selective.
As energy barriers are dominant in determining catalyst selectivities,
various general patterns of selectivity can be deduced. By-products are
almost always the products of reactions with higher energy barriers than
those of the main reaction, so accounting for their relatively slow
formation. It follows that an increase in temperature usually accelerates
by-product formation more than main product formation, i.e. product
selectivity decreases. A comparison of the ICI low-pressure methanol
process with the older, high-pressure process illustrates this point.
Methanol synthesis can be described by the two overall equations (11)
and (12).
CO/C02 + H~CH30H (11)
CO/C0 2 + H~by-products (J 2)
(CH 4 , HCOOCH 3, C 2 H 50H, etc.)

26
 7.7. Fundamentals ofHeterogeneous Catalysis

The Cu/ZnO/AI 2 0 3 catalyst developed by ICI has a very much higher

activity for reaction (11) than the earlier ZnO/Cr203 catalyst had, and as
the rate of reaction (12) was not acceleratcd as much as that of re action
(11) therc was an immediate improvement in selectivity (Chapter 9).
However, the high activity allowed operation at lower temperatures and
pressures, so this in turn brought about a further improvement in
selectivity.
The relationship between activity and selectivity can be more complex
than these examples show. In ammonia oxidation high selectivity
depends on high activity, but for reasons which are different from those
in methanol synthesis (Chapter 10). In some other reactions, especially
organic oxidations, high activity is frequently associated with low
selectivity. We can again take methanol oxidation as an illustration, and
add the re action
HCHO + O 2 - CO, CO 2 , H 2 0 (13)
to reactions (9) and (10). Thus, the requirement for high selectivity is
that reactions (9) should be faster than reactions (10) and (13) (Figure
1.4). A very active oxidation catalyst, such as platinum, has low energy
barriers for all three reactions, so selectivty is poor and oxidation
proceeds to CO, CO 2 and H 2 0. Less-active oxidation catalysts-for
instance, silver or Fe/Mo oxides-are used in formaldehyde processes,
and with these catalysts the differences in energy barriers are high
enough to ensure selectivity for formaldehyde.

1.1.6. Step~ in the Catalytic Process

So far we have made the implicit assumption that process rates are
controlled solely hy the rates of key reactions on the catalyst surface,
but this is not always so. For example, suppose the addition of a new
promoter to the iwn catalyst for ammonia synthesis greatly increased
the proportion of nitrogen molecules which dissociated on colliding with
the surface. If the p 'oportion rose from 1 in 106 to almost all, would this
give a million-fold increase in the rate of ammonia synthesis-and a
reduction in the siz;! of plant converter from 100m3 to, say, 100 cm3 ?
Even apart from thc problems of he at transfer and fluid f10w in trying to
make 1500 tonnes of NH 3 per day in a reactor the size of a wine glass,
the answer is no. lhe separate stages of a heterogeneously catalysed
gas-phase reaction are shown in Table 1.3.
Any of these sta~ es, if slow, may limit the overall rate of a catalytic
reaction. Distinctions are often drawn between catalysts which are
"film-diffusion controlIed'" (i.e. limited by stages 1 and/or 7),
"pore-diffusion controlled" and "reaction controlled" (i.e. limited by

27
Chapter , . Fundamental Principles

Figure 1.4. Schematic representation of the various energy barriers in the selective
and unselective oxidation of methanol. A suitable choice of catalyst (for example
silver) with appropriate energy barriers (a) and (b) can give high selectivity to
formaldehyde. Numerical values are kJ mol - 1 •

stages 3, 4 andJor 5). However , the development of the best industrial

catalysts usually leads, either by design or empiricism, to the elimination
of any strongly-limiting constraint on catalyst performance, so these
simple distinctions rarely apply in practice. The concentration profiles
of reactants and products in and around a typical catalyst pellet are
shown in Figure 1.5. The combined effects of diffusion and reaction give
significant concentration gradients, both within and outside the catalyst
pellets.
We can now see why a large increase in the rate of dissociation of
nitrogen molecules o n an ammonia synthesis catalyst would not give a

28
 1.1. Fundamentals ofHeterogeneous Cats/ysis

Table 1.3. Sequence of stages in the catalysis of agas-phase reaction bya

heterogeneous catalyst

Transport of reactants through the gas phase to the exterior of the catalyst pellet
2 Transport of reaetants through the pore system of the catalyst pellet to a
eatalytieally-aetive site
3 Adsorption of reaetants at the eatalytieally-aetive site
4 Chemieal reactions between reaetants at the catalytieally-aetive site (frequently
several steps)
5 Desorption of products from the eatalytically-active site
6 Transport of produets through the catalyst pore system from the
catalytieally-aetive site to the exterior of the catalyst pellet
7 Transport of produets into the gas phase from the exterior of the catalyst pellet

Notes
In this description the eatalyst is assumed to be in the form of a pellet. The same
stages apply to other types of eatalyst partiele (e.g. spheres made by
granulation, or extrusions)' but stages 2 and 6 elearly do not take plaee in
eatalysts made of wire gauzes or non-porous metal crystals, unless surfaee
roughening becomes so advanced that in effect a pore system is formed.
2 Transport through the catalyst pore system ean be either through the gas phase
or aeross the interior surfaee of the eatalyst surface.
3 Several different eatalytically-active sites may be involved. Adsorption, possibly
followed by reaetion, may oecur at one site, followed by transport of an
intermediate produet to a different site for further reaetions. Transport of the
intermediate product ean be either through the gas phase, if the intermediate is
a stable moleeule, or aeross the catalyst surfaee (the uspillover· effeet).

proportional increase in overall rate: other stages would become of

more significance in controlling the process. Indeed, even with the
present catalyst there is experimental evidence that under some
industrial conditions this occurs. There is a complex interaction between
the relative importance of these different stages and the resulting
selectivity when several products are formed.

1.1.7. Adsorption and Desorption

Table 1.3 shows that adsorption and desorption are both essential and
critical stages of the overall catalytic process. In the act of adsorption, a
molecule approaches the solid surface from the gas phase and is held
dose to (or in) the surface. This is different from the collision and
rebound that occurs at all solid surfaces in contact with gases. Thus, a
molecule which stays on the surface for a time longer than that of a
collision is said to be adsorbed. The removal of an adsorbed molecule is
known as desorption. A distinction is drawn between adsorption, where
the adsorbed material stays on (or at least dose to) the solid surface,

29
Chapter 1. Fundamental Principles

Figure 1.5. Concentration profiles of reactants and products around <,nd in a typical
catalyst pellet under reaction conditions where mass-transfer control is significant.

and absorption, where the absorbed material "soaks" into the bulk of
the solid.
Different types of adsorption are listed in Table 1.4 and are shown for
carbon monoxide in Figure 1.6. We can see the difl'erences by
considering the adsorption of carbon monoxide on a-alurr: ina, copper
metal and nickel metal surfaces. There is no special bonding between
CO and an a-A1 2 0 3 surface, so physical adsorption takes place. The
energy of adsorption is of the same order as that between CO molecules
in liquid CO, so the physisorption is extensive at low temperatures only.
Physisorption is often important in catalysis as aprecursor to
chemisorption. Associative chemisorption occurs with CO on copper
because the energy of interaction is greater than that of physisorption.
Various adsorbed states have been identified, with different adsorption
energies, and although the C-O bond strength is weakened no breaking
of this bond takes place on copper surfaces. This is significant in the
hydrogenation of CO to methanol, when dissociation of th;: C-O bond

30
 ,. ,. Fundamentals of Heterogeneous Catalysis

Table 1.4. Types of adsorption

Type of adsorption Characteristics

Physical Unselective. Low energy of adsorption. Extent of

adsorption adsorption related to boiling point of gas, not
(physisorption) nature of solid surface. No breaking of bonds in
moleeules and negligible changes in bond
energies
2 Associative Selective, strongly dependent on both gas and
chemical solid surface. Higher energies of adsorption than
adsorption those of physisorption. Bonds in the adsorbed
(chemisorption) moleeules are changed in strength but not broken,
Le. moleeule adsorbed wh oie
3 Dissociative Selective, strongly dependent on both gas and
chemical solid surface. Higher energies of adsorption than
adsorption those of physisorption. Bonds in the adsorbed
(chemisorption) moleeules are broken, Le. moleeule adsorbed as
two or more molecular fragments

