Dans un contexte de transition énergétique et de lutte contre le réchauffement climatique, la production d’éthanol de seconde génération semble une voie très prometteuse afin de réduire notre dépendance aux énergies fossiles. Il existe 3 étapes clés pour la production de ce nouveau biocarburant : le prétraitement qui permet de déstructurer la matrice lignocellulosique afin de rendre la cellulose plus accessible aux enzymes, l’hydrolyse enzymatique qui a pour but de produire des sucres fermentescibles et la fermentation qui permet de transformer ces sucres en éthanol. Actuellement, le prétraitement considéré comme le plus efficace, et principalement retenu par les industriels, est le prétraitement par explosion à la vapeur. Cependant, certains aspects comme les effets physicochimiques induits par le prétraitement ainsi que leurs impacts sur les caractéristiques de la biomasse prétraitée restent encore mal compris.Schématiquement, le prétraitement par explosion vapeur peut se décomposer en deux étapes : la première se rapproche d’une cuisson acide réalisée à 150-200°C durant 5 30 min et permet principalement l’hydrolyse des hémicelluloses, alors que la seconde est une détente explosive qui permet un éclatement mécanique du substrat rendant potentiellement la cellulose plus réactive à l’hydrolyse enzymatique. Globalement les effets de ce type de prétraitement sur la biomasse lignocellulosique sont aujourd’hui bien connus mais la compréhension des différents phénomènes physico-chimiques ayant lieu en son sein reste limitée. En effet le découplage de l’étape de cuisson et de l’étape de détente est délicat car, la température du réacteur (qui impacte principalement les réactions de cuisson) est directement liée à sa pression (qui impacte principalement la détente) par la thermodynamique des phases.Ce travail de thèse se propose donc de mieux appréhender l’ensemble des phénomènes physico-chimiques ayant lieu durant le prétraitement par explosion à la vapeur en s’appuyant notamment sur une discrimination expérimentale des phénomènes chimiques (réactions de dépolymérisation) et des phénomènes physiques (détente explosive) ainsi que sur une caractérisation multi-techniques et multi-échelles de la biomasse lignocellulosique obtenue après ce type de prétraitement. L’objectif est aussi de comprendre quelles sont les principales caractéristiques de la biomasse qui expliquent les différences de réactivité observées lors de l’étape d’hydrolyse enzymatique et d’expliquer l’impact du prétraitement par explosion à la vapeur sur les propriétés physicochimiques et donc sur la réactivité. / In a context of energy transition and climate change challenge, the production of second generation ethanol seems to be a very promising way to reduce our dependence on fossil fuels. There are 3 key steps for producing this new biofuel: pretreatment to decompose the lignocellulosic biomass and to make cellulose more accessible to enzyme attacks, enzymatic hydrolysis to produce fermentable sugars and fermentation to convert these sugars into ethanol. Currently, the pretreatment considered to be the most efficient, and mainly retained for industrialization, is the steam explosion pretreatment. However, some aspects such as the physicochemical effects induced by pretreatment and their impacts on the characteristics of pretreated biomass remain misunderstood.Schematically, the steam explosion pretreatment can be separated into two stages: the first is similar to an acid cooking carried out at 150-200°C during 5-30 min and allows mainly the hydrolysis of hemicelluloses, while the second is an explosive release which allows a mechanical bursting of the substrate potentially making the cellulose more reactive to enzymatic hydrolysis. As a whole, the effects of this type of pretreatment on lignocellulosic biomass are now well known, but the understanding of the different physicochemical phenomena occurring within it remains limited. Indeed, decoupling the cooking stage and the expansion stage is complicated because the reactor temperature (which mainly impacts the cooking reactions) is directly related to its pressure (which mainly impacts the explosive release) by the phase thermodynamics.This thesis work aims to better understand all the physicochemical phenomena occurring during a steam explosion pretreatment, based in particular on experimental discrimination of chemical phenomena (depolymerization reactions) and physical phenomena (explosive release) as well as on a multi-technical and multi-scale characterization of the lignocellulosic biomass obtained after this type of pretreatment. The objective is also to understand what are the main characteristics of biomass that explain the differences in reactivity observed during the enzymatic hydrolysis step and to explain the impact of the steam explosion pretreatment on the physicochemical properties and therefore the reactivity.

