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Scientific Resources Relevant to the Catalytic Problems in the Conversion of Coal. Final Report - 1976

Cusumano, J. A.
Dalla Betta R. A.
Levy, R. B.

Catalytica Associates, Inc.

Table of Contents

TOC
236kb		   Summary of Contents iii
Table of Contents iv
List of Tables xii
List of Figures xv
Section 1
590kb		 Acknowledgment xvi
Abstract xvii
Part 1.  Survey of Advances in Catalysis

I

 Introduction 1

II

 Multimetallic Catalysts 4
 

A

 Introduction 4

B

 General Nature of Bimetallic Catalysts 6

C

 Physical Properties of Bimetallic Catalysts 8
 

1

 Thermal Stability 9

2

 Chemical Stability 10

D

 Catalytic Properties 12
 

1

 Activity 13

2

 Activity Maintenance 14

3

 Selectivity 16

E

 The Application of Bimetallic Catalysts for the Catalytic Conversion of Coal 19
 

1

 Hydrogenation/Dehydrogenation 21

2

 Hydrogenolysis 23

3

 Water-Gas Shift 24

F

 Summary 24

G

 References 26
Section 2
659kb

III

 Effects of Catalyst-Support Interaction, Particle Size, and Surface Morphology 30
 

A

 Introduction 30

B

 General Comments 30

C

 Catalyst-Support Interaction and Stabilization 31
 

1

 Addition of Stabilizing Compounds to Catalyst Systems 32

2

 Catalyst-Support Interactions 34
 

a

 Thermal Stability 34

b

 Surface Chemistry 37

D

 Effects of Surface Structure and Particle Size 39
 

1

 General Concept 39

2

 Specific Examples of Particle Size  41

E

 Practical Implications 43
 

1

 Catalyst Support Integration and Stabilization 43

2

 Effect of Structure and Particle Size 44

F

 References 46

IV

 Characterization 50
 

A

 Introduction 50

B

 General Discussion 51

C

 Surface Area by Chemisorption 52
 

1

 Metals 53

2

 Oxides 56

D

 Surface Area by Chemisorption 57

E

 Impact of Characterization in Catalysis 58

F

 References 60
Section 3
898kb

V

 Catalyst Preparation 63
 

A

 Introduction 63

B

 Metallic Catalysts 64
 

1

 Unsupported Metal Catalysts 67

2

 Supported Metal Catalysts 68
 

a

 The Support 68

b

 The Metal 74

C

 Nonmetallic Catalysts 78
 

1

 Unsupported Metal Catalysts 79

2

 Supported Metal Catalysts 80

D

 Practical Implications 82
 

1

 Dispersed Materials 82

2

 Supported Catalysts 83

3

 Controlled Physical Property Supports 84

4

 Stabilized Supports 85

5

 Stabilized Supported Metals 85

6

 Multimetallic Catalysts 86

E

 References 87

VI

 Poisoning and Regeneration 91
 

A

 Introduction 91

B

 General Aspects of Poisoning 92

C

 Sulfur 93
 

1

 General 93

2

 Kinetics and Mechanism 96

3

 Regeneration 97

4

 Activity Maintenance 97

D

 Carbon 98
 

1

 General 98

2

 Modeling of Deactivation 99

3

 Regeneration 101

E

 Other Poisons 102

F

 Concluding Remarks 103

G

 References 104
Section 4
599kb

VII

 Mechanism and Surface Chemistry 107
 

A

 Introduction 107

B

 CO/H2 Synthesis 108
 

1

 General Comments 108

2

 Methanation 110

3

 Liquid Hydrocarbons 113

4

 Implications of Kinetic Studies 116

C

 Water-Gas Shift Reaction 118
 

1

 Summary of Kinetics 118

2

 Technical Implications 120

D

 Hydrodenitrogenation  122
 

1

 General Remarks 122

2

 Single Ring Heterocycles 122

3

 Multi-Ring Heterocycles 123

4

 Interaction of HDN and HDS Reactions 129

5

 Implications for Further Research 130

E

 Hydrodesulfurization 131
 

1

 General Remarks 131

2

 General Kinetic Effects 131
 

a

 Effects of the Sulfur Compound 132

b

 Effects of Hydrogen 133

c

 Effects of Additives 133

d

 Bond Activation 134

3

 HDS of Single Ring Compounds 134

4

 Multi-Ring Heterocycles 135

5

 Implications for Further Research 138
Section 5
462kb

F

 Polynuclear Aromatic Cracking 139
 

1

 General Comments 140

2

 Naphthalene 141

3

 Anthracene 141

4

 Phenanthrene 143

5

 Pyrene 145

6

 Effects of Catalyst Composition 145

7

 Perspective for Further Research 147

G

 Carbon/Coal Gasification 148
 

1

 General Description of Gasification Chemistry 148

2

 Devolatilization 149

3

 Gasification 151
 

a

 Steam Gasification 152

b

 Hydrogasification 154

4

 Perspective for Further Research 156

H

 References 158
Section 6
627kb		 Part 2.  Advances in Supporting Disciplines
Introduction to Part 2 165

