Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Lignocellulosic biomass use for obtaining biofuels has been showing itself with much more evidence during these past years through cellulosic ethanol and biooils, biogases and biochars. Aquatic plants of lignocellulosic basis, Eichhornia crassipes species, commonly known by water hyacinth, represent a major environmental problem due to their invasive nature and their high proliferation rate. In this work we evaluated the possibility of use this biomass source from pyrolysis in a rotary kilns reactor in three different temperatures. The results evidence that the major yield of the liquid fraction (bio-oil + acid extract) was obtained at 500 ºC (42.11%). For 400 ºC and 600 ºC, the biochar and biogas had major production, 37.78% and 42.36%, respectively. Bio-oils characterization by GC/MS produced in microscale allowed an investigation upon the scale-up phenomenon under the bio-oils composition. The results show that, in qualitative terms, the chemical composition of bio-oils was not changed, however, at semiquantitative aspect, show they are produced in distinguish relative percentages. The mainly chemical classes identified in biooils were: acids, alcohols, phenols and sugar derivatives. Bio-oils showed in average, 68% of calorific power of the fuels derived from petroleum, glimpsing enforcement on the energetic area. In the produced biochars, with yields between 37% and 26%, the increase on pyrolysis temperature has provided an increase upon carbon concentration, and a decreasing upon the hydrogen and oxygen concentrations, reflecting in high aromaticity of the materials. These materials ware tested in some aspects about the soils management, nutritional function and water retention. In view of this, the water hyacinth pyrolysis has associated sustainability concepts and green chemistry, putting concepts of renewable energetic sources together and glimpsing an environmental problems inhibition, to offer an alternative to the 2nd generation of bio-fuels production. / O uso de biomassas lignocelulósicas para a obtenção de biocombustíveis apresenta-se com muito mais evidência nos últimos anos através do etanol celulósico e de bio-óleos, biogás e biocarvão. As plantas aquáticas de base lignocelulósica da espécie Eichhornia crassipes, popularmente conhecida por aguapé, representam um grande problema ambiental devido ao seu caráter invasor e sua alta taxa de proliferação. Neste trabalho avaliou-se a possibilidade de aproveitamento dessa fonte de biomassa a partir do processo de pirólise em um reator cilindro rotativo em três diferentes temperaturas. Os resultados demonstraram que o maior rendimento da fração líquida (bio-óleo + extrato ácido) foi obtido a 500 ºC (42,11%). Para as temperaturas de 400 e 600 ºC, o biocarvão e o biogás tiveram maior produção, 37,78% e 42,36%, respectivamente. A caracterização por CG/EM dos bio-óleos produzidos em microescala permitiram investigar o efeito de scale-up sob a composição dos bio-óleos. Os resultados mostraram que em termos qualitativos, a composição química dos bio-óleos não foi alterada, no entanto, no aspecto semiquantitativo mostraram que são produzidos em percentuais relativos distintos. As principais classes químicas identificadas nos bio-óleos foram: ácidos, álcoois, fenóis e derivados de açúcares. Os bio-óleos apresentaram em média 68% do poder calorífico do combustível derivado de petróleo, vislumbrando uma aplicação na área energética. Nos biocarvões produzidos, com rendimento variando de 37% a 26%, o aumento da temperatura de pirólise proporcionou um aumento na concentração de C, e uma diminuição nas concentrações de H e O, refletindo em maior aromaticidade dos materiais. Estes materiais foram testados sob alguns aspectos quanto ao manejo de solos, função nutricional e retenção de água. À vista disto, a pirólise de aguapé relacionou conceitos de sustentabilidade e química verde, unindo o conceito de fontes de energias renováveis com a inibição de problemas de cunho ambientais, ao oferecer uma biomassa alternativa para a produção de biocombustíveis de 2ª geração.