La phytoremédiation est un concept pour la dépollution et de réhabilitation des sols et/ou de friches industrielles contaminés par des éléments traces métalliques (ETMs), utilisant les végétaux pour absorber ou immobiliser les contaminants en présence des organismes microbiens de la rhizosphère. Cette technique a pour conséquence une production de biomasse plus ou moins contaminée qu’il est nécessaire de traiter et également de valoriser. Cependant, la présence d’ETMs peut être problématique dans une approche de conversion en bioraffinerie. Pour répondre à cette question, deux espèces ont été étudiées : une plante herbacée hyperaccumulatrice (Noccaea caerulescens) et un ligneux (Salix viminalis). Deux prétraitements ont été sélectionnés pour cette étude : les prétraitements par explosion vapeur et organosolv, en appliquant différentes conditions opératoires, afin (1) de suivre la distribution des ETMs au cours du traitement, (2) de purifier la matière lignocellulosique et (3) d’évaluer l’effet des ETMs sur les étapes ultérieures d’hydrolyse enzymatique et de fermentation. Pour le prétraitement organosolv la majeure partie des ETMs est récupérée dans le résidu solide cellulosique alors que par explosion à la vapeur, les ETMs sont extraits en grande partie dans les effluents aqueux du traitement. La présence d’ETMs dans les pâtes cellulosiques et les hydrolysats ne montre pas d’effet significatif sur la cinétique d’hydrolyse enzymatique et de fermentation. Concernant spécifiquement Noccaea caerulescens des teneurs relativement importantes en pectines ont été observées, ce qui ouvre des perspectives intéressantes pour la valorisation de cette plante par la production d’un biopolymère d’intérêt industriel. Finalement, les résultats obtenus montrent qu’il serait possible de combiner réhabilitation des sols et valorisation en bioraffinerie de biomasses issues de phytotechnologies soit pour la production du bioéthanol ou la production de molécules plateforme / Phytoremediation is a concept for the depollution and rehabilitation of soils and/or industrial wastelands contaminated by metal trace elements (MTEs), using plants to absorb or immobilize contaminants in the presence of microbial organisms in the rhizosphere. This technique results in a more or less contaminated biomass production that must be treated and also recovered. However, the presence of MTEs can be an issue in a biorefinery conversion approach. To address this question, two species were studied: an hyperaccumulator herbaceous plant (Noccaea caerulescens) and a woody plant (Salix viminalis). Two pre-treatments were selected for this study: steam explosion and organosolv pre-treatments, applying different operating conditions, in order to (1) monitor the distribution of MTEs during the process, (2) purify lignocellulosic material and (3) evaluate the effect of MTEs on subsequent enzymatic hydrolysis and fermentation steps. For organosolv pretreatment, most of the MTEs are recovered in the solid cellulosic residue while by steam explosion, MTEs are mostly extracted in the aqueous effluents of the treatment. The presence of MTEs in cellulosic pastes and hydrolysates does not show a significant effect on the kinetics of enzymatic hydrolysis and fermentation. Concerning specifically Noccaea caerulescens, the plant contains relatively high levels of pectins, which opens up interesting prospects for the valorization of this plant through the production of a biopolymer of industrial interest. Finally, the results obtained show that it would be possible to combine soil rehabilitation and biorefinery valorization of biomasses from phytotechnologies for either bioethanol production or the production of platform molecules

The three main components of wood, namely, cellulose, hemicellulose, and lignin, can be used in various areas. However, since lignin covalently crosslinks with wood polysaccharides creating networks that is an obstacle for extraction, direct extraction of different wood components in high yield is not an easy matter. One potential approach to overcome such obstacles is to treat the wood with specific enzymes that degrade the networks by specific catalysis. However, the structure of wood is so compact that the penetration of the wood fibers by large enzyme molecules is hindered. Thus, the pretreatment of wood prior to the application of enzymes is necessary, for “opening” the structure. One pretreatment method that was performed in this thesis is based on kraft pulping, which is a well-established and industrialized technique. For untreated wood, the wood fibers cannot be attacked by the enzymes. A relatively mild pretreatment was sufficient for wood polysaccharides hydrolyzed by a culture filtrate. A methanol-alkali mixture extraction was subsequently applied to the samples that were pretreated with two types of hemicellulases, Gamanase and Pulpzyme HC, respectively. The extraction yield increased after enzymatic treatment, and the polymers that were extracted from monocomponent enzyme-treated wood had a higher degree of polymerization. Experiments with in vitro prepared lignin polysaccharide networks suggested that the increased extraction was due to the enzymatic untying. However, the relatively