UNIVERSITY OF OKLAHOMA GRADUATE COLLEGE SELECTIVE CONVERSION OF UNSATURATED CARBOXYLIC ACIDS TO OLEFINS OR DIOLEFINS A THESIS SUBMITTED TO THE GRADUATE FACULTY in partial fulfillment of the requirements for the Degree of MASTER OF SCIENCE By MONICA CHIDURALA Norman, Oklahoma 2018 SELECTIVE CONVERSION OF UNSATURATED CARBOXYLIC ACIDS TO OLEFINS OR DIOLEFINS A THESIS APPROVED FOR THE SCHOOL OF CHEMICAL, BIOLOGICAL AND MATERIALS ENGINEERING BY ______________________________ Dr. Steven Crossley, Chair ______________________________ Dr. Daniel Resasco ______________________________ Dr. Bin Wang © Copyright by MONICA CHIDURALA 2018 All Rights Reserved. To my caring parents, Sudhakar and Vijaya, and my brother, Rahul. Thanks for all the love, encouragement, and support. Dedicated to the memory of my grandfather, Badriah Komakula, who always believed in my ability to succeed. You are no longer with us but your belief in me has made this journey possible. Acknowledgements I would like to thank my advisor, Dr. Steven Crossley, who gave me this wonderful opportunity to pursue a Master of Science degree in Chemical Engineering at the University of Oklahoma. Thank you for your kindness and sharing your knowledge with me during my journey as a student. Your passion and enthusiasm for this work has encouraged me to work hard to reach my potential. Thank you for being patient, motivating, and supporting me the past two years while also enriching my learning experience overall. It was an honor learning from you. I would also like to thank my committee members, Dr. Resasco and Dr. Wang, for their valuable guidance in this research. Thank you for taking the time to review my results in group meetings and for also evaluating my thesis. I would like to specially thank all the biofuels group members: Lawrence Barrett, Dr. Nick Briggs, Zheng Zhao, Valeria Herrera, Tania Erazo, Santiago Umbarila, Danny Plus, Felipe Anaya, Dr. Abishek Gumidyala, Nhung Duong, Alejandra Gomez, Ismaeel Alalq, Gap Warakunwit, Michael Zeets, Tong Mou, Tuong Bui, Reda Bababrik, Rajiv Janupala, Cristiane Scaldaferri, Feifei Yang, Camila Abreu, and Carla Herrera. Thank you for your constant help around the lab and for transferring your knowledge. My special thanks to Lawrence for conducting TEM, EDX, and TG of my samples, to Tong for VMD illustrations of the concepts, and to Carla, Feifei, Cristiane, and Camila for valuable discussions to help me improve my experimental methods and analysis. I also want to thank my friends I have met at OU: Jennifer Qiao, Hailey Wang, Wen Yang, Kayla Foley, and Kevin Zhou for your precious friendship and support. iv I want to acknowledge my funding source, National Science Foundation, for supporting my work, and the University of Oklahoma for providing me with the opportunity to contribute to academia. I want to acknowledge my family for moving thousands of miles 15 years ago to give my brother and I a better opportunity to excel in our studies and lives. I am grateful for all that you have done for me. v Table of Contents Acknowledgements ......................................................................................................... iv List of Tables ................................................................................................................... ix List of Figures ................................................................................................................... x Abstract .......................................................................................................................... xvi Chapter 1: Introduction ..................................................................................................... 1 1.1 Biomass as an alternative ..................................................................................... 5 1.1.1 Processing the biomass ............................................................................. 5 1.1.2 Production of γ-valerolactone (GVL), an important platform molecule .. 7 1.1.3 Ring opening of γ-valerolactone (GVL) to produce pentenoic acids ..... 10 1.1.4 Motivation and scope of work ................................................................ 12 Chapter 2: Enhancing pentanol production rate by cofeeding alcohols in the presence of pentanoic acid in the liquid phase ...................................................................... 15 Abstract ..................................................................................................................... 15 2.1 Introduction ........................................................................................................ 16 2.2 Experimental ....................................................................................................... 21 2.2.1 Catalyst preparation ................................................................................... 21 2.2.2 Catalyst characterization ........................................................................... 21 2.2.3 Catalytic activity measurement ................................................................. 23 2.3 Results and discussion ........................................................................................ 24 2.3.1 Catalyst characterization results ................................................................ 24 2.3.2 Catalytic results and discussion ................................................................. 27 2.3.3 Equilibrium test ......................................................................................... 41 vi 2.3.4 Effect of water on the hydrogenation of PEA and esters to alcohols ........ 41 2.3.5 Mechanism and location of the active site ................................................ 43 2.4 Conclusion .......................................................................................................... 46 2.5 Future Directions ................................................................................................ 47 Chapter 3: Enhancing propanol production rate by cofeeding alcohols in the presence of propionic acid in the gas phase ........................................................................... 48 Abstract ..................................................................................................................... 48 3.1 Introduction ........................................................................................................ 49 3.2 Experimental ....................................................................................................... 53 3.2.1 Catalyst preparation ................................................................................... 53 3.2.2 Catalyst characterization ........................................................................... 53 3.2.3 Catalytic activity measurement ................................................................. 55 3.3 Results and Discussion ....................................................................................... 56 3.3.1 Catalyst characterization results ................................................................ 56 3.3.2 Catalytic results and discussion ................................................................. 59 3.4 Conclusion & Future Direction .......................................................................... 66 Chapter 4: Identification of the active site on copper chromite ..................................... 68 Abstract ..................................................................................................................... 68 4.1 Introduction ........................................................................................................ 69 4.2 Experimental ....................................................................................................... 70 4.2.1 Catalyst preparation ................................................................................... 70 4.2.2 Catalyst characterization ........................................................................... 71 4.3 Results and Discussion ....................................................................................... 73 vii 4.3.1 Catalyst characterization results ................................................................ 73 4.3.2 Catalyst activity results .............................................................................. 77 4.4 Conclusion & Future Direction .......................................................................... 79 Chapter 5: Concluding Remarks .................................................................................... 81 Chapter 6: Future Direction ............................................................................................ 83 References ...................................................................................................................... 85 Appendix A1: Preliminary Studies ................................................................................. 94 A1.1 Literature Review ............................................................................................ 94 A1.2 Preliminary Results and Discussion ................................................................ 96 Appendix A2: Supporting information for Chapter 1: Enhancing pentanol production rate by cofeeding alcohols in the presence of pentanoic acid in the liquid phase .......................................................................................................................... 102 Appendix A3: Supporting information for Chapter 2: Enhancing propanol production