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Productiondebioutanolà UNIVERSITÉ DE SHERBROOKE Faculté de Génie En cotutelle avec : ÉCOLE NATIONALE SUPÉRIEURE DES MINES D’ALBI-CARMAUX CONJOINTEMENT AVEC L’INP TOULOUSE PRODUCTION DE BIOUTANOL À PARTIR DE LIGNOCELLULOSE: UN NOUVEAU PROCÉDÉ THERMOCHIMIQUE Thèse de doctorat MARICELLY MARTINEZ AGUILAR Membres du jury : Pr Jean-Michel LAVOIE (Directeur de recherche) Pr Ange NZIHOU (Co-Directeur de recherche) Pre Michèle Heitz Pre Bruna Rego de Vasconcelos Pr Jose Luis Sanchez Sherbrooke (Québec) Canada 2020 RÉSUMÉ __________________________________________ Production de biobutanol à partir de lignocellulose : Un nouveau procédé thermochimique La demande d'énergie au cours des dernières années a augmenté et un grand pourcentage de l'énergie est dérivée des combustibles fossiles, mais l'utilisation de ces carburants a généré des émissions de CO2 et de la pollution environnementale. Pour ce problème, on a mené des recherches sur l'utilisation des énergies alternatives à partir de biomasse lignocellulosique pour produire des carburants qui réduisent les émissions de CO2. Le Canada est un pays avec une abondance de résidus lignocellulosiques qui sont une source pour la production de différents produits chimiques. La première partie de l’étude se concentre sur l’étude cinétique de la production du lévulinate de méthyle et de l’acide lévulinique à partir de la cellulose avec un catalyseur homogène (H2SO4). La deuxième partie porte sur la conversion de la cellulose en lévulinates (molécule plateforme) en utilisant un catalyseur homogène (H2SO4) et un catalyseur solide (Al2(SO4)3). La troisième partie se consacre sur l’étude de l’hydrolyse du lévulinate de méthyle en acide lévulinique en utilisant des catalyseurs à base de cuivre. Des techniques d’analyse tels que le SEM, XRD, TPX ont été utilisés pour étudier les catalyseurs supportés et comprendre leur effet sur la réaction. La quatrième partie du projet porte sur l’étude des résultats obtenus des différentes réactions réalisées pour la production du 2-butanol à partir de la biomasse lignocellulosique en passant par la production du lévulinate de méthyle et de l’acide lévulinique qui sont des molécules plateforme et potentiellement substitutes au biodiesel. Par la suite, l’acide lévulinique est décarboxylé en 2-butanone et le dernier est réduit en 2-butanol en utilisant des catalyseurs bifonctionnels (tel que le Ru / C et le Pt / C) en conditions douces. L’ensemble de ces travaux contribuent à la compréhension des réactions du nouveau procédé de production du butanol. Mots-clés : Cellulose, Biomasse lignocellulosique, Hydrolyse, Thermochimie, Butanol i II SUMMARY __________________________________________ Biobutanol production from lignocellulose by a novel thermal process In the last years, the energy demand has increased and a large pourcentage of this energy is obtained from fossil fuels, but the use of these fuels has generated CO2 emissions and environmental pollution. For this reason, this research was focused on the use of alternative energies from lignocellulosic biomass to produce renewal fuels decreasing CO2 gas emissions. Canada is a country with high quantities of lignocellulosic biomass which can represent a cheap source for the high value added molecules and fuels production. The first part of the study focuses on the kinetic study of the production of methyl levulinate and levulinic acid from cellulose with a homogeneous catalyst (H2SO4). The second part study the conversion of cellulose to levulinates (platform molecule) using a homogeneous catalyst and a heterogeneous catalyst (Al2(SO4)3). The third part is devoted to study the hydrolysis of methyl levulinate to levulinic acid using copper- based catalysts. Analytical techniques such as SEM, XRD, TPX were used to study the supported catalysts and understand their effect on the reaction. The fourth part of the project relates to the study of the production of 2-butanol from lignocellulosic biomass through the production of methyl levulinate and levulinic acid which are platform molecules and potentially substitutes for biodiesel. Thereafter, the levulinic acid is decarboxylated to 2-butanone and the latter is reduced to 2-butanol using bifunctional catalysts (such as Ru/C and Pt/C) under mild conditions. All of this work contributes to understanding the reactions of the new butanol production process. Key words: Cellulose, Lignocellulosic biomass, Hydrolysis, Pyrolysis, Hydrogenation, Biobutanol. III IV V REMERCIEMENTS __________________________________________ Je voudrais remercier Professeur Jean-Michel Lavoie pour m’avoir donné l’opportunité de travailler au sein du Laboratoire des Technologies de la Biomasse au Canada. Pour moi, travailler avec toi a été de meilleures expériences que j’ai eues dans ma carrière