Parce que les ressources fossiles sont épuisables par définition, le carbone nécessaire à la production d'énergie et de matériaux pourrait provenir en grande partie de la biomasse lignocellulosique. Les procédés de fermentation sont capables de fournir une grande variété de produits d'intérêts capables de remplacer les synthons d'origine pétrolière. Cependant, en raison (i) de son caractère insoluble, (ii) de sa structure plus ou moins cristalline et (iii) de la nature des liaisons entre les maillons du polymère, la cellulose est un substrat carboné difficile à valoriser par voie biochimique/fermentaire seule. La pyrolyse rapide ou la liquéfaction de la cellulose sont principalement étudiées pour produire une bio-huile, qui serait valorisée par hydrotraitement catalytique en carburant ou en building blocks. Dans l'état de l'art actuel, les travaux à l'interface de ces deux domaines portant sur une conversion biochimique ou microbiologique de ces bio-huiles sont encore rares. L’objectif de cette thèse est de coupler un procédé de conversion thermochimique de la cellulose, pour la dépolymériser, à un procédé de transformation microbienne pour produire des solvants, des acides et des gaz (butanol, éthanol, acétone, acide acétique, acide butyrique, acide lactique, hydrogène) qui suscitent un fort intérêt dans l’industrie des carburants ou de la chimie verte. Pour ce faire, le bois de hêtre a été fractionné par les méthodes organosolv et chlorite/acide (SC/AA) afin de récupérer une pâte riche en cellulose. Des procédés de liquéfaction hydrothermale et de pyrolyse rapide ont été utilisés pour obtenir des sucres qui ont été finalement transformés par fermentation en synthons. De nombreuses méthodes analytiques ont été développées pour la caractérisation des produits issus de chaque étape du procédé. Enfin, un modèle du procédé utilisant le logiciel commercial Aspen Plus® a été développé pour établir les bilans de matière et énergie du procédé intégré : du fractionnement du bois, puis la liquéfaction de la fraction cellulosique et à la fermentation des bio-huiles / Because fossil resources are exhaustible by definition, the carbon needed for energy and materials production could be obtained from lignocellulosic biomass. Fermentation processes are able to provide a wide variety of interesting products that can replace the crude oil based "building blocks". However, the abundance of lignocellulosic biomass in the environment contrasts with its very low bioavailability. Indeed, because of (i) its insoluble nature, (ii) its more or less crystalline structure and (iii) the nature of the bonds between the polymer fibers, cellulose is a carbon substrate difficult to valorize by biochemical/fermentation processes alone. Fast pyrolysis or liquefaction of cellulose are mainly studied to produce a bio-oil, which would be upgraded by catalytic hydrotreatment into fuels or building blocks. In the current state of the art, studies at the interface of these two fields involving a biochemical or microbiological conversion of these bio-oils are still rare. The aim of this thesis is the coupling of a thermochemical conversion process of cellulose, to depolymerize it, to a microbial transformation process to produce solvents, acids and gases (butanol, ethanol, acetone, acetic acid, butyric acid, lactic acid, hydrogen) that are of great interest for the fuel or green chemistry industry. To do this, beech wood was fractionated by organosolv and chlorite / acid (SC / AA) methods in order to recover a cellulose-rich pulp. Hydrothermal liquefaction and fast pyrolysis processes were used to obtain sugars that were transformed into building blocks by fermentation. Many analytical methods have been developed for the characterization of products from each step of the process. Finally, a model of the process using the commercial software Aspen Plus® was developed to establish mass and energy balances of the integrated process including: the fractionation of the wood, then the liquefaction of the cellulosic fraction and the fermentation of bio-oils

Vinasse, a wastewater rich in organic matter, nutrient and water, is commonly used for fertigation of sugarcane plantation. However, this practice is questionable in the environmental sphere because of problems, such as contamination of groundwater and greenhouse gases emission. Researchers have sought for alternatives that use vinasse in a more sustainable way, e.g., biorefineries that recover resources. In general, the pathways considered are the concentration technologies to reclaim water and nutrient, and the anaerobic digestion (AD) to produce biogas. This thesis reports on a study of five designs of vinasse biorefineries that incorporate anaerobic bioreactors followed by a concentration technology (evaporation (EV), reverse osmosis (RO) or forward osmosis (FO)). Different forms of regeneration of the draw solution (DS) namely evaporation, reverse osmosis and membrane distillation (MD) were also analyzed. The alternatives were compared through an exergy analysis, a method that evaluates efficiency in the conversion of resources by systems. The results showed Alternative 2 (anaerobic digestion + reverse osmosis) was the most efficient (64%), since the treatment of 491.76 m3 vinasse h-1 (exergy content of 60513.8 kW) to recover 80% of water reduced 76% of external water requirement and generated 12% more electricity (2601 kW exergy) for the industry. / O desenvolvimento de biorrefinarias voltadas à recuperação de recursos é uma tendência crescente que visa promover sistemas alternativos para obtenção de energia e materiais de forma mais sustentável. Dentro deste conceito está o aproveitamento da vinhaça das indústrias de cana-de-açúcar de modo a recuperar água, nutrientes e energia como produtos de interesse. Para isso, é necessário avaliar as possíveis configurações tecnológicas voltadas a este objetivo. No presente trabalho, foram estudados cinco designs de biorrefinaria de vinhaça incorporando uma rota de produção de metano, formada pelo processo de digestão anaeróbia, e uma forma de concentração do efluente. Os métodos para obtenção de água foram evaporação, osmose reversa e osmose direta. Neste último, foram analisadas diferentes formas de regeneração da solução de separação: evaporação, osmose reversa e destilação por membranas. A comparação das alternativas de biorrefinaria foi feita pelo método da análise de exergia, que atua na avaliação da eficiência de conversão dos recursos em sistemas. Esta ferramenta possui como medida base o trabalho útil que pode ser obtido a partir das correntes envolvidas no processo. Desta forma, observou-se que tecnologias que empregam calor como energia de entrada tendem a ser menos eficientes do que as que empregam eletricidade. Neste caso, as alternativas com processo de osmose reversa apresentaram maiores eficiências exergéticas, por exemplo, ao se recuperar 70% de água, sua eficiência seria de 64%. Portanto, sugere-se que a digestão anaeróbia da vinhaça seguida da concentração por osmose reversa seria a configuração mais interessante para concepção de uma biorrefinaria de vinhaça.

