Textiles made from natural sources, such as cotton and flax, have advantages over those made of synthetic fibers in terms of sustainability. Unlike major synthetic fibers that have a negative impact on the environment due to poor biodegradability, cotton cellulose is a renewable material.Cotton cellulose fibers exhibit various attractive characteristics such as softness and inexpensiveness. Cellulosic textiles can be easily wetted, since the structure contains a large amount of hydrophilic hydroxyl groups, and when water repellency is needed, this is a disadvantage. Currently, paraffin waxes or fluorinated silanes are used to achieve hydrophobicity, but this contradicts the concept of green chemistry since these chemicals are not biodegradable. The use of bio-based materials like forest residues or side-streams from forest product industries might be a good alternative, since this not only decreases the pressure on the environment but can also increase the value of these renewable resources.Betulin is a hydrophobic extractive present in the outer bark of birch trees (Betula verrucosa). Nowadays, the birch bark containing betulin generated in the paper industry is disposed of by incineration as a solid fuel to provide energy, but this application is not highly valuable and this motivates us to see whether betulin can be used as a hydrophobe to prepare waterproof cellulosic textiles. Methods of dip-coating, film compression molding and grafting were performed to build “betulin-cellulosic textile system” to render the textile with hydrophobicity and other functions. The textile impregnated in a solution of betulin-based copolymer exhibited a contact angle of 151°, which indicated that superhydrophobicity can be reached. AATCC water spray test results showed that cellulosic textile coated with betulin-based film had a water repellency of 80, which is the third highest class according to the rating standards. Betulin-grafted textiles were also prepared and showed a static water contact angle of 136°, and an antibacterial property with a bacterial removal of 99%.This thesis proposes that betulin can be used as a green alternative in functional material preparation. By developing betulin, a more value-added application rather than incineration can be achieved. / <p>QC 20190205</p>

Domsjö Fabriker AB har under en tid haft en stigande vattenförbrukning utan att kunna peka på någon bidragande faktor. Som ett led i denna utredning har en dataanalys över blekeriet med fokus på variabeln Chemical Oxygen Demand (COD) genomförts. Ett antal olika regressionsmodeller skapades med syftet att utreda om ljusheten uppmätt efter kokeriet påverkade halterna COD kort därefter. Men även med syftet att förklara vad som påverkar den slutliga blekningen av cellulosamassan i blekeriet, och framförallt om COD-halten är en bidragande faktor. Resultatet av detta var att ljusheten efter kokeriet inte hade någon påverkan på COD, samt att COD-halten troligen inte har någon påverkan på blekningen då COD inte var del av en accepterad modell som förklarade ljusheten. Då labbproverna av COD är kostsamma och inte har någon påverkan på ljusheten rekommenderas nyttan av labbproverna att ses över. Sammanfattningsvis är det utmanande att modellera sambandet mellan ljushet och övriga variabler i blekeriet. Detta beror på osäkerhet i mätningarna, avsaknaden av samtliga potentiella oberoende variabler, samt att fabriken tros ha stor variation i processen. / Domsjö Fabriker AB has experienced an increase in water consumption over a period of time, without being able to identify any contributing factors. As part of this investigation, a data analysis of the bleachery, focusing on the variable Chemical Oxygen Demand (COD) has been conducted. Several different regression models were constructed with the aim of exploring whether the brightness measured after the cooking process affected the COD levels shortly thereafter. Furthermore, the models aimed to find the factors influencing the final bleaching of the cellulose pulp in the bleachery, particularly with regard to whether COD contributed or not. The results of this analysis revealed that the brightness after the cooking process had no impact on COD, and it was also determined that COD likely does not influence the bleaching process, as COD was not part of an accepted model explaining brightness. Considering that laboratory tests of COD are costly and do not affect brightness, a reconsideration of the utility of these tests is recommended. In conclusion, it is challenging to model the relationship between brightness and other variables in the bleachery due to measurement uncertainty, the absence of all potential independent variables, and the factory's presumed significant variability in the process.

