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Chain-Limiting Operation of Fischer-Tropsch Reactor,
Final Report from September 30, 1999 to March 31, 2003

Nikolopoulos, Apostolos A.
Gangwal, Santosh K.

Research Triangle Institute

In this pdf format, this document has 100 pages and is 1.57MB.

Table of Contents

LIST OF FIGURES v
LIST OF TABLES ix
ABBREVIATIONS AND ACRONYMS iii
ACKNOWLEDGEMENTS v
EXECUTIVE SUMMARY ES 1
1 INTRODUCTION 1
2 EXPERIMENTAL 3
  2.1 Fixed-Bed Reactor (FBR) Set-UP 3
2.2 Continuous Stirred-Tank Reactor (CSTR) Set-Up 6
2.3 Analytical System 8
2.4 Catalytic Materials 11

3

RESULTS AND DISCUSSION 12
  3.1 FT Reaction on a-Alumina in a Fixed-Bed Reactor (FBR) 12
3.2 FT Reaction on 25pbw Co-18pbw Zr-100pbw SiO2 in a Fixed-Bed Reactor (FBR) 14
3.3 FT Reaction on 20% CoOx/Al2O3 (EI catalyst) in a Fixed-Bed Reactor (FBR) 30
3.4 FT Reaction on 0.5% Ru/Al2O3 in a Fixed-Bed Reactor (FBR) 48
3.5 FT Reaction on Fe/K/Cu/SiO2 Catalyst (HPR-43) in a Fixed-Bed Reactor (FBR) 54
3.6 Fixed-bed (RTI) and CSTR data (Syntroleum Corp.) of catalyst HPR-43 61
3.7 FT Reaction on Fe/K/Cu/SiO2 catalyst (HPR-43) in a CSTR (RTI) 63
4 CONCLUSIONS 71
5 RECOMMENDATIONS 73
6 BIBLIOGRAPHY 74
APPENDICES 75
APPENDIX I Fischer-Tropsch Synthesis on a Co-ZrO2 Catalyst: Effect of H2 Pulsing 76
APPENDIX II Effect of periodic pulsed operation on product selectivity in Fischer-Tropsch synthesis on Co-ZrO2/SiO2 78
 