large loss of hemicellulose, particularly including (galacto)glucomannan (GGM), represents a problem with this technique. To improve the carbohydrate yield, sodium borohydride (NaBH4), polysulfide and anthraquinone were used, which increased the yields from 76.6% to 89.6%, 81.3% and 80.0%, respectively, after extended impregnation (EI). The additives also increased the extraction yield from approximately 9 to 12% w/w wood. Gamanase treatment prior to the extraction increased the extraction yield to 14% w/w wood. Sodium dithionite (Na2S2O4) is an alternative reducing agent for the preservation of hemicelluloses because it is less expensive than metal hydrides and only contains sodium and sulfur, which will not introduce new elements to the recovery system. Moreover, Na2S2O4has the potential to be generated from black liquor. Na2S2O4 has some preservation effect on hemicelluloses, and the presence of Na2S2O4 also contributed to delignification. The extraction yield increased to approximately 15% w/w wood. Furthermore, Na2S2O4 has been applied in the kraft pulping process of spruce. The yield and viscosity increased, while the Klason lignin content and kappa number decreased, which represents a beneficial characteristic for kraft pulp. The brightness and tensile strength of the resulting sheets also improved. However, the direct addition of Na2S2O4 to white liquor led to greater reject content. This problem was solved by pre-impregnation with Na2S2O4 and/or mild steam explosion (STEX) prior to the kraft pulping process. Following Na2S2O4 pre-impregnation and mild STEX, the obtained kraft pulp had substantially better properties compared with the properties exhibited after direct addition of Na2S2O4 to the white liquor. The wood structure opening efficiency of mild STEX alone was also tested. The accessibility of the wood structure to enzymes was obtained even at very modest STEX conditions, according to a reducing sugar analysis, and was not observed in untreated wood chips, which were used as a reference. The mechanical effect of STEX appears to be of great importance at lower temperatures, and both chemical and mechanical effects occur at higher STEX temperatures. / <p>QC 20140903</p>

Made available in DSpace on 2014-06-11T19:23:26Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-10-01Bitstream added on 2014-06-13T19:09:12Z : No. of bitstreams: 1 pinto_top_me_sjrp.pdf: 1417990 bytes, checksum: 1ff62a60751622fd662850c2a8565eba (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / O aproveitamento de resíduos agrícolas e agro-industriais como fonte de energia pode se tornar uma alternativa viável. O alvo principal para esta empreitada, pela sua disponibilidade e proximidade das indústrias fermentativas é o bagaço de cana, que ainda retém 2/3 da energia presente na cana, é largamente disponível no Brasil e hoje é parcialmente rejeitado ou subaproveitado. Uma forma de aproveitamento que tem se mostrado bastante promissora refere-se ao uso dessa biomassa na produção do bioetanol. No presente trabalho, avaliou-se o perfil de produção enzimática dos fungos Thermoascus aurantiacus CBMAI 756, Thermomyces lanuginosus, Penicillium viridicatum RFC3 e Trichoderma reesei QM9414, através de fermentação em estado sólido em meio com bagaço de cana e farelo de trigo. Aplicou-se esses extratos enzimáticos na hidrólise de bagaço de cana submetido a diferentes pré-tratamentos térmicos: água quente, explosão a vapor, e água quente em combinação com HCl, H2SO4, H3PO4, H2O2 ou NaOH. Determinou-se os principais inibidores (furfural e 5-hidroximetilfurfural) e açúcares redutores (glicose, xilose, arabinose, galactose, xilobiose e celobiose) gerados no processo. O fungo T. aurantiacus foi o melhor produtor de enzimas celulolíticas (536,3 U/g de CMCase) e hemicelulolíticas (3419,2 U/g de xilanase), apresentando juntamente com o extrato enzimático de T. reesei os melhores rendimentos na sacarificação do bagaço. Os extratos enzimáticos foram mais eficientes na hidrólise do bagaço pré-tratado com NaOH e explosão a vapor com rendimentos de 3,87 e 1,21 mg/mL de açúcares redutores, respectivamente. A mistura dos extratos enzimáticos de T. aurantiacus e T. reesei aumentou em 31,4% a eficiência da hidrolise com o bagaço pré-tratado com explosão a vapor. A concentração dos extratos por precipitação por etanol foi eficiente para a maioria... / The utilization of agricultural and agro-industrial residues as energy source can become a viable alternative. The main target for this venture, for its availability and proximity to fermentation industries is the sugarcane bagasse, which still retains two thirds of the energy present in the cane, is widely available in Brazil and today is partly rejected or underused. One form of exploitation that has shown promising refers to the use of biomass in the production of bioethanol. In this study, we evaluated the profile of enzymatic production of fungi Thermoascus aurantiacus CBMAI 756, Thermomyces lanuginosus, Penicillium viridicatum RFC3 and Trichoderma reesei QM9414 through solid state fermentation in a medium with sugar cane bagasse and wheat bran. These enzymatic extracts were applied on the hydrolysis of sugarcane bagasse under different thermic pre-treatments: hot water, steam explosion, and hot water in combination with HCl, H2SO4, H3PO4, NaOH or H2O2. The main inhibitors (furfural and 5-hydroxymethylfurfural) and reducing sugars (glucose, xylose, arabinose, galactose, xilobiose and cellobiose) generated in the process were determined. The fungus T. aurantiacus was the best producer of cellulolytic (536.3 U/g CMCase) and hemicellulolytic enzymes (3419.2 U/g xylanase), exhibiting along the enzymatic extract from T. reesei the best yields in the saccharification of bagasse. The enzymatic extracts were more efficient in the hydrolysis of bagasse pretreated with NaOH and steam explosion with a yield of 3.87 and 1.21 mg/mL of reducing sugars, respectively. The mixture of enzyme extract of T. aurantiacus and T. reesei increased 31.4% the efficiency of hydrolysis with bagasse pre-treated with steam explosion. The concentration of the extracts by precipitation with ethanol was effective for most enzymatic activities and resulted in an increase of approximately 50% of hydrolysis... (Complete abstract click electronic access below)

CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / CNPq - Conselho Nacional de Desenvolvimento Científico e Tecnológico / FAPEMIG - Fundação de Amparo a Pesquisa do Estado de Minas Gerais / Atualmente, tem-se estudado diversos tipos de pré- tratamentos para reduzir a recalcitrância da biomassa lignocelulósica com intuito de aumentar sua digestibilidade química/enzimática, para que esta possa ser utilizada na produção de etanol e/ou outros bioprodutos de valor agregado. Neste estudo avaliou-se o efeito do pré-tratamento de explosão a vapor catalisada por ácido cítrico e hidróxido de sódio, e do pré-tratamento de deslignificação alcalina nas propriedades químicas e estruturais do bagaço de cana-de-açúcar (BCA), bem como sobre o processo de hidrólise enzimática. O pré-tratamento de explosão a vapor foi realizado em reator de 1,4L sob temperatura de 180 °C com tempo de retenção de 5 min. A etapa de deslignificação com NaOH (2% m:m) foi realizada a 120 °C, sob refluxo de 4h. A caracterização química e estrutural da biomassa in natura e pré-tratada foi realizada por FTIR, MEV, DRX. A hidrólise enzimática foi realizada com volume final de 20 mL constituído de 3% de BCA (massa seca), tampão de citrato de sódio 50 mM (pH=5,0) e 10 FPU do complexo enzimático Cellic® CTec 3. Os frascos foram mantidos sob agitação de 150 rpm a 50ºC por 72 h. Retirou-se alíquotas de 1,5 mL após 0, 12, 24, 36, 48 e 72h para determinação de açúcares redutores totais (ART) pelo método do ácido 3,5-dinitrosalicílico (DNS). O bagaço de cana-de-açúcar apresentou 24,22% de lignina, 27,61% de hemiceluloses e 42,77% de celulose, no entanto após o pré-tratamento de explosão a vapor catalisado com ácido cítrico, obteve-se uma biomassa com menor quantidade de hemiceluloses (16,16%) e com formação de fissuras na parede celular da fibra. O bagaço pré-tratado por explosão a vapor com NaOH apresentou completa desestruturação da fibra, remoção de 65% da lignina e preservação da fração hemicelulósica. Depois de submeter à biomassa lignocelulósica sem tratamento e pré-tratada por explosão a vapor ao processo de deslignificação alcalina observou-se a completa desestruturação da matriz lignocelulósica e a solubilização de 85-90% da lignina em todas as amostras. O índice de cristalinidade da biomassa após os prétratamentos teve uma aumento quando comparado ao material in natura, podendo este ser associado à remoção de componentes amorfos, como a lignina e hemiceluloses, e também da fração amorfa da celulose. Frente ao percentual mássico de biomassa utilizada no processo de hidrólise enzimática valor teórico correspondente a 100% de sacarificação equivale, aproximadamente, a 33,0 g.L-1. Após a hidrólise enzimática (72h) da biomassa in natura e pré-tratada por explosão a vapor obteve-se uma maior concentração de ART e um maior percentual de sacarificação para o bagaço de cana obtido a partir da explosão a vapor com NaOH (23,05 g.L-1, 69,15% de sacarificação). Já na hidrólise da biomassa in natura após processo de deslignificação alcalina a concentração de ART aumentou em 18,33 g.L-1, enquanto que para o bagaço pré-tratado por explosão a vapor com água, ácido cítrico e NaOH seguido da deslignificação alcalina o aumento de ART, correspondeu a 19,67 g.L-1, 19,93 g.L-1 e 6,87 g.L-1. Diante da produção de ART após deslignificação notou-se que o percentual de sacarificação para a biomassa sem tratamento elevou-se de 11,88% para 69,15%, enquanto que para o bagaço após explosão a vapor e deslignificação este percentual ficou entre 82,05% - 89,79%. Por fim, cabe ressaltar que no BCA previamente pré-tratado por explosão a vapor com NaOH, a remoção de lignina após o segundo pré-tratamento teve um acréscimo de apenas 20% e a concentração de ART de 6,87 g.L-1. Dessa forma, acredita-se que ao aumentar a concentração da solução de NaOH para realizar a explosão a vapor poderia-se não necessitar da realização da etapa de deslignificação. / Nowadays, there is various types of studied pre-treatments to reduce the lignocellulosic biomass recalcitrance in order to increase its chemical / enzymatic digestibility, so that it can be used in ethanol production and / or