O etanol é um dos biocombustíveis oriundos de fontes renováveis mais promissor e ambientalmente amigável. Visando-se ao atendimento de uma demanda crescente por este álcool, o aproveitamento integral dos materiais lignocelulósicos é uma alternativa interessante e, desta forma, trabalhos de pesquisa têm sido desenvolvidos visando-se à viabilização de biorrefinarias de produção integrada de etanol 1G e 2G. O presente trabalho teve como objetivo principal desenvolver e analisar economicamente modelos de biorrefinaria integrada 1G2G que empregam pré-tratamento ácido diluído, avaliando-se o impacto econômico do destino da hemicelulose para produção de etanol. Para isso, foram definidos cenários que incluíssem todas as etapas do processo de produção de etanol 1G e 2G, sendo avaliados dois teores de sólidos no reator de pré-tratamento (5% e 10%) e, para cada caso, três relações tempo e conversão da hidrólise enzimática, sendo estas de 45%, 51% e 55% para tempos de reação de 24h, 48h e 72h, respectivamente. Para cada condição, considerou-se a fermentação de pentose (C5) ou seu envio para tratamento de efluentes, constituindo-se, assim, 12 cenários. Foram realizadas as simulações destes cenários auxiliadas pelo pacote computacional Aspen Plus®, obtendo-se os dados de balanço de massa e energia, permitindo assim a realização da análise de viabilidade econômica empregando a plataforma Biorrefinaria Virtual de Cana - BVC. Foi possível observar que a produção de etanol 2G empregando pré-tratamento ácido diluído foi responsável por um aumento na produção de etanol de até 35%. Avaliando-se os cenários, observou-se que quando o reator de pré-tratamento foi operado com maior teor de sólidos, menor consumo de energia térmica foi necessário, requerendo menor quantidade de bagaço na caldeira e aumentando o rendimento final de etanol. Com relação ao custo de investimento, este correspondeu a R$799,2 milhões para a biorrefinaria 1G, enquanto que os cenários integrados 1G2G apresentaram valores cerca de 40% superiores. Dentre as áreas mais expressivas no custo de investimento, estão a de pré-tratamento e geração e distribuição de vapor. No que concerne ao custo de produção de etanol, os cenários que apresentaram menor valor para etanol 2G corresponderam ao uso de 10% de sólidos no reator de pré-tratamento com fermentação de C5. As áreas mais expressivas para esse custo foram os custos com insumos e capital. Todavia, os cenários com 5% de sólidos no reator de pré-tratamento e sem fermentação de C5 resultaram em menor custo de produção global de etanol (1G2G), sendo o custo com cana, insumos e capital os mais expressivos. Com base na taxa interna de retorno, esta se apresentou abaixo da taxa mínima de atratividade para todos os cenários, ocasionando um valor presente líquido negativo, inferindo-se que, nas condições avaliadas, a metodologia empregada nos cenários está inviável do ponto de vista de um investidor. No entanto, a análise econômica auxiliou a identificação dos gargalos tecnológicos do processo de produção integrada de etanol 1G2G quando estes empregam pré-tratamento ácido diluído, favorecendo a definição de metas operacionais a serem solucionadas em trabalhos de pesquisa. / Ethanol is one of the most promising and environmentally friendly biofuels obtained from renewable energy sources. Aiming at meeting a growing demand for this fuel, the integral use of lignocellulosic materials is an interesting alternative and, in this way, research Works have been performed to make viable biorefineries for integrated production of 1G and 2G ethanol. The present work had as main objective to develop and to analyze economically models of 1G2G integrated biorefineries using dilute acid pretreatment, evaluating the economic impact of using hemicellulose for ethanol production. Alternative scenarios were defined including all steps of the 1G and 2G ethanol production process. Two different solids contents were evaluated in the pre-treatment reactor (5% and 10%) and, for each case, three values of time and conversion for the enzymatic hydrolysis step were considered, namely 45%, 51% and 55% for reaction times of 24h, 48h and 72h, respectively. For each condition, the fermentation of pentose (C5) or its sending for effluents treatment was supposed, constituting, thus, 12 scenarios. Simulations of these scenarios were carried out using the software Aspen Plus®, generating mass and energy balance data, thus allowing carrying out economic viability analysis using the Virtual Sugarcane Biorefinery (VSB) platform. Production of 2G ethanol using