LIST OF FIGURES
Figure 1.1 Product distribution (a-plot) for FT synthesis 1
Figure 2.1.1 Process flow diagram of the fixed-bed reaction system 3
Figure 2.1.2 Schematic diagram of the fixed-bed reactor 5
Figure 2.2.1 Process flow diagram of the continuous stirred-tank reaction system 6
Figure 2.3.1 On-line GC analysis of the permanent gases - TCD signal 8
Figure 2.3.2 On-Line GC analysis of the light hydrocarbons (C1-C15) FID signal 9
Figure 2.3.3 Off-line GC analysis of the wax hydrocarbons (C10-C70) FID signal 10
Figure 3.1.1 CO conversion of a-alumina @208ºC; P=300 psig; SV=6000 h-1 12
Figure 3.1.2 Effect of H2 pulse (1 min per 1 hour) on the outlet H2:CO ratio of a-alumina at 270ºC; P = 300 psig; SV = 6000 h-1 13
Figure 3.2.1 Effect of H2 pulse frequency on the CO conversion of Co-ZrO2/SiO2; P=300 psig; SV=6000 h-1 16
Figure 3.2.2 Effect of H2 pulse frequency on the C1 selectivity of Co-ZrO2/SiO2; P=300 psig; SV=6000 h-1 16
Figure 3.2.3 Effect of H2 pulse frequency on the product yield of Co-ZrO2/SiO2; P=300 psig; SV=6000 h-1 17
Figure 3.2.4 Effect of H2 pulse duration on the outlet H2:CO ratio of Co-ZrO2/SiO2; P=300 psig; SV=6000 h-1 18
Figure 3.2.5 Effect of H2 pulse duration on the CO conversion of Co-ZrO2/SiO2; P=300 psig; SV=6000 h-1 19
Figure 3.2.6 Effect of H2 pulse duration on the CO conversion of Co-ZrO2/SiO2; P=300 psig; SV=6000 h-1 19
Figure 3.2.7 Effect of H2 pulse duration on the product distribution (a-plot) of Co-ZrO2/SiO2; P=300 psig; SV=6000 h-1 20
Figure 3.2.9 Effect of temperature on the rate of CO conversion of Co-ZrO2/SiO2; P=300 psig; SV=7000 h-1 23
Figure 3.2.10 Effect of reactant partial pressure on the C1-C9 hydrocarbon amounts of Co-ZrO2/SiO2; T = 225/224ºC; P=300 psig; SV=7000 h-1 23
Figure 3.2.11 Effect of reactant partial pressure on the C2-C9 olefin/paraffin ratio of Co-ZrO2/SiO2; T = 225/224ºC; P=300 psig; SV=7000 h-1 24
Figure 3.2.12a Effect of time after a 1-min H2 pulse on the amount of C1-C8 formed on Co-ZrO2/SiO2; T = 225/224ºCP=300 psig; SV=7000 h-1 26
Figure 3.2.12b Effect of time after a 1-min H2 pulse on the amount of C2-C8 formed on Co-ZrO2/SiO2; T = 225/224ºCP=300 psig; SV=7000 h-1 26
Figure 3.2.13 Effect of steam addition and 1-min H2 pulse on the amount of C1-C8 formed on Co-ZrO2/SiO2; T = 225/224ºCP=300 psig; SV=7000 h-1 28
Figure 3.2.14 Effect of steam addition and 1-min H2 pulse on the amount of C2-C9 olefin / paraffin ratio of Co-ZrO2/SiO2; T = 225/224ºCP=300 psig; SV=7000 h-1 29
Figure 3.3.1 Effect of temperature on the rate of CO conversion of Co / Al2O3; P = 300 psig, SV=6000 h-1 30
Figure 3.3.2 Effect of space velocity on the chain growth probablility (a) and on the CO productivity of Co / Al2O3; T = 204ºC; P = 300 psig 31
Figure 3.3.3 Effect of space velocity on the wt% product fraction of Co / Al2O3; T = 204ºC; P = 300 psig 32
Figure 3.3.4a Effect of space velocity on the C2-C9 olefin/paraffin ratio of Co / Al2O3; T = 204ºC; P = 300 psig; F = 200-400 scc/min 33
Figure 3.3.4b Effect of space velocity on the C2-C9 olefin/paraffin ratio of Co / Al2O3; T = 204ºC; P = 300 psig; F = 200-100 scc/min 33
Figure 3.3.5 Effect of total reaction pressure on the chain growth probability (a) and on the CO productivity of Co / Al2O3; T = 203-204ºC; SV=6000 h-1 34
Figure 3.3.6 Effect of total reaction pressure on C2-C9 Olefin/paraffin ration of Co / Al2O3; T = 203-204ºC; SV=6000 h-1 35
Figure 3.3.7 Effect of N2 pulse on wt% product fraction of Co / Al2O3; T = 204ºC; P=300 psig; SV=6000 h-1 37
Figure 3.3.9 Effect of H2 pulse frequency on the CO conversion Co / Al2O3; T = 206ºC; P=300 psig; SV=6000 h-1 39
Figure 3.3.10 Effect of H2 pulse frequency on the C1 selectivity of Co / Al2O3; T = 204-209ºC; P=300 psig; SV=6000 h-1 39
Figure 3.3.11 Effect of H2 pulse frequency on the product yield of Co / Al2O3; T = 204-206ºC; P=300 psig; SV=6000 h-1 40
Figure 3.3.12 Effect of H2 pulse frequency on the C2-C9 olefin/paraffin ratio of Co / Al2O3; T = 204-206ºC; P=300 psig; SV=6000 h-1 41
Figure 3.3.13 Effect of time after a 1-min H2 pulse per 1 hour on the C2-C9 olefin/paraffin ratio of Co / Al2O3; T = 206ºC; P=300 psig; SV=6000 h-1 42
