Synthesis and conversion of furfural-batch versus continuous flow Yantao Wang To cite this version: Yantao Wang. Synthesis and conversion of furfural-batch versus continuous flow. Chemical engineer- ing. Université de Technologie de Compiègne, 2019. English. NNT : 2019COMP2474. tel-02171959 HAL Id: tel-02171959 https://tel.archives-ouvertes.fr/tel-02171959 Submitted on 3 Jul 2019 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Par Yantao WANG Synthesis and conversion of furfural-batch versus continuous flow Thèse présentée pour l’obtention du grade de Docteur de l’UTC Soutenue le 22 mars 2019 Spécialité : Génie des Procédés Industriels et développement durable : Transformations intégrées de la matière renouvelable (EA-4297) D2474 Université de Technologie de Compiègne Ecole Doctorale : Sciences pour l‘ingénieur Thèse présentée par Yantao WANG Pour le titre de Docteur en Génie des Procédés Industriels et du Développement Durable Synthesis and conversion of furfural- batch versus continuous flow Thèse dirigée par le Professeur Christophe LEN Soutenue le 22 Mars 2019 devant le jury composé de : Nadine Essayem Directeur de Recherche CNRS, IRCELyon Rapporteur Karine Vigier de Oliveira Professeur, Université de Poitiers Rapporteur Rafael Luque Professeur, Universidad de Cordoba Examinateur Timothy Noël Associate Professeur, Eindhoven university of Technology Examinateur Oliviers Bals Maître de Conférences, Université de Technologie de Compiègne Examinateur Christophe Len Professeur, Université de Technologie de Compiègne Directeur de thèse 1 / 342 Acknowledgements This PhD work was done in the laboratory Transformations Intégrées de la Matière Renouvelable (TIMR, EA4297) of the Université de Technologie de Compiègne under the supervision of Prof. Christophe Len. I would like to thank Georges Santini, director of the Ecole Supérieure de Chimie Organique et Minérale (ESCOM) for letting me work in his establiment. I would also like to thank Prof. Rafael Luque, leader of FMQ-383 NANOVAL group in Universidad de Cordoba (Spain) for giving me the opportunity to do a visiting PhD in his group. I also thank the China Scholorship Council for its financial support. First of all, I would like to thank the Director of my thesis, Prof. Christophe Len for his scientific help, support and guidance during this PhD. I particularly thank Prof. Len for his trust and for giving me the opportunities to present my work at international conferences. I want to express my gratitude to the members of the jury that participated in my PhD defense. I would especially like to acknowledge the referees of my thesis, Nadine Essayem and Karine Vigier de Oliveira. Thank you for the time you devoted and the feedback that you provided. Besides, I would like thank Prof. Luque again and Prof. Konstantinos S. Triantafyllidis from the department of chemistry, Aristotle University of Thessaloniki (Greece) for helping me to apply the Short Term Scientific Mission (STSM, COST ACTION). I thank the COST program for the grant awarded and the Prof. Rafael for his supervision. I particularly thank Fédéric Delbcq for guiding me to perform the experiments, teaching me French during 2 / 342 the first two years, I really appreciate his help when I was confusing, and thanks him for the time he spent on my manuscript too. I would like to thank my colleagues from our group, with which I had the pleasure to experiment with: Sarra, Deyang, Clement, Sophie, Audrey and Denis. I thank Pepijn, Weiyi, Antonio, Alfonso and all colleagues from Rafael‘s group, we spent very good time together during my visit. Special thanks to Pepijn who help me a lot to draft the project COST ACTION, finish the STSM and handle the data. Big thanks to my colleague and the best French friend Sarra Tadrent, we did experiments together, studied together, went to conferences together, also have fun and enjoyed meals together. Too many happy memories deserve to be remembered. Of course, I want to thank my Chinese friends: Jinhua Xiao, Ruqing Bai, Peng Du and Caiyun Liu et al. I still remember that we rode bike and visited many places. And every year, we celebrated Chinese New Year together. Yes, we‘re like a family. I‘d like to thank my supervisor again, because he gave me chance to continuous my PhD study in Paris, we learned a lot and more importantly, we made lots of excellent Chinese friend here, especially Longsheng Zheng and Bin He. We are from the same group, and we‘re F4 for lunch. Of course, I would like to say a big and loving thanks to my parents and to my sister Xia Wang. Thank you for your support and your encouragements, especially when I was homesick. Thank you for trying to understand my work and for listening to me when I needed it. I know that I can always count on you. And, last but not least: My wife- Shuang Zhong. Meeting you was one of the greatest things that happened to me during this PhD. We were falling in love with each other when we met. Although we 3 / 342 were separated by miles in first two years, the heart is close to the heart. Love makes us crazy, and we are ready to be crazy for a lifetime. The happiest thing is that we got married, and you come with me in Paris. Thank you for your daily support, for comforting me when I felt bad, for your jokes, for your delicious dishes, and for believing in me. 4 / 342 Table of contents Acknowledgements ........................................................................................................ 2 Table of contents ............................................................................................................ 5 List of Tables ............................................................................................................... 12 List of Figures .............................................................................................................. 14 List of Schemes ............................................................................................................ 19 GENERAL INTRODUCTION .................................................................................... 22 CHAPTER 1 Furfural synthesis................................................................................... 28 Context and literature review ................................................................................... 28 1.1 Furfural ........................................................................................................... 28 1.2 Bio-resources for the production of furfural ................................................... 30 1.3 Advanced methods for furfural production .................................................... 37 1.4 Recent advances in furfural synthesis ............................................................ 49 CHAPTER 2 .............................................................................................................. 126 2.1 Sulfonated sporopollenin as an efficient and recyclable heterogeneous catalyst for dehydration of D-xylose and xylan into furfural .............................................. 126 2.1.1 Introduction ............................................................................................... 126 2.1.2 Modification of the surface of sporopollenin ............................................ 127 2.1.3 Effect of reaction temperature ................................................................... 129 2.1.4 Effect of reaction time ............................................................................... 131 5 / 342 2.1.5 Effect of catalyst and substrate loading ..................................................... 132 2.1.6 Effect of NaCl addition.............................................................................. 134 2.1.7 Effect of catalysts recovery ....................................................................... 135 2.1.8 Furfural production from xylan ................................................................. 136 2.1.9 Conclusions ............................................................................................... 138 2.2 Comprehensive study of an expeditious conversion of pre-hydrolyzed alginic acid to furfural in Cu (II) biphasic systems using microwaves .............................. 140 2.2.1 Introduction ............................................................................................... 140 2.2.2 Preliminary experiments ............................................................................ 141 2.2.3 Conversion of D-glucuronic acid in water-CPME mixture ....................... 142 2.2.4 Conversion of alginic acid in water-CPME mixture ................................. 143 2.2.5 Conversion of alginic acid in water-MTHF mixture ................................. 149 2.2.6 Conversion of alginic acid in water-MIBK mixture .................................. 151 2.2.7 Reusability of the aqueous phase containing CuCl2 .................................. 152 2.2.8 Comprehensive study of the furfural origin .............................................. 153 2.2.9 Conclusions ..............................................................................................