dilute acid pretreatment was responsible for an increase in ethanol production of up to 35%. When the pretreatment reactor was operated with higher solids content, lower thermal energy consumption was necessary, requiring less bagasse in the boiler and thus increasing the final ethanol yield. Regarding to investment cost, it was of R$ 799.2 million for 1G biorefinery, compared to a value 40% higher observed for integrated 1G2G scenarios. Among the most significant areas of investment cost are the pretreatment and the generation and distribution of steam. With relation to the cost of etanol production, scenarios that presented the lowest value for 2G ethanol corresponded to the use of 10% solids in the pre-treatment reactor associated to C5 fermentation. The most significant areas for this cost were the input and capital costs. However, the scenarios with 5% solids in the pre-treatment reactor without C5 fermentation resulted in a lower global ethanol production cost (1G2G), with sugarcane, chemical inputs and capital cost representing the most significant fraction. Based on the internal rate of return, this was lower than the minimum attractiveness rate of return for all scenarios, resulting in a negative net present value, allowing inferring that, under the evaluated conditions, the methodology used in the scenarios would be unviable from an investor viewpoint. However, the economic analysis helped to identify technological bottlenecks of the integrated 1G2G etanol production process using dilute acid pretreatment, favoring the definition of operational goals to be solved in research works.

O aumento da conscientização ecológica, observado nos últimos anos, levou às indústrias investirem em alguns sistemas de produção tecnologicamente menos impactantes ao meio ambiente, como é o caso das biorrefinarias. No setor de celulose e papel as indústrias podem ser consideradas como biorrefinarias pois produzem bioenergia e bioprodutos a partir da utilização da biomassa, tais como energia elétrica e polpa celulósica. No processo de polpação kraft, obtém-se o licor negro o qual contém compostos orgânicos e inorgânicos provenientes da matéria prima e dos reagentes químicos e aditivos utilizados no processo. Com isso, o licor negro contém além da lignina dissolvida da madeira, alguns subprodutos formados em reações específicas e que podem ser recuperados, destacando-se entre esses o metanol, o qual pode chegar a compor 1% do licor negro. O metanol celulósico extraído na etapa de tratamento de condensado contaminado contém diversos compostos noviços ao meio ambiente e por este motivo o metanol celulósico é utilizado como combustível, sendo incinerado para geração de energia e para redução dos contaminantes a formas menos nocivas ao meio ambiente. Assim, obter o metanol celulósico significa purificá-lo para que possa ser aplicado para outros fins mais nobre, como por exemplo, aplicado como reagente nas indústrias químicas. Com isso, o presente estudo teve por objetivo avaliar o potencial de operação de uma unidade de recuperação e de purificação de metanol celulósico acoplado a uma moderna unidade de produção de polpa celulósica. Para isso, foram realizadas visitas técnicas à unidade industrial e efetuada uma ampla revisão bibliográfica do processo de evaporação de licor negro e de formação dos compostos presentes no metanol celulósico de forma a definir as condições e métodos de modelagem e simulação mais apropriados para o desenvolvimento desta dissertação. O estudo foi divido em duas etapas, sendo que a primeira consistiu na utilização do simulador comercial WinGEMS® para construção de um modelo computacional de uma unidade de evaporação de licor negro, o qual mostrou-se adequado para a determinada aplicação através de validações comparativas entre os resultados da simulação com valores reais de operação. Na sequência, desenvolveu-se um modelo computacional para o planejamento de uma unidade de obtenção e purificação de metanol celulósico via software Aspen Plus® sendo acoplado ao modelo anterior. Em síntese, a metodologia aplicada mostrou-se satisfatória para o presente estudo sendo possível simular com propriedade uma unidade de evaporação de licor negro e avaliar o impacto industrial de se acoplar uma unidade de purificação de metanol celulósico a indústria celulósica, no que tange a dimensionamentos de equipamentos, quantificação dos insumos e eficiência de purificação de metanol celulósico. / The increase in ecological awareness observed in recent years has led industries to invest in some production systems technologically