other bioproducts value. This study evaluated the effect of steam explosion pretreatment catalyzed by citric acid and sodium hydroxide, and alkaline delignification pretreatment over chemical and structural properties of sugarcane bagasse, as well as the enzymatic hydrolysis process. Steam explosion pretreatment was conducted in a 1.4 L reactor at temperature of 180 °C and 5 min hold time. The delignification step with NaOH (2% m:m) was performed at 120 °C under reflux for 4 hours. Chemical and structural characterization of raw and pretreated biomass was performed by FTIR, SEM and XRD. Enzymatic hydrolysis was performed with final volume of 20 mL consisting 3% SCB on dryweight basis, sodium citrate buffer 50 mM (pH = 5.0) and 10 FPU of Cellic® Ctec 3 enzyme complex. Flasks were kept under agitation of 150 rpm at 50 °C during 72 h. It was analyzed 1.5 mL aliquots after 0, 12, 24, 36, 48 and 72 hours to determinate total reducing sugars (TRS) by acid 3,5-dinitrosalicílic method (DNS). Sugarcane bagasse showed 24.22% lignin, 27.61% hemicelluloses and 42.77% of cellulose, however after steam explosion pretreatment catalyzed by citric acid, it was obtained a biomass with lesser hemicelluloses amount (16.16%) and cracks formation on fiber cell wall were observed. The bagasse pretreated by steam explosion by NaOH showed complete destructuring of fiber and lignin removal was 65%, while hemicellulosic fraction was preserved. After submitting untreated and pretreated lignocellulosic biomass by steam explosion to alkaline delignification process, complete destructuring and solubilization of the lignocellulosic matrix was observed with 85-90% lignin removal in all samples. The crystallinity index of biomass after pretreatments increased when compared to raw material and this could be associated to amorphous components removal, such as lignin and hemicelluloses, and also the amorphous cellulose fraction. The theoretical value corresponding to 100% of saccharification corresponds to approximately 33.0 g·L-1, compared to the mass percentage of biomass used in the enzymatic hydrolysis process. After 72 h enzymatic hydrolysis of raw and pretreated biomass by steam explosion, the highest concentration of total reducing sugars (TRS) and the highest percentage of saccharification were obtained for sugarcane bagasse (23.05 g·L-1, 69,15% saccharification). In in nature biomass hydrolysis, after alkaline delignification process, ART concentration increased 18.33 g·L-1, while pretreated biomass by steam explosion with water, citric acid and NaOH followed by alkaline delignification increase TRS to 19.67 g·L-1, 19.93 g·L-1 and 6.87 g·L-1. After delignification, it was noted that saccharification percentage for untreated biomass increased from 11.88% to 69.15%, while for bagasse after steam explosion and delignification this percentage was between 82.05% - 89.79%. Lastly, it should be noted that in biomass previously pretreated by NaOH steam explosion, lignin solubilization after the second pretreatment had an increase of only 20% and TRS concentration of 6.87 g·L-1. Thus, it is believed that increasing NaOH solution concentration to perform steam explosion could not need to implement delignification step. / Dissertação (Mestrado)

Off-gassing of hazardous compounds is, together with self-heating and dust explosions, the main safety hazards within large-scale biomass storage and handling. Formation of CO, CO2, and VOCs with concurrent O2 depletion can occur to hazardous levels in enclosed stored forest products. Several incidents of CO poisoning and suffocation of oxygen depletion have resulted in fatalities and injuries during cargo vessel discharge of forest products and in conjunction with wood pellet storage rooms and silos. Technologies for torrefaction and steam explosion for thermal treatment of biomass are under development and approaching commercialization, but their off-gassing behavior is essentially unknown. The overall objective of this thesis was to provide answers to one main question: “What is the off-gassing behaviour of thermally treated lignocellulosic biomass during storage?”. This was achieved by experimental studies and detailed analysis of off-gassing compounds sampled under realistic conditions, with special emphasis on the VOCs. Presented results show that off-gassing behavior is influenced by numerous factors, in the following ways. CO, CO2 and CH4 off-gassing levels from torrefied and stream-exploded biomass and pellets, and accompanying O2 depletion, are comparable to or lower than corresponding from untreated biomass. The treatments also cause major compositional shifts in VOCs; emissions of terpenes and native aldehydes decline, but levels of volatile cell wall degradation products (notably furans and aromatics) increase. The severity of the thermal treatment is also important; increases in torrefaction severity increase CO off-gassing from torrefied pine to levels comparable to emissions from conventional pellets, and increase O2 depletion for both torrefied chips and pellets. Both treatment temperature and duration also influence degradation rates and VOC composition. The product cooling technique is influential too; water spraying in addition to heat exchange