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The Hydrogenation of Carbon Monoxide on Cobalt Catalysts - 1979

Rautavouma, A. O. I.

Technische Hogeschool Eindhoven

Table of Contents 68kb

Section 1
463kb

1

Introduction
  1.1. Coal conversion 1
1.2. The Fischer-Tropsch synthesis 3
1.3. Mechanisms proposed for the Fischer-Tropsch synthesis 4
1.4. The present state of the art 6
1.5. The aim and outline of this thesis 9

2

Apparatus and Analysis
 

2.1

Introduction 11

2.2

The reaction system 11
 

2.2.1

Flow scheme and reactor 12

2.2.2

Analysis 13

2.2.3

Characterization of the flow reactor 15

2.3

The thermobalance 15

2.4

The adsorption apparatus 16

2.5

Definitions 17
 

2.5.1

Rates 18

2.5.2

Product distribution and selectivities 18
Section 2
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3

Preparation and Characterization of the Catalysts
 

3.1

Introduction 21

3.2

Preparation of the catalysts 22

3.3

Crystal structure of the catalysts 23

3.4

Reduction of the catalysts 25
 

3.4.1

Experimental 25

3.4.2

Reduction by hydrogen 26

3.4.3

Reduction by carbon monoxide 37

3.4.4

Reduction of Co3O4 by mixtures of hydrogen and carbon monoxide 41

3.5

Adsorption of hydrogen and carbon monoxide 42
Section 3
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4

Activity and Selectivity of Cobalt Catalysts
 

4.1

Introduction 44

4.2

Standard experiments 45
  4.2.1 Cobalt on alumina 45
4.2.2 Unsupported cobalt 46
4.2.3 Discussion 48

4.3

Influence of the hydrogen and carbon monoxide concentrations 49

4.4

Influence of the temperature 54
 

4.4.1

Cobalt on alumina 54

4.4.2

Unsupported cobalt 56

4.5

Influence of various catalyst treatments 57
 

4.5.1

Cobalt on alumina 57

4.5.2

Unsupported cobalt 63

4.6

Other cobalt catalysts 65

4.7

Discussion 66
Section 4
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5

Formation of Carbonaceous Species
 

5.1

Introduction 71

5.2

Carbonization followed in the thermobalance 72
  5.2.1 Experimental 72
5.2.2 Carbonization by carbon monoxide 73
5.2.3 Carbonization by synthesis gas 80
5.2.4 Discussion 82

5.3

Flushing of the catalysts after the Fischer-Tropsch synthesis 85
 

5.3.1

Introduction 85

5.3.2

Experimental 86

5.3.3

Flushing with hydrogen 86

5.3.4

Flushing with helium 89

5.3.5

Discussion 90
Section 5
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6

Kinetics
 

6.1

Introduction 92

6.2

Reaction orders 93
 

6.2.1

Experimental 93

6.2.2

Overall orders 94

6.2.3

Orders of various products 97

6.3

Influence of the residence time 100

6.4

Apparent energies of activation 101

6.5

Discussion 103
 

6.5.1

Overall orders of reaction 103

6.5.2

Initiation 107
Section 6
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6.5.3

Chain growth 115

6.5.4

Reaction models 118

6.5.5

Olefin-paraffin ratio 122

7

Final Discussion
 

7.1

Initiation 126

7.2

Chain growth 130

7.3

Termination 133
Section 7
550kb
Literature 135
Appendix: Equations used in model calculations 143
List of Symbols 147
Summary 149
Yhteenveto (Summary in Finnish) 151
Samenvatting (Summary in Dutch) 153
Curriculum 156
Acknowledgements 157