Moleeule Physical Associative Dissociative Reaction and

approaches adsorption chemisorption chemisorption absorption
surface

Increasing interaction with metal surface

Figure 1.6. Schematic representation of the adsorption, and possible subsequent

reaction, of carbon monoxide on various solid surfaces.

could lead to the formation of methane and water (Chapter 9). The
removal of CO in the methanation reaction (Chapter 7) does require its
conversion to methane and water as in equation (14)
CO + 3Hz-~CH4 + H 20 (14)
which is catalysed by nickel. Here dissociative chemisorption of CO
occurs and the CO molecule is broken on adsorption as in equation (15)
thus facilitating the methanation reaction.
Co-C(a) + 0(8) (15)

31
Chapter 1. Fundamental Principles

1.1.8. Catalyst Design

In the previous section we saw how the patterns of adsorption on
different solids led to the choice of appropriate metals as catalysts for
different reactions. The design of a catalyst covers all aspects from the
choice of catalytically-active material to the method of forming
particles. This exercise can be detailed, rigorous and extensive, as
described by Dowden, 1 1 starting from fundamentals to get the best
catalyst for a new process; but sometimes the design of a new catalyst
may be only a minor modification of an existing industrial <:atalyst. The
optimum catalyst is the one that provides the necessary combination of
properties, including activity, selectivity and life, at an accc~ptable cost.
These requirements always put conflicting demands on the catalyst
designer, and much of the designer's art consists of the achkvement of a
suitable compromise 1a •
At the start of catalyst design a consideration of both desirable and
undesirable reactions in the overall process leads to a choice of
catalytically-active materials for possible catalysts. Suitabk promoters
are frequently needed to get adequate performance: these may either
modify the catalyst structure, so improving stability, or enhance the
catalytic reactions to give better activity or selectivity. The relative
importance of some factors l2 influencing the activity of metal catalysts in
some simple reactions is shown in Table 1.5. The nature of the metal is
Table 1.5. Effects of metal structure. promoters and type of metaion Ictivity for
some catalytic reaction (from reference 12)

Reaction Effect" of
Structure Promoters Tvpe of metal

H2 + D;z-+2HD VS S M
C2H4 + H;z-+C2H6 VS S M
Cyclo-C3 HB + H;z-+C3 HB VS S M
CBHB+ 3H;z-+CBH'2 VS S M
C2HB+ H;z-+2CH 4 S L VL
N2 + 3H;z-+2NH 3 M L VL

BThe order of magnitude of the effect is classified as folIows:

1<VS<10. 10<S<loo. 100<M<104 • 1Q4<L<10B• 10B<VL.

always the most important factor. The dependence of intrinsic activity

on the refractory support is usually sm all , but there are some
remarkable exceptions. In most catalysts some refractory support
material is needed to give adequate physical stability. This support has
to be compatible with the active catalytic phases, both in the reactor and

32
 ,. ,. Fundamentals 0' Heterogeneous Catalysis

during catalyst manufacturc. Thc maximum reaction rate is obtained by

maximizing the available surface area of the active phase. The actual
size and shape of the fabricated catalyst is influenced by considerations
such as he at and mass transfer, and reactor pressure drop.
There is insufficient space here to go through the full design exercise
for evcn one catalyst, but to give some impression of thc factors
involved we will look at catalysts for the high- and low-temperature
water-gas shift processes. These processes are very similar, as they both
involve reaction (16) but the two catalysts used have no component in
common. In the high-temperature stage of the water-gas shift process
(Chapter 6), both the temperature range (350--450"C) and the high
partial pressure of CO (typically 1-3 bar) allow the use of eatalysts of
only moderate activity. The main critical requirement is seleetivity-the
avoidance of any measurable methan at ion [reactions (14) and (17)1.
H 20+ CO-+H z + CO2 (16)
CO2 + 4H r CH 4 + 2H 20 (17)
Many metals catalyse the shift reaction, but without the necessary
selectivity. Magnetite, Fe304, is suffieiently active for process purposes,
has negligible activity for methanation and it is the chemically stable
form of iron under the reaction conditions. It is also quite resistant to
various poisons such as HzS (which may be present in the process gas)
because the sulphided form has significant activity. However. pure
Fe304 of adequate surface area is not sufficiently refractory: the
crystallites would sinter rapidly in use. with consequent loss of surface
area and, hence, activity. A more refractory material has to be
combined with the magnetite to inhibit sintering, and chromia, Cr203.
has been found to be both sufficiently refractory and compatible. Some
sintering of the active Fe304 phase still occurs, but it is sufficiently slow
for the Fe304/CrZ03 catalyst to have a useful plant life of several years. 13
The moderate activity of the Fe30JCr203 catalyst allows the use of
medium to large pellets (lCI Catalyst 15-4, 8.5 mrn X 11.0 mrn; ICI
Catalyst 15-5, 5.4 mm x 3.6 rnrn) without too great a loss of activity
from pore diffusion. The large pellets are beneficial in giving physically
strong catalysts and a low reactor pressure drop.
Much higher catalyst activity is required for thc low-temperature
water-gas shift proccss because both temperature (200-250°C) and CO
partial pressure are much lower. Magnetite is inadequate and a meta I
active phase has to be used. The need to avoid methanation rest riets the
choice among thc more common metals to copper. 14 Tbe disadvantages
of copper as the activc phase lie in the ease with whieh it both sinters
and is poisoned. especially by chlorine and sulphur compounds. The use

33
Chapter ,. Fundamental Principles

of zinc oxide and alumina as refractory supports greatly limits the

sintering of the copper crystallites, and it gives two further bt!nefits. The
precipitation of mixed copper/zinc carbonates (Section 1.2.6) leads to
the eventual formation of very small and weil dispened copper
crystallites.
Zinc oxide also acts as an absorbant for catalyst poisons, thus further
extending catalyst life. Tbe optimum proportion of copper depends on
the copper and support crystallite sizes. 15 A typical reduced LT shift
catalyst contains about 20% Cu by volume, with both Cu and ZnO
crystallites about 5 nm in size. A catalyst with about 40% Cu by volume
would need the support crystallites to be <3 nm (impossible in practice)
to give a greater copper area and hence greater activity. Mt!dium-sized
catalyst pellets are used (ICI Catalyst 53-1,5.4 mm X 3.6 mrn), partly to
minimize the effect of pore diffusion, which is more significant than with
a high-temperature shift catalyst because of the higher intrinsic activity,
and partly to ensure that poisons are held in a concentrated ;~one next to
the reactor inlet (see also Section 1.4).

1 ,·2.catal y st
Manufacture

1.2.1. Introduction
Successful catalyst production necessarily involves the making of
catalysts which fulfil all of the process requirements described in Section
1.1.8 and which can also be transported, charged to the reactor and
activated. This has to be done reproducibly and at reasonable cost.
Catalyst makers achieve their aims by a judicious use of practical
skills, knowledge of fundamental principles and many years'
experience. lt• It is therefore not surprising that there is much less in thc
open literature on catalyst manufacture than there is on catalyst use,
testing or fundamentals (but see references 17-19). Attention to detail
in catalyst manufacture is crucial to success. because small changes in
procedure can have large effects on catalyst performance. Some of the
ways in which industrial catalysts are made are outlined below.