increased CO2 and VOCs off-gassing from torrefied pine chips, as well as O2 depletion. Moreover, the composition of emitted gases co-varied with pellets’ moisture content; pellets of more severely treated material retained less moisture, regardless of their pre-conditioning moisture content. However, no co-variance was found between off-gassing and pelletization settings, the resulting pellet quality, or storage time of torrefied chips before pelletization. Pelletization of steam-exploded bark increased subsequent VOC off-gassing, and induced compositional shifts relative to emissions from unpelletized steam-exploded material. In addition, CO, CO2 and CH4 off-gassing, and O2 depletion, were positively correlated with the storage temperature of torrefied softwood. Similarly, CO and CH4 emissions from steam-exploded softwood increased with increases in storage temperature, and VOC off-gassing from both torrefied and steam-exploded softwood was more affected by storage temperature than by treatment severity. Levels of CO, CO2 and CH4 increased, while levels of O2 and most VOCs decreased, during storage of both torrefied and steam-exploded softwood.CO, CO2 and O2 levels were more affected by storage time than by treatment severity. Levels of VOCs were not significantly decreased or altered by nitrogen purging of storage spaces of steam-exploded or torrefied softwood, or controlled headspace gas exchange (intermittent ventilation) during storage of steam-exploded bark. In conclusion, rates of off-gassing of CO and CO2 from thermally treated biomass, and associated O2 depletion, are comparable to or lower than corresponding rates for untreated biomass. Thermal treatment induces shifts in both concentrations and profiles of VOCs. It is believed that the knowledge and insights gained provide refined foundations for future research and safe implementation of thermally treated fuels as energy carriers in renewable energy process chains.

Depuis des millénaires, le chanvre est cultivé pour ses fibres. Longues et résistantes, elles peuvent notamment entrer dans la composition de matériaux textiles et composites, secteurs industriels en plein essor. Cependant, leur manque d’homogénéité et la complexité de leur affinage ne leur permettent pas encore d’être compétitives face aux fibres synthétiques ou de coton. Mais des fibres de chanvre fines pourraient être produites à partir de fibres brutes en utilisant un traitement par explosion à la vapeur à bas coût, faible consommation d’énergie et avec un faible impact environnemental. Une caractérisation morphologique, chimique et mécanique des fibres a été réalisée avant et après traitement dans le but d’optimiser les paramètres de ce procédé, selon une méthodologie de plan d’expériences. Ces essais ont montré que l’explosion à la vapeur pouvait être utilisée pour produire des fibres correspondant aux critères imposés par l’industrie textile et des matériaux composites. Des éléments ont aussi été apportés sur une éventuelle industrialisation de l’explosion à la vapeur. Là encore, les résultats montrent que ce procédé pourrait être industriellement compétitif en termes de coûts, de consommation en eau et en énergie, et de rendements. Enfin, des fibres ont été produites à partir de sols pollués contenant des métaux lourds. Les teneurs en métaux dans les différentes parties de la plante et dans les fibres ont été mesurées avant et après explosion à la vapeur. Les résultats obtenus ouvrent de nouvelles perspectives quant à un usage durable de Technosols (notamment des friches industrielles) pour la production de fibres de chanvre à usage industriel / Hemp plants have been cultivated for their usable fibers for thousands of years. The fibers are long and resistant and can be utilized for creation of textile and composite materials, relevant to burgeoning industrial sectors. However, due to their lack of homogeneity and the complexity of their refining, hemp fibers are unable to compete with synthetic and cotton fibers. But fine hemp fibers could be successfully produced from technical fibers using a steam explosion treatment at a low cost, a low energy consumption and with a low environmental impact. To optimize the parameters of this process, a morphological, chemical, and mechanical characterization was performed before and after steam explosion using a design of experiments methodology. These experiments showed that this process can be used to produce hemp fibers with the standards defined by the textile and composite materials industries. Some features have also suggested some prospects in the industrialization of steam explosion for fibers production. These results showed that this process could be industrially competitive in terms of costs, water and energy consumption and yield. Finally, phytoremediation-borne hemp fibers were produced from soils contaminated with trace elements. The metals concentrations in plant components and in the fibers were measured before and after steam explosion treatment. The results offer new insights and prospects for a sustainable use of Technosols (in particular brownfield sites) by the production of hemp fibers

