THE APPLICATION OF GREEN CHEMISTRY AND ENGINEERING TO NOVEL SUSTAINABLE SOLVENTS AND PROCESSES A Thesis Presented to The Academic Faculty by Gregory Alan Marus In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the School of Chemical and Biomolecular Engineering Georgia Institute of Technology May 2012 THE APPLICATION OF GREEN CHEMISTRY AND ENGINEERING TO NOVEL SUSTAINABLE SOLVENTS AND PROCESSES Approved by: Dr. Charles A. Eckert, Advisor School of Chemical and Biomolecular Engineering Georgia Institute of Technology Dr. Charles L. Liotta, Co-Advisor School of Chemistry & Biochemistry Georgia Institute of Technology Dr. Facundo Fernandez School of Chemistry & Biochemistry Georgia Institute of Technology Dr. Carson Meredith School of Chemical and Biomolecular Engineering Georgia Institute of Technology Dr. Amyn Teja School of Chemical and Biomolecular Engineering Georgia Institute of Technology Date Approved: December 9th, 2011 For my Family – and all their love, vision and support ACKNOWLEDGEMENTS I would first like to thank my advisors, Dr. Eckert and Dr. Liotta, as both have been integral in guiding my development through graduate school. I especially would like to thank Dr. Eckert for his encouragement to pursue innovative ideas and collaborate with researchers to find unique solutions. I thank Dr. Liotta for his enthusiasm and passion for research. I thank my committee members, Dr. Fernandez, Dr. Meredith, and Dr. Teja for their advice, support, and helpful comments throughout this research. I thank Deborah Babykin for helping with the administrative tasks and purchase orders, which have made my time here easier. I would also like to thank all members of the Eckert-Liotta group, both former and current, as their friendships have enriched my life and suggestions have helped me view research in a different light. I especially thank the post-docs in the group, including Pamela Pollet for her guidance and suggestions in research and life in general, Eduardo Vyhmeister for his knowledge inside and out of the laboratory, and Rani Jha for her insightful discussions. I also want to acknowledge the undergraduates who have helped me work on many of the research projects, including Jacob, Sean, Michael, Martin, and Renee. I thank my family and friends for their loving support and truly enriching experiences. Lauren has always been a source of inspiration and pride and someone who I have enjoyed sharing my life with, Leslie for her support and being the amazing person she is, and my parents for their love and vision. iv TABLE OF CONTENTS Page ACKNOWLEDGEMENTS iv LIST OF TABLES viii LIST OF FIGURES ix LIST OF SYMBOLS AND ABBREVIATIONS xiii SUMMARY xv CHAPTER 1 Chapter I: Introduction 1 1.1 References 5 2 Chapter II: Novel Switchable Solvents 6 2.1 Introduction 6 2.2 Experimental 16 2.3 Results 21 Toward a scalable synthesis of PS 23 Kinetics 24 Dilution 26 Inhibitor effect 28 Separation 31 2.4 Conclusions 36 2.5 References 37 3 Chapter III: Continuous Flow Processing 40 3.1 Introduction 40 3.2 Experimental 47 v 3.3 Results 53 (S)-CMK 61 Implementation to Continuous Flow 63 3.4 Conclusions 67 3.5 References 68 4 Chapter IV: Biomass-Based Processing in Novel Switchable Solvents 71 4.1 Introduction 71 4.2 Experimental 81 4.3 Results 86 Separation 86 Reaction 91 Reaction in PS with In-Situ Acid Catalysis 93 Reaction in BS with Amberlyst-15 94 4.4 Conclusions 99 4.5 References 100 5 Chapter V: Conclusions and Recommendations 103 5.1 Conclusions 103 5.2 Recommendations 106 APPENDIX A: CO2-Enhanced Sub-Critical Water As A Sustainable Biomass Pretreatment Solvent 112 A.1 Introduction 112 A.2 Experimental 119 A.3 Results 123 A.4 Conclusions 130 A.5 References 131 APPENDIX B: HYSYS Simulation of Piperylene Sulfone 133 vi B.1 Introduction 133 B.2 Results 134 B.3 Conclusions 137 VITA 147 vii LIST OF TABLES Page Table 3-1: MPV Reductions of benzaldehyde, acetophenone, and (S)-CMK. 56 Table 4-1: Factorial design table containing the independent variables and ranges used. 97 Table 4-2: Fractional factorial design table showing design points for each experiment. 98 Table B-1: Composition workbook for PS production in HYSYS. 139 Table B-2: Material streams workbook for PS production in HYSYS. 141 Table B-3: Energy streams (heat flow) workbook for PS production in HYSYS. 143 Table B-4: Unit operations workbook for PS production in HYSYS. 144 Table B-5: Economic analysis for PS production costs based on HYSYS simulation. 145 viii LIST OF FIGURES Page Figure 2-1: Decomposition of piperylene sulfone to form trans-1,3-pentadiene and SO2. 8 Figure 2-2: Schematic showing the use of piperylene sulfone as a reaction media, the separation from products, and subsequent reformation and recycle. 