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The Selective Epoxidation of Allyl Alcohol to Glycidol

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The Selective Epoxidation of Allyl Alcohol to Glycidol THE SELECTIVE EPOXIDATION OF ALLYL ALCOHOL TO GLYCIDOL A THESIS SUBMITTED FOR THE DEGREE OF DOCTOR OF PHILOSOPHY Luke Martin Harvey B. Eng. (Newcastle), B. Sci. (Newcastle) Department of Chemical Engineering The University of Newcastle, Australia November 2020 This research was supported by an Australian Government Research Training Program (RTP) Scholarship STATEMENT OF ORIGINALITY I hereby certify that the work embodied in the thesis is my own work, conducted under normal supervision. The thesis contains no material which has been accepted, or is being examined, for the award of any other degree or diploma in any university or other tertiary institution and, to the best of my knowledge and belief, contains no material previously published or written by another person, except where due reference has been made. I give consent to the final version of my thesis being made available worldwide when deposited in the University’s Digital Repository, subject to the provisions of the Copyright Act 1968 and any approved embargo. Luke Harvey 25 November 2020 I ACKNOWLEDGMENT OF AUTHORSHIP I hereby certify that the work embodied in this thesis contains published paper/s/scholarly work of which I am a joint author. I have included as part of the thesis a written declaration endorsed in writing by my supervisor, attesting to my contribution to the joint publication/s/scholarly work. By signing below I confirm that Luke Martin Harvey contributed the design of the experimental program, conducted experiments, data analysis and scientific writing to the paper/ publication entitled “Influence of impurities on the epoxidation of allyl alcohol to glycidol with hydrogen peroxide over titanium silicate TS-1” and contributed the epoxidation chemistry portion of the experimentation and scientific writing to the paper/ publication entitled “Enhancing allyl alcohol selectivity in the catalytic conversion of glycerol; influence of product distribution on the subsequent epoxidation step”. Prof. Michael Stockenhuber 25 November 2020 II Acknowledgements I would like to offer my gratitude to my supervisors, Professor Michael Stockenhuber and Professor Eric Kennedy for their consistent support and encouragement. I can safely say that the next generation of young researchers are off to the best possible start to their careers with mentors of this calibre. I would like to acknowledge the University of Newcastle, the Australian Government Research Training Program and African Explosives Ltd. for the financial assistance in maintaining this work. Thank you to the technical staff in the Faculty of Engineering and Built Environment at the University of Newcastle. In particular, Scott Molloy, for his continued friendship, guidance and assistance without which we would be utterly lost. Jane Hamson and Justin Houghton for their assistance with laboratory administration, undergraduate teaching and running a tight ship. Glenn Bryant for his holistic expertise and assistance, particularly in the design and construction of XAS instrumentation. I truly appreciate my fellow post-graduate colleagues, Penghui, Vincent, Jim, for their contributions to developing the group and in particular Dr. Matthew Drewery for keeping the lab running smoothly and being a great friend who I can always bounce ideas off of. Thank you to my parents, Belinda and Mark, for always being there with love and encouragement when it is most needed and my brother, Mitch, for sharing a laugh when you have the time. III Abstract With the predicted global increase in biodiesel production, it is anticipated that a market oversupply of glycerol, the major by-product (approximately 10 wt%) of biodiesel manufacture, will occur. It is thus desirable to produce value-added species from waste glycerol. One commercially attractive product is glycidol (2,3-epoxy-1-propanol), a stabiliser used in the manufacture of vinyl polymers, oil additive and a precursor to novel energetic polymeric compounds. In principle, glycerol may be dehydrated to glycidol, however the more commonly used route is through acrolein (acrylaldehyde). This work examines first enhancing the production of allyl alcohol from glycerol using alkali metal-modified iron oxide catalysts supported on alumina. In this case, a feed of 35 wt% glycerol was supplied to a plug flow reactor at 340°C under N2 carrier gas. It was found that the product distribution varies according to the acid-base characteristics of the catalyst, modified by the alkali metal. The rubidium-modified iron oxide catalyst was found to provide the best allyl alcohol total yield, where the potassium-modified catalyst provided the highest selectivity to allyl alcohol. The effect of the product