less harmful to the environment, such as biorefineries. The industries form the pulp and paper sector, can be considered as biorefineries because they produce bioenergy and bioproducts from the use of biomassa, such as electric power and cellulosic pulp. In the kraft pulping process, the black liquor is obtained, wich contains organic and inorganic compounds from the raw material and from the chemicals reagents and additives used in the process. Black liquor contains, in addition to the dissolved lignin of the wood, some by-products formed in specific reactions and that can be recovered, among them methanol, which can make up 1% of the black liquor. The cellulosic methanol extracted in the treatment stage of contaminated condensate contains several compounds that are harmful to the environment and for this reason the cellulosic methanol is used as fuel, being incinerated for energy generation and for the reduction of contaminants to forms less harmful to the environment. Thus, obtaining the cellulosic methanol means purifying it so that it can be applied to other, more noble purposes, for example, as a reagent in the chemical industry. The aim of this study was to evaluate the potential of a cellulosic methanol recovery and purification unit coupled to a modern cellulosic pulp production unit. Technical visits were made to the industrial unit and a vast bibliographical review of the process of evaporation of black liquor and formation of the compounds present in the cellulosic methanol was carried out in order to define the conditions and the most appropriate modeling and simulation methods for the development of this dissertation. The study was divided in two stages, the first one consisted of the use of the WinGEMS® commercial simulator to construct a computational model of a black liquor evaporation unit, which proved to be suitable for the given application through comparative validations between simulation results with actual operating values. In the sequence, a computational model was developed for the planning of a cellulosic methanol purification and purification unit using Aspen Plus® software being coupled to the previous model. In summary, the applied methodology proved to be satisfactory for the present study, being it possible to properly simulate a black liquor evaporation unit and to evaluate the industrial impact of coupling a cellulosic methanol purification unit to the cellulosic industry, in terms of equipment design, input quantification and cellulosic methanol purification.

BIM é uma proteína pro-apoptótica membro da família Bcl-2. No sistema imune, BIM tem sido descrita como reguladora da homeostase de linfócitos. Porém, o papel do BIM no estabelecimento da resposta imune de linfócitos T CD8+ ainda não foi investigado. Sendo os vetores adenovirais fortes ativadores destas células, investigamos o papel de BIM na qualidade e na frequência de linfócitos T CD8+ em camundongos C57Bl/6 selvagens, bim+/- e bim-/- imunizados com 2x106 PFU Ad.cOVA / 100 μl. Observou-se que camundongos bim-/- apresentam uma redução da lise específica desencadeada pelos linfócitos CD8+, assim como uma menor freqüência de linfócitos CD8+ produtores de IFNγ. Contrariamente, os camundongos bim-/- não mostraram diferencias no controle da progressão tumoral, o que poderia estar relacionado ao acumulo de linfócitos efetores apresentado nestes animais. Em conclusão, camundongos bim-/- apresentam uma menor freqüência de linfócitos T CD8+ com capacidade efetora, sugerindo um importante papel de BIM na produção destas células. / BIM is a pro-apoptotic protein member of the Bcl-2 family. In the immune system, BIM has been described as a regulator of lymphocyte homeostasis. However, the role of BIM on the establishment of the immune response mediated by CD8+ T lymphocytes has not been studied yet. As the adenoviral vectors are strong activators of these cells, we investigated the role of BIM on the quality and frequency of antigen-specific CD8+ T cells, wild-type, bim+/- and bim-/- C57Bl/6 mice immunized with 2x106 PFU Ad.cOVA / 100μl. We observed that bim-/- mice showed a lower frequency of IFN-γ-producing CD8+ T cells along with a reduction in the specific lysis triggered by CD8+ lymphocytes. Surprisingly, bim-/- mice did not show differences in the control of tumor progression, which could be related to the accumulation of effector lymphocytes presented in these animals. In conclusion, bim-/- mice present a lower frequency of CD8+ lymphocytes with effector capacity, suggesting an important role of BIM in their production.

