| 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 |
