T. P. 709

Synthetic Liquid Fuels From Hydrogenation of Carbon Monoxide. Part 1. Review of Literature - 1948

H. H. Storch
R. B. Anderson
L. J. E. Hofer
C. O. Hawk
H. C. Anderson
N. Golumbic

Cover Page 45kb

Table of Contents 261kb

Section 1
Introduction 1
Acknowledgments 2
Review of literature 2
Introduction 2
1913-28 2
1928-32 2
Industrial development 6
German expansion of commercial plants using Fischer-Tropsch synthesis 6
Special application of Fischer-Tropsch reaction in Germany 8
Synthesis of isoparaffins and aromatic hydrocarbons 8
Manufacture of higher alcohols in Germany by modified Fischer-Tropsch synthesis 9
Fischer-Tropsch plants in Japan 10
Great Britain 10
Italy, Australia, Scotland, Spain, and Canada 11
United States 12
General reviews 13
Engineering development 15
Indirect heat-transfer reactors 15
Multistage operation 15
Normal-pressure operation 19
Medium-pressure operation 20
Fluidized fixed bed, internal heat exchanger 21
Light-hydrocarbon-product recovery 21
Recycle operations 21
Cobalt catalysts 21
Iron catalysts 22
Direct heat-transfer operation 23
Gaseous heat-transfer reactors 23
Hot-gas recycle 23
Fluidized fixed bed external heat exchanger 24
Liquid heat-transfer operation 24
Foam process 24
Modified foam process 24
Disadvantages of foam process 24
Duftschmid process 25
Solid heat-transfer operation 25
Catalysts 26
Nickel catalysts 26
Cobalt-nickel catalysts 27
Section 2
Cobalt catalysts 28
Fischer's cobalt catalysts 28
German commercial normal cobalt catalysts 28
Other cobalt catalysts 28
Preparation of cobalt catalysts 29
Conditioning of nickel and cobalt catalysts 32
Reactivation of cobalt catalysts 33
Recovery of spent cobalt catalysts 34
Analysis of cobalt catalysts 35
Iron catalysts 35
Iron-copper catalysts 35
Sintered-iron catalysts 38
Effect of alkali addition in precipitated-iron catalysts 38
Conditioning of iron catalysts 39
Ruthenium catalysts 39
Effect of carrier on catalysts 39
Effect of sulfur compounds on catalyst activity 40
Pressure, diluents, hydrogen : carbon monoxide ratio, throughput, temperature, absorption, and probable reaction mechanism 42
Effect of pressure 42
Effect of diluents 45
Hydrogen : carbon monoxide ration 45
Throughput 46
Temperature 49
Adsorption  50
Discussion of reaction mechanism 51
Energy of activation 55
Section 3
Properties of Fischer-Tropsch synthesis products 56
Primary products 56
Kogasin 56
Diesel oil 57
Paraffin wax 58
Fatty acids 59
Secondary products 59
Gasol 59
Gasoline 59
Refining primary gasoline 59
Cracking of primary liquid products 60
Storage tests 61
Determination of octane number 62
Lubricating oil 62
Fatty acids and related products 65
Miscellaneous products 67
Fischer-Tropsch cost estimates 68
Bureau of Mines research on effect of catalyst preparation, reduction, and induction procedures on activity 71
Catalyst-testing experiments 71
Introduction and summary 71
Preparation of catalyst 75
Description of apparatus 77
Section 4
Synthesis-gas manufacture 88
Conditioning procedures 88
Reactivation procedures 90
Effect of variations in methods of catalyst preparation, reduction, induction, and synthesis conditions on activity and durability 91
Iron catalysts 91
Deleterious effect of chlorides on unpromoted iron catalysts prepared from ferric salts 97
Effect of alkali on activity of unprompted iron catalysts 97
Effect of conditions of precipitation of active unpromoted iron catalysts 98
Effect of different induction procedures and operating pressures for unpromoted iron catalysts 98
Tests on promoted iron catalysts 103
Section 5
Nickel and cobalt catalysts 108
Preliminary tests using Hyflo Super-Cel as carrier; durability test at 100 p. s .i. and effect of nitrogen in the synthesis gas 108
Later tests on promoted cobalt catalysts:  Reproducibility of catalyst preparations and tests, comparison of 30- and 90-cm. catalyst depths, effect of different induction procedures, efficiencies of different kieselguhrs as carriers, space-time yield at different space velocities, and variation of reaction temperature with flow at constant contraction 112
Characteristics of products from cobalt catalysts 129
Section 6
Correlation of physical properties of catalysts with their activity 131
X-ray diffraction patterns and magnetic properties of iron catalysts 131
Introduction 131
Experimental methods 132
X-ray diffraction studies 132
Magnetic studies 132
Ferric oxides and ferric oxide hydrates 137
X-ray diffraction studies of unpromoted iron catalysts 144
Magnetic studies of unpromoted iron catalysts 151
Section 7
Magnetic and X-ray diffraction studies of promoted iron catalysts 156
Surface properties of Fischer-Tropsch catalysts 158
Cobalt Fischer-Tropsch catalysts 159
Iron Fischer-Tropsch catalysts 171
Appendix on preparation of catalysts 173
Preparation of unpromoted iron catalysts 173
Preparation of No. 10 catalysts 174
Preparation of No. 47 catalysts 175
Preparation of No. 50 catalysts 175
Preparation of No. 68 catalysts 176
Preparation of other unpromoted iron catalysts 177
Preparation of promoted iron catalysts 178
Preparation of Ruhrchemie iron catalysts 180
Preparation of cobalt and nickel catalysts 181
Equipment used in preparing catalysts 184
Section 8
Indexes 187
Numerical patent index 187
Author index 190
Subject index 195