1.2.2. Unsupported Metals

In most processes which need meta I catalysts a prime requirc!ment is the
use of a large metal surface area. and this area can be maintained only
by the spreading of the metal ac ross a refractory support (S,ection 1.1).
Accordingly, few industrial catalysts are used in the form of
unsupported metals, but there are some instances where tht: rate of the

34
 1.2. Catalyst Manufacture

catalysed reaction is so fast that a small metal area is capable of

supplying enough product, and so a support is not necessary. The other
functions of a support (such as the absorption of poisons) are also
necessarily absent, so this may impose operating conditions such as the
high purity of methanol feed needed for a formaldehyde plant.
Poisoning of platinum gauzes was one of the reasons for their
replacement by the now conventional vanadium-based catalysts in
sulphuric acid plants (Chapter 10).
One of the most widely used unsupported metal catalysts is the
precious metal gauze as used, for example, in the oxidation of ammonia
to nitric oxide in nitric acid plants. A very fast rate is needed to obtain
the necessary selectivity to nitric oxide, so a low metal surface area and
short contact time are used. These gauzes are woven from fine wires (a
few thousandths of an inch in diameter) of platinum alloy, usually
platinum-rhodium. Severallayers of these gauzes, which may be up to 3
m in diameter, are used, often with "getter" gauzes to catch the
platin um lost from the ga uze in use (Chapter 10). Methanol oxidation to
formaldehyde is another process in which an unsupported metal catalyst
is used, but here the metal is normally in the form of a bed of granules,
altbough gauzes are also used (Chapter 10). For optimum catalyst
efficiency tbe silver is made as granules of agglomerated dendritic
crystals.
Raney nickel catalysts (Section 1.2.3) (used in some organic
hydrogenations) are sometimes regarded as unsupported metal
catalysts, but their high metal areas are probably maintained by traces
of residual alumina acting as a support.

1.2.3. Fused Catalysts

The manufacture of catalysts by fusion of either metals or oxides is not
extensively used. Although clearly the technique can give very good
mixing of all of the catalyst components (unless phase separation occurs
during melting or subsequent cooling) and catalysts of high density can
be obtained, problems arise in forming and activation. The product of
fusion obviously has negligible surface area, so the internal areas
necessary for catalysis can be developed only during activation; Le. by
the removal of some component of the catalyst, or some other method
of generating porosity. However, in many cases where fusion routes
might be potentially useful the removal of oxygen (or some other
component) from the fused catalyst either occurs far too slowly or leads
to collapse of the structure.
The most important catalyst made in this way is the promoted iron
ammonia synthesis catalyst20 (Chapter 8). The key feature wh ich allows

35
Chaprer ,. Fundamental Principles

the usc of 3 fusion method is the way in which the iron oxide. FelO•• is
reduced by hydrogen . On reduction iron metal is formed as a porous
solid of the same overall dimensions as the original iron oxide. For pure
FelO. the removal of oxygen eorresponds 10 3weight )oss olf 28%, but
because metallic iron is denser than FelO. the resulting theoretical
porosity is 52%. In praclice. ammonia synthesis catalysts contain small
amounts of other solids. so the weight loss and porosity achieved on
reduction 3re less than theoretical.
Ammonia synthesis catalysts are made ' 6 by the fusion (in an electric
furnace at -16OO"C) of magnetite, FelO., of a suitably pure grade,
together with the promoters. typically calcium. potassium and alumina.
in a "triply-promoted" catalyst. Tbe appropriate purity of the raw
materials is of critical importance in fused catalysts becaus(: there is no
subsequent stage in catalyst manufacture during which poisons can be
removed (as can be done with precipitated catalysts) The only
opportunity for the removal of poisons is during catalyst activation
(Section 1.4). Conventional forming techniques (pelleting, extrusion
and granulation) are not practical with fused catalysts, so the common
practice is cooling of the mett, followed by crushing and siz(: grading. to
give particles of the required dimension ranges (Chapter 8). A flow
sheet for the process is shown in Figure 1.7. Very good rr.ixing of the
components is attained in the fusion stage. but some segregation, on a
micro-scale, occurs in the cooled solid. 21 This separation of components
is nO{ sufficient 10 affect the final catalysts, since further migration to the
optimum distribution for activity occurs on activationlreduclion. 21

Figure 1.7. Flow sheet 'ar a plant 10 make an ammonium synlhesis c:atalysl by the
fusion route.

36
 7.2. Cst/Jlyst Manufacture

Raney nickel 22 is preparcd as a nickel-aluminium alloy by

conventional mctallurgical techniques. The aluminium is removed with
aqueous sodium hydroxide. to leave porous nickel (of high surface areal
which contains a small amount of stabilizing alumina, formed in the
extraction process. The resulting eatalyst is of high arca (e.g. 100 m2
g-l) and activity, and is useful for mild. low·temperature
hydrogenations. but it is sensitive to poisons and is rapidly deactivated
at higher temperatures. Raney cobalt and Raney copper catalysts can
also be made by the same techniques.

1.1.4. Wet Methods ofCatalyst Manufaclure

Most industrial catalysts are made (Figure 1.8) either by precipitation,
when active phase and support are made together, or bt the
impregnation of an active phase on to a preformed support. 16-19. The
process used depends on many factors , such as the chemistry of the
catalyst components and their possible precursors, the concentrations of
different components required, physical strength required, reaction
conditions of catalyst in use and the need and ease of removing
contaminants. It is usuaJly easier to get a high concentration of thc
catalytically active phase by precipitation than by impregnation
processes, but the development of adequate strength can be more
difficult. Sometimes the processes are combined, as when a precipitated
catalyst is impregnated with potassium hydroxide solution to give the
required level of alkali doping.

Figure 1.8. Aerial view of Ihe ICI factory 81 Clilheroe (lancashire, England) for the
manufacture of catalysts.

37
Chapter 1. Fundamental Principles

1.2.5. Fundamentals of Precipitation Processes

Precipitated catalysts are generally prepared by rapid mlxmg of
concentrated solutions of metal salts, and a typical flowsheet is shown in
Figure 1.9. The product precipitates in a finely divided form of high
surface area. Precipitated mixed hydroxides or carbonates are most
frequently prepared. The re action
2Ni(N0 3h + 2NaOH + Na2C03 -. Ni2(OHhC0 3 + 4NaN0 3 (18)
is typical, but the precipitates are usually non-stoichiometric and often
amorphous. After filtration and washing the precipitate is dricd and
heated to decompose the hydroxides/carbonates to the corresponding
oxides. The final size of crystallites present in precipitated catalyst are
typically in the range 3-15 nm, while overall surface areas can be 5~200
m2 g-1 or more. These va lues can change markedly in use (Section 1.4),
but the activity of precipitated catalyst is nevertheless usually high.
The main aims in the use of a precipitation process for catalyst
manufacture are the intimate mixing of the catalyst comp0",~nts and the
formation of very small particles to give a high surface area. The
necessary degree of mixing can be achieved either by the formation of
very sm all crystallites, in close proximity, of the different components or
by the formation of mixed crystallites containing the catalyst
constituents. Hydroxides, carbonates or basic carbonates are the
favoured precipitated intermediates for the following reasons:
1. The solubilities of these salts of transition metals and other catalytic
components are very low. Conseqently, very high supel'saturations,
leading to very small precipitate particle sizes, can be reac:hed.
2. The solubilities of the precursors, typically metal nitrates and sodium
hydroxide or carbonate, are high, so concentrated solu':ions can be
used, again giving high supersaturations.
3. Hydroxides and carbonates are readily decomposed, by heat, to
oxides of high area without leaving catalyst poisons as, for example,
sulphur residues from the calcination of sulphates.
4. Many mixed hydroxides, carbonates and hydroxycarbonates are
known, so there is a good chance of getting a mixed compound of the
required composition for given components.
5. Environmental difficulties arising from the calcination of hydroxides
and carbonates are minimal.

