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Innovative Catalyst System for Slurry-Phase Fischer-Tropsch Synthesis: Cobalt Plus a Water-Gas-Shift Catalyst.  Final Technical Report - 1991

Satterfield, Charles N.
Yates, Ian C.
Chanenchuk, Claire

Massachusetts Institute of Technology at Cambridge
Department of Chemical Engineering

Table of Contents 65kb

Executive Summary 1

I

 The Fischer-Tropsch Synthesis with a Mechanical Mixture of a Cobalt Catalyst and a Copper-Based Water-Gas-Shift Catalyst:  Abstract 571kb 3
  I.A Introduction 4

I.B

 Experimental 6
 

I.B.1

 Water-Gas-Shift (WGS) Catalysts 6

I.B.2

 Fischer-Tropsch Catalyst 8

I.B.3

 Combined System 9

I.C

 Results and Discussion: Water-Gas-Shift Catalyst Alone 10
 

I.C.1

 Stability 10

I.C.2

 Effect of Pressure 11

I.C.3

 Effect of Inlet H2/CO Ratio 11

I.C.4

 Effect of Temperature 12

I.C.5

 Effect of 1-Butene 12

I.D

 Results and Discussion: Fischer-Tropsch plus Water-Gas-Shift Catalyst 14
 

I.D.1

 Fischer-Tropsch Activity 14

I.D.2

 Water-Gas-Shift Activity 16

I.D.3

 Product Selectivity 16

I.E

 Conclusions 20

I.F

 References to Part I 22

Table I-1

 Reduction Procedure for Water-Gas-Shift Catalysts 24

Table I-2

 Process Changes for Cu/ZnO/Al2O3 Alone 26

Table I-3

 Standard Operating Conditions and Product Distributions for Combined Systems and Cobalt Catalyst Alone 27
Tables and Figures for Part I 168kb 28-38

II

 The Intrinsic Kinetics of the Fischer-Tropsch Synthesis on a Cobalt Catalyst:  Abstract 385kb 39
 

II.A

 Introduction 39

II.B

 Background 40

II.C

 Experimental Section 43

II.D

 Results and Discussion 46

II.E

 Comparison to Literature Data 51

II.F

 Conclusions 52

II.G

 Nomenclature 53

II.H

 Literature Cited 54

Table II-1

 Summary of Kinetic Studies of the Fischer-Tropsch Synthesis on Cobalt-Based Catalysts 56
Table II-2 Activity for Repeated Conditions of 240ºC, 0.79 Mpa, H2/CO=2, and Synthesis Gas Feed Rate of 0.067 NI/min/g of Catalyst 57
Tables and Figures for Part II 103kb 58-63

III

 The Hydrocarbon Selectivity of Cobalt Fischer-Tropsch Catalysts:  Abstract 428kb 64
 

III. A

 Introduction 65

III. B

 Literature Review 66

III. C

 Hydrocarbon Carbon Number Distributions 68
 

III.C.1

 Representative Product Distributions 69

III.C.2

 The Effect of Operating Parameters 70

III.C.3

 Space Velocity 71

III.C.4

 Pressure 72

III.C.5

 Temperature 72

III.C.6

 Reactor H2/CO Ratio 72

III. D

 Selectivity to Various Product Classes 73

III.E

 Secondary Reactions of 1-Alkenes 75
 

III.E.1

 Rate of Ethane Formation from Ethene 75

III.E.2

 Rate of n-Butane Formation from 1-Butene 75

III.E.3

 Rate of 2-Butene Formation from 1-Butene 76

III.E.4

 Summary 77
III. F Conclusions 78
III.G Literature Cited 79
Tables and Figures for Part III 85kb 81-88
IV The Effect of 1-Alkene Addition on Hydrocarbon Product Distribution on a Cobalt Catalyst:  Abstract 490kb 89
  IV. A Introduction 90
IV. B Experimental Procedure 93

IV. C

 Evidence for Incorporation on Cobalt 94

IV. D

 Mathematical Modeling of Incorporation 97
 

IV.D.1

 Initiation and Termination by 1-Alkenes 97

IV.D.2

 Initiation, Termination, and Propagation by 1-Alkenes 100

IV. E

 A Model for the Double-a Distribution 102

IV. F

 Explanations of Selectivity Trends 103
 

IV.F.1

 Cobalt 103

IV.F.2

 Iron 105

IV. G

 Conclusions 105

IV. H

 Nomenclature 107

IV. I

 Literature Cited 108

Table IV-1

 Interpretation of Observed Process Variable Effects on Cobalt 110
Tables and Figures for Part IV 104kb 111 - 117