Dans le contexte de pénurie des ressources, croissance démographique, dégradation de l’environnement, la production d’aliments riches en protéines (en particulier) pour l’homme et les animaux devrait augmenter pour répondre à la demande. De nouvelles ressources sont actuellement explorées : légumineuses, algues, insectes... Ces derniers représentent une source de protéines plus durable comparée aux sources conventionnelles. Bien qu’ils soient consommés par de nombreuses populations en Asie, en Afrique et en Amérique du Sud, ce n’est pas le cas en Europe. Ainsi, pour faciliter leur utilisation dans l’alimentation européenne, les insectes peuvent être transformés en ingrédients afin de les incorporer dans des formulations d’aliments. Cependant, il existe très peu de données sur les méthodes de transformation à l’échelle pilote ou industrielle et sur l’impact du procédé sur la qualité des produits finis. Ce travail avait pour objectifs de mettre au point à l’échelle pilote un procédé de production de farine d’insecte pour l’alimentation, de caractériser cette farine et les autres produits obtenus, de caractériser les propriétés de la fraction protéique soluble et d’étudier l’impact du procédé sur les propriétés de celle-ci. Le Tenebrio molitor, candidat à l’élevage industriel, a été sélectionné pour cette étude. Un procédé thermomécanique de production de farine a été mis au point à l’échelle pilote. Il a permis la production d’une farine d’insecte riche en protéines de 72% (bs) avec 14% (bs) de lipides et 4% (bh) d’eau. Le profil en acides aminés des protéines de cette farine répond aux besoins de la nutrition animale et de l’alimentation humaine avec une bonne efficacité protéique (estimée à 2,5). Le rendement de la production de 20% (bh) (64% bs) est semblable à celui de la production de farine de poisson (20% bh). Parallèlement, l’huile d’insecte, principale coproduit a également été produite. Elle est riche en acides palmitiques, et en acides gras essentiels ω9 et ω6. Elle peut être utilisée en alimentation ou dans d’autres domaines. Bien que le procédé ait un impact sur les propriétés physicochimiques des protéines solubles après la transformation des larves en farine, les fractions protéiques solubles de la farine et des larves ont les mêmes propriétés moussantes et émulsifiantes semblables à celles du lait et de ASB à 4 et 2% respectivement. Les protéines de la farine ou des larves peuvent être également utilisées pour leurs propriétés fonctionnelles. Ce travail contribue à la compréhension des protéines d’insectes et à l’extrapolation industrielle dans une perspective de conception de la bioraffinerie. / In the context of resource scarcity, population growth, environmental degradation, and food supplies dependency, the production of protein-rich feed and food should increase in order to meet the demand. New resources are currently being explored as vegetal, algae, insects... This last one is environmentally friendly and represents a more sustainable protein source as compared to conventional livestock farming. Although insects are consumed by a lot of people in Asia, Africa and South-America, this is not the case in Europe. In order to meet European consumers' preferences, they need to be processed or transformed into ingredients to become a part of formulation products (i.e. powders). However, very little knowledge regarding processing methods at a pilot or industrial scale, and the composition and impact of process on the properties of insect-based ingredient exists and is available. The aim of this work was to design a process for the production of meal rich in proteins from insect at a pilot scale, to characterize it for feed and food applications, to characterize the properties of its soluble proteins, and to study the impact of the process on these properties. The Tenebrio molitor, candidate for rearing at an industrial scale, was chosen in the frame of this study. A thermo-mechanical process was designed at a pilot scale. It allowed the production of a protein-rich insect meal of 72% (bs) with 14% (bs) of lipids and 4% (bh) of water. The amino acid profile of this meal proteins meets the needs of animal nutrition and human nutrition with good protein efficiency (estimated at 2.5). The production yield of 20% (bh) (64% bs) is similar to that of fishmeal production (20% bh). In parallel, insect oil (co-product) were also produced. It is rich in acid palmitic, and essential fatty acids ω9 and ω6. It can be used in feed, food, cosmetic or bioenergy. Although the process has an impact on the physicochemical properties of soluble proteins after the transformation of larvae into flour, the soluble protein fractions of flour and of larvae have the same foaming and emulsifying properties similar to those of milk and BSA at 4 and 2% respectively. The meal proteins could be used in feed and food for their functional properties. This work contributes to insect protein understanding and the industrial extrapolation in a perspective of biorefinery designing.

The biorefinery concept is attractive. Increasing international concerns over issuessuch as climate change have led to political as well as social pressures for a shift fromfossil fuels to renewable resources and biomass is one abundant renewable resource.Biomass has the potential of supplying many of the fuels and chemicals which arecurrently dependent on petroleum. Much development is still needed in the field ofbiorefineries and a systematic approach to evaluate and compare process technologiesand to suggest optimizations seems necessary.The objective of this thesis is to develop entropy analysis as a possible evaluation toolfor optimization of biorefinery processes. This is a new application of entropyanalysis which is rarely discussed in the literature. The scientific basis of the entropyanalysis is described and the proposed methodology is explained. The position ofentropy analysis among other system analysis tools such as exergy analysis and lifecycle assessment is discussed along with entropy analysis earlier applications.A case study is introduced which is the IBUS (Integrated Biomass