38
 ...
~
Q
iii
~
...
~
;:,
c::
Q;'
<)
VJ c:
\0 Figure 1,9, A flow sheet for a plant to make catalysts by the precipitation route. ib
Chapter 1. Fundamental Principles

1.2.6. Catalyst Manufacture by Precipitation Processes

An example of the complexity of development work with prccipitatcd
catalysts can bc taken from thc lei work on the copper/zmc/alumina
catalysts for methanol synthesis. 24 • 25 Earlier work had o;hown that
copper catalysts were active but unstable, so activity was rapidly lost.
The eopper particles in these catalysts are thc essential eatalytic
material, whilc the other components are thc stabilizers In earlier
catalysts made by convcntional bateh methods these stabilizt:rs were not
effective because the particles were not sm all enough and were not
uniformly mixed. In the batch method involving the addition of alkali to
an acid solution, the catalyst which is obtained at the beginning of the
precipitation is formed under acid eonditions, whereas latl!r, as more
alkali is added, it is produced under alkaline conditions. This affects
both the composition of the catalyst and the size of the particles (Figure
1.10). The catalyst produeed under the acid eonditions at the beginning
of the precipitation is rieh in aluminium and deficient in zi ne, while at
the end, under alkaline eonditions, the eatalyst is low in copper. The
catalyst particle size is also affected by the pH: under aeidie and alkaline
eonditions large particles are produced, but under neutral conditions
they are much smaller. The best catalyst is obtained by predpitation at
around pH 7, and this was achieved by a precipitation procedure in
which the aeidic and alkaline solutions were mixed continuously.
Very fine precipitates can, however, cause severe problems in the
later stages of processing and mueh skill and empirical development is
needed to reach thc optimum process. If the precipitatei:; too fine it
may pass through thc filter or block the filter pores. Even when a
satisfactory filter cake is made, thc removal of sodium and other
unwanted ions ean be diffieult. Salt solutions held in the filter eake are
readily displaced, but salts can be adsorbed on the high surfaee area of a
fine precipitate. Washing with water may not then be enough to reduee
sodium levels to the specification fOT the final catalyst, and special
teehniques have to be used.
The precipitation proeess outlined above represents the simplest form
in which it is used, many catalyst production routes involve
more complex OT additional steps. The addition of asolid component
either during or just after precipitation is common. Ageing periods after
precipitation, or after washing out unwanted materials, may be needed
to achieve the desired ehemieal or physical state of the eatalyst
intermediate. This may not always be advantageous beeause some
crystal growth may occur in a precipitate in contaet with the filtrate.
Crystallization, espeeially from concentrated solutions, is one of the
less-well understood ehemical processes, so scale-up (Figure 1.11) from
laboratory experiments has to be done with eare.

40
 1.2. Catalyst Manufactufa

Figure 1.10. Variation with pH of the properties of copper/zinc oxide catalysts

prepared by precipitation . Deviation from the optimum value of pH affms com-
position of the catalyst, and the size of the particles, and other physical properties.

Figure 1.1 1. Semi-technicat unit for catalyst preparation, an intermediate stage in

scale-up from taboratory to full-sca le manufactute.

1.2.7. Impregnation Processes

As indicated in Section 1.2.4, the choke of a preClpltation or an
impregnation route far catalyst preparation is determined by a complex
interplay between many different factors. 16 . 2S In Table 1.6 several

41
Chspter 1. Fundamentsl Principles

examples are given where impregnation techniques have marked

advantages over other procedures. Tbe flowsheet for a planl for making
an impregnated catalyst is shown in Figure 1.12. Tbe great virtue of
impregnation processes is the separation of the making of the active
phase and the support phase, wh ich is clearly not possible in the case of
precipitated catalyst manufacture. The support is normally a porous
refractory oxide, usually fired at a high temperature to give stability.
High-area carbons are used for some impregnated catalysts, especially
metals of the platinum group. The disadvantage of impregnation lies in
the limited amount of material which can be incorporated n a support
by an impregnation stage. Multiple impregnation/dryinglfiring cycles
can be used to increase the levels of active components, but only at a
significant cost in catalyst manufacture.

Figure 1.12. Flow sheet for a plant tor the manutacture of catalysts b'( the impregn-
ation of pre-formed supports with a compound of the active metal.

In the absence of specific interactions between the prefonned support

and the components of the impregnating solution, the impregnation
process stages can be described quite simply. A solution is made up
containing the component to be put on the catalyst. In the next stage
either the support is dipped into a tank of this solution or the solution is
sprayed on (or added to) the support-the latter procedure is sometimes

42
 1.2. Catalyst Manufacture

labia 1.6. Catalysts made by impregnation processes

Catalyst Reason 10r use 01 impregnation

techniques

Supported platinum-group Good metal dispersion and no loss

metal catalysts of metal within support phases
2 Catalysts tor high-temperature Support can be stabilized to resist
processing reaction conditions before active
phase incorporated
3 Catalysts with an uneven distri- Precipitation methods give uniform
bution of components, e.g. catalysts, at least on a macro-scale:
active phase on exterior impregnation can concentrate
components where required
4 Alkali-doped catalysts Alkali would be removed at washing
stages of precipitation route
5 Metal/zeolite catalysts Usually more convenient to add
metal by ion-exchange after zeolite
synthesis rather than include metal
in zeolite synthesis
6 Supported molten-salt catalysts Usually more convenient to add
molten salt phase (e.g. V20s-K2S04
for sulphuric acid catalysts) to
preformed support, e.g. silica

describcd as the "incipient wetness" technique. In both methods the

take-up of the solution is governed by the porosity of the support, so the
level of active component incorporated in the catalyst is a function of
the solution concentration and support porosity. After absorption of the
solution into the pore system of the support, a drying stage is used to
remove water. This has to be carried out so that the impregnated
component remains within thc support pore system and does not
mi grate to the exterior surface of the support. If this stage is done
correctly, the support thcn has crystallites of thc impregnated
componcnt, typically a mctal nitrate. in the intersticcs of the pore
system. Most impregnated catalysts are calcined in air after drying, thus
convcrting the soluble salt to insoluble oxide. Calcination can also have
other effects; for instance. the firing of a potash-doped catalyst for
naphtha-steam reforming helps to "fix" the potassium by re action with
the refractory phases to give kalsilite, a potassium aluminosilicate. 26
This is resistant to hydrolysis by steam. and without this "anchor" the
potash would be lost rapidly as volatile potassium hydroxide in steam
during usc.
Interactions between impregnating solution and support are
commonplace. and indeed useful. in the impregnation process. Three

43
Chapter ,. Fundamental Principles

types of interaction can be recognized although the boundaries of the

classification are somewhat arbitrary.
1. Specific adsorption. lf the impregnating component (e.g. Cl metal ion)
is more strongly adsorbed on the support surface than the molecules
of the solvent (usually water). metal ions are removed from the
impregnating solution as it passes into the support, with the result
that the impregnated metal is concentrated in the outer layer of the
support pellet. This "shell" catalyst can ensure that maximum use is
made of the catalytic metal in reactions that are strongl) limited by
pore diffusion (Section 1.1). Further treatment with water andlor
other solutions can give different distributions. For example, in
coking or poisoning conditions there can be advantages in having the
active phase in a layer below the pellet surface.
2. Some high-area solids (zeolites form the most important class) have
significant ion-exchange capacity . Tbus, metal ions in the
impregnating solution will exchange with ions already pmsent in the
support surface before impregnation. Since this gives almost an
atom-by-atom deposition over the surface, the metal distribution,
initially at least. is very good. As with adsorption, the amount of
metal taken up by the support is not simply determined by
concentration and support porosity, but is a complex function of
ion-exchange equilibria and diffusion rates in the liquid phase. 27
Ion-exchange, like less-specific adsorption, can be u!Jed to give
non-uniform distributions of metals. Some high-area solids which are
not conventional ion-exchange materials may nevertheJess display
ion-exchange properties; for example, the residual sodium in a
precipitated alumina may be held in the surface and behave in this
way.
3. A stage beyond ion-exchange is the possiblity of re action and
precipitation in the pores of the support. Tbus, the residual sodium
on the surface of a precipitated alumina may increase the pH of an
impregnating solution to the point at which metal hydroxides are
precipitated. While this technique can again be of use in getting a
non-uniform distribution of metal, its unexpected occurrence can
sabotage attempts to reach a uniform distribution.

1.2.8. Forming Stages

Precipitated catalysts and supports for impregnation need tc be formed
into suitably sized particles for use in the reactor. Tbe size and shape of
the catalyst pie ces (Figure 1.13) is a compromise between the wish to

44
 1.2. Catalyst Menufeerure

minimize pore diffusion effects in thc catalyst particles (requiring small

sizes) and pressure drop across the reactor (requiring large particle
sizes).

