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Hydrogenation of 2-Methylnaphthalene in a Trickle Bed Reactor Over Bifunctional Nickel Catalysts

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Hydrogenation of 2-Methylnaphthalene in a Trickle Bed Reactor Over Bifunctional Nickel Catalysts The University of Maine DigitalCommons@UMaine Electronic Theses and Dissertations Fogler Library Fall 12-2020 Hydrogenation of 2-methylnaphthalene in a Trickle Bed Reactor Over Bifunctional Nickel Catalysts Matthew J. Kline University of Maine, [email protected] Follow this and additional works at: https://digitalcommons.library.umaine.edu/etd Part of the Catalysis and Reaction Engineering Commons, and the Petroleum Engineering Commons Recommended Citation Kline, Matthew J., "Hydrogenation of 2-methylnaphthalene in a Trickle Bed Reactor Over Bifunctional Nickel Catalysts" (2020). Electronic Theses and Dissertations. 3284. https://digitalcommons.library.umaine.edu/etd/3284 This Open-Access Thesis is brought to you for free and open access by DigitalCommons@UMaine. It has been accepted for inclusion in Electronic Theses and Dissertations by an authorized administrator of DigitalCommons@UMaine. For more information, please contact [email protected]. HYDROGENATION OF 2-METHYLNAPHTHALENE IN A TRICKLE BED REACTOR OVER BIFUNCTIONAL NICKEL CATALYSTS By Matthew J. Kline B.S. Seton Hill University, 2018 A THESIS Submitted in Partial Fulfillment of the Requirements For the Degree of Master oF Science (in Chemical Engineering) The Graduate School The University of Maine December 2020 Advisory Committee: M. Clayton Wheeler, Professor of Chemical Engineering, Advisor Thomas J. Schwartz, Assistant ProFessor oF Chemical Engineering William J. DeSisto, ProFessor oF Chemical Engineering Brian G. Frederick, ProFessor oF Chemistry Douglas W. BousField, Professor of Chemical Engineering Copyright 2020 Matthew J. Kline All Rights Reserved ii HYDROGENATION OF 2-METHYLNAPHTHALENE IN A TRICKLE BED REACTOR OVER BIFUNCTIONAL NICKEL CATALYSTS By Matthew J. Kline Thesis Advisor: Dr. M. Clayton Wheeler An Abstract of the Thesis Presented in Partial Fulfillment oF the Requirements for the Degree of Master of Science (in Chemical Engineering) December 2020 Biomass thermal conversion processes, such as pyrolysis, tend to produce mixtures of mono- and poly-aromatic species. While the high aromatic content is desirable in gasoline fractions, middle-distillate cuts, particularly jet Fuel and diesel, require upgrading via hydrogenation and ring opening to achieve better combustion characteristics. There have been many proposed methods For producing drop-in Fuels from woody biomass, one of them being Thermal DeOxygenation (TDO). The TDO process converts organic acids From cellulose hydrolysis into a low-oxygen bio-oil containing large amounts of substituted naphthalene compounds. Poly-aromatic molecules, such as those Found in TDO oil, have low cetane numbers (CN), particularly due to their high aromatic content. Even after deep hydrogenation, certain combustion characteristics, such as speciFic volume, hydrogen content, and CN may still be below required specifications. Thus, naphthenic ring opening coupled with aromatic hydrogenation is the desired process to enhance the fuel characteristics. This research Focuses on the hydrogenation of 2-methylnaphthalene (2-MN) to increase the CN. These reactions are performed industrially using a precious metal catalyst (e.g., based on palladium or platinum), but because of their intrinsically high cost and sensitivity to impurities, we Focused on supported nickel catalysts to perform the desired reactions. We hydrogenated 2-MN in a down-flow trickle-bed reactor at a variety of operating conditions. In this research, we compared several Ni catalysts to a commercial Ni catalyst with respect to reaction rate and product selectivity. Impregnated Ni catalysts showed higher activation energies and lower reaction rates than the commercial catalysts, but coprecipitated Ni catalysts produced products with similar selectivities as the commercial catalyst. We Found that higher amounts oF Ni in the coprecipitated catalysts slightly increased the cis/trans-methyldecalin ratio, whereas higher temperatures decreased the same ratio. Impregnated coprecipitated catalysts with Ni and a precious metal also changed the cis/trans-methyldecalin ratio. Although bimetallic IrNi and PdNi catalysts barely altered the ratio, the PtNi catalyst was selective towards trans-methyldecalin, whereas RuNi was selective towards cis- methyldecalin. We provided a possible explanation For that observed selectivity as well as other trends throughout this research. DEDICATION I would like to dedicate this thesis to my family. I wish to thank my parents, George and Pam, for their unconditional love and for instilling in me an extremely strong work ethic. I would like to thank my siblings, Rachel, Adam, and Joshua, for being there For me every step oF the way and For acting