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Catalytic Conversion of Fructose, Glucose and Industrial Grade Sugar Syrups to 5-Hydroxymethylfurfural, a Platform for Fuels and Chemicals

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Catalytic Conversion of Fructose, Glucose and Industrial Grade Sugar Syrups to 5-Hydroxymethylfurfural, a Platform for Fuels and Chemicals Western University Scholarship@Western Electronic Thesis and Dissertation Repository 8-17-2016 12:00 AM Catalytic Conversion of Fructose, Glucose and Industrial Grade Sugar Syrups to 5-Hydroxymethylfurfural, A Platform for Fuels and Chemicals Sadra Souzanchi The University of Western Ontario Supervisor Dr. Chunbao (Charles) Xu The University of Western Ontario Joint Supervisor Dr. Zhongchao (Chao) Tan The University of Western Ontario Graduate Program in Chemical and Biochemical Engineering A thesis submitted in partial fulfillment of the equirr ements for the degree in Doctor of Philosophy © Sadra Souzanchi 2016 Follow this and additional works at: https://ir.lib.uwo.ca/etd Part of the Catalysis and Reaction Engineering Commons, Environmental Engineering Commons, Other Chemical Engineering Commons, and the Polymer and Organic Materials Commons Recommended Citation Souzanchi, Sadra, "Catalytic Conversion of Fructose, Glucose and Industrial Grade Sugar Syrups to 5-Hydroxymethylfurfural, A Platform for Fuels and Chemicals" (2016). Electronic Thesis and Dissertation Repository. 4070. https://ir.lib.uwo.ca/etd/4070 This Dissertation/Thesis is brought to you for free and open access by Scholarship@Western. It has been accepted for inclusion in Electronic Thesis and Dissertation Repository by an authorized administrator of Scholarship@Western. For more information, please contact [email protected]. Abstract HydroxyMethylFurfural (HMF) as a versatile and poly-functional compound derived from dehydration of biomass has attracted increasing attentions in research over the past decades. HMF is an important intermediate and platform chemical, which can be converted into different useful chemicals as well as the promising biofuels. It can be obtained from acid- catalyzed dehydration of different C6-based carbohydrates such as glucose, fructose, sucrose and cellulose. In this thesis, a cost-effective process for catalytic conversion of simple sugars (particularly glucose and fructose) and industrial grade sugar syrups to HMF was studied in a novel biphasic continuous-flow tubular reactor using inexpensive heterogeneous solid catalysts and biphasic media (aqueous/organic). Commercial and synthesized heterogeneous catalysts were used for the catalytic experiments and their activities in terms of conversion, selectivity and yield were compared. It is assumed that catalytic conversion of glucose to HMF involves two-step reaction pathway of glucose isomerization to fructose and subsequent fructose dehydration to HMF. Thus, the experimental approach for this research was to first isomerize glucose to fructose using heterogeneous solid base catalysts and then dehydrate fructose to HMF using heterogeneous solid acid catalysts. Thereafter, continuous single-step conversion of glucose and industrial grade sugar syrups derived from corn and wood to HMF was investigated. In each section, fresh catalysts were characterized comprehensively and the stability of some selected catalysts and feasibility of catalyst recycling were examined. The effects of different experimental conditions including reaction temperature, feeding flow rate, initial feedstock concentration, catalyst loading, presence of extracting organic solvent and phase transfer catalyst were also studied. At the best operating conditions, the maximum fructose yield of 25% was achieved from isomerization of glucose over magnesium oxide catalyst and maximum HMF yields of 60%, 45% and 53% were obtained from dehydration of fructose (over Amberlyst 36 catalyst), glucose (over niobium phosphate catalyst) and HFCS-90 (over niobium phosphate catalyst), respectively. The deactivation mechanism of some selected catalysts was also investigated by analysing the used catalysts and the insoluble humins produced during the reaction as the main by-product responsible for the catalyst deactivation. The kinetics of glucose dehydration reaction over niobium phosphate catalyst was also studied. Keywords: 5-Hydroxymethylfurfural (HMF), Glucose, Fructose, Isomerization, Dehydration, Biphasic continuous-flow tubular reactor, Heterogeneous solid catalyst, Niobium phosphate, Amberlyst 36, Hydrotalcite, Magnesium oxide, Catalyst characterization, Catalyst deactivation, Catalyst stability, Catalyst reusability, Catalyst recycling, Catalyst regeneration, High fructose corn syrup (HFCS), Glucose corn syrup (GCS), TMP-Bio Sugar, Glucose dehydration reaction kinetics, Humins characterizations ii Co-Authorship Statement Chapter 3: Catalytic Isomerization of Glucose to Fructose using Heterogeneous Solid Base Catalysts in a Continuous-Flow Tubular