Catalytic Conversion of Glycerol to Propylene
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CATALYTIC CONVERSION OF GLYCEROL TO PROPYLENE GLYCOL: SYNTHESIS AND TECHNOLOGY ASSESSMENT ______________________________________________________ A Dissertation presented to the Faculty of the Graduate School University of Missouri- Columbia ______________________________________________________ In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy _______________________________________________________ by CHUANG-WEI CHIU Dr. Galen J. Suppes, Dissertation Supervisor DECEMBER 2006 The undersigned, appointed by the Dean of the Graduate School, have examined the dissertation entitled CATALYTIC CONVERSION OF GLYCEROL TO PROPYLENE GLYCOL: SYNTHESIS AND TECHNOLOGY ASSESSMENT Presented by Chuang-Wei Chiu a candidate for the degree of Doctor of Philosophy and hereby certify that in their opinion it is worthy of acceptance. ___________________________________ Dr. Galen J. Suppes ___________________________________ Dr. Thomas R. Marrero ___________________________________ Dr. Eric J. Doskocil ___________________________________ Dr. Qingsong Yu ___________________________________ Dr. Fu-hung Hsieh ___________________________________ Dr. Leon G. Schumacher ACKNOWLEDGEMENTS I would like to express my gratitude and respect to my advisor, Dr. Galen J. Suppes, for his unfailing assistance, guidance and patience; which made it possible for me to complete this research project. I also wish to express my sincere appreciation to other members of his dissertation committee Drs. Thomas R. Marrero, Eric J. Doskocil, Qingsong Yu, Fu-hung Hsieh, and Leon G. Schumacher for their valuable suggestions and critical reviews of the dissertation. Appreciation is extended to Drs. Rusty Sutterlin and Mohanprasad Dasari for provided me the guidance of an experienced researcher throughout my experimental work. I would like to thank the research team for their constant help and support. I also thank the faculty and staff of the Department of Chemical Engineering for their friendship during my academic years. Finally, I wish to express my deepest gratitude to my parents for their understanding patience and many sacrifices throughout this work. Their endless support and love gave me the courage to carry out my dream. ii TABLE OF CONTENTS ACKNOWLEDGEMENTS .................................................................................... II TABLE OF CONTENTS...................................................................................... III LIST OF TABLES ................................................................................................X LIST OF FIGURES............................................................................................XIII CHAPTER 1 INTRODUCTION............................................................................ 1 1.1 Glycerol By-product from Biodiesel Production .............................................. 1 1.2 New Use of Glycerol....................................................................................... 2 1.3 Applications of Propylene Glycol .................................................................... 3 1.4 Improved Process for Converting Glycerol to Propylene Glycol ..................... 4 1.5 Research Objectives ...................................................................................... 6 CHAPTER 2 REMOVAL OF RESIDUAL CATALYST FROM SIMULATED BIODIESEL’S CRUDE GLYCEROL FOR GLYCEROL HYDROGENOLYSIS TO PROPYLENE GLYCOL ....................................................................................... 9 2.1 Abstract ........................................................................................................ 10 2.2 Introduction................................................................................................... 11 2.2.1 Hydrogenolysis Catalysts .......................................................................... 12 2.2.2 Phosphate Crystallization and Precipitation............................................... 13 2.3 Experimental Section.................................................................................... 15 2.3.1 Materials.................................................................................................... 15 2.3.2 Experimental Procedures .......................................................................... 16 2.3.3 Analytical Methods .................................................................................... 17 2.4 Results and Discussion ................................................................................ 18 iii 2.4.1 Reaction Profiles of Hydrogenolysis of Glycerol to Propylene Glycol ........ 18 2.4.2 Effect of Residual Salts on Glycerol Hydrogenolysis ................................. 19 2.4.3 Removal of Phosphate in Batch Reactors ................................................. 20 2.4.3.1 Effect of Filtrate pH................................................................................. 20 2.4.3.2 Effect of Lime Addition............................................................................ 21 2.4.4 Removal of Phosphate by a Packed-Column Method ............................... 22 2.4.4.1 Effect of Residence Time........................................................................ 22 2.4.4.2 Effect of Column Temperature................................................................ 22 2.4.5 Efficiency Factor Comparison.................................................................... 24 2.5 Conclusions.................................................................................................. 25 2.6 Acknowledgments ........................................................................................ 26 CHAPTER 3 DEHYDRATION OF GLYCEROL TO ACETOL VIA CATALYTIC REACTIVE DISTILLATION................................................................................ 35 3.1 Abstract ........................................................................................................ 36 3.2 Introduction................................................................................................... 37 3.3 Experimental Section.................................................................................... 39 3.3.1 Materials.................................................................................................... 39 3.3.2 Experimental Setup ................................................................................... 40 3.3.2.1 Batch Reactive Distillation ...................................................................... 40 3.3.2.2 Semi-batch Reactive Distillation ............................................................. 40 3.3.3 Analytical Methods .................................................................................... 41 3.4 Results and Discussion ................................................................................ 42 3.4.1 Catalyst Screening and Selection.............................................................. 42 iv 3.4.2 Batch versus Semi-batch Processing ........................................................ 43 3.4.3 Effect of Glycerol Feed Flow Rate ............................................................. 44 3.4.4 Effect of Catalyst Loading.......................................................................... 45 3.4.5 Effect of Initial Water Content .................................................................... 46 3.4.6 Catalyst Stability—Ability to Reuse Catalyst.............................................. 46 3.5 Conclusions.................................................................................................. 47 3.6 Acknowledgements ...................................................................................... 48 CHAPTER 4 LOW-PRESSURE VAPOR-PHASE PACKED BED REACTOR FOR PRODUCING PROPYLENE GLYCOL FROM GLYCEROL...................... 58 4.1 Abstract ........................................................................................................ 58 4.2 Introduction................................................................................................... 59 4.2.1 Hydrogenolysis Catalysts .......................................................................... 60 4.2.2 Reaction Mechanism ................................................................................. 60 4.3 Experimental Section.................................................................................... 62 4.3.1 Materials.................................................................................................... 62 4.3.2 Catalyst Activation Procedures.................................................................. 63 4.3.3 Experimental Setup ................................................................................... 64 4.3.3.1 Vapor-phase Packed Bed Experiment.................................................... 64 4.3.3.2 Liquid-phase Packed Bed Experiment.................................................... 65 4.3.4 Analytical Methods .................................................................................... 66 4.4 Results and Discussion ................................................................................ 67 4.4.1 Liquid-phase versus Vapor-phase Packed Bed Method............................ 68 4.4.2 Vapor-Phase Packed Bed Reaction with Gas Purge................................. 69 v 4.4.3 Effect of Catalyst Loading.......................................................................... 71 4.4.4 Effect of Reaction Temperature................................................................. 74 4.4.5 Effect