Study of Lignin to Value Added Chemicals

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Study of Lignin to Value Added Chemicals STUDY OF LIGNIN TO VALUE ADDED CHEMICALS Thesis by Ane Sequeiros Echeverria For the degree of Doctor in Renewable Material Engineering Director: Jalel Labidi Chemical and Environmental Engineering Department Faculty of Engineering of Gipuzkoa Donostia-San Sebastian 2016 (cc)2016 ANE SEQUEIROS ECHEBERRIA (cc by 4.0) Agradecimientos Me gustaría agradecer en primer lugar a mi director de tesis el Dr. Jalel Labidi la oportunidad de realizar esta tesis doctoral bajo su dirección en estos 4 años. Además, también me gustaría agradecerle las numerosas oportunidades que me ha dado para asistir a congresos y cursos. Agradezco al Departamento de Desarrollo Económico y Competitividad del Gobierno Vasco la oportunidad que me han brindado al ser beneficiaria de la beca de formación de jóvenes investigadores. Más en concreto me gustaría agradecer a todos mis compañeros del grupo de “procesos de biorefinería” por ayudarme en el plano laboral y personal durante estos 4 años para ir avanzando en mi investigación y hacer más ameno cada día en el laboratorio. Durante mi tesis he tenido la oportunidad de realizar una estancia en el extranjero para completar mi investigación. Tuve el placer de estar 3 meses en el Leibniz Instute for Catalysis (Rostock-Alemania) bajo la supervisión del profesos Hans de Vries. Agradecer a todo el grupo de investigación la paciencia que tuvieron al introducirme en el mundo de la catálisis y ayudarme con todas mis dudas. No quisiera terminar sin agradecer a mi familia y a mis amigos por todo lo que han tenido que aguantar durante este proceso de aprendizaje. A mi pareja que ha escuchado con paciencia todos mis comentarios y dudas que he tenido y ayudarme a seguir adelante en los momentos más oscuros. En definitiva; gracias a todos porque sin vosotros esta tesis no hubiera sido posible. Summary The depletetion of the fossil resources arise several challenges that are trying to be addressed by greener alternatives such the biomass. In this thesis one of the main components of the biomass and due to its aromatic scructure was selected to be studied extensively. During the development of this thesis several lignin extraction methods were studied to seek for the purest lignin. Afterwars, three agro-forestal raw materials and an industrial residue were analyzed by pyrolysis to know which raw material was the one with the highest syringyl and guaiacyl groups for further depolymerization. During this stage, lignin was used to produce polyols from microwave heating; experimental conditios were applied with the objective of polyol with high yield and high hydroxyl groups. Finally, syringol and guaiacol two main monomers that could be obtained from the depolimerization of lignin under mild conditionds were used as raw materials to produce aromatic acids. For this target three different pathways were subjected to a test being the fist one the alkoxy carbonylation the second the oxidative carbonylation and the third one the bromination followed by the Grignard reaction. Table of content Objectives and methodology…………………………….…..I Chapter 1: Introduction 1.1 Overview............................................................ 3 1.2 Biomass as a renewable resource ...................... 5 1.3 Lignocellulosic biomass ..................................... 7 1.3.1. Non structural components .............................. 8 1.3.2. Cellulose .......................................................... 9 1.3.3. Hemicelluloses ............................................... 11 1.3.4. Lignin ............................................................. 13 1.3.5. Lignin applications ......................................... 16 1.4 Raw materials ................................................. 18 1.4.1. Olive tree pruning .......................................... 18 1.4.2. Apple tree pruning ......................................... 20 1.4.3. Almond shell .................................................. 21 1.5 References ....................................................... 23 Chapter 2: Lignin extraction and characterization…29 2.1 Lignin extraction processes .................................... 31 2.1.1.Sulphite process ............................................. 32 2.1.2.Kraft process ................................................... 32 2.1.3.Alkaline treatment .......................................... 34 2.1.4.Organosolv process ......................................... 34 2.4.1.1.Alcohol organosolv processes ....................... 36 2.4.1.2.Acid organosolv processes ............................ 37 2.1.5.Ionic liquid process ......................................... 37 2.2 Objective ................................................................ 38 2.3 Chemical characterization of almond shell ............. 