Combustion of coal is one of the primary sources of electricity generation worldwide today. Coal contains different chemicals that cause particulate matter(PM) and sulfur dioxide (SO2) emissions. These are health hazards and are responsible for deteriorating the ambient air quality. Particulate matter also forms ash deposits inside the coal combustor, which in turn decreases the energy efficiency of the power plants. Using biomass as a fuel in these utility boilers can potentially reduce the problems of particulate matter emissions and ash deposition, and can significantly reduce the SO2 emissions. However, biomass needs to be pretreated to make its properties similar to coal in terms of energy density, grindability, and durability before it can be fired in utility boilers. Steam explosion is one of the leading biomass pretreatment methods that enhances the physicochemical properties of biomass. A comprehensive review of the steam explosion process, its product properties, its comparison with other treatment processes, as well as its economic analysis and lifecycle assessment, have been explored in this work. Steam-exploded biomass has been co-combusted with bituminous coal in a 1500 kWth combustor to analyze the ash aerosol particle size distribution, composition, and deposition behavior. The primary results of these tests showed that both particulate matter emissions and ash deposition amount reduced significantly as more biomass was co-fired with coal. The submicron-sized particulate matter concentration showed a high correlation with the final mass of ash deposits (R2 > 0.96). Predicting ash deposition rates is important during the combustion of solid fuels. A Machine Learning tool was applied and trained with a fuel composition database of 92 fuels obtained from a thermodynamic equilibrium software (FactSage). When fully operational, this model should be integrated with an existing ash deposition model, which should make it self-sufficient in terms of generating equilibrium composition data. SO2 emissions were analyzed during the co-combustion of biomass and coal, and a synergistic decrease in SO2 emissions was observed with higher biomass blends. Experiments were conducted in a full-scale 471 MWe furnace to analyze the SO2 emissions, and an 85%-15% blend of coal and biomass was responsible for a 28.1% reduction in emissions and 22.1% reduction in the lime slurry utilization in the flue gas desulfurization (FGD) towers compared to pure coal combustion. Ash deposit characterizations by energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD) combined with thermodynamic equilibrium simulations revealed that calcium and potassium were responsible for this synergistic reduction as these metals captured the SO2 from the flue gases and retained them in the ash phase. The SO2 research was important since the current literature is deficient in research conducted at suspension-fired full-scale utility boilers to reduce SO2 emissions by co-firing coal and biomass blends. The research in this dissertation should provide valuable insights to the energy industries that are considering a transformation of fuel portfolio from coal to biomass and explore how the mineral matter present in pretreated biomass would behave inside a utility boiler. The primary conclusions are that during the co-combustion of coal and biomass, ash deposition mass and particulate matter ash load decreased, and SO2 emission saw a synergistic reduction in emissions due to higher calcium and potassium content in biomass compared to pure coal combustion.

Neste trabalho, foi realizada a caracterização de ligninas de palha de cana-de-açúcar. O isolamento das ligninas se deu por acidólise branda e por polpação soda, precedida ou não por pré-tratamento com ácido diluído ou por explosão a vapor. A palha de cana e as ligninas foram caracterizadas por Cromatografia Líquida de Alta Eficiência (CLAE), Espectrometrias no Infravermelho (FT-IR) e no Ultravioleta (UV), por Ressonância Magnética Nuclear de Prótons (1H RMN), Cromatografia de Permeação em Gel (GPC), Análise Termogravimétrica (TGA) e Calorimétrica (DSC), Análise Elementar e de Poder Calorífico Superior (PCS). A lignina técnica isolada por acidólise branda apresentou fórmula C9Har2,31Hal4,14O1,27(OH)ph0,58(OH)al1,19(OCH3)1,11 e relação H:G:S de 1 : 3,22 : 3,68, com 20% de condensação e massa molar média de 1908 Da. A cinética de termodegradação dessa lignina em atmosfera inerte se deu com energia de ativação de 13,90 kJ.mol-1, constante pré-exponencial 0,4799 min-1 e 42% em massa de carvão residual. Foram determinados, ainda, o coeficiente de extinção a 280 nm de 26,03 L.g-1 e o Poder Calorífico Superior de 23,72 kJ.g-1. A partir das informações obtidas em todas as análises, foi proposta uma estrutura para esta lignina. A deslignificação via polpação soda mostrou-se eficiente na remoção de lignina da matriz e foi verificado que, durante o processo, ocorre o rompimento de ligações entre a lignina e carboidratos, entretanto, algumas dessas ligações não são rompidas e o resíduo do processo, denominado lignina, contêm cerca de 17% carboidratos. A lignina soda apresentou poder calorífico superior de 25,14 kJ.g-1, 36% em massa de carvão residual e cinética de termodegradação com energia de ativação de 12,73 kJ.mol-1 e k0=0,4195 min-1. Foi