Converting Low Value Lignocellulosic Residues Into Valuable Products Using Photo and Bioelectrochemical Catalysis
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University of Windsor Scholarship at UWindsor Electronic Theses and Dissertations Theses, Dissertations, and Major Papers 2-17-2016 CONVERTING LOW VALUE LIGNOCELLULOSIC RESIDUES INTO VALUABLE PRODUCTS USING PHOTO AND BIOELECTROCHEMICAL CATALYSIS Wudneh Ayele Shewa University of Windsor Follow this and additional works at: https://scholar.uwindsor.ca/etd Recommended Citation Shewa, Wudneh Ayele, "CONVERTING LOW VALUE LIGNOCELLULOSIC RESIDUES INTO VALUABLE PRODUCTS USING PHOTO AND BIOELECTROCHEMICAL CATALYSIS" (2016). Electronic Theses and Dissertations. 5667. https://scholar.uwindsor.ca/etd/5667 This online database contains the full-text of PhD dissertations and Masters’ theses of University of Windsor students from 1954 forward. These documents are made available for personal study and research purposes only, in accordance with the Canadian Copyright Act and the Creative Commons license—CC BY-NC-ND (Attribution, Non-Commercial, No Derivative Works). 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CONVERTING LOW VALUE LIGNOCELLULOSIC RESIDUES INTO VALUABLE PRODUCTS USING PHOTO AND BIOELECTROCHEMICAL CATALYSIS By Wudneh Shewa A Dissertation Submitted to the Faculty of Graduate Studies through the Department of Civil and Environmental Engineering in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy at the University of Windsor Windsor, Ontario, Canada 2016 © 2016 Wudneh Shewa CONVERTING LOW VALUE LIGNOCELLULOSIC RESIDUES INTO VALUABLE PRODUCTS USING PHOTO AND BIOELECTROCHEMICAL CATALYSIS by Wudneh Shewa APPROVED BY: __________________________________________________ A. Margaritis, External Examiner Western University __________________________________________________ C. Weisener The Great Lakes Institute for Environmental Research (GLIER) __________________________________________________ X.Xu Civil and Environmental Engineering __________________________________________________ P. Henshaw Civil and Environmental Engineering __________________________________________________ J. Lalman, Advisor Civil and Environmental Engineering January 29, 2016 DECLARATION OF CO-AUTHORSHIP / PREVIOUS PUBLICATION I. Co-Authorship Declaration I hereby declare that this thesis incorporates the outcome of a joint research undertaken in collaboration with Dr. Subba Rao Chaganti under the supervision of Professor Daniel Heath. The collaboration is covered in Chapters 3, 6 and Appendix F of the thesis. In all cases, the key ideas, primary contributions, experimental designs, data analysis and interpretation, were performed by the author, and the contribution of co- authors was primarily through the provision of microbiological data. I am aware of the University of Windsor Senate Policy on Authorship and I certify that I have properly acknowledged the contribution of other researchers to my thesis, and have obtained written permission from the co-authors to include the above material in my thesis. I certify that, with the above qualification, this thesis, and the research to which it refers, is the product of my own work. II. Declaration of Previous Publication This thesis includes two original papers that have been previously published in a peer reviewed journal and in a conference proceeding, as follows: Thesis Chapter Publication title/full citation Publication status Chapter 3 Electricity generation and biofilm formation Published in microbial fuel cells using plate anodes constructed from various grades of graphite. J. Green Eng., 2014, 4, 13-32. Chapter 5 Producing electricity using a microbial fuel Published cell fed with feedstock chemicals produced from the photocatalysis of a lignin model chemical. Proceedings of the Water Environment Federation, 2014, 13, 2484-2503. I certify that I have obtained a written permission from the copyright owner(s) to include the above published material(s) in my thesis. I certify that the above material describes work completed during my registration as graduate student at the University of Windsor. I declare that, to the best of my knowledge, my thesis does not infringe upon anyone’s copyright nor violate any proprietary rights and that any ideas, techniques, iii quotations, or any other material from the work of other people included in my thesis, published or otherwise, are fully acknowledged in accordance with the standard referencing practices. Furthermore, to the extent that I have included copyrighted material that surpasses the bounds of fair dealing within the meaning of the