Translations of German Documents
on the Development of Iron Catalysts
for the Fischer-Tropsch Synthesis--Part I1

Max Leva2

Title Page

Table of Contents

Foreword

TOM Reel 101 Doc. PG-21559-NID, "Report On The Middle-Pressure Synthesis With Iron Catalysts, June 1940"
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Page
Foreword xxi
TOM Reel 101 Doc. PG-21559-NID, "Report On The Middle-Pressure Synthesis With Iron Catalysts, June 1940" 1
Introduction 1
I. The Catalyst 2
A. Precipitation of Catalyst 2
1. Starting material 3
2. Precipitation with sodium carbonate 3
3. Precipitation with ammonia 3
4. The addition of Kieselguhr 5
B. Pretreatment of the Catalyst 5
1. Induction with CO-H2 mixture during the synthesis 5
a. Mixed gas and atmospheric pressure 5
b. CO-rich gas and atmospheric pressure 5
c. CO-rich gas and elevated pressure 6
2. Induction with CO and H2 mixtures in a process separate from that of the synthesis 7
a. Induction at various pressures and synthesis at ordinary pressure 7
b. Induction at ordinary pressure and synthesis at elevated pressure 7
c. Induction at reduced pressure and various temperatures, synthesis at elevated pressure 9
d. Influence of the induction pressure upon the synthesis at elevated pressure (induction temperature, 325șC.) 10
3. Induction with CO 10
a. Influence of the induction temperature at 1/10 atmosphere pressure 11
b. Influence of induction pressure 13
c. Induction time 13
d. Mixture of CO with other gases 15
4. Theory of Induction Process 15
II. The Synthesis 17
A. The Synthesis Gas 17
B. The Synthesis Pressure 20
C. The Reaction Temperature 23
1. Influence of Induction 24
2. Influence of Gas Composition 25
3. Effect of Too Low Starting Temperature 26
4. Temperature and Reaction Products 26
D. The Influence of Alkali Contents of an Iron Catalyst Upon Its Activity and Upon the Nature of the Reaction Products 27
E. Treatment with Hydrogen Before and After the Synthesis 29
1. Pretreatment with Hydrogen 29
2. Hydrogen Treatment Between Induction and Synthesis 29
3. Hydrogen Treatment During the Synthesis 29
F. Catalysts Based on Ferrous Salts 30
G. The Influence of the Addition of Copper 31
H. The Effect of the Addition of Kieselguhr 32
III. The Reaction Products 34
A. Liquid Hydrocarbons 35
B. Paraffin 37
C. Gasol 38
D. Oxygen-containing Products 39
1. The Reaction Water 39
2. The Hydrocarbons 40
E. City Gas 40
IV. General Problems 42
A. Synthesis Gas Production 42
B. Space-Time Yields and Apparatus Details 43
C. Pelleting of the Catalyst 45
D. Some Details on the Further Processing of the Primary Products 46
Conclusion 49
Literature 51
 

TOM Reel 101 Doc. PG-21574-NID, "Lecture and Discussion on Iron Catalysts for the Middle-Pressure Synthesis, by Dr. H. Pichler With a Preface by Director Franz Fischer, September 9, 1940"
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TOM Reel 101 Doc. PG-21574-NID, "Lecture and Discussion on Iron Catalysts for the Middle-Pressure Synthesis, by Dr. H. Pichler With a Preface by Director Franz Fischer, September 9, 1940" 1
Introduction by Franz Fischer 1
I. Introduction 2
II. The Catalyst 4
A. Precipitation of the Catalyst 4
B. Pretreatment of the Catalyst 4
1. Induction with Mixtures of CO and H2 During the Synthesis 5
a. Experiments at atmospheric pressure 5
b. CO-rich gas and elevated pressure 6
2. Induction of the Catalyst By a Separate Process Preceding the Actual Synthesis 7
a. Induction at ordinary pressure and synthesis at higher pressure 7
b. Induction at different pressures and synthesis at ordinary pressure 7
c. Influence of the induction temperature upon the progress of the synthesis 7
3. The Influence of the Induction Upon the Synthesis Temperature 8
a. Time of induction 9
III. The Synthesis 10
A. The Synthesis Gas 10
B. The Synthesis Pressure 11
C. The Reaction Temperature 12
D. The Influence of the Alkali Contents on the Iron Catalysts 13
E. Treatment of the Catalyst with Hydrogen 15
F. The Effect of Addition of Kieselguhr 16
G. The Construction of the Apparatus 16
IV. The Products of Reaction 16
A. Liquid Hydrocarbons 16
B. Paraffin 17
C. Gasol 18
D. Oxygen-containing Products 19
E. City Gas 19
V. Conclusion 19
Literature 21
 