38 2.4 Materials and methods ........................................... 39 2.4.1.Lignin extraction by different methods ............ 39 2.4.2.Liquid fraction characterization ...................... 40 2.4.3.Lignin characterization ................................... 40 2.5 Different treatment study results ........................... 41 2.5.1. Liquid fraction……………………………………..41 2.5.2. Lignin characterization…………………………..43 2.5.3. Lignin structure and molecular weight………44 2.6 Conclusions ........................................................... 51 2.7 References .............................................................. 52 Chapter 3: Determination of S/G ratio by Py/GC- MS………………………………………………………………….57 3.1. Pyrolysis ................................................................ 59 3.2. Different methods to measure the S/G ratio……….62 3.3. Objective…………………………………………………….63 3.4. Materials and methods…………………………………..63 3.4.1. Raw materials and lignin extraction process.63 3.4.2. Lignin recovery from the black liquor………..64 3.4.3. Liquid fraction characterization and lignin characterization……………………………………………65 3.5. Different raw material and treatment results………67 3.5.1. Raw materials……………………………………..67 3.5.2. Characterization of the liquid fraction and lignin purity analysis…………………………..………………...69 3.5.3. Lignin structure and molecular weight………71 3.5.4. Lignin chemical composition by Py-GC/MS..74 3.6. Conclusions……………………………………………….85 3.7. References…………………………………………………87 Chapter 4: Polyol production from lignin by microwave heating ……………………….......................................91 4.1. Introduction………………………………………..………93 4.2. Objective……………………………………………..……..98 4.3. Material and methods………………………..………….99 4.3.1.Olive tree pruning and lignin extraction process……………………………………………………..……..99 4.3.2.Liquefaction under microwave heating .......... 101 4.3.3.Experimental design ..................................... 102 4.3.4.Hydroxyl number .......................................... 103 4.4. Analysis of the polyols…………………………………..105 4.4.1. Olive tree pruning lignin characterization ..... 105 4.4.2. Liquefaction experimental design ................. 105 4.4.3. Fourier transformed infrared spectroscopy (FTIR) …………………………………………………………………112 4.4.4.Gel permeation chromatography (GPC) ......... 114 4.4.5.Thermogravimetric analysis (TGA) ................. 116 4.5. Conclusion………………………………………………..117 4.6. References…………………………………………………119 Chapter 5: Aromatic acids from lignin monomers..123 5.1 Introduction ......................................................... 125 5.1.1. Commodities from lignin .............................. 125 5.1.2 Lignin to monomers ...................................... 128 5.2 Formation of aromatic acids via Pd catalysed alkoxy carbonylation ............................................................. 132 5.2.1. Mesylation and tosylation of the starting material………………………………………………………135 5.2.2. Alkoxy carbonylation of MsG using different conditions, ligands, bases and catalysts……………..141 5.2.3. Alkoxy carbonylation of TsG using different conditions, ligands and catalysts………………………146 5.3 Formation of aromatic acids via oxidative carbonylation…………………………………………………..151 5.3.1. Oxidative carbonylation using different substrates, oxidants and reaction conditions………………………153 5.4 Formation of aromatic acids via bromination and Grignard reaction ....................................................... 161 5.4.1. Bromination of guaiacol and syringol with different solvent……………………………………………163 5.4.2. Grignard reaction………………………………..172 5.4.2.1. Grignard reaction for brominated guaiacol and syringol ………………………………………………………..173 5.5 References ............................................................ 175 Chapter 6: Conclusions…………………………………….181 1. Conclusion ............................................................. 183 2. Future works .......................................................... 186 3. Publications ........................................................... 187 Appendix…………………………………………….…………193 1. Appendix I .............................................................. 195 1.1. Characterization procedures of lignocellulosic biomass and solid fractions ........................................ 195 1.1.1. Sample preparation (TAPPI T257-cm85) ....... 195 1.1.2. Moisture content (TAPPI T264-cm97) ........... 195 1.1.3. Ash content at 525 ºC (TAPPI T211-om93) ... 196 1.1.4. Solvent extractives (TAPPI T204-cm97) ......... 198 1.1.5. Acid-insoluble lignin (TAPPI T222-om98) ...... 199 1.1.6. Holocellulose content (Wise and Col.) ........... 201 1.1.7. α-cellulose content (Rowell) .......................... 202 1.2. References ....................................................... 203 2. Appendix II ............................................................
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