Ce travail porte sur la production de bio-huile par liquéfaction hydrothermale de résidus agroalimentaires, réalisée en réacteur batch. L’objectif est d’étudier l’influence des paramètres opératoires sur la production de bio-huile, et de contribuer à la compréhension des mécanismes de conversion hydrothermale de la biomasse. La liquéfaction hydrothermale des résidus agroalimentaires a été étudiée à partir de l’exemple des drêches de cassis, résidus de pressage des baies. Une étude paramétrique a évalué l’influence de la température, du temps de réaction, de la concentration de biomasse et de l’ajout d’hydroxyde de sodium sur le rendement des produits. Cette étude a permis d’identifier des conditions opératoires favorables à la production de bio-huile, dont le rendement peut notamment bénéficier du recyclage de la phase aqueuse en tant que solvant réactionnel (rendement maximal de bio-huile : 31 %). La caractérisation physico-chimique de la bio-huile montre que celle-ci possède certaines propriétés proches du pétrole brut et de certains fiouls lourds, notamment grâce à sa faible teneur en oxygène en comparaison des huiles de pyrolyse. La bio-huile peut être considérée comme un bio-pétrole brut, mais nécessite toutefois un raffinage conséquent avant de potentielles applications. La conversion hydrothermale de molécules modèles, sélectionnées à partir de l’analyse de la composition des drêches de cassis, a été étudiée à une température de 300 °C et un temps de réaction de 60 min. Cinq monomères modèles (glucose, xylose, acide glutamique, guaiacol et acide linoléique) et deux polymères modèles (cellulose microcristalline et lignine alkali) ont été choisis pour cette étude. Une méthodologie basée sur les plans d’expérience de mélange a été mise en œuvre, afin d’aboutir à la construction de schémas réactionnels, et à l’élaboration de corrélations modélisant les rendements des produits en fonction de la composition initiale des mélanges. L’analyse des produits montre que la conversion hydrothermale des résidus agroalimentaires résulte principalement de dégradations primaires et d’interactions binaires entre les composants de la biomasse. Les corrélations obtenues à partir des composés modèles permettent de décrire avec un bon accord les rendements des produits de conversion hydrothermale de mélanges modèles et de plusieurs résidus agroalimentaires : drêches de brasserie, marc de raisin et akènes de framboise. / This work presents a study of hydrothermal liquefaction of food processing residues using a batch reactor, to produce bio-oil. The objective is to study the influence of operating conditions on bio-oil production, and to contribute to the understanding of the reaction mechanisms occurring during hydrothermal conversion of biomass. Hydrothermal liquefaction of food processing residues was studied using blackcurrant pomace, a berry pressing residue, as an example. A parametric study evaluated the influence of temperature, holding time, biomass concentration and the use of sodium hydroxide as additive on the yields of products. This study allowed the identification of favorable operating conditions to produce bio-oil. The bio-oil yield can in particular benefit from recycling the aqueous phase as reaction solvent (maximum bio-oil yield: 31%). Physicochemical characterization of the bio-oil showed that it has some similarities with heavy crude oil and heavy oils, especially thanks to a lower oxygen content than pyrolysis oils. The bio-oil can be considered as a bio-heavy crude oil, but it still requires significant upgrading before any potential applications. Hydrothermal conversion of model molecules, selected from the characterization of blackcurrant pomace, was studied at a temperature of 300 °C and a holding time of 60 min. Five model monomers (glucose, xylose, glutamic acid, guaiacol and linoleic acid) and two model polymers (microcrystalline cellulose and alkali lignin) were chosen for this study. A mixture design of experiments methodology was followed, to combine reactivity studies with the elaboration of correlations describing the mass yields of products as a function of the initial mixture composition. Analysis of the products shows that hydrothermal conversion of food processing residues is mainly due to degradations of individual compounds and binary interactions between components of biomass. The correlations obtained from the model compounds describe with good accuracy the mass yields of the products from hydrothermal conversion of a model mixture and several food processing residues: brewer’s spent grains, grape marc and raspberry achenes.

This project is primarily focused on improving the storage stability of bio-oils or pyrolysis oils by varying feedstock, reactor, and storage conditions. Pyrolysis oil is a complex medley of oxygenated chemicals (aliphatic and aromatic) that are well known to undergo unstable polymeric reactions (auto-catalyzed) if suitable additives are not utilized. These reactions can be severely detrimental to the long-term storage stability of pyrolysis oils. Hence, a detailed investigation was conducted in four phases namely: 1) pyrolysis oil production 2) additive prescreening 3) concentration optimization and 4) stability testing. During the first phase a lab-scale semi-continuous auger reactor is utilized to produce 16 pyrolysis oils. The reactor variables include pyrolysis temperature and vapor residence time. The feed stocks include pine wood, pine bark, oak wood, and oak bark. During the second phase a range of chemical additives (26) are prescreened to obtain three best performing additives. Anisole, glycerol, and methanol are consequently utilized to perform concentration optimization studies during the third phase. Viscosity, water content, and pH of pyrolysis oils are timely measured to assess the accelerated storage stability of pyrolysis oils during the phases 2-3. During the fourth phase, pyrolysis oils produced from three different reactor systems (lab-scale auger, large-scale auger, and entrained flow) were tested for their storage stability. Viscosity, water content, pH, density, and acid value are timely measured to assess the ambient and accelerated storage stability of pyrolysis oils during phase 4. Extrinsic variables such as light and filtration are utilized during the experimental testing of phase 4. The rheological data (Newtonian/non-Newtonian) enhanced the understanding of pyrolysis oil storage stability both qualitatively and quantitatively. The stability performance of a chemical additive is very much dependent on the concentration and its organic functional group. Consequently, alcohols fared above all the other functional groups in stabilizing the pyrolysis oils. Glycerol is observed to have special blending and homogenizing properties compared to all other additives. Feedstock seems to be the single most important factor affecting storage stability of pyrolysis oils. Consequently, pine wood resulted in the most stable pyrolysis oil whereas pine bark resulted in the least stable pyrolysis oil.