TOM Reel 101 Doc. PG-21581-NID, "Recent Investigations on Iron Catalysts"
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TOM Reel 101 Doc. PG-21581-NID, "Recent Investigations on Iron Catalysts" 1
I. Introduction 1
II. Iron-copper Catalysts from Ferrous Compounds 2
A. Solution of Iron-Metal in Formic Acid and Precipitation with Sodium Bicarbonate 2
B. Precipitation from Salts with Sodium Bicarbonate without Alkalization Thereafter 3
C. Influence of a Separate K2CO3 Addition 5
D. Effect of Mode of Alkalization Upon the Reaction 9
E. Influence of Form of Catalyst 9
F. Influence of Na2CO3 Addition 10
G. Influence of Copper Content 11
III. Iron-Copper 3-Component Catalysts Prepared from Ferric Compounds 12
A. Fe-Cu-MnO Catalysts 12
1. Thermal Decomposition of the Nitrates 12
2. Precipitation with Alkalis 13
a. Precipitation with NaOH, (KOH and NH3) 14
b. Precipitation with Na2CO3 (K2CO2, (NH4)2CO3) 17
3. Variation of the Copper and Manganese Contents in the Fe-cu-MnO Catalysts 19
4. Significance of Alkali Addition to the Fe-Cu-MnO Catalysts 20
B. Fe-Cu With Zn, Cr, Al, and Sn Catalysts 21
C. Catalysts of Special Composition 22
IV. Needle-Iron ore Catalysts 23
A. Preparation of the Synthetic Needle Iron Ore ( ” Fe2O3·1H2O) 23
1. Results of Experiments 23
B. Simplified Preparation of Needle Iron Ore 26
V. Influence of pretreatment of Iron Catalysts 29
A. Influence of CO Pretreatment 29
1. Influence of CO Induction at Synthesis Temperature 29
2. Influence of CO Pretreatment at Higher-Than-Synthesis Temperature 30
B. Pretreatment with Mixed Gas at Higher Temperatures 32
C. Influence if H2 Pretreatment 32
1. Hydrogen Treatment at Reaction Temperature 33
2. Hydrogen Treatment at High Temperatures 33
VI. Influence of Carriers 33
A. Fe-Cu-Carrier Catalysts from Ferrous Salts 34
B. Fe-Cu-MnO-Carrier Catalysts from Ferric Salts 37
C. Carrier-plus-Decomposed Nitrates Catalysts 37
D. Carrier-plus-Precipitated Catalysts 38
E. Preparation of Some Fe-Cu-MnO0Kieselguhr Catalysts 39
1. 1(4Fe-1Cu-1MnO):1 Kieselguhr Catalyst 39
2. 1(4Fe-1Cu-1MnO):0.5 Kieselguhr Catalyst 40
3. 1(4Fe-1Cu-1MnO):2 Kieselguhr Catalyst 40
4. 1(4Fe-1Cu-1MnO):3 Kieselguhr Catalyst 41
5. 1(4Fe-1Cu-1MnO):4 Kieselguhr Catalyst 41
F. General Considerations on the Kieselguhr Catalyst 41
VII. Course of the Reaction with the Iron Catalyst 43
VIII. Experiments on Water Formation 46
A. Influence of Gas Composition (CO to H2 Ratio) Upon the CO2 and H2O Formation 47
1. Experiments with Mixed Gas (CO:H2 = 1:1.9) 47
2. Experiments with H2-Rich Gas 50
3. Experiments with CO-Deficient Gas 52
B. Influence of Alkali Contents 53
C. Experiment Using a CO2-Rich Starting Gas 54
D. Water and CO2 Formation on Iron-Carrier Catalysts 55
1. Experiments with Fe-Cu-MnO-Kieselguhr Catalysts 56
2. "Three-Layer Experiment" with Fe-Kieselguhr Catalysts 60
3. Experiments with Tonsil as Carrier 62
IX. Best Catalyst Developed 65
X. Regeneration of Catalyst 66
A. Regeneration of Fe-Cu Catalysts 67
B. Regeneration of Cu-Free Catalysts 68
XI. Regeneration of the Exit Gases 68
A. Use of Coke at High Temperature 69