like you cared about my research. I appreciate all that my family has done to help me grow and succeed; without you guys, none of this would be possible. iii ACKNOWLEDGEMENTS This thesis is a culmination of two years of work, which would not have been possible without the help of many people. Firstly, I would like to acknowledge and thank my thesis advisor, Dr. Clay Wheeler. With your guidance, instruction, and mentorship, I have been able to learn an incredible amount oF inFormation not only From the laboratory work but also From our conversations. Your help and support were invaluable and have helped me grow as a researcher and as a person. I would also like to thank my graduate committee consisting of Dr. Thomas Schwartz, Dr. William DeSisto, Dr. Brian Frederick, and Dr. Douglas BousField for their guidance and contributions to this research. Next I would like to thank Dr. Sampath Karunarathne. For the entirety oF this research, I worked side-by-side with Sampath to design catalysts that would work not only For my reactions but also For TDO oil upgrading. Many of our conversations yielded valuable results that helped with our projects. I would also like to thank the members of the UMaine Catalysis group, led by Dr. Thomas Schwartz. In particular, I would like to thank Daniela Stück, Christopher Albert, Jalal Tavana, Hussein Abdulrazzaq, and Elnaz Jamalzade for their assistance and help on this research project. I would like to thank the Department of Chemical and Biomedical Engineering as well as the Forest Bioproducts Research Institute (FBRI) For allowing me to use their laboratory space as well as their analytical instruments. I would like to thank Nick Hill For his technical assistance with my reactor as well as Amy Luce For her help in ensuring that my project went smoothly. Lastly, this project would not have been possible without receiving funding. This research was funded by the Department of Transportation grant DTRT13-G-UTC43 through Maine Maritime Academy as well as the Department of DeFense grant SP4701-18-C-0047. iv TABLE OF CONTENTS DEDICATION ................................................................................................................................................. III ACKNOWLEDGEMENTS ............................................................................................................................... IV LIST OF TABLES ......................................................................................................................................... VIII LIST OF FIGURES ......................................................................................................................................... IX LIST OF ABBREVIATIONS ............................................................................................................................ XII Chapter 1. INTRODUCTION ..................................................................................................................................... 1 MOTIVATION .................................................................................................................................. 1 PETROLEUM REFINING ................................................................................................................... 2 BACKGROUND ......................................................................................................................... 2 AROMATIC FRACTIONS OF PETROLEUM ................................................................................. 5 PETROLEUM REFINING REACTIONS ........................................................................................ 7 CETANE NUMBER ............................................................................................................................ 9 THERMAL DEOXYGENATION (TDO) OIL ........................................................................................ 12 UPGRADING CHEMISTRY .............................................................................................................. 16 HYDROGENATION ................................................................................................................. 18 MODEL COMPOUNDS ................................................................................................. 18 THERMODYNAMIC LIMITATIONS ............................................................................... 22 2. CATALYSTS IN OTHER HYDROGENATION STUDIES .............................................................................. 25 CATALYST SUPPORTS .................................................................................................................... 25 SILICA .................................................................................................................................... 26 ALUMINA .............................................................................................................................
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