THE SELECTIVE SYNTHESIS OF AROMATICS AND FURANS FROM BIOMASS-DERIVED COMPOUNDS by Eyas Mahmoud A dissertation submitted to the Faculty of the University of Delaware in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemical Engineering Summer 2016 © 2016 Eyas Mahmoud All Rights Reserved THE SELECTIVE SYNTHESIS OF AROMATICS AND FURANS FROM BIOMASS-DERIVED COMPOUNDS by Eyas Mahmoud Approved: __________________________________________________________ Abraham M. Lenhoff, Ph.D. Chair of the Department of Chemical and Biomolecular Engineering Approved: __________________________________________________________ Babatunde A. Ogunnaike, Ph.D. Dean of the College of Engineering Approved: __________________________________________________________ Ann L. Ardis, Ph.D. Senior Vice Provost for Graduate and Professional Education I certify that I have read this dissertation and that in my opinion it meets the academic and professional standard required by the University as a dissertation for the degree of Doctor of Philosophy. Signed: __________________________________________________________ Raul F. Lobo, Ph.D. Professor in charge of dissertation I certify that I have read this dissertation and that in my opinion it meets the academic and professional standard required by the University as a dissertation for the degree of Doctor of Philosophy. Signed: __________________________________________________________ Dionisios G. Vlachos, Ph.D. Member of dissertation committee I certify that I have read this dissertation and that in my opinion it meets the academic and professional standard required by the University as a dissertation for the degree of Doctor of Philosophy. Signed: __________________________________________________________ Donald A. Watson, Ph.D. Member of dissertation committee I certify that I have read this dissertation and that in my opinion it meets the academic and professional standard required by the University as a dissertation for the degree of Doctor of Philosophy. Signed: __________________________________________________________ Paul J. Dauenhauer, Ph.D. Member of dissertation committee ACKNOWLEDGEMENTS I would like to thank the Department of Chemical and Biomolecular Engineering at the University of Delaware for accepting me into the program and giving me the opportunity to pursue my doctorate. I acknowledge my advisor, Professor Raul F. Lobo, for providing me with access to research equipment and the opportunity to publish my research. I would also like to thank my thesis committee members: Professors Donald Watson, Dionisios G. Vlachos, and Paul Dauenhauer for reviewing my dissertation. The research presented in this thesis was funded by the U.S. Department of Energy under a grant given to the Catalysis Center for Energy Innovation (CCEI), an Energy Frontier Research Center. The National Science Foundation (NSF) provided funding for a graduate student fellowship. iv TABLE OF CONTENTS LIST OF TABLES ....................................................................................................... xi LIST OF FIGURES ................................................................................................... xiii LIST OF SCHEMES ................................................................................................ xvii ABSTRACT ............................................................................................................ xviii Chapter 1 INTRODUCTION AND BACKGROUND….................................................. 1 1.1 Background and Motivation…………………………………................ 1 1.2 Renewable Synthesis of Aromatics and Furans….................................. 2 1.3 Catalysis………………………………………...................................... 6 1.4 Zeolites………………………………………..………..………...……. 8 1.5 Nuclear Magnetic Resonance Spectroscopy (NMR)…….................... 10 1.6 Factorial Design and ANOVA……...................................................... 15 1.7 Overview of Thesis………….……...................................................... 20 REFERENCES……..………………………............................................................... 23 2 EXPERIMENTAL METHODS…...………….....….………………….….... 26 2.1 Overview… .......................................................................................... 26 2.2 Zeolite Synthesis and Ion Exchange..................................................... 27 2.2.1 Hydrothermal Synthesis…….………….................................. 27 2.2.2 Ion Exchange……….……….………….................................. 30 2.2.3 Solid-State Ion Exchange……….……...………………......... 31 2.3 Materials Characterization…………………...…................................. 31 2.3.1 Powder X-Ray Diffraction (XRD)……................................... 31 2.3.2 N2 adsorption Isotherm Measurements.................................... 