B. Use of Coke at High Temperature in the Presence of Illuminating Gas 69
C. Use of Coke at High Temperature in the Presence of Broken Clay 70
XII. Two-Stage Experiments with Water-Gas and Mixed Gas on Iron-Copper Catalysts 70
A. Water-gas Experiment 70
B. Mixed Gas Experiments 72
1. Without Regeneration of the End-Gas After the First Stage 72
2. With Regeneration of the End-Gas After the First Stage 72
C. Two-Stage Experiment With Water-Gas 74
XIII. Importance of the Iron Catalysts for the Simultaneous Production of CO-Deficient City Gas and Benzine in Gas Woks 76
XIV. Reduction of the CO2 On Iron Catalysts 79
IV. Copper-Free Iron Catalysts 80
A. Preliminary Experiments 81
B. Principal Experiment 83
1. Dumped Weight and Mode of Preparation 83
a. Precipitation 83
b. Precipitations with soda 83
c. Precipitations with potash 85
d. Precipitations with sodium hydroxide 85
2. Catalytic Investigations of Catalysts With Various Dumped Weights 86
3. Determination of the Alkali Quantity Needed for Alkalization 87
a. Estimation of alkali quantity according to chlorine contents 87
b. Excess alkalization and removal of unabsorbed alkali quantities by suction and washing, respectively 88
c. Precipitation in the presence of fixed alkali 88
d. Exhaustive washing of the ferric nitrate catalysts precipitated with soda 89
4. Most Effective Iron One-Component Catalyst 89
a. Method of preparation 89
b. Alkalization and catalytic activity  89
c. Catalytic activity during life-tests 90
d. Pelleting and catalytic activity 91
e. Conversion of CO with water vapor at synthesis temperature 91
5. Regeneration Experiments 92
a. With H2 at synthesis temperature 92
b. With superheated steam at synthesis temperature 92
c. Oxidation with air at synthesis temperature 93
6. Alkalization With Sodium Carbonate 93
7. Multi-Component Catalysts Which Were Precipitated Like the Best Iron One-Component Catalyst 93
a. Iron-copper catalysts 93
b. Iron-zinc oxide catalysts 94
8. Ferric Nitrate Decomposition Catalysts 94
XVI. Reaction products from Iron Catalysts 95
A. Content of Unsaturated Hydrocarbons 95
B. Paraffin Extraction 95
C. Acid Products 97
XVII. Advantages and Disadvantages of Iron Catalysts 98

 

TOM Reel 101 Doc. PG-21577-NID, "Research on the Behavior of Iron Catalysts when Operated With H2-Rich Synthesis Gas 489kb pdf 1
I. Introduction 1
II. Tests with Iron Catalysts Containing 1/4 Percent K2CO3 Using H2-Rich Gas 1
A. Multi-Stage Operation 1
B. Gas Recycle Experiments 3
C. Flow Experiment 3
D. Influence of Catalysts Induction 4
E. Influence of Operating Pressure 5
F. Tests with 1CO+6H2 Gas Mixture 6
G. Experiment with Catalyst Containing One Percent Alkali 7
III. Tests with Iron-Copper Catalysts 7
A. Influence of Pressure 7
B. Normal Pressure Experiment 8
Appendix XIII

1  The Bureau of Mines will welcome reprinting this paper, provided the following acknowledgment is used:
     "Reprinted from Bureau of Mines Information Circular _____."

2  Chemical engineer, Research and Development Division, Bureau of Mines, Central Experiment Station,
     Pittsburgh, Pa.