I

 Reactor Engineering and Catalyst Testing 166
 

A

 Introduction 166

B

 General Review of Test Reactors 168
 

1

 Description of Reactor Types 168
 

a

 Integral Reactors 171

b

 Differential Reactors 174

c

 Pulsed Microreactors 176

2

 Applicability of Test Reactors 176

3

 Tests for Kinetic Control 179

C

 Analysis of Selected Reactor Systems 180
 

1

 Batch Three Phase Reactors 181

2

 Flow Three Phase Reactor 184

3

 Counter-Current Liquid Phase Reactors 185

4

 Supercritical-State Reactors 186

5

 High Pressure Thermobalances 190

D

 Concluding Remarks 191

E

 References 193
Section 7
870kb

II

 Inorganic Chemistry 197
 

A

 Introduction 197

B

 Scope of Inorganic Chemistry 198
 

1

 Oxides 198
 

a

 Thermal Stability 204

b

 Chemical Stability 204

c

 Other General Properties of Catalytic Interests 205

d

 Zeolites 207

2

 Sulfides 210
 

a

 Thermal Stability 211

b

 Chemical Stability 212

c

 Compositions of Interest 214

3

 Carbides and Nitrides 215
 

a

 Thermal Stability 215

b

 Chemical Stability 215

c

 Structures and Compositions of Interest 216

4

 Borides, Silicides, and Phosphides 217
 

a

 Thermal Stability 218

b

 Chemical Stability 218

c

 Structure and Stoichiometry 219

5

 Organometallic Compounds 220
 

a

 Polynuclear Organometallic Complexes 221

b

 Anchoring of Homogeneous Catalysts 222

c

 Potential Applications 223

6

 Molten Salts 224

C

 Implications for Coal Conversion 226
 

1

 Thermal Stability 227

2

 Chemical Stability 228

3

 Structures and Compositions of Interest 231

D

 Conclusions 233

E

 References 235
Section 8
650kb

III

 Materials Science 240
 

A

 Introduction 240

B

 Monolithic Supports 241
 

1

 General Properties 241

2

 Catalytic Applications 245

C

 Intermetallic Compounds 246
 

1

 General Properties 247

2

 Supporting Data 250

3

 Catalytic Applications 252

4

 Future Directions 254

D

 Miscellaneous Materials 256

E

 Sintering 258
 

1

 Theoretical Aspects 258

2

 Experimental Data 262

3

 Future Directions 265

F

 References 267
Section 9
643kb

IV

 Surface Science 271
 

A

 Introduction 271

B

 Concepts Relevant to Catalysis on Metals and Alloys 271
 

1

 Surface Overlayers 272

2

 Structural Effects 273

3

 Theoretical Aspects 276

C

 Physical Techniques 279
 

1

 Electron Spectroscopies 279
 

a

 Description of Techniques 279

b

 Applications to Catalysis 286

2

 Ion Spectroscopies 290
 

a

 Description of Techniques 290

b

 Applications to Catalysis 292

D

 Summary and Conclusions 294

E

 References 297
Section 10
694kb		 Part 3.  Specific Coal Conversion Processes

I

 Introduction 301

II

 Preface to Sections III and IV - An Overview of Pertinent Petroleum Refining Operations 304
 

A

 Fuel Products From Coal Liquids 304
 

1

 Motor Gasoline 304

2

 Jet Fuel 305

3

 Gas Turbine Fuel 306

4

 Diesel Fuels 306

5

 Heating Oils 308

6

 Residual Fuels 309

B

 Petroleum Processing 310

III

 Upgrading of Hydrocarbonization Liquids from the Coalcon Process 313
 

A

 Introduction 313

B

 Process Description 314

C

 Nature of the Product 316
 

1

 Heavy Liquid Fraction 317

2

 Light Liquid Fraction 330

D

 Summary of Constraints and Process Requirements for Upgrading Coalcon Liquids 333
 

1

 Upgrading of the Heavy Liquid Fraction:  General Problems 333

2

 Upgrading of the Heavy Liquid Fraction:  Specific Applications 335

3

 Light Liquid Fraction 337
Section 11
675kb

E

 Impacting Areas and Recent Research Developments 338
 

1

 Short Term Developments 338
 

a

 Activity and Selectivity 339

b

 Activity and Maintenance 342

2

 Long Term Developments 344
 

a

 New Synthesis Procedures 344

b

 New Materials 345

c

 Reaction Studies 345

3

 Supporting Research 347

F

 Conclusions 347

G

 References 350

IV

 Refining Coal Liquids from the COED, H-Coal and Synthoil Processes to High-Octane Gasoline, Jet Fuel and Diesel Fuel 352
 

