Par Sarah LE GUENIC Dehydration in aqueous media Thèse présentée pour l’obtention du grade de Docteur de l’UTC Soutenue le 1er décembre 2015 Spécialité : Génie des Procédés Industriels et du Développement Durable D2238 Université de Technologie de Compiègne Ecole Doctorale : Sciences pour l’ingénieur Thèse présentée par Sarah LE GUENIC Pour le titre de Docteur en Génie des Procédés Industriels et du Développement Durable Dehydration in aqueous media Thèse dirigée par : Christophe LEN et Claire CEBALLOS Soutenue le 1er décembre 2015 devant le jury composé de : François JEROME Directeur de Recherche CNRS, Université de Poitiers Rapporteur Rafael LUQUE Professeur, Universidad de Cordoba Rapporteur Florent ALLAIS Professeur, AgroParisTech Examinateur Stéphane OCTAVE Docteur, Université de Technologie de Compiègne Examinateur Christophe LEN Professeur, Université de Technologie de Compiègne Directeur de thèse Claire CEBALLOS Docteur, Ecole Supérieure de Chimie Organique et Directrice de thèse Minérale 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 Pr. Christophe LEN and Dr. Claire CEBALLOS. I would like to thank Pr. André PAUSS, director of the laboratory, for giving me the opportunity to do this PhD. I would also like to thank Georges SANTINI, director of the Ecole Supérieure de Chimie Organique et Minérale (ESCOM) for letting me work in his school. I also thank the French Ministère de l’Enseignement Supérieur et de la Recherche for its financial support. First of all, I would like to thank the Director and Co-director of my thesis, Pr. Christophe LEN and Dr. Claire CEBALLOS, for their scientific help, support and guidance during this PhD. I particularly thank Pr. 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, François JEROME and Rafael LUQUE. Thank you for the time you devoted and the feedback that you provided. During my PhD work, I had the opportunity to do a Short Term Scientific Mission in the team of Pr. Herbert SIXTA, in the Department of Forest Products Technology, in Aalto University (Helsinki, Finland). I thank the COST program for the grant awarded and the Pr. SIXTA for his supervision. Thanks to Jean BUFFIERE, Olga ERSHOVA and Rita HATAKKA from the Biorefineries’ team for their help with the reactor, the HPLC and in the laboratory. I would like to thank my colleagues from the OCAT team, with which I had the pleasure to collaborate: Carole, Claire, Denis, Estelle, Floriane, Frédéric, Gérald, Gwenaëlle, Muriel and Nicolas T. I particularly thank Nicolas T. and Denis for their many scientific advices, for their jokes and for the good times we spent together. Thanks to i Frédéric for the time he spent on my manuscript. I thank the interns, who participated on my project, for their work and implication: Quentin, Fabrice, David and Loïc. I thank Lysiane, from TIMR, for her help and the whole staff of ESCOM for their hospitality. Special thanks to France, Anissa, Bernard, Pierre-Yves, Joachim and Nathalie for the fun talks we had during coffee breaks. This PhD would not have been the same without the fun and friendly atmosphere of the lab. Big thanks to Rémi, Nicolas G., Clément, Sophie, Audrey and Christina. Of course, I particularly thank Hasret and Nico who made this long journey with me, who suffered and laughed with me, who cheered me up when I was down and supported me through the important moments. The three PhD Babies have grown up and have become doctors. Now, one chapter in the story closes, but a whole new adventure begins! I would also like to thank all the PhD students that I have met during these 3 years for the nice moments: the RED² team – Christophe, Marina, Benjamin, Fabien, Florian, Pierre, Pierre, Tifenn, Tony, Rémy and Gaëtan, the Acoustic Boys – Antoine, Romain and Julien, and the TIMR Girls – Sylène, Maria and Atena. A special thanks to my friends, Clémentine, Audrey, Marion, Claire, Tania and Ghania. Even if it was sometimes hard to find a date to see each other, spending time with you was always a good moment which cheered me up and made me forget (for a time!) the hard work waiting for me. Of course, I would like to say a big and loving thanks to my parents and to my sister Marion and my brother Benjamin. Thank you for your support and your encouragements, 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. More broadly, I thank Dany, Evann, Gaële, Frédérique, Katia and the kids for their support. And, last but not least: Yorick. Meeting you was one of the greatest things that happened to me during this PhD. 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. ii Table of contents ACKNOWLEDGEMENTS .................................................................................................. I TABLE OF CONTENTS ................................................................................................... III ABBREVIATIONS ......................................................................................................... VII LIST OF FIGURES .......................................................................................................... IX LIST OF TABLES ............................................................................................................ XI LIST OF SCHEMES ....................................................................................................... XII GENERAL INTRODUCTION ............................................................................................. 1 CHAPTER I ...................................................................................................................... 5 CONTEXT AND LITERATURE REVIEW .......................................................................... 5 1. GREEN CHEMISTRY: DEFINITION AND TOOLS ........................................................................................ 7 a. Green Chemistry: Origin and Twelve Principles ....................................................................... 7 b. Water as a green solvent ............................................................................................................ 10 i. General points on green solvents ........................................................................................................... 10 ii. Sub- and supercritical water .................................................................................................................. 14 c. Alternative activation methods ................................................................................................. 17 i. An overview of the different methods .................................................................................................... 17 ii. Microwave chemistry .............................................................................................................................. 19 2. DEHYDRATION OF POLYHYDROXYLATED COMPOUNDS IN WATER ........................................................ 25 a. Without a catalyst ....................................................................................................................... 25 b. Homogeneous catalysis .............................................................................................................. 26 i. Mineral and organic acids ...................................................................................................................... 26 ii. Metal sulphates ....................................................................................................................................... 27 iii. Metal chlorides ....................................................................................................................................... 29 iv. With the addition of CO2 ....................................................................................................................... 30 c. Heterogeneous catalysis ............................................................................................................. 30 i. Modified silicates and aluminosilicates ................................................................................................. 31 ii. Mixed oxides ........................................................................................................................................... 32 iii. Ion-exchange resins ................................................................................................................................ 33 iv. Solid metal phosphates ........................................................................................................................... 34 d. Enhancing selectivity .................................................................................................................. 34 3. ISSUE AND OBJECTIVES ...................................................................................................................... 36 BIBLIOGRAPHY ........................................................................................................................................... 37 iii CHAPTER II ..................................................................................................................