Lakehead University Knowledge Commons,http://knowledgecommons.lakeheadu.ca Electronic Theses and Dissertations Electronic Theses and Dissertations from 2009 2017 Tall oil production process and characterization Aro, Thomas Daniel https://knowledgecommons.lakeheadu.ca/handle/2453/4095 Downloaded from Lakehead University, KnowledgeCommons Tall Oil Production Process and Characterization By Thomas Daniel Aro Supervisor: Pedram Fatehi, PhD, P.Eng. Thesis Presented to the Faculty of Graduate Studies of Lakehead University of Thunder Bay in Partial Fulfillment of the Requirements for the Degree of Master of Science in Environmental Engineering Lakehead University August 2017 Acknowledgements I would like to start by thanking Dr Pedram Fatehi for his advice, patience, and support throughout my research. His guidance allowed me to work to the best of my ability to produce a final product that I am proud of. The BURL group was helpful with training on new instruments and provided guidance in times of need. I cannot thank my fellow group members enough. Thanks also to my committee member and reviewer, Dr Baoqiang Liao and Dr Sudip Rakshit, for examining my thesis. To Lakehead University, the Chemical Engineering Department, and the Environmental Engineering program, I am grateful for my opportunities to learn and study in an excellent learning environment. They have allowed for my growth as a student and researcher as I look to start my career. Finally, thanks to my friends and family for their support and encouragement throughout. Without that and their words of advice, I wouldn’t have been able to finish, let alone accomplish as much as I have. I’ve learned that sometimes it’s enough to let it call the shots, but other times you have to let it take absolute control. Praise be to the LC. Made ‘er. TFD. i Table of Contents Acknowledgements .......................................................................................................................... i List of Figures ................................................................................................................................ vi List of Tables .................................................................................................................................. x Abstract .......................................................................................................................................... xi 1. Chapter 1: Introduction ............................................................................................................ 1 1.1. Overview .......................................................................................................................... 1 1.2. Objectives ......................................................................................................................... 4 1.3. Novelty of study ............................................................................................................... 4 References ................................................................................................................................... 5 2. Literature Review – Tall oil production from black liquor: Challenges and opportunities .... 7 2.1. Abstract ............................................................................................................................ 7 2.2. Introduction ...................................................................................................................... 7 2.3. Tall oil compositions ........................................................................................................ 9 2.4. Current commercial tall oil production process ............................................................. 10 2.4.1. Isolation of tall oil soap from black liquor in the kraft pulping process ................. 11 2.4.2. Production of crude tall oil from tall oil soap ......................................................... 11 2.4.3. Purification of crude tall oil and its fractions’ uses ................................................ 13 2.5. Alternative processes...................................................................................................... 14 2.5.1. Alternatives to the extraction of tall oil soap from black liquor ............................. 15 2.5.1.1. Impact of polymer addition ............................................................................. 15 2.5.1.2. Impact of insoluble neutral colloids ................................................................ 15 2.5.1.3. Alkaline washing of tall oil soap ..................................................................... 17 2.5.2. Alternatives to the production of crude tall oil from tall oil soap ........................... 18 2.5.2.1. Direct electrolysis of tall oil soap .................................................................... 18 2.5.2.2. Use of carbon dioxide in acidulation ............................................................... 19 2.5.2.3. Use of boron compounds in acidulation .......................................................... 21 2.5.2.4. Use of sodium sesquisulfate in acidulation ..................................................... 22 2.5.3. Alternatives to purification and fractionation of crude tall oil ............................... 23 2.5.3.1. Separation of fatty and rosin acids .................................................................. 23 2.5.3.2. Production of biodiesel from crude tall oil ...................................................... 25 ii 2.5.3.3. Production of biodiesel from fatty acids of tall oil using methanol ................ 26 2.5.3.4. Production of lignin by-products from acidulation of tall oil soap ................. 28 2.6. Conclusions .................................................................................................................... 29 2.7. Acknowledgement .......................................................................................................... 30 References ................................................................................................................................. 30 3. Literature Review – Production and application of lignosulfonates and sulfonated lignin ... 37 3.1. Abstract .......................................................................................................................... 37 3.2. Introduction .................................................................................................................... 38 3.3. Pathways to produce lignosulfonates and sulfonated lignin .......................................... 41 3.3.1. Lignosulfonates from sulfite spent liquor ............................................................... 41 3.3.2. Separation of lignosulfonates from sulfite spent liquor .......................................... 44 3.3.3. Sulfonated lignin from kraft black liquor ............................................................... 47 3.4. Alternative methods for producing lignosulfonates and sulfonated lignin .................... 48 3.4.1. Sulfuric acid treatment ............................................................................................ 48 3.4.2. Nitration .................................................................................................................. 50 3.4.3. Alkaline hydrolysis of lignosulfonates ................................................................... 51 3.4.4. Hydroxypropyl sulfonation ..................................................................................... 52 3.4.5. Hydroxymethylation ............................................................................................... 53 3.4.6. Methanolylphenol-lignosulfonate esters ................................................................. 54 3.4.7. Oxidation................................................................................................................. 55 3.4.8. Sulfomethylation ..................................................................................................... 55 3.4.9. Oxidation, hydroxymethylation, and sulfomethylation .......................................... 57 3.4.10. Phenolation and sulfonation .................................................................................... 60 3.4.11. Reduced-sulfur lignosulfonates and derivatives ..................................................... 63 3.5. Impact of properties on application ................................................................................ 65 3.5.1. Dispersant and concrete additive ............................................................................ 66 3.5.2. Lead-acid storage batteries ..................................................................................... 68 3.5.3. Flocculant ................................................................................................................ 69 3.5.4. Metal adsorbent ....................................................................................................... 70 3.5.5. Dust suppressant ..................................................................................................... 71 3.5.6. Antioxidant and pharmacological effects ............................................................... 71 3.5.7. Composites .............................................................................................................. 73 iii 3.5.8. Ion-exchange resin .................................................................................................. 74 3.6. Summary .......................................................................................................................