professionnelle. Merci de m’avoir guidé et encouragé surtout aux moments les plus difficiles de ma vie et de mon doctorat. Un grand merci au Professeur Ange Nzihou pour m’avoir donné l’opportunité de travailler pendant un an avec son équipe au laboratoire RAPSODEE à Albi, France. Vos connaissances et vos exigences m’ont m’ont tiré vers le haut chaque jour dans votre équipe. Un grand merci au Professeur David Chiaramonti pour m’avoir donné l’opportunité de travailler en Florence pendant un mois avec son équipe de travail RE-CORD. Merci de m’avoir permis d’utiliser vos installations et de m’avoir accompagné pendant ce temps. Un grand merci à Doan et Xavier pour votre aide et votre collaboration sur plusieurs aspects de mon projet qui ont été indispensables pour le mener à bien. Un grand merci à Thierry Ghislain, Sophie Beauchemin, Emmanuelle Bahl et Maxime Lessard pour m’avoir aidé dans les analyses de mes échantillons et surtout pour votre amitié. Un grand merci à Simon pour m’avoir aidé avec mes réacteurs et mes appareils brisés. Merci aussi aux techniciens à Albi, Mikael, Jean-Marie, Séverine et Sylvie pour m’avoir aidé pour les analyse des échantillons et la mise en marche de mes réacteurs. La réalisation de ce projet m’a montré que le travail est un lieu où l’on peut trouver des personnes qui peuvent changer sa vie et la rendre plus heureuse, c’est pour ça que je voudrais remercier mes amis à Sherbrooke : James, Marine, Emmanuelle, Sophie, Thierry, Bruna, Maxime, Rajesh, VI Mike, Erik, Iulian, JB, Axel, Florian, Adrian, Emy, et à Albi : Lina, Aissatou, Thomas, Son, Ana, Severin, Antonio, qui ont été là pour m’aider, et pour m’encourager pendant mon projet de recherche. Je voudrais remercier les personnels à Florence en Italie : Ramin, Gulia et Lorenzo pour m’avoir aidé pendant mon séjour et surtout m’avoir fait découvrir mon café préféré (Latte macchiato decaffeinato). Merci à ma famille, ma maman, mon papa, mes tantes, ma sœur, mon frère, mes cousins, les copines de mes cousins et mes amis de m’avoir supporté dans ce projet. Merci à ma maman, mon papa et ma tante de m’avoir donné la force pour continuer surtout aux moments les plus difficiles. Merci à mes amis Luz Marina, Luz Arley, David, Jean-Dominique, Alejandro, Gina, Pao, Mario, mon équipe à Tecnoparque à Medellin, qui ont été toujours là pour moi pour m’aider dans les bons et les mauvais moments. Cette thèse est faite pour toi maman, tu m’as montré ton courage pour affronter les problèmes, merci de ton amour et de ta patience toujours avec moi, tout ce que j’ai et je suis est grâce à toi. Je t’aime. Cette thèse a été faite avec beaucoup d’amour, merci à tous, je vous aime. VII VIII TABLE DES MATIÈRES __________________________________________ Table des matières 1. Introduction ....................................................................................................................... 1 1.1 Contexte ............................................................................................................................. 1 1.2 Objectif de la recherche ..................................................................................................... 4 1.2.1 Objectif général .................................................................................................................. 4 1.2.2 Objectifs spécifiques .......................................................................................................... 4 2. État de l’art ......................................................................................................................... 6 2.1 Contexte ............................................................................................................................. 6 2.2 La biomasse lignocellulosique ............................................................................................ 8 2.3 Le bioraffinage pour la valorisation de la biomasse ........................................................ 12 2.4 La production du 2-butanol ............................................................................................. 14 2.4.1 Production de l’acide lévulinique et l’esters lévulinate ................................................... 18 2.4.2 Décarboxylation du lévulinate de méthyle en 2-butanone ............................................. 24 2.4.3 Hydrogénation du 2-butanone en 2-butanol ................................................................... 29 2.5 Mécanismes de réaction pour la production du 2-butanol ............................................. 37 2.5.1 Mécanisme de l’hydrolyse de la cellulose ....................................................................... 37 2.5.2 Mécanisme de réaction de la conversion du glucose en méthyl glucopyranose ............ 39 2.5.3 Mécanisme de réaction
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