Utilization System)project in Denmark. The idea in IBUS is to integrate the biomass plant with a powerplant to utilize the surplus steam from the power plant for the internal use of thebiorefinery. The suggested method of entropy analysis is applied to this case study tocompare different processes for production of ethanol along with solid biofuel andanimal feed from Danish wheat straw. The evaluation is a gate to gate analysis inwhich production of energy carriers are also included in addition to biorefining ofwheat straw. A parallel life cycle assessment study with equivalent system boundariesis also carried out to compare the results with a conventional environmental systemsanalysis method.The results from the entropy analysis of the IBUS case study show that fermentationof C5 and C6 sugars by yeast is the most efficient process thermodynamically whilefermentation of only C6 sugars by yeast is the least efficient among the three casesstudied. Integration of the biorefinery with a coal fired CHP plant is identified as awise choice by the results of the entropy analysis method.For the IBUS process alternatives investigated in this study, the entropy results andthe LCA results (aggregated environmental load) are in correlation; entropy results areconsistent with weighting results based on two different weighting methods namelyEco indicator 99 and EPS 2000. Entropy generation is also in correlation withproduction cost for the processes analyzed in this evaluation. Another observation isthat cooling in the biorefining process contributes highly in the generation of entropy.This potential improvement option is not surfaced by the LCA conducted.The potential for further investigation and development of the tool is recognizedreflecting on some interesting observations in the results. Improvement of the tool ishighly possible for example by supplementing other implications of entropy inprocess design such as "waste potential entropy" concept which is developed as aneco-toxicity measure. / Uppsatsnivå: D

A utilização de biomassa vegetal como matéria-prima para a obtenção de produtos químicos exige pré-tratamentos que levem à desestruturação do complexo lignocelulósico, sendo o principal desafio a remoção seletiva e quantitativa da lignina. O bagaço de cana-de-açúcar, como todo material lignocelulósico, é composto por celulose, polioses e lignina, como principais componentes macromoleculares, e vem sendo alvo de pesquisas para produção de bioetanol e produtos com maior valor agregado. A heterogeneidade das ligninas obtidas como subprodutos dos processos de deslignificação é uma das responsáveis pela limitação de possíveis aplicações industriais. Contudo, os recentes desenvolvimentos no etanol celulósico levarão a um aumento da quantidade de lignina disponível numa base global. Estas considerações futuras têm renovado o interesse no isolamento e conversão de lignina em produtos químicos de maior valor agregado. Neste sentido, o isolamento e a caracterização destas ligninas são de fundamental importância. Neste trabalho apresentamos os resultados de estudos de deslignificação do bagaço de cana-de-açúcar pela aplicação de diferentes processos de polpação (processos Soda, Sulfito e Organossolve etanol/água). Estes processos foram avaliados segundo o rendimento do pré-tratamento e seletividade frente aos componentes macromoleculares dos materiais lignocelulósicos. A segunda etapa do trabalho descreve a caracterização das ligninas obtidas nos diferentes processos de polpação, visando posteriores modificações e aplicações como derivados oxidados e na preparação de novos materiais poliméricos termoplásticos e/ou termorrígidos. Os processos produziram diferentes ligninas, sendo essas diferenças observadas na distribuição de massas molares, quantidade de hidroxilas, estabilidade térmica, quantidade de impurezas, etc. A utilização do fracionamento por solventes foi efetivo na obtenção de diferentes massas molares e menores polidispersividades. As condições empregadas nas poliesterificações produziram polímeros com características diferentes, como viscosidade, temperatura de transição vítrea e estabilidade térmica. / The use of plant biomass as a feedstock for the production of chemicals requires pre-treatments which lead to disruption of the lignocellulosic complex, the main challenge being selective and quantitative removal of lignin. Sugarcane bagasse is a lignocellulosic material composed of cellulose, lignin and polyoses as major macromolecular components, and has been the subject of research for bioethanol production and products with higher added value. The heterogeneity of lignins obtained as byproducts of delignification processes is one reason for the limitation of possible industrial applications. However, recent developments in cellulosic ethanol will raise the amount of lignin available on a global basis. These forward-looking statements have renewed interest in the isolation and conversion of lignin in chemical products with higher added value. In this sense, the isolation and characterization of lignins is of fundamental importance. We present the results of studies of delignification of sugarcane bagasse by applying different pulping processes (Soda, Sulfite and organosolv ethanol / water processes). These processes were evaluated according to the performance of pre-treatment and selectivity against macromolecular components of lignocellulosic materials. The second stage of the work describes the characterization of lignins obtained in different pulping processes, aiming to further modifications and applications as oxidized derivatives and the preparation of new polymeric materials thermoplastic and / or thermosetting. Processes produced different lignins, and these differences in distribution of molecular weight, amount of hydroxyls, thermal stability and amount of impurities. The use of solvent fractionation was effective in getting different molar masses and lower polydispersities. The conditions employed in esterification reaction produced polymers with different characteristics, such as viscosity, glass transition temperature and thermal stability.

