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Doctoral Dissertation Template UNIVERSITY OF OKLAHOMA GRADUATE COLLEGE MECHANISTIC UNDERSTANDING OF CATALYTIC UPGRADING REACTIONS OF BIOMASS-DERIVED C2 OXYGENATES A DISSERTATION SUBMITTED TO THE GRADUATE FACULTY in partial fulfillment of the requirements for the Degree of DOCTOR OF PHILOSOPHY By TU NGUYET PHAM Norman, Oklahoma 2014 MECHANISTIC UNDERSTANDING OF CATALYTIC UPGRADING REACTIONS OF BIOMASS-DERIVED C2 OXYGENATES A DISSERTATION APPROVED FOR THE SCHOOL OF CHEMICAL, BIOLOGICAL AND MATERIALS ENGINEERING BY ______________________________ Dr. Daniel E. Resasco, Chair ______________________________ Dr. Steven P. Crossley ______________________________ Dr. Friederike C. Jentoft ______________________________ Dr. Lance L. Lobban ______________________________ Dr. Daniel T. Glatzhofer © Copyright by TU NGUYET PHAM 2014 All Rights Reserved. To my loving family Acknowledgements I am thankful to many wonderful people, who have not only made this dissertation possible but also made my graduate student life so enjoyable that I will treasure forever. First and foremost, I would like to express my deepest gratitude to my advisor and mentor, Professor Daniel E. Resasco. It has been a privilege and honor for me to be a part of his group, and to experience his in-depth knowledge and endless passion in research. He introduced and showed me the beauty of catalysis world and taught me to love research. I am grateful for his faith in my ability, which has lifted up my confidence and helped me to become who I am today. His guidance, understanding, encouragement and support made these five years very memorable and enjoyable for me and it is honestly difficult to leave it all behind. I also owe much gratitude to Dr. Tawan Sooknoi for his invaluable discussion and instruction. He has demonstrated to me the tremendous power of applying fundamental organic chemistry in understanding a catalysis system. My special appreciation also goes to Dr. Steven Crossley and Dr. Jimmy Faria, whose instruction, help, enthusiasm and encouragement was invaluable not only for my research projects but also for my career development. I am grateful to Dr. Friederike Jentoft, Dr. Lance Lobban and Dr. Richard Mallinson for their helpful criticism and enlightening discussion in the group meeting. I would like to thank Dr. Daniel T. Glatzhofer for being my committee member. I greatly appreciate Dr. Rolf Jentoft and James Miles for their tremendous help with instruments and reactors. The department staff, Vernita, Terry, Donna, Wanda, and iv Kelly have been helping me with purchasing and paperwork, which has ensured smooth progress of my research. I would especially like to thank all current and past group members, whom I have had the pleasure to interact and collaborate with. I appreciate the help, support and enjoyable friendship of Paula, Kyu, Veronica, Pilar, Amalia, Air, Mohannad, Santiago, Lu, Anh, Yen, Hai, Taiwo, Ali, Yi, Onn, Bokie, Lei, Abhishek, Miguel, Felipe, Daniel, Malli, Zheng, Shaolong, Tan, Nick, Ayut, Wesley, Karl, and Joseph. I am thankful to have wonderful friends, Phuong, Bao-Yen, Linh, Ha, Dzung, Nhung, Andrea, Cristian, Camille and Gap for becoming my second family here. I am truly grateful to Dachuan, for his love, care and wonderful sense of humor. Words cannot express my gratefulness to my amazing and incredible family. I am lucky and blessed to have their unconditional and endless love, understanding and support in my life. Without them, I would never have gotten where I am today. Finally, I would like to acknowledge the financial supports for this work from Department of Energy, Abengoa Research and National Science Foundation. v Table of Contents Acknowledgements ......................................................................................................... iv List of Tables .................................................................................................................... x List of Figures ................................................................................................................ xii Abstract ........................................................................................................................ xvii A. General Introduction and Research Direction ....................................................... 1 A.1. Energy Outlook ......................................................................................................... 1 References ......................................................................................................................... 4 A.2. Research Direction ................................................................................................... 5 B. Catalytic Upgrading of Acetic Acid - Derived Biomass by Ketonization ............. 7 B.1. Biomass Conversion Processes to Liquid Fuel ......................................................... 7 References ....................................................................................................................... 15 B.2. Literature Review on Ketonization ......................................................................... 17 B.2.1. Ketonization Mechanism ............................................................................... 17 B.2.1.1. Ketene Mechanism ............................................................................... 26 B.2.1.2. β-ketoacid Intermediate ........................................................................ 31 B.2.1.3. Other Mechanisms ................................................................................ 34 B.2.2. Ketonization Catalysts ................................................................................... 37 B.2.2.1. Interaction of Carboxylic Acids with Oxide Surfaces .......................... 39 B.2.2.2. Acid-base Properties ............................................................................. 43 B.2.2.3. Redox Properties ................................................................................... 45 B.2.2.4. Effect of Dopants and Catalyst Pretreatments ...................................... 46 References ....................................................................................................................... 52 vi B.3. Research Objectives ................................................................................................ 57 B.4. Ketonization of Acetic Acid over Ru/TiO2/Carbon Catalysts in the Aqueous Phase ............................................................................................................................ 58 B.4.1. Introduction .................................................................................................... 58 B.4.2. Experimental Techniques .............................................................................. 60 B.4.2.1. Catalyst Preparation .............................................................................. 60 B.4.2.2 Catalyst Characterization ....................................................................... 61 B.4.2.3. Reaction Studies ................................................................................... 62 B.4.3. Results ............................................................................................................ 63 B.4.3.1 Catalyst Characterization Results .......................................................... 63 B.4.3.2 Catalytic performance of TiO2/C and Ru/TiO2/C catalysts ................... 72 B.4.4. Conclusion ..................................................................................................... 79 References ....................................................................................................................... 81 B.5. Reaction Kinetics and Mechanism of Ketonization of Aliphatic Carboxylic Acids with Different Carbon Chain Lengths over Ru/TiO2 Catalyst ........................... 85 B.5.1. Introduction .................................................................................................... 85 B.5.2. Experimental .................................................................................................. 86 B.5.2.1. Catalyst Synthesis ................................................................................. 86 B.5.2.2. Catalyst Characterization ...................................................................... 87 B.5.2.3. Kinetic Measurements .......................................................................... 87 B.5.3. Results ............................................................................................................ 88 B.5.3.1. Catalyst Characterization ...................................................................... 88 B.5.3.2. Catalytic Activity Measurements .......................................................... 89 vii B.5.3.2.1. Removal of transport and thermodynamic limitations in kinetic measurements ......................................................................................... 89 B.5.3.2.2. Ketonization products from the various acids ................................... 92 B.5.3.2.3. Kinetics results. Differential reactor analysis .................................... 93 B.5.3.2.4. Reaction rate data and kinetic fitting. Integral reactor analysis ........ 94 B.5.4. Discussion .................................................................................................... 110 B.5.4.1. Nature of Catalyst Active Sites ........................................................... 110 B.5.4.2. Nature of the Adsorbed Species under Reaction Conditions .............. 112 B.5.4.3.
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