10 Figure 2-3: Influence of sulfone structure on melting point (butadiene sulfone, isoprene sulfone, 2,3-dimethylbutadiene, and piperylene sulfone). 11 Figure 2-4: Plot of sulfone half-life as a function of temperature. 12 Figure 2-5: TGA of the decomposition of piperylene sulfone. 13 Figure 2-6: Comparison of the solvatochromic properties of DMSO and PS. 14 Figure 2-7: Synthesis of PS with an inhibitor from trans-1,3-pentadiene and SO2. 21 Figure 2-8: Kinetic expression for the formation of piperylene sulfone (PS). 25 Figure 2-9: Effect of diluting piperylene with excess sulfur dioxide. 27 Figure 2-10: Structures of inhibitors: (A) neutral inhibitor and (B) ionic inhibitor. 28 Figure 2-11: Effect of neutral inhibitor (N-phenyl-2 naphthylamine) on PS yield at 295K. 29 Figure 2-12: Effect of the ionic inhibitor (8-anilino-1-naphtalenesulfonic acid magnesium salt) on PS yield at 295K. 30 Figure 2-13: Schematic of sustainable CO2 separation of ionic inhibitor. 32 Figure 2-14: Beer-Lambert law used to correlate the measured absorbance to concentration. 33 1 Figure 2-15: H NMR of PS after sustainable CO2 separation. 35 13 Figure 2-16: C NMR of PS after sustainable CO2 separation. 35 Figure 3-1: Process used by the Roundtable to identify the key green engineering areas. 41 Figure 3-2: Key green engineering research areas as identified by the Pharmaceutical Roundtable. 41 ix Figure 3-3: Schematic of the Corning continuous flow reactor. 49 Figure 3-4: The mixing and linear reactor modules of the Corning® glass reactor. 50 Figure 3-5: Six-membered transition state of the aluminum complex during reduction. 54 Figure 3-6: MPV reduction of benzaldehyde with 50 mol% catalyst in isopropanol. 55 Figure 3-7: MPV reduction of acetophenone with 50 mol% catalyst in isopropanol. 55 Figure 3-8: MPV reduction of (S)-CMK with 50 mol% catalyst in isopropanol. 56 Figure 3-9: Tetrameric State of Aggregation in Al(OiPr)3. 57 Figure 3-10: Dimeric State of Aggregation in Al(OtBu)3. 58 Figure 3-11: Reaction yield as a function of time for the MPV reduction of benzaldehyde 59 Figure 3-12: Reaction yield as a function of time for the MPV reduction of (S)-CMK. 60 Figure 3-13: MPV reduction of benzaldehyde in batch reactors at 65°C. 61 Figure 3-14: Conversion of (S)-CMK to (S,S) and (S,R)-CMA at various Al(OtBu)3 catalyst loadings in isopropanol. 63 Figure 3-15: Continuous flow reactor schematic. 64 Figure 3-16: MPV Reduction of benzaldehyde in the continuous flow reactor. 65 Figure 3-17: Batch and continuous flow MPV reduction of benzaldehyde. 66 Figure 3-18: MPV Reduction of acetophenone in the continuous flow reactor. 67 Figure 4-1: Simplified reaction scheme for the production of HMF and subsequent derivatives. 72 Figure 4-2: Structure of HMF and a few of the many useful monomers derived from HMF. 73 Figure 4-3: Pathways for the acid catalyzed dehydration of hexoses to yield HMF. 76 Figure 4-4: Illustrative example of the cyclization of D-fructose. 77 Figure 4-5: Schematic of the two phase method employed by Dumesic. 80 Figure 4-6: Short-path distillation apparatus for the thermal separation of butadiene sulfone. 82 x Figure 4-7: Buchi kugelrohr used for the separation of butadiene sulfone from HMF. 83 Figure 4-8: Proposed mechanism for the DMSO catalyzed dehydration of fructose to HMF. 87 Figure 4-9: Decomposition of piperylene sulfone using the retro-cheletropic switch. 88 Figure 4-10: Decomposition of butadiene sulfone using the retro-cheletropic switch. 88 Figure 4-11: Dehydration reaction of fructose with an acid catalyst to form HMF. 92 Figure 4-12: Sulfurous acid generated through leveraging the equilibrium reaction of butadiene sulfone and combination of water with sulfur dioxide. 93 Figure 5-1: Schematic of the homo-Nazarov cyclization of cyclopropyl vinyl ketones.108 Figure 5-2: Schematic showing the acid hydrolysis of polysaccharides in the production of HMF from glucose. 111 Figure A-1: A representative structure of cellulose composed of β (1 Æ 4) linked D-glucose units. 113 Figure A-2: A representative structure of hemicelluloses. 114 Figure A-3: A representative structure of lignin 114 Figure A-4: Schematic showing the pretreatment objectives of lignocellulosic biomass. 115 Figure A-5: The formation of carbonic acid from the reaction of CO2 with water. 117 Figure A-6: Illustration of the Parr reactor used in the CO2-enhanced sub-critical water experiments. 120 Figure A-7: Experiment comparing the change in carbohydrate concentration after adding CO2. 124 Figure A-8: Concentration of four primary carbohydrates extracted after pretreatment. 126 Figure A-9: Contour plot of glucose concentration as a function of temperature and time. 127 Figure A-10: Contour plot of xylose concentration as a function of pressure and time.128 Figure A-11: Contour plot of xylose concentration as a function of pressure and temperature.