O etanol é um dos biocombustíveis oriundos de fontes renováveis mais promissor e ambientalmente amigável. Visando-se ao atendimento de uma demanda crescente por este álcool, o aproveitamento integral dos materiais lignocelulósicos é uma alternativa interessante e, desta forma, trabalhos de pesquisa têm sido desenvolvidos visando-se à viabilização de biorrefinarias de produção integrada de etanol 1G e 2G. O presente trabalho teve como objetivo principal desenvolver e analisar economicamente modelos de biorrefinaria integrada 1G2G que empregam pré-tratamento ácido diluído, avaliando-se o impacto econômico do destino da hemicelulose para produção de etanol. Para isso, foram definidos cenários que incluíssem todas as etapas do processo de produção de etanol 1G e 2G, sendo avaliados dois teores de sólidos no reator de pré-tratamento (5% e 10%) e, para cada caso, três relações tempo e conversão da hidrólise enzimática, sendo estas de 45%, 51% e 55% para tempos de reação de 24h, 48h e 72h, respectivamente. Para cada condição, considerou-se a fermentação de pentose (C5) ou seu envio para tratamento de efluentes, constituindo-se, assim, 12 cenários. Foram realizadas as simulações destes cenários auxiliadas pelo pacote computacional Aspen Plus®, obtendo-se os dados de balanço de massa e energia, permitindo assim a realização da análise de viabilidade econômica empregando a plataforma Biorrefinaria Virtual de Cana - BVC. Foi possível observar que a produção de etanol 2G empregando pré-tratamento ácido diluído foi responsável por um aumento na produção de etanol de até 35%. Avaliando-se os cenários, observou-se que quando o reator de pré-tratamento foi operado com maior teor de sólidos, menor consumo de energia térmica foi necessário, requerendo menor quantidade de bagaço na caldeira e aumentando o rendimento final de etanol. Com relação ao custo de investimento, este correspondeu a R$799,2 milhões para a biorrefinaria 1G, enquanto que os cenários integrados 1G2G apresentaram valores cerca de 40% superiores. Dentre as áreas mais expressivas no custo de investimento, estão a de pré-tratamento e geração e distribuição de vapor. No que concerne ao custo de produção de etanol, os cenários que apresentaram menor valor para etanol 2G corresponderam ao uso de 10% de sólidos no reator de pré-tratamento com fermentação de C5. As áreas mais expressivas para esse custo foram os custos com insumos e capital. Todavia, os cenários com 5% de sólidos no reator de pré-tratamento e sem fermentação de C5 resultaram em menor custo de produção global de etanol (1G2G), sendo o custo com cana, insumos e capital os mais expressivos. Com base na taxa interna de retorno, esta se apresentou abaixo da taxa mínima de atratividade para todos os cenários, ocasionando um valor presente líquido negativo, inferindo-se que, nas condições avaliadas, a metodologia empregada nos cenários está inviável do ponto de vista de um investidor. No entanto, a análise econômica auxiliou a identificação dos gargalos tecnológicos do processo de produção integrada de etanol 1G2G quando estes empregam pré-tratamento ácido diluído, favorecendo a definição de metas operacionais a serem solucionadas em trabalhos de pesquisa. / Ethanol is one of the most promising and environmentally friendly biofuels obtained from renewable energy sources. Aiming at meeting a growing demand for this fuel, the integral use of lignocellulosic materials is an interesting alternative and, in this way, research Works have been performed to make viable biorefineries for integrated production of 1G and 2G ethanol. The present work had as main objective to develop and to analyze economically models of 1G2G integrated biorefineries using dilute acid pretreatment, evaluating the economic impact of using hemicellulose for ethanol production. Alternative scenarios were defined including all steps of the 1G and 2G ethanol production process. Two different solids contents were evaluated in the pre-treatment reactor (5% and 10%) and, for each case, three values of time and conversion for the enzymatic hydrolysis step were considered, namely 45%, 51% and 55% for reaction times of 24h, 48h and 72h, respectively. For each condition, the fermentation of pentose (C5) or its sending for effluents treatment was supposed, constituting, thus, 12 scenarios. Simulations of these scenarios were carried out using the software Aspen Plus®, generating mass and energy balance data, thus allowing carrying out economic viability analysis using the Virtual Sugarcane Biorefinery (VSB) platform. Production of 2G ethanol using dilute acid pretreatment was responsible for an increase in ethanol production of up to 35%. When the pretreatment reactor was operated with higher solids content, lower thermal energy consumption was necessary, requiring less bagasse in the boiler and thus increasing the final ethanol yield. Regarding to investment cost, it was of R$ 799.2 million for 1G biorefinery, compared to a value 40% higher observed for integrated 1G2G scenarios. Among the most significant areas of investment cost are the pretreatment and the generation and distribution of steam. With relation to the cost of etanol production, scenarios that presented the lowest value for 2G ethanol corresponded to the use of 10% solids in the pre-treatment reactor associated to C5 fermentation. The most significant areas for this cost were the input and capital costs. However, the scenarios with 5% solids in the pre-treatment reactor without C5 fermentation resulted in a lower global ethanol production cost (1G2G), with sugarcane, chemical inputs and capital cost representing the most significant fraction. Based on the internal rate of return, this was lower than the minimum attractiveness rate of return for all scenarios, resulting in a negative net present value, allowing inferring that, under the evaluated conditions, the methodology used in the scenarios would be unviable from an investor viewpoint. However, the economic analysis helped to identify technological bottlenecks of the integrated 1G2G etanol production process using dilute acid pretreatment, favoring the definition of operational goals to be solved in research works.

