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Characterization and Utilization of Hot-Water Extracted Lignin for Formaldehyde-Free Resin Applications

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Characterization and Utilization of Hot-Water Extracted Lignin for Formaldehyde-Free Resin Applications SUNY College of Environmental Science and Forestry Digital Commons @ ESF Dissertations and Theses Spring 4-23-2018 CHARACTERIZATION AND UTILIZATION OF HOT-WATER EXTRACTED LIGNIN FOR FORMALDEHYDE-FREE RESIN APPLICATIONS Prajakta Dongre [email protected] Follow this and additional works at: https://digitalcommons.esf.edu/etds Recommended Citation Dongre, Prajakta, "CHARACTERIZATION AND UTILIZATION OF HOT-WATER EXTRACTED LIGNIN FOR FORMALDEHYDE-FREE RESIN APPLICATIONS" (2018). Dissertations and Theses. 58. https://digitalcommons.esf.edu/etds/58 This Open Access Dissertation is brought to you for free and open access by Digital Commons @ ESF. It has been accepted for inclusion in Dissertations and Theses by an authorized administrator of Digital Commons @ ESF. For more information, please contact [email protected], [email protected]. CHARACTERIZATION AND UTILIZATION OF HOT-WATER EXTRACTED LIGNIN FOR FORMALDEHYDE-FREE RESIN APPLICATIONS by Prajakta Dongre A dissertation submitted in partial fulfillment of the requirements for the Doctor of Philosophy Degree State University of New York College of Environmental Science and Forestry Syracuse, New York April 2018 Department of Paper and Bioprocess Engineering Approved by: Biljana Bujanovic, Major Professor Thomas Amidon, Co-Major Professor Robert W. Malmsheimer, Chair, Examining Committee Bandaru V. Ramarao, Faculty Chair S. Scott Shannon, Dean, The Graduate School Gary M. Scott, Director, Division of Engineering © 2018 Copyright Prajakta Dongre All rights reserved Acknowledgements I would like to thank my advisor Dr. Biljana Bujanovic for her constant guidance and continually encouraging me to push boundaries. Dr. Amidon, for his ever-ready helping hand and understanding. I appreciate Dr. Arthur Stipanovic for his support on thermal analysis, Dr. Mark Driscoll for his continued support on the hot-press and adhesive testing, Dr. Gary Scott for help on statistical analysis, and Dr. Robert Malmsheimer for feedback on the thesis. I would be remiss not to mention Debbie Dewitt for her words of reassurance, and the many times we solved the world’s problems in your office, shall always be fond memories for me. Lynn Mickinkle, without whom we would all come to a standstill at PBE – thank you. I would also sincerely appreciate the generous support of SUNY-ESF for the raw materials for this work, Dave Kiemle for support with NMR analysis, Mr. Burry and George Westby for continued assistance on the tensile tester, and Sean Hohm and Mr. Appleby for Pilot plant operations. I appreciate Fred Matt from USDA-FPL for carbohydrate analysis, and Paul Elsesser, Dr. Deanna Higgins and Dr. Feng Dong from Borgwarner Inc. for consultation on friction paper tests. This work is funded by the USDA-McIntire-Stennis “Novel Green Adhesives from the ESF Biorefinery” Project. I would like to thank my colleagues and friends Aditi Nagardeolekar, Chris Wood, Cher Jing, Kuoting Wang, Jake Finkelstein and Mathew Ovadias for helping me in some of my experiments. I would also like to acknowledge the many friends that I have made over the years in Syracuse – Chen, Gina, Jenny, Alan, Derek, Neil, Mangesh, Ericka, Dan, Shraddha, Sravani, Jennifer, Shama, Nidhi, Parvathy and so many more. Your support has been invaluable. Finally, my family, Aai, Baba and Amu, have been a source of continuous support and encouragement for me, and I am most grateful for their belief in me. iii Table of Contents CHAPTER I: INTRODUCTION ........................................................................................................................ 1 1.1 Biorefineries/Lignocellulosic biomass .......................................................................................................... 1 1.2 Outline ........................................................................................................................................................... 4 CHAPTER II: OBJECTIVES ............................................................................................................................. 5 CHAPTER III: LITERATURE REVIEW .......................................................................................................... 7 3.1 Chemical composition ................................................................................................................................... 7 3.2 Cellulose........................................................................................................................................................ 8 3.3 Hemicelluloses .............................................................................................................................................. 9 3.4 Lignin .......................................................................................................................................................... 16 3.4.1 Biosynthesis of lignin ........................................................................................................................... 18 3.5 Lignin-carbohydrate complex (LCC) .......................................................................................................... 22 3.6 Pretreatment methods .................................................................................................................................. 23 3.6.1 Acid Pretreatment................................................................................................................................. 25 3.6.2 Alkaline Pretreatment ........................................................................................................................... 26 3.6.3 Organosolv Pretreatment ...................................................................................................................... 26 3.6.4 Biological Pretreatment ........................................................................................................................ 27 3.6.5 Electron beam irradiation treatment (EBI) ........................................................................................... 27 3.6.6 Hydrothermal treatment ....................................................................................................................... 28 3.7 Quantitative Studies and Qualitative Studies of Lignin Isolation ............................................................... 31 3.7.1 Lignin content determination ............................................................................................................... 31 3.8 Lignin in Polymer Applications .................................................................................................................. 33 3.8.1 Resins ....................................................................................................................................................... 33 CHAPTER IV: MATERIALS AND METHODS ............................................................................................ 44 4.1 Materials ................................................................................................................................................ 45 4.2 Methods (Experimental): ............................................................................................................................ 45 4.2.1 Lignin Isolation and Characterization .................................................................................................. 45 4.2.2 Ash ....................................................................................................................................................... 46 4.2.3 Molecular Weight Distribution ............................................................................................................ 47 4.2.4 Nuclear Magnetic Spectroscopy (NMR) .............................................................................................. 47 4.2.5 Acetylation ........................................................................................................................................... 48 4.2.6 Free Phenolic Hydroxyl Group Content (PhOH) ................................................................................. 48 4.2.7 Kappa number ...................................................................................................................................... 49 4.2.8 Thermogravimetric Analysis (TGA) .................................................................................................... 49 4.2.9 Differential Scanning Calorimetry (DSC) ............................................................................................ 49 4.2.10 Electron beam irradiation (EBI) ......................................................................................................... 49 4.2.11 Preparation of lignin based resins ...................................................................................................... 50 iv 4.2.12 Mechanical testing on glass fiber filters ............................................................................................. 53 4.2.13 Mechanical testing on friction paper .................................................................................................. 55 4.2.14 Mechanical testing on kraft paper ...................................................................................................... 55 CHAPTER V: RESULTS AND DISCUSSION ............................................................................................... 56 5.1 Characterization of Crude Lignins .........................................................................................................
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