distribution on the success of the allyl alcohol epoxidation reaction was then examined. It was found that acrolein in particular is detrimental to the epoxidation reaction, decreasing the allyl alcohol conversion from ca. 50% to 21%. It also has the effect of decreasing the reaction kinetics to 0.14 times the control rate. This research then focuses on using operando FTIR to determine the mechanism of catalyst inhibition. Instead, a previously unreported oxidation of the vinyl group in allyl alcohol to carbonyl. This reaction was not found to occur IV VI over the Ti-free equivalent material, silicalite-1, hence a titanium species was suggested to be the catalytic site for this transformation. Last, the operando XAFS experiments undertaken in order to determine the structure of the Ti species facilitating the vinyl oxidation reaction is discussed. Using direct interpretation of the post-edge XANES spectra, pre- edge, and theoretical fitting of the EXAFS, it was found that the most likely mechanism is framework titanium with coordinated (-OO-) and H2O groups being dehydrated to a 6-coordinate (HO)2-Ti-(OSi)4 upon re-heating the catalyst wafer. We propose that this is framework titanium with a coordinated -OH ligand which is responsible for the newly-reported vinyl oxidation mechanism. V List of Publications Peer-Reviewed Journal Articles Harvey, L.; Kennedy, E.; Dlugogorski, B. Z.; Stockenhuber, M.; “Influence of impurities on the epoxidation of allyl alcohol to glycidol with hydrogen peroxide over titanium silicate TS-1”; Applied Catalysis A: General 2015, 489, 241. Harvey, L.; Sánchez, G.; Kennedy, E. M.; Stockenhuber, M.; “Enhancing allyl alcohol selectivity in the catalytic conversion of glycerol; influence of product distribution on the subsequent epoxidation step”; Asia- Pacific Journal of Chemical Engineering 2015, 10, 598. Harvey, L.; Kennedy, E.; Stockenhuber, M.; “In-Situ XAFS study of an alternative reaction pathway in the TS-1 titanium-peroxo system” (under review). VI Conference Papers Harvey, L.; Kennedy, E.; Stockenhuber, M.; “The Oxidation of Olefins Over TS-1 Using Hydrogen Peroxide: An Operando FTIR/XAFS Study” International Conference on Environmental Catalysis; United Kingdom, 2020 Harvey, L.; Kennedy, E.; Stockenhuber, M.; “Operando ftir study on the oxidation of functionalised olefins over TS-1 using hydrogen peroxide”; 19th International Zeolite Conference (IZC’19); Australia, 2019 Harvey, L.; Kennedy, E.; Stockenhuber, M.; “The Effect of Extraneous Chemical Impurities on the Epoxidation of Functionalised Olefins”; 8th World Congress on Oxidation Catalysis; Poland, 2017 Harvey, L.; Kennedy, E.; Stockenhuber, M.; “Evidence for the Presence of a Stable Peroxo Species Formed on Titanium Silicalite”; 9th International Conference on Environmental Catalysis (9th ICEC), Australia, 2016 Harvey, L.; Kennedy, E.; Stockenhuber, M.; “Selective Epoxidation of Allyl Alcohol to Glycidol over TS-1: The effect of Solvent and Organic Impurities”; The Seventh Tokyo Conference on Advanced Catalytic Science and Technology (TOCAT7), Japan, 2014 VII Table of Contents Chapter 1. Introduction ...................................................................... 1 1.1 Background ………………………………………………………………..2 1.1.1 Fossil Fuels and Their Use ................................................................. 2 1.1.2 Biodiesel Production and the Glycerol ‘Glut’ ...................................... 3 1.1.3 The Biodiesel Manufacture Process ................................................... 6 1.2 Pathways to Value-Added Products…………………………………….7 1.2.1 Uses and Reactions of Glycidol ......................................................... 8 1.2.2 Allyl alcohol production from glycerol ............................................... 13 1.3 References ………………………………………………………………17 Chapter 2. Literature Review on the Catalytic Epoxidation of Unsaturated Hydrocarbons ........................................................................ 19 2.1 Catalysis………………………………………………………………….20 2.1.1 Catalyst Energetics .......................................................................... 22 2.1.2 Selectivity of Catalysts ..................................................................... 25 2.1.3 Catalytic Mechanisms ...................................................................... 27 2.1.4 Langmuir-Hinshelwood ..................................................................... 27 2.1.5 Eley-Rideal Model ............................................................................ 28 2.1.6 Mars van Krevelen (MvK) Model ...................................................... 29 2.1.7 Autocatalysis .................................................................................... 29 2.2 The Chemistry of Epoxides……………………………………………..31 2.3 Allyl Chemistry……………………………………………………………31 2.4 Epoxidation Chemistry…………………………………………………..33
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