|
Part 1 |
|
|
Objective and Summary of Results |
i |
|
1.0 |
Introduction |
1 |
|
1.1 |
General Introduction |
1 |
|
1.2 |
Thermodynamics of Oxygenate Synthesis |
2 |
|
1.3 |
Reaction Mechanisms |
2 |
|
1.4 |
Catalysts |
8 |
|
1.5 |
Active Sites for Oxygenate Formation |
11 |
|
1.6 |
Effect of Alkali Promotion |
12 |
|
1.7 |
Effect of Support |
16 |
|
1.8 |
Objectives and Scope of this Study |
18 |
|
2.0 |
Experimental |
21 |
|
2.1 |
Catalysts Preparation and Characterization |
21 |
|
2.2 |
CO Hydrogenation Studies |
24 |
|
2.3 |
Addition of Ethylene to CO/H2 Reactants |
27 |
|
2.4 |
Addition to Ethanol to CO/H2 Reactants |
28 |
|
2.5 |
Addition of Acetaldehyde to CO/H2 Reactants |
28 |
|
3.0 |
Investigation of Mechanisms of Oxygenate and Hydrocarbon Formation over Group VIII Metals: Silica Supported Ni, Ru, Rh and Pd |
29 |
|
3.1 |
Background |
29 |
|
3.2 |
Results |
35 |
|
3.2.1 |
CO Hydrogenation |
35 |
|
3.2.2 |
Addition of Ethylene to CO/H2 |
38 |
|
3.2.3 |
Addition of Ethanol to CO/H2 |
40 |
|
3.2.4 |
Addition of Acetaldehyde to CO/H2 |
42 |
|
3.3 |
Discussion |
44 |
|
3.3.1 |
Addition of Ethylene |
44 |
|
3.3.2 |
Addition of Ethanol |
46 |
|
3.3.3 |
Addition of Acetaldehyde |
47 |
|
3.3.4 |
Reaction Mechanisms |
48 |
|
3.4 |
Conclusions |
52 |
|
4.0 |
Support Effects on Oxygenate Synthesis over Rh Catalysts |
54 |
|
4.1 |
Background |
54 |
|
4.2 |
Results |
55 |
|
4.2.1 |
CO Hydrogenation |
55 |
|
4.2.2 |
Addition of Ethylene to CO/H2 |
61 |
|
4.2.3 |
Addition of Ethanol to CO/H2 |
63 |
|
4.2.4 |
Addition of Acetaldehyde to CO/H2 |
67 |
|
4.3 |
Discussion |
67 |
|
4.3.1 |
Effect of Reaction Pressure |
69 |
|
4.3.2 |
Effect of Support on Product Distribution |
70 |
|
4.4 |
Conclusions |
75 |
|
5.0 |
Effect of Alkali Promotion of Rh/TiO2 |
76 |
|
5.1 |
Background |
76 |
|
5.2 |
Results |
76 |
|
5.2.1 |
Alkali-Promoted Rh/Tio2 |
76 |
|
5.2.2 |
Addition of Ethylene to CO/H2 |
87 |
|
5.3 |
Discussion |
89 |
|
5.3.1 |
Formation of Acetone and Ethyl Acetate during CO Hydrogenation |
89 |
|
5.3.2 |
Effect of Alkali Promotion |
90 |
|
5.4 |
Conclusions |
94 |
|
6.0 |
Effect of Alkali Promotion of Rh/La2O3 |
95 |
|
6.1 |
Background |
95 |
|
6.2 |
Results |
95 |
|
6.2.1 |
Effect of Alkali Promotion |
98 |
|
6.2.2 |
Addition of Ethylene to CO/H2 |
104 |
|
6.2.3 |
Addition of Propylene to CO/H2 |
108 |
|
6.2.4 |
Addition of Ethanol to Co/H2 |
111 |
|
6.3 |
Discussion |
113 |
|
6.3.1 |
Effect of the Addition of Ethylene, Proplyene, and Ethanol to CO/H2 on Product Distribution |
113 |
|
6.3.2 |
Effect of Alkali Promotion |
118 |
|
6.4 |
Conclusions |
122 |
|
Part 2 |
|
7.0 |
The combined effects of Alkali Promoters and Supports on the Synthesis of Oxygenated Compounds over Rhodium Catalysts |
124 |
|
7.1 |
Background |
124 |
|
7.2 |
Results |
126 |
|
7.2.1 |
Rh and Li-Rh |
126 |
|
7.2.2 |
Alkali-Promoted Rh Catalysts |
129 |
|
7.3 |
Discussion |
137 |
|
7.4 |
Conclusions |
140 |
|
8.0 |
Effect of Potassium Promoters on Methanol Synthesis Over Pd/SiO2 |
141 |
|
8.1 |
Background |
141 |
|
8.2 |
Results |
141 |
| |
|
8.2.1 |
Pd/SiO2 and K-Pd/SiO2 |
141 |
|
8.2.2 |
Addition of Ethylene to CO/H2 |
143 |
|
8.3 |
Discussion |
146 |
|
8.4 |
Conclusions |
150 |
|
9.0 |
The Synthesis of Methanol on Pd and Rh Catalysts: A Comparison |
151 |
|
9.1 |
Background |
151 |
|
9.2 |
Results |
152 |
|
9.2.1 |
Addition of Ethylene to CO/H2 |
155 |
|
9.2.2 |
Addition of Ethylene to CO/H2 |
155 |
|
9.2.3 |
Addition of Ethanol to CO/H2 |
155 |
|
9.3 |
Discussion |
158 |
|
9.4 |
Conclusions |
167 |
|
10.0 |
Final Discussion |
170 |
|
10.1 |
Reaction Mechanisms |
170 |
|
10.2 |
Effect of Support |
177 |
|
10.3 |
Effect of Alkali Promoters on Supported Rh Catalysts |
179 |
|
10.4 |
Concluding Remarks |
185 |