Abstract Lignins have polyphenolic structures, making them candidates to replace phenols and polyphenols in polymers. Lignins are highly recalcitrant, making their refining challenging, requiring harsh temperatures and pressures. Lignins could be partially modified under milder conditions for their use in biopolymers. The main purpose of this research was to upgrade Indulin AT, a kraft pine lignin, to enhance its properties. The first part of this thesis dealt with formic acid aided pressurized hot water extraction (FAPHWE) of hemicelluloses from birch hardwood as the first step in separating the components of a lignocellulosic feedstock (LCF). More than half of the hemicelluloses were extracted as hydrolysis products, while keeping the cellulose hydrolysis products in the extract under 5% and the lignin under 3%. In the second part of this work, a method to determine the amount of phenolic hydroxyl groups (OHph) in lignins was assessed. The Δε IDUS method was found to be useful for comparing the OHph of pine kraft and birch milox lignins, albeit not as precise as carbon-13 nuclear magnetic resonance spectroscopy (13C-NMR). The third part of this thesis explored the tuning of the molar mass (MM) and OHph of Indulin AT by aqueous ethanol fractionation. The results showed that a higher water content favored the extraction of fractions with low MM and low OHph. A high ethanol content favored the extraction of fractions with medium MM and high OHph. A 50–60 wt% ethanol content allowed for near complete solubilization of Indulin AT, which could be beneficial for a single-phase chemical reaction. The fourth part of this research dealt with the depolymerization of Indulin AT in an ethanol-water solvent with formic acid as hydrogen donor. The properties of interest were MM, polydispersity (PDI), OHph, and formaldehyde uptake capability (FUC). The results of the reaction were affected predominantly by temperature. Higher temperatures led to lower MM and PDI, and higher OHph and FUC. The results of this thesis suggest that, in a biorefinery, the first step before delignification of an LCF could be FAPHWE. It was found that the properties of Indulin AT (OHph, FUC, and MM) could be enhanced by chemical depolymerization and physical fractionation. Modified lignins with higher OHph and FUC could be utilized in biopolymer applications such as phenolic resins and polyurethanes. / Tiivistelmä Ligniini on rakenteeltaan polyfenoli, mikä tekee siitä mahdollisen fenolien korvaajan polyfenolien valmistuksessa. Ligniinin rakenne on hyvin kestävä, mikä tekee sen jalostuksesta haastavaa vaatien usein korkean lämpötilan ja paineen käyttöä. Tästä huolimatta ligniiniä voidaan tietyssä määrin muokata miedommissa olosuhteissa, mikä lisää sen käyttökelpoisuutta biopolymeerien raaka-aineena. Tämän tutkimuksen tarkoitus oli jalostaa Indulin AT -kraft ligniiniä siten, että sen ominaisuudet paranevat. Aluksi väitöstyössä tarkasteltiin puun hemiselluloosan muurahaishappokatalysoidun kuumavesiuutton soveltuvuutta lignoselluloosaraaka-aineiden fraktioinnin ensimmäiseksi vaiheeksi. Yli puolet hemiselluloosasta voitiin uuttaa monosakkarideiksi samalla, kun selluloosasta uuttui alle 5 % ja ligniinistä alle 3 %. Seuraavaksi arvioitiin fenolisten hydroksyyliryhmien määritysmenetelmää. Δε IDUS metodin havaittiin olevan hyödyllinen ainakin sulfaattimenetelmän havupuuligniinien ja Milox-prosessin koivuligniininäytteiden vertailussa, vaikkakaan se ei ole yhtä tarkka kuin ydinmagneettiseen resonanssispektroskopiaan (NMR) perustuva analyysi. Tämän jälkeen tutkittiin mahdollisuuksia tuottaa etanoli-vesiliuosfraktioinnilla jakeita, joissa ligniinillä on haluttu molekyylikoko ja fenolisten hydroksyyliryhmien pitoisuus. Tulokset näyttivät, että korkea vesipitoisuus suosii pienen molekyylikoon ja matalan OHph -pitoisuuden sisältäviä jakeiden uuttumista. Korkea etanolipitoisuus suosii keskikokoisen molekyylikoon jaetta, jossa ligniinillä on korkea OHph -pitoisuus. 50–60 m-% etanolipitoisuudessa Indulin AT liukenee lähes täydellisesti, mikä voi olla edullista kemiallisten reaktioiden toteuttamiseen yhdessä faasissa. Lopuksi tutkimuksessa tarkasteltiin ligniinin osittaista depolymerisointia etanoli-vesiliottimessa muurahaishapon toimiessa vetylähteenä. Tarkasteltavat tuotteen ominaisuudet olivat molekyylikoko, polydispersiteetti, fenolisten hydroksyyliryhmien määrä ja formaldehydin sitomiskapasiteetti. Lämpötilan havaittiin olevan merkittävin depolymerisointireaktioon vaikuttava tekijä. Korkea lämpötila johtaa pienempään molekyylikokoon ja kapeampaan molekyylikokojakaumaan sekä suurempaan hydroksyyliryhmien määrään ja formaldehydin sitomiskykyyn. Tämän työn tulokset viittaavat siihen, että hemiselluloosan vesiuutto happamissa olosuhteissa voi olla biojalostamon ensimmäinen vaihe, ennen delignifiointia. Lisäksi havaittiin, että ligniinin ominaisuuksia voidaan muokata kemiallisella depolymerisoinnilla ja fysikaalisella fraktioinnilla. Korkeamman hydroksyyliryhmäpitoisuuden ja formaldehydin sitomiskyvyn muokattuja ligniinejä voidaan hyödyntää biopolymeerisovellutuksissa, kuten fenolisissa hartseissa ja polyuretaaneissa.