Figure 1.13. A seleetion of industrial eatalysts, showing the variation in size and
shap8 of eatalyst partieles neeessary for different uses.

The three main processes used in catalyst manufacture to make

conveniently sized partieies from powders are pelleting (Figure 1.14),
extrusion (Figure 1.15) and granulation (Figure 1.16). The products of
each process arc compared in general terms in Tablc 1.7. The choice of
method depends of the size, shape and density of the catalyst particle
required, on the strength required and on the properties of the starting
powder. If the catalytic reaction is not pore-diffusion limited, or at least
not very much so, in catalyst particles with dimensions of a few
millimetres. then the maximum conversion from a reactor is obtained by
fiJling it with as much catalyst as possible, and thc catalyst particles
should be of maximum density. (Tbc usual range of densities available
generally has little influence over the extent of pore-diffusion control.)
It is ctear from Table 1.7 that pelleting is the preferred fonning
technique for catalysts intended for this type of use.
On the other hand, the choiee is different for processes in which the
activity of the catalysts are strongly limited by pore-diffusion. Under

45
manufacturemanufacture
manufacture

Figure 1.14. A Iypical machine used in 'he manufacture of catalyst pellets.

Figure 1.15. A typical machine used to exuude catalysts.

46
 7.2. Cet.lyst M.nuf.cture

Figure 1.16. AlYpical machine used to form catalyst particles by granulation .

these conditions only the outside layer of the catalyst particle is

effectively used. so the maximum activity from a reactor is obtained
with catalyst particles of maximum superficial area. As smaller particles
can bc made more easily by granulation or extrusion than by pelleting,
these are the preferred methods of forming. Cross-sectional shapcs of
langer periphery than a circlc (e.g. a "clover leaf') can give even larger
superficial areas on extruded catalysts. and these have been used in
some hydrodesulphurization catalysts. Occasionally just a decrease in
pellet size can give a sufficient increase in activity under pore-diffusion
limitcd conditions. With the rise in temperature moving down a HT
water-gas shift rcactor the proccss moves tram almost pure reaction
control to substantial pore-diffusion control. l ) Consequently, there are
advantages in the use of large, dcnse pellets in thc inlet regions of the
reactor and small pellets in the exit region of the reactor. 28

47
Chapter ,. Fundamental Prinäples

Table 1.7. Relative merits of different types of catalyst particle

Typeof Properties
particle

Pellet Cylindrical shape. Denser and stronger than oxtrusions or

granules. Convenient size range from about !i mm to
about 20 mm. Raschig rings as weil as cylind,~rs can be
made, but otherwise limited in shape. Two stages of
eompaetion often needed
Extrusions Usually long irregular eylindrical shape, but other shapes
of larger external surfaee area (e.g. -ciover-IElat")
possible. Less dense than pellets. Convenient size from
about 1 mm diameter upwards. Also possiblo to make
hollow matriees (e.g. ear exhaust eatalysts)
Granules Spherieal shape only. Less dense than pellet!i.
Convenient size from about 2 mm diameter l pwards

The choice between extrusion and granulation for sm all catalyst

particles depends primarily on the nature of the powder pn:cursor: not
all powders can be either extruded or granulated satisfac':orily, even
with the help of special additives (e.g. plasticizers or cements). The
requirements of the forming process lead to constraints on earlier stages
of the process. 15 Thus, in the pelleting of methanol synthesis catalysts 16
it is important to control the amount of hydroxide anel carbonate
remaining from the calcination stage. An excess weakens the pellets
after reduction, whereas an inadequate proportion prod'lces fragile
pellets because the hydroxide and carbonate have a role in binding the
oxides under press ure in the pelleting machine.

1 '.3. Catalyst
Testing

1.3.1.lntroduction
"Commit your blunders on a small scale and make your profits on a
large scale." This principle, given by Baekeland29 in his P(:rkin Medal
address in 1916, summarizes the whole basis of catalyst testing. In
catalyst testing there are two obvious features which can be (:mphasized.

48
 1.3. Cat8/yst Testing

The first is that some simulation of wh at will (or could) happen to the
catalyst is required for each test. but it is not possible to do all of the
tests simultaneously. The results from various tests are combined in
order to predict full-scale behaviour. The second point to be
emphasized is that all of these figures have to be "right". or very nearly
so.
All of the properties which can affect catalyst activity. selectivity and
life need to be investigated. no matter whether a novel process or a new
catalyst for an existing process is being examined-or. indeed. for
ensuring the constant quality of a production catalyst. A range of
experimental techniques is used in the small-scale simulation of the
different aspects of the full-scale process. but the equipment rarely
resembles a full-scale reactor. Baekeland stated that the principle
quoted above "should guide everybody who enters into a new chemical
enterprise. even if it taxes the patience of some men who cannot
conceive that one single apparently minor detail in a chemical process
may upset all the good points and lead to ruin". 29

1.3.2. Chemical and Physical Properties

Many of the chemical and physical properties of a catalyst influence the
performance of the catalyst in a full-scale reactor. A wide range of
properties, c1assified as bulk chemical properties. surface chemical
properties and physical properties, is determined, usually on a routine
basis, as part of catalyst testing. In contrast with the various techniques
developed for the assessment of catalyst performance. most of the
analytical procedures used to determine other catalyst properties are
standard techniques which require little modification for these
applications.

1.3.3. Bulk Chemical Properties

Techniques used to determine these properties are given in Table 1.8.
The first three methods-clemental analysis. X-ray diffraction and
electron microscopy-are of widest application in the determination of
the chemical nature of a catalyst. The advances in electron microscopy
over the past decade have made this potentially the most powerful
technique available for uncovering the chemical nature of catalysts. 30
80th the element analysis and crystal structure of particles identified in
the field can be determined. 31 The other experimental techniques given
in Table l.8 tend to be used in special cases only. Thus. in an
investigation of a poisoned catalyst, GC/MS can identify poisons
present, and electron probe analysis or radiography will give the
distribution of the poison across the catalyst structure.

49
Chapter ,. Fundamental Principles

Table 1.8. Techniques used for bulk chemical properties of catalysts

Technique Properties determined

Element analysis (qualitative and Bulk elemental eomposition

quantitative)
X-ray diffraetion Crystalline phases present,
erystallite sizes
Eleetron mieroseopy and assoeiated Partiele shapes and sizes,
X-ray fluoreseenee and eleetron partiele compositions,
diffraetion particle erystal struetu res
Miero-probe analysis Variation in eomposition aeross
pellet
Radiography with radioaetive Distribution of radioaetive
isotopes eomponent
Nuelear magnetie resonanee (NMR) Chemieal environment of element
Mössbauer speetroseopy Chemieal environment of element

IR
Visible speetroseopy Types of ehemieal bond pres,mt
UV
Extended X-ray adsorption fine- Types of ehemieal bond preslmt
strueture analysis (EXAFS)
Thermal analysis (DTA, TGA) Phase changes, weight ehan~les on
heating
Temperature-programmed Size and temperature range clf
reduction (TPR) reduetion stages
Combined gas chromatography and Analysis of volatile eomponents
mass speetrometry (GClMS)

1.3.4. Surface Chemical Properties

As heterogenous catalysis is a surface phenomenon, the determination
of surface properties (Table 1.9) plays a large part in catalyst
characterization. Some techniques (e.g. LEED) can be used only with
single crystal surfaces, and not with practical catalysts, and are not
included in Table 1.9 (for further details see, for exampJe, reference
32). No single technique can give a full description of the nature of the
surface, so the use of several techniques is essential. As different
equipment is used under various conditions, it is also essential to ensure
that it is really the same catalyst surface which is being examined in each
experiment. Some of thc modern techniques of surface physi,:s, listed at

50
 1.3. Catalyst Testing

Table 1.9. Sometechniques used for determination of surface properties of

catalysts

Technique Properties determined

Photoelectron spectroscopy Chemical identity of surface layers

(UPS, XPS)
Auger spectroscopy Chemical identity of surface layers
Secondary ion mass spectrometry Chemical identity of surface lavers
(SIMS)
Temperature-programmed Chemical identity of adsorbed
desorption, flash desorption surface species
Physisorption of gases (e.g. N2 ) Total surface area
Chemisorption of CO, H2 or O2 Surface area of metal components
Surface reaction of N2 0 Surface area of metal components
Chemisorption of bases Surface concentration of acidic sites
(e.g. NH 3 , pyridine)
Chemisorption of acidic gases Surface concentration of basic sites
(e.g.C0 2 )