34 2.3.3 Scanning Electron Microscopy (SEM) and Energy Dispersive MMMMMMMMMM X-ray Spectroscopy (EDS)……...…….…………..……...…. 37 2.3.4 Inductively Coupled Plasma Analysis (ICP)…….……….…. 38 2.3.5 Ultraviolet-Visible Optical Spectroscopy (UV-Vis)….......…. 39 2.3.6 Fourier Transform Infrared Spectroscopy (FTIR)…………... 40 2.3.7 Temperature Programmed Desorption Thermogravimetric BBBBBBBBBBBBBBAnalysis (TPD-TGA)..…………...…………………............. 41 2.3.8 Solid-State Nuclear Magnetic Resonance (SSNMR)…........... 43 vi 2.4 Reaction Product Characterization…..................................................... 45 2.4.1 Gas Chromatography (GC)…………………………..…........ 45 2.4.2 Mass Spectroscopy (MS)…...…………..…...……..…........... 46 2.4.3 High-Performance Liquid Chromatography (HPLC).............. 46 2.4.4 Nuclear Magnetic Resonance (NMR) Spectroscopy...…….... 47 2.4.5 Organic Elemental Analysis..……………………................... 47 2.4.6 Reaction Procedure………....……………...……................... 48 2.5 Summary…………………….…...…...………..................................... 48 REFERENCES..………………………...…......……….............................................. 50 3 RENEWABLE PRODUCTION OF PHTHALIC ANHYDRIDE FROM CCCC BIOMASS-DERIVED FURAN AND MALEIC ANHYDRIDE.................... 52 3.1 Introduction............................................................................................ 52 3.2 Experimental Methods........................................................................... 56 3.2.1 Diels-Alder Reactions.............................................................. 56 3.2.2 Dehydration Reaction.............................................................. 59 3.2.3 Polymer Separation….............................................................. 61 3.2.4 Analytical NMR Experiments…………..…………….......…. 62 3.2.5 Attenuated Total Reflectance (ATR) Infrared Spectroscopy (IR) ……………………………………………………………………………………….. 62 3.2.6 Elemental Analysis………………...…................................... 63 3.2.7 Karl-Fischer Titration……………...…................................... 63 3.3 Results and Discussion ........................................................................... 63 3.3.1 Diels-Alder Reaction of Furan and Maleic Anhydride ........... 63 3.3.2 Dehydration of exo-4,10-dioxa-tricyclo[5.5.2.1.0]dec-8-ene- mmmmmmmmmmm 3,5-dione................................................................................... 66 3.3.2.1 Mixed-Sulfonic Carboxylic Anhydrides.................. 70 3.4 Conclusions............................................................................................. 76 REFERENCES..…………………...…...…......……….................................. 78 vii 4 DIELS-ALDER AND DEHYDRATION REACTIONS OF BIOMASS- mmmDERIVED FURAN AND ACRYLIC ACID FOR THE SYNTHESIS OF mmmBENZOIC ACID…............................................................................................ 82 4.1 Introduction............................................................................................. 82 4.2 Experimental Methods…........................................................................ 87 4.2.1 Materials Synthesis…….......................................................... 87 4.2.2 Analytical Methods…….......................................................... 89 4.2.3 Diels-Alder Reactions……….................................................. 89 4.2.4 Dehydration Reaction….......................................................... 92 4.2.5 TPD-TGA……….………..….................................................. 93 4.2.6 UV-Vis Spectroscopy……….................................................. 94 4.2.7 FTIR Spectrocopy………...…................................................. 94 4.2.8 Elemental Analysis…….....…................................................. 94 4.2.9 29Si NMR Spectroscopy………..……...………..…………… 94 4.3 Results and Discussion............................................................................ 95 4.3.1 Materials Characterization....................................................... 95 4.3.2 Sequential Diels-Alder-Dehydration Reaction of Furan and mmmmmmmmmmm Methyl Acrylate……………………………………………. 101 4.3.3 Diels-Alder- Reaction….........................................................102 4.3.4 Dehydration of the Diels-Alder Adduct................................. 112 4.4 Conclusions……......................................………..………………...… 116 REFERENCES..………....…...…......………................................................ 118 5 THE SOLVENT-FREE SYNTHESIS OF P-XYLENE FROM 2,5- mmmmDIMETHYLFURAN AND ETHYLENE CATALYZED BY METAL- mmmmEXCHANGED FAUJASITE ZEOLITES…................................................. 122 5.1 Introduction .........................................................................................