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Analyzing and Exploiting Biomass Thermal Deconstruction Jake Kendall Lindstrom Iowa State University

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Analyzing and Exploiting Biomass Thermal Deconstruction Jake Kendall Lindstrom Iowa State University Iowa State University Capstones, Theses and Graduate Theses and Dissertations Dissertations 2019 Analyzing and exploiting biomass thermal deconstruction Jake Kendall Lindstrom Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/etd Part of the Oil, Gas, and Energy Commons Recommended Citation Lindstrom, Jake Kendall, "Analyzing and exploiting biomass thermal deconstruction" (2019). Graduate Theses and Dissertations. 17242. https://lib.dr.iastate.edu/etd/17242 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Graduate Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. Analyzing and exploiting biomass thermal deconstruction by Jake Kendall Lindstrom A dissertation submitted to the graduate faculty in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Major: Mechanical Engineering Program of Study Committee: Robert C. Brown, Major Professor Theodore Heindel Wenzhen Li Mark Mba Wright Brent Shanks The student author and the program of study committee are solely responsible for the content of this dissertation. The Graduate College will ensure this dissertation is globally accessible and will not permit alterations after a degree is conferred. Iowa State University Ames, Iowa 2019 Copyright © Jake Kendall Lindstrom 2019. All rights reserved. ii DEDICATION For Laura Norman, my steadfast partner. iii TABLE OF CONTENTS Page ACKNOWLEDGMENTS .............................................................................................................. vi ABSTRACT ................................................................................................................................... vii PREFACE ..................................................................................................................................... viii CHAPTER 1 CONDENSED PHASE REACTIONS DURING THERMAL DECONSTRUCTION OF BIOMASS ............................................................................................ 1 Introduction to Condensed Phase Reactions during Thermal Deconstruction of Biomass .......... 2 Thermochemical Processes .......................................................................................................... 5 Processes Yielding Chiefly Solids ........................................................................................... 6 Torrefaction.......................................................................................................................... 6 Slow pyrolysis ...................................................................................................................... 8 Processes Yielding Chiefly Liquids ....................................................................................... 10 Solvent liquefaction ........................................................................................................... 11 Fast pyrolysis ..................................................................................................................... 12 Processes Yielding Chiefly Gases.......................................................................................... 13 Gasification ........................................................................................................................ 15 Combustion ........................................................................................................................ 16 Understanding Condensed Phase Reactions .............................................................................. 17 Challenges in Investigating Condensed Phase Reactions ...................................................... 18 The Role of Cell Wall Structure in Thermal Deconstruction ................................................ 22 Use of Computational Chemistry to Understand Thermal Deconstruction ........................... 26 Computational methodology .............................................................................................. 27 Formation of liquid products ............................................................................................. 29 Formation of gaseous products .......................................................................................... 38 Char formation ................................................................................................................... 39 Computational studies of large scale polymers .................................................................. 39 Conclusions ................................................................................................................................ 40 References .................................................................................................................................. 41 CHAPTER 2 COMPETING REACTIONS LIMIT LEVOGLUCOSAN YIELD DURING FAST PYROLYSIS OF CELLULOSE ......................................................................... 52 Abstract ...................................................................................................................................... 52 Keywords ................................................................................................................................... 52 Introduction ................................................................................................................................ 52 iv Materials and Methodologies ..................................................................................................... 59 Results and Discussion .............................................................................................................. 66 Conclusions ................................................................................................................................ 72 Conflicts of Interest.................................................................................................................... 75 Acknowledgements .................................................................................................................... 75 References .................................................................................................................................. 75 CHAPTER 3 CELLULOSE SOLID PHASE THERMAL DEPOLYMERIZATION .................. 80 Abstract ...................................................................................................................................... 80 Communication body ................................................................................................................. 80 Conclusions ................................................................................................................................ 90 Conflicts of interest .................................................................................................................... 90 Acknowledgements .................................................................................................................... 91 Notes and references .................................................................................................................. 91 CHAPTER 4 STRUCTURAL AND CHEMICAL CHANGES IN PLANT CELL WALLS DURING EARLY STAGES OF THERMAL DECONSTRUCTION .......................................... 95 Abstract ...................................................................................................................................... 95 Introduction ................................................................................................................................ 96 Thermal deconstruction of biomass particles ............................................................................. 97 Chemical deconstruction .......................................................................................................... 100 Cell wall structural degradation ............................................................................................... 104 Cell wall mechanical properties ............................................................................................... 107 Conclusions .............................................................................................................................. 109 Methods ................................................................................................................................... 110 Acknowledgments.................................................................................................................... 113 Data availability ....................................................................................................................... 114 References ................................................................................................................................ 114 CHAPTER 5 OVERSIGHTS IN THE ANALYSIS OF BIOMASS THERMAL DECONSTRUCTION ................................................................................................................. 118 Abstract .................................................................................................................................... 118 Introduction .............................................................................................................................. 118 Overuse of proxies for real biomass
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