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The Copper-Catalysed Dehydrogenation of Methanol

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The Copper-Catalysed Dehydrogenation of Methanol i . THE COPPER-CATALYSED DEHYDROGENATION OF METHANOL by STEPHEN PATRICK TONNER B.Sc.(Hons.) A Dissertation submitted to the School of Chemical Engineering and Industrial Chemistry in partial fulfilment of the requirements for the degree of Doctor of Philosophy. The University of New South Wales May 1984 ii. Doctor of Philosophy (1984) University of New South Wales (School of Chemical Engineering Sydney, Australia and Industrial Chemistry) TITLE: The Copper-Catalysed Dehydrogenation of Methanol AUTHOR: Stephen Patrick TONNER, B.Sc. (Hons.), U.N.S.W. SUPERVISORS: Professor D.L. Trinm Associate Professor M.S. Wainwright NO. OF PAGES: i-xvi; 1-295. RESEARCH PUBLICATIONS: 1. Tonner, S.P., Wainwright, M.S., Trimm, D.L., and Cant, N.W., J. Chem. Eng. Data, 28, 59 (1983). 2. Tonner, S.P., Trinun, D.L., Wainwright, M.S., and Cant, N.W., J. Mol. Catal., 18, 215 (1983). 3. Evans, J.W., Tonner, S.P., Wainwright, M.S., Trimn, D.L., and Cant, N.W., Proceedings of the 11th Australian Chemical Engineering Conference, Brisbane, 509, Sept. (1983). 4. Tonner, S.P., Wainwright, M.S., Trimm, D.L., and Cant, N.W., Appl. Catal., In Press. 5. Tonner, S.P., Trinm, D.L., Wainwright, M.S., and Cant, N.W., Ind. Eng. Chem. Prod. Res. Dev., In Press. 6. Cant, N.W., Tonner, S.P., Trinm, D.L., and Wainwright, M.S., Submitted to J. Catal., April (1984). iii. CANDIDATES CERTIFICATE This is to certify that the work presented in this thesis was carried out in The School of Chemical Engineering and Industrial Chemistry University of New South Wales, and has not been submitted previously to any other university or technical institution for a degree or award. Stephen Patrick TONNER B.Sc. {Hons.), U.N.S.W. iv. ABSTRACT Copper catalysts have been shown to be highly active and selective for the dehydrogenation of methanol to methyl formate at atmospheric pressure, and over the temperature range 180-240°C. Copper chromite catalysts, which were particularly effec­ tive for the reaction, were characterized in detail in order to determine the mechanism of catalyst reduction, and to understand the nature of the active surface. Elemental analysis, surface area determination, X-ray diffraction and thermal gravimetric analysis were used to show that the active catalyst consisted of copper crystallites supported on chromia or cuprous chromite. Differences in activity, selectivity and stability amongst the copper chromite catalysts were related to the extent of catalyst reduction, and the degree of copper dispersion. The specific activity of the copper chromite catalysts was low when compared with that for silica-supported and pure copper. Mass transfer effects and overestimation of metal surface area were ruled out, and the result was attributed to electronic interaction between copper and copper-chromium oxides. In the absence of support interaction, dehydrogenation activity was simply proportional to the available copper surface area. Differences in selectivity amongst various copper catalysts were related to the activity of the support phase for the decarbony­ lation of methyl formate. The effectiveness of Raney copper catalysts was also examined, but despite exhibiting high initial activity, these v. catalysts underwent dramatic deactivation. To explain this phenomenon, a model was proposed involving the blockage of active surface within the catalyst pores by the polymerization of formaldehyde, an intermediate in the reaction mechanism. Experiments with deuterium, isotopically labelled methanol and formaldhyde were carried out to investigate the reaction mechanism in detail. The very large kinetic isotope effect that was observed was consistent with the dehydrogenation of adsorbed methoxide to formaldehyde as being the rate controlling step. A thermodynamic isotope effect, that served to decrease the concentration of surface methoxide, was also identified. Identification of the mechanism whereby fonnaldehyde was converted to methyl formate, was not possible due to transesterification. vi. ACKNOWLEDGEMENTS This thesis could not have been completed without the assistance and co-operation of a great number of people. I would particularly like to express '1\Y gratitude to: My supervisors, Professor David Trinn and Associate Professor Mark Wainwright, for their patience and comradeship, and for being consistently approachable. Dr. Noel Cant for his valuable assistance with the isotope experiments, and for his contribution to all aspects of the research. My fellow postgraduate students, especially John Evans and John Honig, for their good company. I wish them all the very best with their careers. Ashley Deacon for his lively technical assistance. Mrs. Vi Weatherill for sacrificing so nuch free time to type the thesis. My parents, and all '1\Y family, for their understanding and encouragement over twenty five years. To these and numerous other acquaintances, many thanks. vii. TABLE OF CONTENTS ABSTRACT iv ACKNOWLEDGEMENTS Vi TABLE OF CONTENTS vii LIST OF TABLES xi LIST OF FIGURES xiii CHAPTER 1 INTRODUCTION 1 2. LITERATURE REVIEW 4 2.1. Production of, and Use of Methyl Formate 4 2.1.1. Synthesis of methyl formate by carbonylation 4 2.1.2. Uses of methyl formate 9 2. 