A

 Introduction 352

B

 COED Liquids 353
 

1

 Nature of COED Liquids 353

2

 Refining Problems 363
 

a

 High-Octane Gasoline 364

b

 Jet Fuel 366

c

 Diesel Fuels 368

C

 H-Coal Liquids 370
 

1

 Nature of H-Coal Liquids 370
Section 12
820kb

2

 Refining Problems 378
 

a

 High-Octane Gasoline 378

b

 Jet Fuel 380

c

 Diesel Fuels 380

D

 Synthoil Liquids 380
 

1

 Nature of Synthoil Liquids 381

2

 Refining Problems 388
 

a

 High-Octane Gasoline 389

b

 Jet Fuel 390

c

 Diesel Fuels 391

E

 Impacting Areas and Recent Research Developments 392
 

1

 Selective Hydrocracking of Polynuclear Aromatics 392

2

 Hydrotreating Processes 398
 

a

 Hydrosulfurization 399

b

 Hydrodenitrogenation 401

3

 Activity Maintenance 404

F

 Conclusions 408
 

1

 Selective Hydrocracking of Polynuclear Aromatics 409
 

a

 Short Range Programs 409

b

 Long Range Programs 409

2

 Hydrotreating Processes 410
 

a

 Short Range Programs 410

b

 Long Range Programs 411

3

 Activity Maintenance 411

a

 Long Range Programs 411

G

 References 412
Section 13
794kb

V

 Conversion of SRC to Low Sulfer, Low Nitrogen Liquid Boiler Fuels 416
 

A

 Introduction 416

B

 Catalyst Constraints and Process Requirements for SRC Upgrading 418
 

1

 Activity 418

2

 Selectivity 419

3

 Activity Maintenance 420

C

 Important Research Developments 421
 

1

 Short Term Developments 421
 

a

 Activity and Selectivity 422

b

 Activity Maintenance 426

2

 Long Term Developments 427
 

a

 New Synthesis Methods 427

b

 New Materials 428

3

 Supporting Research 430

D

 Summary and Conclusions 432

E

 References 435

VI

 Catalytic Hydrocracking of Coal or Lignite to Low Sulfur, Low Nitrogen Liquid Boiler Fuels 437
 

A

 Introduction 437

B

 Summary of Major Constraints and Objectives 439

C

 Impacting Areas and Recent Research Developments 440
 

1

 Short Term Developments 441
 

a

 Activity and Selectivity 441

b

 Stability 445

2

 Long Term Developments 446
 

a

 Novel Preparative Procedures 446

b

 New Catalytic Materials 447

c

 Novel Concepts and Techniques 448

3

 Supporting Research 449
 

a

 Activity and Selectivity 450

b

 Stability 451

D

 Conclusions 451

E

 References 453
Section 14
608kb

VII

 Combination Shift Conversion and Catalytic Methanation of Synthesis Gas to SNG 456
 

A

 Introduction 456

B

 Summary of Major Problem Areas and Catalyst Development Objectives 459
 

1

 Sulfur Poisoning 459

2

 Other Poisons 463

3

 Catalyst Thermal Stability 463

4

 Carbon Deposition 466

5

 Summary 468

C

 Impacting Areas and Recent Research Developments 468
 

1

 Short Term Programs 469
 

a

 Poison Resistant Catalysts 469

b

 Thermally Stable Catalysts 471

c

 Engineering Developments 472

2

 Long Term Research and Development 474
 

a

 Mechanism of Sulfur Tolerance 474

b

 New Catalytic Materials 475

c

 Regeneration of Synthesis Catalysts 476

d

 Homogeneous Methanation Catalysts 477

3

 Supporting Research 478

D

 Conclusions 480

E

 References 483
Section 15
495kb

VIII

 Catalytic Gasification of Coal or Lignite to Synthesis Gas and/or SNG 486
 

A

 Introduction 486

B

 Major Constraints 487
 

1

 Catalyst-Coal Contacting 489

2

 Catalyst Deactivation 492

3

 Catalyst Recovery 495

C

 Important Research Developments 495
 

1

 Short Term Programs 496
 

a

 Testing 496

b

 New Catalytic Materials 496

c

 Preparative Procedures 498

d

 Mechanism of Gasification Reactions 505

2

 Long Term Research Areas 506
 

a

 Intercalation 507

b

 Volatile Catalysts 510

D

 Conclusions 510

E

 References 513
Section 16
888kb

IX

 Advanced Synthesis pf Selected Feedstocks, Diesel Fuel and LPG from CO and H2 516
 

A

 Introduction 516

B

 Summary of Major Problem Areas and Catalyst Development Objectives 520
 

1

 Selectivity 521

2

 Sulfur Poisoning 529

3

 Carbon Deposition 532

4

 Activity Maintenance 533

5

 Synthesis of Diesel Fuel and LPG 534

C

 Research and Development Areas Pertinent to Fischer-Tropsch Synthesis 536
 

1

 Short-Term Programs 537
 

a

 Examination of Common Catalytic Materials 537

b

 Poison Resistant Catalysts 540

2

 Long-Term Research and Development 543
 

a

 New Catalytic Materials 543

b

 Bifunctional Catalysts 551

c

 Isosynthesis 553

d

 Homogeneous Hydrocarbon Synthesis 555

3

 Supporting Research 557

D

 Conclusions 559

E

 References 562