Canada Copyright Act, I certify that I have obtained a written permission from the copyright owner(s) to include such material(s) in my thesis. I declare that this is a true copy of my thesis, including any final revisions, as approved by my thesis committee and the Graduate Studies office, and that this thesis has not been submitted for a higher degree to any other University or Institution. iv ABSTRACT Depleting fossil fuel resources, environmental damage and energy security are key factors driving the search for renewable energy supplies. Anaerobic digestion (AD), a well-developed technology, is widely used globally to produce an energy rich biogas from degradable organic matter. An alternative technology under development which produces electricity from the degradation of organic matter is microbial fuel cells (MFCs). Lignin, an abundant renewable organic chemical, is difficult to degrade using biological methods. This dissertation is focused on generating electricity from lignin-rich organic matter using a two-step process which included producing a chemical feedstock using photocatalysis followed by a bioelectrochemical conversion in an MFC. Studies were conducted using sodium lignosulfonate (LS), a model lignin compound, and black liquor (BL), a lignin-rich waste product from pulp and paper industries. Titanium dioxide (TiO2) plus ultraviolet light was used in the photocataysis step. Optimization and modeling of the photocatalytic degradation process was performed using the Box-Behnken design method to achieve a maximum biological oxygen demand (BOD5) to chemical oxygen demand (COD) ratio. The effluent from the photocatalytic degradation process was fed into a single chamber air-cathode microbial fuel cell (SCMFC) to generate electricity. In this study, commonly available electrode materials were selected, evaluated and compared with a focus on selecting the best performing type of electrode. Cyclic voltammetry and linear sweep voltammetry were used to evaluate the performance of the electrodes. The biofilm microbial diversity and performance of SCMFCs fed pretreated v LS (PrLS) and pretreated black liquor (PrBL) were compared to SCMFCs fed glucose at the same COD loadings and operating conditions. The energy production from PrBL using SCMFCs was also compared with the anaerobic digestion (AD) process. A total biogas production of 195±30 mL CH4 per g CODadded was obtained from two-stage AD of PrBL. The PrBL feed SCMFCs, generated maximum current and power densities of 8045±440 mA m-3 and 2815±120 mW m-3, respectively. The SCMFCs removed 89.3±0.8% of the COD of PrBL and achieved coulombic and potential efficiencies of 7.8±0.6% and 65.7% respectively. This dissertation demonstrated that combining photocatalysis together with a bioelectrochemical process was useful for treating and generating electricity from lignin rich waste matter simultaneously. vi DEDICATION I dedicate this dissertation to my wife Mahder, son Daniel and daughter Grace. vii ACKNOWLEDGEMENTS First and foremost, I would like to express my sincere gratitude to my advisor Dr. Jerald A. Lalman for the continuous support of my PhD study and for his patience, motivation, and immense knowledge. He has also helped and encouraged me to take part in other research projects that are related to my PhD study. Besides my advisor, I would like to thank Dr. Chris Weisener, Dr. Iris Xiaohong Xu and Dr. Paul Henshaw for serving on my dissertation committee, and spending time reading and correcting my dissertation. My sincere thanks to our technical staff Mr. Bill Middleton, lab technician, and Mr. Matthew St. Louis, technologist, for unreserved technical cooperation and help in the lab by providing the required material for the research work. Mr. Middleton was especially helpful in assisting with conducting the HPLC/MS work. I would like to thank Dr. Lalman’s research team members (past and present). I gained knowledge and learned technical skills from post-doctoral fellows (Dr. Subba Rao Chaganti, Dr. Chungman Moon, Dr. Saravanan Rengaraj and Dr. Brahmaiah Pendyala) and all other fellow lab mates. Special thanks to Dr. Subba Rao Chaganti, who helped me in analyzing microbial samples. I want to extend my sincere gratitude to Dr. Sathyanarayanan Sevilimedu Veeravalli, Dr. Saravanan Ramiah Shanmugam and Dr. Saady Noori for being good colleagues and assisiting whenever I needed them. Also, I thank Drs. Selva Ganesan and Venkatachalam Ponnusami from SASTRA University (Tamil Nadu, India) who assisted with identifying compounds based on liquid chromatograph – mass spectrometry LC-MS data. I am grateful to Consulting Engineers of