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The Fischer-Tropsch Synthesis

Robert Bernard Anderson
Department of Chemical Engineering
McMaster University
Hamilton, Ontario, Canada

With a chapter on the Kölbel-Engelhardt Synthesis
by H. Kölbel and M. Ralek
Institute of Technical Chemistry
Technical University
Berlin (West), Germany

Academic Press, Inc.

Copyright 1984

Content

1. Introduction  
  1.1 Scope of the Book 1
  1.2 A Short Historical Sketch 2
  1.3 A Brief Appraisal of the Present Status of he Fischer-Tropsch Synthesis 6
    References 7
2. Thermodynamics of the Fischer-Tropsch Synthesis  
  2.1 Thermodynamics of Producing Organic Molecules 9
  2.2 Thermodynamics of Reactions of Catalytic Materials 18
  2.3 Thermodynamics of Carbon, Carbides, Nitrides, and Carbonyls 21
  2.4 Summary 23
    References 24
3. Carbides, Nitrides, and Carbonitrides of Iron as Catalysts in the Fischer-Tropsch Synthesis  
  3.1 Introduction 26
  3.2 Preparation and Composition of Catalysts 28
  3.3 Preparation of Carbides, Nitrides, and Carbonitrides of Iron in Catalytic Form 29
  3.4 Synthesis Tests with Carbides of Iron 31
  3.5 Synthesis Tests with Nitrides and Carbonitrides of Iron 57
  3.6 Structural and Chemical Changes in Catalysts during Pretreatment and Synthesis 80
    References 97
4. Tests of Catalysts  
  4.1 Introduction 100
  4.2 Platinum-Group Metal Catalysts 100
  4.3 Cobalt and Nickel Catalysts 122
  4.4 Iron Catalysts 140
  4.5 Molybdenum and Tungsten Catalysts 159
    References 169
5 Mechanism of the Fischer-Tropsch Synthesis  
  5.1 Introduction 174
  5.2 Detailed Characterizations of Synthesis Products 175
  5.3 Prediction of Carbon-Number Distributions 186
  5.4 Origin and Prediction of Branched Species 190
  5.5 Incorporation of Molecules Other than Olefins 202
  5.6 Mechanisms Based on Analogies to Organometallic Chemistry and the Quest for a Homogeneous Fischer-Tropsch Synthesis 205
  5.7 Mechanisms with Intermediates Containing Oxygen 208
  5.8 Surface Carbides and/or CH1-3 Radicals as Intermediates 211
    References 225
6. Sulfur Poisoning of Fischer-Tropsch Catalysts  
  6.1 Introduction 229
  6.2 Sulfur Poisoning of Iron Catalysts 230
  6.3 Sulfur Poisoning of Cobalt, Nickel, Ruthenium, and Rhenium Catalysts 249
  6.4 Sulfur Poisoning of Molybdenum and Tungsten Catalysts 257
  6.5 Concluding Statement 261
  6.6 Addendum 262
    References 262
7. The Kölbel-Engelhardt Synthesis
H. Kölbel and M. Ralek		  
  7.1 Introduction 265
  7.2 Reaction Mechanism 266
  7.3 Stoichiometry 267
  7.4 Thermodynamics 268
  7.5 Catalyst 268
  7.6 Kinetics 269
  7.7 Fixed-Bed Reactor Synthesis 275
  7.8 Comparison of Fischer-Tropsch and Kölbel-Engelhardt Reactions 278
  7.9 Conclusion for Large-Scale Operation 280
  7.10 Liquid-Phase Kölbel-Engelhardt Synthesis of High Molecular Weight Paraffinic Hydrocarbons 285
  7.11 Direct Synthesis of Amines 287
  7.12 Technical and Economic Prospects 288
    References 290
  Addendum 293
  Index 295