verificado que as polpas soda que sofreram pré-tratamentos apresentaram um menor teor de lignina e maior solubilização de hemiceluloses. Estes tratamentos se mostraram eficientes na hidrólise dos complexos lignina-carboidrato e a ligninas obtidas apresentaram os menores teores de carboidrato residual e características estruturais diferentes das demais, mostrando-se mais condensadas em função das reações que ocorrem em meio ácido. Os coeficientes de extinção a 280 nm foram iguais a 24,2 L.g-1 e 23,3 L.g-1, respectivamente para as ligninas de explosão a vapor e pré-tratamento ácido e suas fórmulas estruturais determinadas por 1H RMN foram, respectivamente, C9Har1,59Hal4,12O0,84(OH)ph0,61(OH)al0,88(OCH3)1,51 e C9Har2,12Hal4,23O1,64(OH)ph0,83(OH)al0,58(OCH3)1,10. / In this work, the characterisation of lignins of sugarcane straw was made. The lignins were isolated by moderate acidolysis and soda process, preceded or not by either diluted acid or steam explosion pretreatments. The sugarcane straw and the lignins were characterised by High Performance Liquid Chromatography (HPLC), Infrared (FT-IR) and Ultraviolet (UV) Spectrometry, Proton Nuclear Magnetic Resonance (H1-RMN), Gel Permeation Chromatography (GPC), Thermogravimetrica analysis (TGA) and Differential Scattering Calormietry (DSC), Elemental Analysis and Heat Power (HP). The technical lignin isolated by moderate acidolysis has the formula C9Har2.31Hal4.14O1.27(OH)ph0.58(OH)al1.19(OCH3)1.11, H:G:S ratio of 1 : 3.22 : 3.68, is 20% condensed and its avarage molecular weight is 1908 Da. The thermal degradation kinetics analysis of this lignin in inert atmosphere was carried out, the results obtained were: activation energy of 13.80 kJ.mol-1, pre-exponential constant of 0.4799 min-1 and 42% residual char. The extinction coefficient obtained at 280 nm was 26.03 L.g-1 and the heat power 23.72 kJ.g-1. A structure was proposed for this lignin based on all the information obtained from these analyses. The delignification via soda process was efficient at removing lignin; during the process, the breaking of bonds between the lignin and carbohydrates was noticed, nevertheless, some of these bonds were not broken and the process residue, hereinafter called lignin, contains about 17% carbohydrates. The soda lignin has heat power of 25.14 kJ.g-1, 36% residual char and the thermal degradation kinetics ocurred with activation energy of 12.73 kJ.mol-1 and k0=0.4195 min-1. It was found that pretreated soda pulps have a lower lignin content and higher solubilisation of complexes, the lignins obtained had the lowest residual carbohydrates contents and different structural features from the untreated ones, being more condensed due to the reactions that occur in acid medium. The extinction coefficients at 280 nm obtained are 24.2 L.g-1 and 23.3 L.g-1, the structural formulas determined by 1H RMN are C9Har1.59Hal4.12O0.84(OH)ph0.61(OH)al0.88(OCH3)1.51 and C9Har2.12Hal4.23O1.64(OH)ph0.83(OH)al0.58(OCH3)1.10 for the steam explosion and acid pretreatment lignins, respectively.

Cette thèse s'intéresse à la simulation numérique de l'explosion vapeur. Ce phénomène correspond à une vaporisation instantanée d'un volume d'eau liquide entraînant un choc de pression. Nous nous y intéressons dans le cadre de la sûreté nucléaire. En effet, lors d'un accident entraînant la fusion du cœur du réacteur, du métal fondu pourrait interagir avec de l'eau liquide et entraîner un tel choc. On voudrait alors connaître l'ampleur de ce phénomène et les risques d'endommagements de la centrale qu'il implique. Pour y parvenir, nous utilisons pour modèle les équations d'Euler dans un cadre Lagrangien. Cette description a l'avantage de suivre les fluides au cours du temps et donc de parfaitement conserver les interfaces entre l'eau liquide et sa vapeur. Pour résoudre numériquement les équations obtenues, nous développons un nouveau schéma de type Godunov utilisant des flux nodaux. Le solveur nodal développé durant cette thèse ne dépend que de la répartition angulaire des variables physiques autour du nœud. De plus, nous nous intéressons aux changements de phase liquide-vapeur. Nous proposons une méthode pour les prendre en compte et mettons en avant les avantages qu'il y a à l'implémentation de ce phénomène dans un algorithme Lagrangien. / This thesis studies numerical simulation of steam explosion. This phenomenon correspond to a fast vaporization of a liquid leading to a pressure shock. It is of interest in the nuclear safety field. During a core-meltdown crisis, molten fuel rods interacting with water could lead to steam explosion. Consequently we want to evaluate the risks created by this phenomenon.In order to do it, we use Euler equations written in a Lagrangian form. This description has the advantage of following the fluid motion and consequently preserves interfaces between the liquid and its vapor. To solve these equations, we develop a new Godunov type scheme using nodal fluxes. The nodal solver developed here only depends on the angular repartition of the physical variables around the node.Moreover, we study liquid-vapor phase changes. We describe a method to take it into account and highlight the advantages of using this method into a Lagrangian framework.