IR
Visible spectroscopy Types of chemical bond present
UV
High-resolution electron energy- Type of chemical bond present
1055 spectroscopy (HREELS)
Extended X-ray absorption fine- Atomic structure of surfaces and
structure analysis (EXAFS) adsorbates
Work function determination Surface ionization
NMR Chemical environment of element
Electron microscopy Chemical identity and structure of
surface layers
Isotopic labelling of reagents or Chemical origin of adsorbed species
catalysts

the top of Tablc 1.9, provide a wider range of chcmical surface

information, especially concerning minor components such as poisons,
than could bc obtaincd by thc older, selectivc chemisorption
methods. 33-3fi
For example, in rccent work 21 on the surface composition and
topography of both unreduced and reduced ammonia synthesis
catalysts, scanning Auger e1ectron spcctroscopy, X-ray photoelcctron
spectroscopy and scanning e1ectron microscopy were used. The

51
Chapter ,. Fundamental Principles

application of these techniques has given much detailed information on

the microstructure of the reduced iron component, and the distribution,
on a micro-scale, of the catalyst promoters. Nevertheless, Emmett and
his co-workers,37 with the few, somewhat primitive techniques available
some 50 years ago, achieved a broad understanding both of the nature
of the promoted-iron ammonia synthesis catalyst, and of how it worked,
which still holds today.

1.3.5. Physical Properties

A relatively small range of techniques is used to monilor physical
properties38 of catalysts, and these are listed in Table 1.10. The strength
0/ catalyst particles is needed to assess the possiblity of failure in use.
Apart from chemical causes such as pellet rupture upon excessive
coking, two different physical stresses are imposed Oll industrial
catalysts: first, in the loading of a catalyst into a reactor (Chapter 3) and
second, when the catalyst bed is installed in the reactor. Even under
steady operating conditions catalyst particles are stressed by the weight
of the catalyst bed above, and by the pressure drop across the catalyst
bed due to gas flow. Catalyst break-up during loading is simulated
(Figure 1.17) by the use of a standard tumbling test to determine
attrition loss,39 but all estimates are done by comparison w,th standard

Table 1.10. Selected techniques used for determination of physical pl'operties of

catalysts

Technique Properties determined

Pellet crushing Compression strength

Pellet tumbling Attrition loss
Physisorption isotherms Textural properties
Porosimetry Pore size distribution
Controlled packing Bulk density and packing
characteristics
Inert gas flow through catalyst bed Fluid flow properties. including
pressure drop
Single-pellet reactor Pore-diffusion coefficient
Non-steady state gas flow through Diffusion characteristics
catalyst bed

52
 1.3. C.t./yst Testing

·o!r•
~
i
..;
~

Figure 1.17. Typical apparatus used

to test pellet strength by measuring
forces necessary to crush them. The
photograph (right) shows a ring
placed on the plattem before it is
correctly aligned and crushed.

53
~
~
 ChBpt8f ,. Fundamental PrinciplBs

materials. since there is no direet relationship between the test and

lasses in plants. Similarly, comparativc measurements are used in the
erushing tests which simulate statie loads in a reactor. Ob'{iously , the
way in which a crushing strength is determined depends on the shape of
thc catalyst particle. Spheres and lang extrudated cylinders can be
crushcd only along a diameter, but pellets can be crushcd cither along
the axis or along a diameter of the cylinder. The lauer. th(: horizontal
crushing strength. correlates beuer with behaviour in the plant.
Many of the physical properties required can be d<!scribed as
properties 0/ ,he texture 0/ the cata/yst or properties (e.g. pore diffusion
coefficients) which are determined by catalyst textun:. Average
properties are generally used (a eomplete description of the texture of a
catalyst pellet is not possible):
(a) spe:cific surface area (Le. total accessible areal;
(b) specific porosity (i.e. total accessible pore volume);
(e) pore size distribution (in distribution of pore volume as a funetion of
pore radius) ;
(d) mcan pore radiusand
(e) partieIe size distribution.
Pores are c1assified as macroporcs (>>>-35 nm), micropores «2 nm)
or mesopores (intermediate size). Mercury porosimetry and the analysis
of physical adsorption isotherms are the two principal means of
obtaining a description of thc texture of a catalyst. Th::se can bc
combined with information on particle size and shape t.ram X·ray

Figure 1.18. A modern laboratory for the determination of catalyst micromeritics.

54
 1.3. CBtBlyst Testing

diffraction work and electron microscopy. The pore shape can be

deduced, but rarely without ambiguity, from physical adsorption
isotherms: the only pore shapes known with accuracy have been
determined by X-ray diffraction of a crystal structure (e.g. zeolites).
Standard methods are available.4(}-44 In recent years these methods have
been automated, and a modern laboratory is shown in Figure 1.18.
Diffusion characteristics of catalyst particles can be estimated by
analysis of transient flows, but a more direct method involves the use of
a single-pellet reactor44 in which diffusion and reaction are measured
simultaneously.

) .3.6. Catalyst Performance

To assess catalytic performance a reactor of some form is needed. The
type of experimental reactor, and how it is operated, has to be chosen
carefully and it depends on the nature of the information required. 45-50

Research catalysts

Coarse laboratory screening

Fine laboratory screening

Studiesof
reaction
mechanism

Semitechnical tests Plant sidestream tests

Kinetics determination Full-scale plant tests

Production catalyst

Figu re 1.19. Flow sheet showing the stages of catalyst development from explora-
tory work through to catalyst production.

55
ChBpter 1. Fundamental Principles

The flow sheet in Figure 1.19 shows the stages of catalyst d(~velopment
from exploratory work through to catalyst production. Few research
programmes follow the full sequence: most speculative research
projects fail and many development projects start from a considerable
body of knowledge. Studies of the re action mechanism Iconsidered
below) can be carried out at any stage. For example, mechanistic studies
may be used to interpret unexpected results in the coarse screening at
the start of catalyst development, but work is still being done on the
mechanism of ammonia synthesis some 70 years after tht:, successful
development of a commercial catalyst.
1.3.7. Coarse Laboratory Screening
At each stage of development various catalyst formulations are rejected
as unsuitable, and this rejected fraction is largest at the initiallaboratory
stage, which may be considered "coarse screening". The catalysts tested
here are either speculative catalysts for an existing, possibly even
well-established, industrial process, or a range of plausible catalysts for
a new process. The primary aim in coarse testing is the separ.ltion of the
promising catalysts from the useless catalysts. It is impoI1:ant at this
stage that, as far as possible, no promising formulation is rejected. Tbe
experimental requirements to achieve coarse screening at a reasonable
cost are given in Table 1.11. Although the criteria for acceptance at this
stage are coarse, Le. semiquantitative or even qualitative, successful
coarse testing required much experimental finesse.

Table 1.11. Experimental requirements for coarse screening of c:atalysts

Simple criteria (e.g. minimum aetivity or seleetivity to desired product) to rejeet

useless formulations
2 Rapid tests, preferably with several catalysts simultaneously
3 Small catalyst sampies only needed for evaluation
4 Determination of intrinsic catalyst performance
5 Able to cope with as wide a variety of catalysts as possible

Tbe requirements in Table 1.11 are most easily achieved with

microreactor systems. A modern installation with full computer control
of operation and analysis is shown in Figure 1.20. Most microreactor
systems consist of continuous-flow reactors, and the use of crushed
catalyst minimizes any disguise of true activity by pore dEfusion and
inadequate heat transfer. Sometimes, however, a pulse microreactor
(Figure 1.21), the first type of microreactor to be developed,51 can give
results which are unobtainable by other techniques. 52 As weil as being of

56
 1.3. Cstslyst Testing

Figure 1.20. A modern laboratory installation of miCforeactor systems for eatalyst

lesting .