2. Reactions Invol v:ing the Dehydrogenation of Alcohols 14 2.2.1. Introduction to alcohol dehydrogenation 14 2.2.2. Dehydrogenation of ethanol 18 2.2.3. Dehydrogenation of methanol to formaldehyde 23 2.3. Aspects of Methyl Formate Synthesis by Dehydrogenation of Methanol 26 2.3.1. Introduction 26 2.3.2. Reaction mechanism 29 2.3.3. Steam reforming of methanol 36 2.3.4. Hydrogenolysis of methyl formate 39 2.4. Copper Chromite Catalysts 40 2.4.1. Introduction 40 2.4.2. The structure of copper chromite catalysts 44 3. PROJECT OBJECTIVES 52 viii. TABLE OF CONTENTS (Cont'd.) CHAPTER Page 4. EXPERIMENTAL TECHNIQUES 53 4.1. Catalyst Testing 53 4.1.1. Apparatus 53 4.1.2. Chromatographic analysis 57 4.1.3. Sources and purity of chemicals employed 59 4.1.4. Calculations 60 4.2. Catalysts 65 4.2.1. Copper chromite catalysts 65 4.2.2. Supported catalysts 67 4.2.3. Raney copper catalysts 68 4.2.4. Other catalysts 70 4.2.5. Catalyst pre-treatment 72 4.3. Catalyst Characterization 72 4.3.1. Atomic absorption analysis 72 4.3.2. Surface area characterization 4.3.2.1. Measurement of total area by nitrogen adsorption 73 4.3.2.2. Measurement of copper area by reaction with nitrous oxide 76 4.3.2.3. Single-point nitrogen adsorption 80 4.3.3. X-ray diffraction 81 4.3.4. Thermal gravimetric analysis 83 5 INVESTIGATION OF COPPER CHROMITE CATALYSTS 86 5.1. Introduction 86 5.2. Catalyst Characterization 88 5.2.1. Elemental Analysis 88 5.2.2. Measurement of total surface area and pore size distribution 90 5.2.3. Copper surface areas 91 5.2.4. X-ray diffraction 94 5.2.5. Thermal gravimetric analysis 102 5.3. Discussion 106 5.4. Conclusions 111 ix. TABLE OF CONTENTS (Cont'd.) CHAPTER Page 6 PRELIMINARY INVESTIGATIONS 112 6.1. Introduction 112 6.2. Thermodynamic Yields of Methyl Formate 112 6.3. Results 118 6.3.1. Activity and selectivity of copper chromite catalysts 118 6.3.2. Catalyst stability 122 6.4. Discussion 125 6.5. Conclusions 135 7 PROPERTIES OF COPPER-BASED CATALYSTS FOR METHANOL DEHYDROGENATION 136 7.1. Introduction 136 7.2. Preparation and Characterization of Catalysts 137 7.2.1. Copper powder 137 7.2.2. Copper supported on silica 137 7.2.2.1. Impregnated catalysts 137 7.2.2.2. Ion exchanged catalysts 140 7.2.3. Copper supported on alumina 143 7.2.4. Copper supported on magnesia 145 7.2.5. Copper supported on chromia 146 7.3. Preliminary Investigations 147 7.4. Results 152 7.5. Discussion 154 7.6. Catalyst Selection 171 7.7. Conclusions 172 x. TABLE OF CONTENTS (Cont'd.) CHAPTER Page 8 BEHAVIOUR OF RANEY COPPER CATALYSTS 174 8.1. Introduction 174 8.2. Results 176 8.3. Discussion 188 8.4. Conclusions 200 9 REACTION MECHANISM 202 9.1. Introduction 202 9.2. Isotope Effects in Catalysis 208 9.3. Experimental 211 9.4. Isotope Experiments 216 , 9. 4.1. Results 216 9.4.2. Discussion 228 9.5. Experiments with Formaldehyde 234 9.5.1. Results 234 9.5.2. Discussion 237 9.6. Conclusions 241 10 CONCLUSIONS AND RECOMMENDATIONS 243 REFERENCES 248 APPENDICES 265 xi. LIST OF TABLES TABLE Page 2.1. Calculated equilibrium conversions of formaldehyde to methyl formate by 2HCHO ~ HCOOCH3 27 4.1. Retention times for gas chromatographic analysis 58 4.2. Relative molar responses (to methanol) 59 4.3. Sources and purity of chemicals employed 59 4.4. Suppliers and nominal compositions of copper chromite catalysts 66 4.5. Schedule for caustic soda addition in the preparation of Raney catalysts 69 4.6. Characteristics of Raney catalysts 70 4.7. Miscellaneous catalysts 71 5.1. Characteristics of copper chromite catalysts 89 5.2. Changes in surface area and crystallite size on reduction 92 5.3. Effect of N20 sample size on copper surface area 93 5.4. Tabulated values for X~ray diffraction maxima 95 5.5. Observed and predicted weight losses due to catalyst reduction 104 5.6. Weight loss by TGA for copper chromite catalysts 104 5.7. Predicted and observed weight losses for catalyst reduction at 220°C 106 5.8. Composition of copper chromite catalysts after reduction 110 6.1. Activation/deactivation of catalyst 0203 124 7.1. Characteristics of copper/silica catalysts prepared by impregnation 138 xii. LIST OF TABLES (Cont 1 d.) TABLE Page 7.2. Properties of reduced catalyst samples 148 7.3. Effect of methanol concentration on reaction rate as predicted from the kinetic expression of Myazaki and Yasumori [122] 164 7.4.
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