|
Nomenclature |
xii |
|
Introduction |
1 |
|
Part I |
Preparation and Characterization of Methanol Synthesis Catalysts |
6 |
|
Literature Review |
7 |
|
|
Zinc Catalysts |
7 |
|
|
Copper Catalyst |
10 |
|
|
Catalysts Preparation |
13 |
|
Experimental Apparatus and Methods |
16 |
|
|
Catalyst Preparation |
16 |
|
|
Catalyst Characterization |
17 |
|
|
|
X-Ray Diffraction |
17 |
|
|
|
X-Ray Photoelectron and Auger electron spectroscopies |
18 |
|
Surface area and micropore distribution |
20 |
|
Results of Catalyst Characterization |
22 |
|
|
Cation Composition of the Binary Oxides |
22 |
|
|
X-Ray Powder Diffraction |
25 |
|
|
Guinier X-Ray |
32 |
|
|
Surface Oxidation States |
35 |
|
Surface Area and Micropore Distribution |
44 |
|
Discussion of Results |
48 |
|
Part II |
Chemisorption and Methanol Synthesis Catalysts |
52 |
|
Literature Review |
53 |
|
|
Adsorption on Zinc Oxide |
53 |
|
|
Adsorption on Copper and Copper Oxide |
61 |
|
|
Adsorption on Alumina and Chromia |
65 |
|
|
Adsorption on Mixed Oxides |
67 |
|
|
Fourier Transform Infrared Spectroscopy |
68 |
|
Experimental Apparatus and Methods |
70 |
|
|
Fourier Transform Infrared Spectrometer |
70 |
|
|
Infrared Photoacoustic Spectroscopy |
72 |
|
|
Sample Preparation for Transmission Infrared Studies |
74 |
|
Results of Atmospheric Adsorption |
76 |
|
|
Adsorption on Zinc Oxide |
76 |
|
|
Adsorption on Binary Oxides |
86 |
|
|
Adsorption on Ternary Oxides |
145 |
|
|
Photoacoustic Spectra |
175 |
|
Discussion of Results |
187 |
|
Part III |
In situ Characterization of Methanol Synthesis Catalysts |
198 |
|
Literature Review |
199 |
|
|
Thermodynamics |
199 |
|
|
Kinetics |
208 |
|
|
Reaction Mechanisms |
212 |
|
|
High Pressure Spectroscopic Cells |
222 |
|
Experimental Apparatus and Methods |
223 |
|
|
Reactor System |
223 |
|
|
|
High Pressure Section |
223 |
|
|
|
Atmospheric Section |
229 |
|
|
|
Vacuum Section |
231 |
|
High Pressure Infrared Cell |
232 |
|
Gas Chromatography |
235 |
|
|
Safety Considerations |
239 |
|
Results of in situ Characterization |
241 |
|
|
Catalytic Reactivity |
241 |
|
|
|
Binary catalysts |
242 |
|
|
|
Ternary catalysts |
247 |
|
|
Infrared Spectra at High Pressure |
249 |
|
|
|
Gaseous carbon monoxide |
249 |
|
|
|
Species on zinc oxide |
251 |
|
|
|
Species on binary catalysts |
255 |
|
|
|
Species on ternary catalysts |
266 |
|
Discussion of Results |
279 |
|
Summary and Future Recommendations |
285 |
|
References |
291 |
|
Acknowledgements |
306 |
|
Appendix A |
Calculation of XPS Binding Energies |
307 |
|
Appendix B |
Calculation of BET Surface Area and Micropore Distribution |
309 |
|
Appendix C |
Thermodynamics of the Water-Gas Shift Reaction |
320 |
|
Appendix E |
Mass Flow Controller Calibration Curves |
322 |
|
Appendix F |
Relative Response Factors |
327 |