Figura 1.21. Flow sheet for a pulse mieroreactor system.

57
Chapter 1. Fundamental Principles

value for discovering the intrinsic performance of experimental

catalysts, pulse microreactor systems can also be very useful in studies of
catalyst poisoning. 53
So far, it has been tacitly assumed that the reaction used for the tests
is the same as the reaction occurring in the full-scale reactor. Tbe ideal
test (of more import~nce in the fine screening) should encompass:
(a) the real catalyst
(b) the real reaction
(c) the real conditions.
Any departure from this ideal must be regarded as a potential source of
error in the testing. For example, some attempts were made 45 to use
methanol decomposition, rather than the synthesis rea,::tion, as a
screening test for methanol synthesis catalysts because of experimental
simplicity (e.g. operation at atmospheric pressure). Whlle a broad
correlation was found between test performance and activity in
methanol synthesis, there were too many exceptions for acceptance of
methanol decomposition activity as a standard test. Those d Iscrepancies
can be understood 54 as a consequence of catalyst variability: the nature
of the surface of many catalysts, induding methanol synthesis catalysts,
is markedly dependent on the gases with which they are in contact.

1.3.8. Fine Laboratory Screening

In the fine screening of catalysts an accurate quantitative assessment of
activity and selectivity is required, so the simulation of fuH-s<:ale practice
is doser than for coarse testing. Microreactor systems are widely
used45-47 for this testing, and automation allows high productivity in
their use. As in most activity testing, experimental formulalions should
be compared with a "standard" catalyst, although with sul'ficient care
and skill it is now possible to operate catalyst test unh for most
heterogeneous catalytic processes so that a test catalyst gives an
accurately reproducible performance. Where such good reproducibility
has not been attained the causes are usually inadequate temperature
control, trace poisons in reactants, non-steady state conditions or poor
reactor design.
Activities of catalysts are sometimes based on conversions achieved in
tests at constant space velocity . This procedure should not be used,
because a quantitative comparison is not possible without a fuH
knowledge of the kinetics. Tbis also applies to selectivity det,~rminations
because selectivity is defined in terms of conversions to the various
possible products. The procedure can also give false answers for

58
 1.3. Catalyst Testing

reactions which are near equilibrium. The correct procedure involves

more experimental work, but with modern computer control this is not
too arduous. Instead of a single run at fixed space velocity , aseries of
runs is carried out under constant conditions except for space velocity ,
which is varied. A comparison of the space velocities required for
different catalysts to give the same conversion (from interpolation of
experimental results) gives directly the relative amounts of catalyst
needed to obtain the same conversion. This gives the ratio of catalyst
activities directly. For similar reasons, comparisons of selectivity should
always use values obtained at constant conversion.
Catalyst poisoning can be much more troublesome in small-scale
testing than in full-scale practice.
1. It can be difficult to obtain laboratory gases that are as pure as those
in a plant.
2. Space velocities used in catalyst testing are higher than in plant
practice, so more poison is fed to the catalyst.
3. In plants with recycle (ammonia and methanol syntheses), only the
make-up gas carries fresh poison to the catalyst.
As a result, even with the same poison conte nt in the feed gas, the rate
of poisoning in a test reactor can be 50 times that in a plant.
Other difficulties arise from "poisoning profiles". In a large reactor a
poison front often develops, deactivating catalyst ne ar the inlet.
Although the shape of the poison profile is a complex function of mass
and heat transfer, and poisoning and reaction kinectics, the poison front
is gene rally sharper and narrower in a long reactor than in a short
reactor. Thus an extent of poisoning which, in a full-scale reactor may
deactivate only 1% or 2% of the catalyst bed at the inlet (i.e. a barely
perceptible effect), can affect all of the catalyst in a very small
laboratory reactor.
In both coarse and fine catalyst testing the measured catalyst activities
must be those of the catalyst itself, free from any intrusion by
mass-transfer or heat-transfer phenomena. Many tests for these effects
have been proposed in the literature, but most are inadequate. Madon
and Boudart55 examined these problems in some detail, and concluded
that a diagnostic test in which the concentration of active sites in the
catalyst is varied gives the most reliable assurance of freedom from
mass- and heat-transfer effects. If the observed activity of the catalyst is
directly proportional to the concentration of active sites, then the
experimenter can be reasonably sure that catalyst activity is really being
determined. Any different variation of observed catalyst activity with
active site concentration can be analysed to determine the nature of the

59
Chaptaf ,. FundamantaIP,inc;ples

interfering arteract. Most of the literature o n this diagnostic tesl

concerns supported metal catalysts. but it can also be applied to oxide
catalysts. e.g. FeJOJCr20J. used for the high-temperature water-gas
shift reaction. I)
Somctimes the special features of a process lead to the development
of special melhods of fine catalyst testing. In one example~ it was
necessary to compare accurately the activity of various clbalt oxide
catalysts for ammonia oxidation. A reaetor was devised (Figure 1.22) in
which a single pellet was mounted on a thermocouple and the pellet
temperature was measured as a function of the gas rate. The pellet.
together with the sUTTounding gas and apparatus. was first heated to
reaction ignition temperature. when the pellet temperature rose
because of the exotherrnie reaction. The gas flow ratt: was then
gradually increased until . quite suddenly. the pellet temperature fell to
vinually the gas temperature as ignition was lost. The gas ntte at which
extinction of the oxidation process occurred was taken as a measure of
the catalyst activity.

Metered
NHyair mhcture

Gas mixture
preheater

Healer winding
G..
preheat winding pellet
thermocouple
Catalyst pellet
thermocouple

pellet
pellet

Figure 1.22. Special reactor. using a single catalyst pellet, for the testing of cobalt
oxide catalysts in ammonia oxidation.

1.3.9. Semi-technical Catalyst Testing

Semi-teehnical testing with integral reactocs is the next sellle-up from
laboratory screening. with typically between 100 ml and I I of catalyst in
the rcactor (Figure 1.23). Onee widely uscd for eatalyst testing,
smaller-scale testing has taken over much of the work, mainly for

60
 1.3. Caralysr Tesring

Figure 1.23. A modern building for semi-technical catalyst test units. with full
computer control and data-Iogging.
reasons of both eonvenience and accuracy. Semi-technical and pilot
plants are, however, still of value in two broad areas: the larger-seale
operation, espeeially if continued for weeks or months, provides an
"insurance poliey" by indicating whether same type of cataslophic
failure is Iikely. This is especially necessary if the eatalyst has some
hitherto untried features. The other main use lies in product quality,
eIe.; for example, operation elose to plant conditions gives reliable
information on by-produet formation. Multiple sampling points along
an integral reactor have been used S1 to obtain more infonnation in eaeh
run.

1.3.10. Reaetion Kineties

The prediction of reaelor performance, either for plant design or for the
optimization of the pcrfonnance of an existing plant, requires a

61
ChBpter ,. Fundamental Principles

knowledge of tbe re action kinetics. Kinetic expressions an: sometimes

determined in an attempt to deduce catalytic mecbanism, but tb at
exercise is quite different from tbe development of a semi-ernpirical rate
equation wh ich is required only to give the rate of re action , to whatever
desired accuracy, over tbe range of temperature, pressure and
composition found in tbe plant reactor. There are tberefore tbree broad
requirements for kinetics measurement.
1. Use of tbe real plant catalyst (or at least one in tbe later stages of
development, so tbat prediction of plant performance is required) in
tbe form of pellets, etc., used in tbe reactor. Crusbed catalyst sbould
not be used, because tbe performance of wb oie pellets is Ileeded.
2. Experiments sbould cover all plant conditions, so tbat all uses of tbe
resulting kinetic equation represent an interpolation from
experimental values ratber tban an extrapolation.
3. Tbe rate of re action must be determined to sufficient ac;curacy as a
function of temperature, pressure and composition of ':be reacting
gas.
Continuous stirred tank reactors (CSTRs) are customarily
recommended for kinetics measurement because of tbe matbematical
simplicity of treating tbe results. In a CSTR tbe conditions are constant
tbrougbout, so tbe measurement of tbe rate of formation of 1be products
(from tbeir concentrations in tbe reactor exit stream and tbe flow rate)
gives tbe rate directly for a given set of conditions. In an int(:gral or plug
flow reactor (PFR) conditions vary along tbe reactor, so a different
treatment of results is needed. Some form of kinetic equation bas to be
postulated and tben integrated to fit inlet and exit conditions. However,
witb current computing facilities tbis exercise can be done readily, so tbe
cboice of reactor type is no longer as dear-cut as it used to be.
Moreover, tbe mucb better temperature control reacbed witb
microreactor systems ensures better data for equation fitting. However,
CSTRs do still bave two significant advantages.
1. Unless tbe catalyst particles are quite small (e.g. from a tluidized bed
reactor), it is mucb easier to accommodate full-sized particles
(pellets, granules or extrudates) in a CSTR tban in a microreactor
(PFR).
2. Tbe direct determination of re action rate means tbat its variation
witb experimental parameters is obvious to tbe experimt:nter during
tbe course of tbe work, so a mucb better "feei" for what is ta king
place in tbe system can be obtained.