Reactor: Catalyst Screening Study Authors: Sadra Souzanchi, Laleh Nazari, Tirumala Kasanneni, Zhongshun Yuan, Zhongchao Tan, Chunbao (Charles) Xu The experimental work was conducted by Sadra Souzanchi under the supervision of Prof. Charles (Chunbao) Xu and Prof. Zhongchao Tan and the guidance of Dr. Zhongshun Yuan. Data analysis, results interpretation and writing were performed by Sadra Souzanchi assisted by Laleh Nazari and Tirumala Kasanneni. The paper was reviewed and revised by Prof. Charles Xu and Prof. Zhongchao Tan and the manuscript has been submitted to "Catalysis Today” journal for publication. Chapter 4: Catalytic Isomerization of Glucose to Fructose using Activated Hydrotalcite Catalyst in a Continuous-Flow Tubular Reactor: Effects of Reaction Conditions Authors: Sadra Souzanchi, Laleh Nazari, Tirumala Kasanneni, Zhongshun Yuan, Zhongchao Tan, Chunbao (Charles) Xu The experimental work was conducted by Sadra Souzanchi under the supervision of Prof. Charles (Chunbao) Xu and Prof. Zhongchao Tan and the guidance of Dr. Zhongshun Yuan. Data analysis, results interpretation and writing were performed by Sadra Souzanchi assisted by Laleh Nazari and Tirumala Kasanneni. The paper was reviewed and revised by Prof. Charles Xu and Prof. Zhongchao Tan and the manuscript is to be submitted for publication. Chapter 5: Catalytic Dehydration of Fructose to 5-HMF using Heterogeneous Solid Acid Catalysts in a Biphasic Continuous-Flow Tubular Reactor Authors: Sadra Souzanchi, Laleh Nazari, Tirumala Kasanneni, Zhongshun Yuan, Zhongchao Tan, Chunbao (Charles) Xu The experimental work was conducted by Sadra Souzanchi under the supervision of Prof. Charles (Chunbao) Xu and Prof. Zhongchao Tan and the guidance of Dr. Zhongshun Yuan. iii Data analysis, results interpretation and writing were performed by Sadra Souzanchi assisted by Laleh Nazari and Tirumala Kasanneni. The paper was reviewed and revised by Prof. Charles Xu and Prof. Zhongchao Tan and the manuscript is to be submitted for publication. Chapter 6: Catalytic Dehydration of Glucose to 5-HMF using Heterogeneous Solid Acid Catalysts in a Biphasic Continuous-Flow Tubular Reactor Authors: Sadra Souzanchi, Laleh Nazari, Tirumala Kasanneni, Zhongshun Yuan, Zhongchao Tan, Chunbao (Charles) Xu The experimental work was conducted by Sadra Souzanchi under the supervision of Prof. Charles (Chunbao) Xu and Prof. Zhongchao Tan and the guidance of Dr. Zhongshun Yuan. Data analysis, results interpretation and writing were performed by Sadra Souzanchi assisted by Laleh Nazari and Tirumala Kasanneni. The paper was reviewed and revised by Prof. Charles Xu and Prof. Zhongchao Tan and the manuscript is to be submitted for publication. Chapter 7: HMF Production from Industrial Grade Sugar Syrups Derived from Corn and Wood using Niobium Phosphate Catalyst in a Biphasic Continuous-Flow Tubular Reactor Authors: Sadra Souzanchi, Laleh Nazari, Tirumala Kasanneni, Zhongshun Yuan, Zhongchao Tan, Chunbao (Charles) Xu The experimental work was conducted by Sadra Souzanchi under the supervision of Prof. Charles (Chunbao) Xu and Prof. Zhongchao Tan and the guidance of Dr. Zhongshun Yuan. Data analysis, results interpretation and writing were performed by Sadra Souzanchi assisted by Laleh Nazari and Tirumala Kasanneni. The paper was reviewed and revised by Prof. Charles Xu and Prof. Zhongchao Tan and the manuscript is to be submitted for publication. iv Dedication To my beloved wife, Laleh, for her love, devotion and for being there for me throughout the entire of this journey & To my loving parents, Ali and Shahin, for their endless love, encouragement and support v Acknowledgements Though only my name appears on the cover of this dissertation, it would not have been possible to publish this work without the help of so many people who have contributed to its body of work. I owe my gratitude to all those people who have made this dissertation possible and because of whom my graduate experience has been one that I will cherish forever. Foremost, I would like to express my special appreciation and sincere gratitude to my supervisors Professor Charles (Chunbao) Xu and Professor Zhongchao Tan for their continuous support of my PhD study and research, for their patience, motivation, enthusiasm, immense knowledge and valuable guidance. I would also like to thank Dr. Zhongshun (Sean) Yuan for his suggestions and insightful comments on my project as well as Dr. Sohrab Rohani, my advisory committee member, for the assistance he provided at all levels of the research project. I also extend my gratitude to my examination board: Dr. Pascale Champagne from Queen’s University and Drs. Ajay Ray, Anand Prakash and Yang Song from the University of Western Ontario, for their efforts in reviewing my thesis. Their comments and suggestions have greatly improved this work. I thank Fang (Flora) Cao, Caitlin Marshall, Rob Taylor, and Thomas Johnston for their contributions and assistance
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