Figure 3.3.14 Effect of time after a 1-min H2 pulse per 1 hour on the paraffin vs. olefin 5-min; 30-min ratio of Co / Al2O3; T = 206ºC; P=300 psig; SV=6000 h-1 42
Figure 3.3.15 Effect of H2 pulse duration on the CO conversion of Co / Al2O3; T = 204ºC; P=300 psig; SV=6000 h-1 43
Figure 3.3.16 Effect of H2 pulse duration on the C1 selectivity of Co / Al2O3; T = 204ºC; P=300 psig; SV=6000 h-1 44
Figure 3.3.17 Effect of H2 pulse duration on the product yield of Co / Al2O3; T = 204ºC; P=300 psig; SV=6000 h-1 45
Figure 3.3.18 Effect of H2 pulse duration on the C2C9 paraffin ratio of Co / Al2O3; T = 204ºC; P=300 psig; SV=6000 h-1 45
Figure 3.3.19 Effect of reactant partial pressure on the C2C9 olefin/paraffin ratio of Co / Al2O3; T = 203ºC; P=300 psig; SV=6000 h-1 46
Figure 3.3.20 Effect of steam addition on the C1 selectivity of Co / Al2O3; T = 203ºC; P=300 psig; SV=6000 h-1 47
Figure 3.4.1 Effect of H2 pulse duration on the outlet H2:CO ratio of Ru/Al2O3; P=400 psig; SV = 3000h-1 48
Figure 3.4.2 Effect of H2 pulse on the CO conversion of Ru/Al2O3; P=400 psig; SV = 3000 h-1 49
Figure 3.4.3 Effect of the H2 pulse on the C1 selectivity of Ru/Al2O3; P = 400 psig; SV = 3000 h-1 49
Figure 3.4.4 Effect of the activation process on the CO conversion of Ru/Al2O3; P=400 psig; SV = 3000 h-1 50
Figure 3.4.5 Effect of temperature on the rate of CO consumption of Ru/Al2O3; P=400 psig; SV = 3000 h-1 51
Figure 3.4.6 Effect of H2 pulse on the CO conversion of Ru/Al2O3; P=400 psig; SV = 3000 h-1 52
Figure 3.4.7 Effect of H2 pulse on the C1 selectivity of Ru/Al2O3; P=400 psig; SV = 3000 h-1 53
Figure 3.5.1 Effect of H2 pulse on the outlet H2 ratio of HPR-43; P=300 psig; SV = 6000 h-1 55
Figure 3.5.2 Effect of H2 pulse on the CO conversion of HPR-43; P=300 psig; SV = 6000 h-1 55
Figure 3.5.3 Effect of H2 pulse on the C1 selectivity of HPR-43; P=300 psig; SV = 6000 h-1 56
Figure 3.5.4 Effect of H2 pulse on the product distribution of HPR-43; P=300 psig; SV = 6000 h-1 57
Figure 3.5.5 Effect of a 24% CO2/N2 pulse on the product distribution of HPR-43; P=300 psig; SV = 6000 h-1 57
Figure 3.5.6 Effect of CO pulse on the outlet H2:CO ratio of HPR-43; P=300 psig; SV = 6000 h-1 58
Figure 3.5.7 Effect of CO pulse on the outlet H2:CO ratio of HPR-43; P=300 psig; SV = 6000 h-1 59
Figure 3.5.8 Effect of CO pulse on the C1 selectivity of HPR-43; P=300 psig; SV = 6000 h-1 59
Figure 3.5.9 Effect if CO pulse on the product distribution of HPR-43; P=300 psig; SV = 6000 h-1 60
Figure 3.6.1 Percent CO conversion and rate (cc CO/ cc cat / h) from CSTR run of HPR-43; P=300 psig; SV = 6000 h-1 61
Figure 3.7.1 Effect of reaction pressure on the CO conversion and CO productivity of HPR-43; T = 270ºC; SV = 1868 h-1 64
Figure 3.7.2 Effect of reaction pressure on the product yield of HPR-43; T = 270ºC; SV = 1868 h-1 64
Figure 3.7.3 Effect of reaction pressure on the C2-C8 olefin/paraffin ratio of HPR-43; T = 270ºC; SV = 1868 h-1 65
Figure 3.7.4 Effect of reaction temperature on the CO conversion and CO productivity of HPR-43; P = 350 psig; SV = 1868 h-1 66
Figure 3.7.5 Effect of reaction temperature on the product yeild of HPR-43; P = 350 psig; SV = 1868 h-1 66
Figure 3.7.6 Effect of reaction temperature on the C2-C8 olefin/paraffin ratio of HPR-43; P = 350 psig; SV = 1868 h-1 67
Figure 3.7.7 Effect of feed H2:CO ratio on the CO conversion and CO productivity of HPR-43; T = 240ºC; P = 350 psig; SV = 1868 h-1 68
Figure 3.7.8 Effect of feed H2:CO ratio on the product yield of HPR-43; T = 240ºC; P = 350 psig; SV = 1868 h-1 69
Figure 3.7.9 Effect of feed H2:CO ratio no the C2-C8 olefin/paraffin ratio of HPR-43; T = 240ºC; P = 350 psig; SV = 1868 h-1 69
 

LIST OF TABLES

Table 3.2.1 Effect of "blank" pulse on the performance of Co-ZrO2/SiO2; T = 220ºC 15
Table 3.2.2 Effect of inert (N2) pulse on the performance of Co-ZrO2/SiO2; T = 224ºC 15
Table 3.2.3 Effect of steam addition and H2 pulse on the activity/selectivity of Co-ZrO2/SiO2; T = 224/223ºC P=300 psig; SV=7000 h-1 27
Table 3.3.1 Effect of inert (N2) pulse on the activity/selectivity performance of Co/Al2O3; T = 204ºC; P = 300 psig; SV = 6000 h-1 36
Table 3.6.1 Performance of fixed-bed reactor (FBR) vs. CSTR for FT reaction on HPR-43 62