62
 1.3. Catalyst Testing

There are three broad types of CSTRs which can be used for the
measurement of catalyst kinetics (Table 1.12 and Figure 1.24). All three
systems work weil at moderate temperatures and pressures dose to
1 bar. Difficulties arise when measurements are required at elevated
temperatures andJor pressures. The Boreskov system is now little used:
the available pumps for severe conditions are less suitable, temperature
control in the reactor often proves to be difficult and the gas
volume/catalyst volume ratio is much larger than in plant reactors. Both
Carberry/Brisk and Berty systems have been used successfully for
high-pressure/high-temperature systems, but the Berty reactor has
several fundamental advantages over the earlier systems (Table 1.13).
The relative merits of these reactors remains the subject of some
controversy.58
The prediction of catalyst performance in a full-scale reactor must
include the changes which occur during catalyst life (Section 1.4), and
the way this is done depends on the mode of deactivation. When a
poison front (as for example in LT shift beds) or a coking front (as in

Table 1.12. Type of continuous stirred tank reactor (CSTR) used in the
determination of catalyst kinetics

Type of reactor Method of mixing

Boreskov External recycle of products and reactants.

Recycle ratio high enough for near-constant
conditions in reactor
Carberry/Brisk High-speed rotation of catalyst basket in reactor
Berty Internal recycle of products and reagents within reactors
Recycle ratio high enough for near-constant conditions in
reactor

Table 1.13. The advantages of the Berty-type reactors over Carberry-Brisk reactors
for catalyst kinetics measurement

1 The gas flow through the catalyst bed is well·defined and calculable
2 As the catalyst bed is stationary. its properties (e.g. temperature) can be
measured directly
3 Little if any catalyst breakage
4 As the rotor is an impeller rather than a catalyst basket it is smaller and can be
balanced accurately
5 The gas volume/catalyst volume ratio can. if necessary, be kept closerto the
plantvalue

63
 Reactants Products
Static catalyst
Statk
Reactants bed
Rotor
Static catalyst
bed Recycle
pump
Rotating Reactants
catalyst
~ basket
.~
u
~
~
c:
'I>
E (AI
lAI
l
Products IBI (CI
ICI
~
c:
a.t
t
Products
..:
~
~ Figure 1.24. Three types 01
measurement 01
of continous-stirred tank reactor ICSTRI
of catalyst reaction kinetics.
(CSTRI used for
tor the
~
 1.3. Catalyst Testing

substitute natural gas production by naphtha-steam reforming) passes

down the bed, giving complete deactivation, then the change is solely a
decrease in effective catalyst volume, and so is readily accommodated in
reactor modelling. In other cascs (e.g. HT shift and ammonia synthesis)
when the loss in activity occurs throughout the bed largely due to slow
sintering of the active phase of the catalyst, a change in the kinetic
equation is necessary for correct reactor modelling. This is commonly
done by the usc of a factor, called "relative catalyst activity", by which
the whole kinetic expression is multiplied. This can be justified for
catalysts, such as HT shift catalyst, l3 in which decay involves a loss of
the number of active sites but no change in the site properties. 59 • ()()
However, a change in the characteristics of the active phase or in the
balance between pore-diffusion and re action rates can cause
more extensive changes in form and constants of the kinetic equa-
tion. fl ). 62 The simpler procedure of using an overall factor for activity is
almost always used in practice, since the errors introduced are usually
acceptable. Operation at constant exit concentration by adjustment of
feed rate to compensate for decay is recommended. 49
Catalyst activation for kinetic studies presents fewer problems. As
long as feed and reduction gases are as pure as plant gases (to avoid
poisoning during activation), catalyst activation by a well-defined and
reproducible procedure based on full-scale practice gives catalysts of a
constant performance which is within the range found in plants.

1.3.11. Catalyst Ageing

The simulation of catalyst ageing is the most difficult of all the
simulations of catalyst performance. What we need to achieve is a
catalyst treatment wh ich is equivalent to some months or years in the
full-scale reactor, so that all of the tests described above for fresh
catalysts can be repeated with aged catalysts. There are two broad aims
in this work: to find out how far the catalyst performance has
deteriorated (i.e. the changes in catalyst activity and selectivity) and
why this has happened. The simplest technique is that of using catalysts
discharged from the full-scale plant. Except for fluidized-bed processes,
where catalysts are frequently added and removed, it is usually difficult
to obtain catalyst sampIes othcr than at a plant shutdown, so the catalyst
decay cannot be followed. Also, plant-discharged catalyst may not be in
the same state as it was in the reactor.
An alternative procedure is the use of a laboratory accelerated-ageing
procedure. This can give useful qualitative information, but its
limitations can be shown by two examples. If catalyst decay is due to
poisoning at a level of 1 part in 109 , thcn 1 year of plant poisoning could

65
Chapter 1. Fundamental Principles

be simulated by the use of 50 ppm of poison for 10 min. However, the

adsorption and subsequent reactions of the poison would be quite
different under thc two sets of conditions. Similar problems arise with
accelerated sintering. Suppose a catalyst suffers a 50% los5 of area in 1
year of plant duty at 250°C. If this follows typical sintering kinetics with
an activation energy of 167 kJ mol-I, then treatment at 400°C for 100
min will also give a 50% loss of area, Le. accelerated ageing. However,
if another phase of the catalyst, with equivalent sintering kinetics but an
activation energy of 251 kJ mol-I, also loses 50% surface area at 250°C,
then the same accelcrated ageing will cause a 79% loss of an!a.
Tbe third technique for monitoring catalyst ageing is the use of a
sidestream reactor (Le. an experimental reactor attached to a full-scale
plant using actual plant feed). This has the advantage of operating in
real plant time, so the problems of accelerated ageing do not arise. Tbe
catalyst undergoes treatment that is very similar to that experienced by
catalyst in the plant reactor, but at the same time its performance can be
monitored readily. Tbe disadvantages of a sidestream reactor are that it
requires large quantities of catalyst, and is restricted to plant gas
composition and operation.

1.3.12. Mechanism ofthe Catalytic Reaction

The first stages in unravelling the mechanism of catalytic reaction are
the identification of thc reaction steps, the sequence of wh ich consitutes
the overall process, and the parts of the catalyst on which these re action
steps occur. Next we wish to know the rates of the indivic,ual re action
steps and which, if any, are in quasi-equilibrium and which effectively
limit the rate of the overall process. We also need to know the
energetics of these steps and the energies of adsorption of the
intermediates. When the intcrmediates have been identified, their
structures (bond lengths and energies) and their method of bonding to
the catalyst surface may be probed. Catalysts decay in practice, so we
also want to know about the mechanism of decay-what happens in the
catalyst to change its properties, and how does this affect all of the
details of the mechanism of the catalytic reaction itself?
The books and other references for furt her reading given in Appendix
1 provide descriptions of the many methods used to unravel the
mechanisms of catalytic re action , together with examples from all
categories of reaction. Here we shall look briefly at some work done
towards elucidating the mechanisms of two catalytic syntheses, those of
ammonia and methanol.

66
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