Grape pomace (GP) is one of the most abundant and underutilized fruit-derived wastes. GP is generated during winemaking, occupying over 60% of the total solid winery wastes. GP may cause serious environmental problems if it is not properly handled. On the other hand, it is rich in valuable compounds that are worthy of recovery. Although research has been working on GP upgrading, the utilizations are limited to producing a single product (e.g., grape seeds oil or polyphenol powders), which leads to large volumes of secondary wastes left. Therefore, the goal of this study is to develop an integrated process for the comprehensive utilization of GP by the production of multiple value-added products and evaluate its economic feasibility at a commercial scale. First, the chemical composition of different industrial GPs was analyzed to lay the foundation for the process design. Based on the analyzed chemical composition, an integrated process was developed to produce grape oil, polyphenols, and biofuels from GP. In this process, GP was extracted by hexane to produce oil, followed by aqueous ethanol solution extraction to obtain polyphenols. The solid residue rich in structural carbohydrates was then pretreated by alkali to partially remove lignin and enzymatically hydrolyzed to produce monomer sugars. The produced sugars were used as feedstock to produce acetone, butanol and ethanol (ABE) through anaerobic fermentation. Under the optimized conditions, the process was able to produce 71.9 g crude oil, 322.8 g crude polyphenols (equivalent to 72.6 g gallic acid), and 20.7 g ABE from 1 kg dry GP. Besides the valuable products, the process co-generated a large amount (50% of input GP biomass) of secondary waste, which is rich in lignin. Therefore, we further converted the secondary waste to biochars and evaluated their potential application in water purification by removing lead (Pb) from contaminated water. Based on the results, the produced biochar showed a high Pb adsorption ability (134 mg/g), with 66.5% of lead removal achieved within the first 30 min. Experimental and modeling results indicated that both physisorption and chemisorption mechanisms were involved in the Pb adsorption of the biochar. Finally, techno-economic analysis was conducted to evaluate the economic feasibility of the integrated processing of GP into oil, polyphenols, and biochar at an industrial scale. The results showed that compared with generating of single product or dual products, the integrated process aiming to produce multiple products had the best economic performance with the net present value (NPV), internal rate of return (IRR), and payback period of $135.0 million, 47.5%, and 1.8 years, respectively. Sensitivity analysis showed that plant capacity and polyphenol selling price had major impacts on process economics. Therefore, a suggestion for implementing this integrated process is to invest more in the polyphenol production and purification process to generate high-quality polyphenols with a high selling price and running the plant with a large capacity. Overall, we explored a novel integrated process that aims to produce multiple value-added products to increase the economic gain for the wine industry, and at the same time, potentially reduce the environmental burdens caused by GP disposal. / Doctor of Philosophy / During wine making, a large amount of solid waste is generated, and the major one is called grape pomace (GP). GP is mainly consisted of grape skins, seeds, and some stems. Normally, GP is discarded as waste; however, if it is not handled properly, GP may cause serious damages to the environment such as contaminating soil and stream water. On the other hand, GP has valuable compounds that could be recovered for other applications. Previous researchers used GP to produce a single product, which still leads to a large amount of components not used. Therefore, the aim of the current study is to design a process to comprehensively utilize GP to produce multiple value-added products. The developed process can produce grape seed oil, polyphenols, and biofuels from GP. The solid residue generated from the designed process was further converted into biochar, which can be used as an excellent adsorbent to remove lead (Pb) from contaminated water. Based on the economic model results, the developed process to convert GP into grape seed oil, polyphenols, and biochar could be a promising investment at an industrial scale. Generally speaking, various valuable products were obtained from low value GP waste, which could not only reduce the potential environmental problems caused by waste disposal, but also provide different value-added products for food, pharmacy, chemical, and energy industries.

Le concept d’une algoraffinerie primaire traitant les principaux composants de microalgues (lipides, protéines, glucides et pigments) a été étudié. Une séquence d'opérations unitaires a été mis en œuvre afin d'obtenir des fractions enrichies de ces biomolécules tout en conservant leur integrité dans le procédé en aval. L'étude a été principalement centrée sur Chlorella vulgaris, une espèce connue pour sa paroi cellulaire rigide. La majorité de la fraction lipophile (lipides et pigments) a été récupérée en utilisant du dioxyde de carbone supercritique avec de l'éthanol en tant que co-solvant, sans opération unitaire de cassage cellulaire préalable. La fraction hydrophile (protéines et polysaccharides) a été récupérée dans la phase aqueuse après broyage à billes comme méthode de cassage cellulaire. Par la suite, la phase aqueuse a été séparée en trois fractions par un procédé d'ultrafiltration en deux étapes. Ainsi, les amidons, les pigments, les protéines et les sucres ont été séparés les uns des autres avec succès. Une analyse du cycle de vie sera nécessaire pour estimer le coût et la durabilité du procédé de fractionnement. / A primary algorefinery, concept that deals with the main components of microalgae (lipids, proteins, carbohydrates and pigments), has been studied. A sequence of unit operations has been implemented in order to obtain separated enriched fractions of these biomolecules by conserving their integrity in the downstream process. The study was mainly centred on Chlorella vulgaris, a species known for its rigid cell wall. Most of the lipophilic fraction (lipids and pigments) was recovered using supercritical carbon dioxide with ethanol as a co-solvent, without a preliminary unit operation of cell disruption. The hydrophilic fraction (proteins and polysaccharides) was recovered in the aqueous phase after bed milling as cell disruption method. Subsequently, the aqueous phase was fractionated into three fractions by means of a process of two-stage ultrafiltration. Thus, starches, pigments, proteins and sugars were successfully separated from each other. A life cycle assessment will be necessary to estimate the cost and the sustainability of the fractionation process

L'objectif de ces travaux vise à évaluer les performances techniques et environnementales d'un procédé de fractionnement et de purification d'hémicelluloses de pailles et sons de blé. La démarche employée consiste dans un premier temps à évaluer la faisabilité du procédé à une échelle pilote. Celui-ci implique notamment une opération de fractionnement par extrusion bi-vis et des étapes de concentration-purification par une combinaison d'ultrafiltration et de chromatographie sur résine. Il est comparé à un procédé plus classique où l'extrait extrudé subit une évaporation et une précipitation éthanolique. L'étude des compositions chimiques des extraits et des poudres produites à chaque étape du procédé permet d'observer que l'extrusion bi-vis donne des rendements plus faibles que d'autres techniques d'extraction, mais présente des avantages en termes d'échelle, de continuité du procédé, et de faibles consommations d'eau. Par ailleurs, l'ultrafiltration est une technique intéressante car elle permet une purification et une concentration des extraits simultanées et la chromatographie sur résine s'est avérée être une solution attractive pour la décoloration des extraits. Dans un second temps, la méthodologie d'analyse du cycle de vie (ACV) a été appliquée au procédé. Celle-ci a mis en avant le fort impact environnemental généré par certaines opérations unitaires et a donné lieu à l'identification de priorités d'actions pour l'amélioration du procédé. Ainsi, le scénario mettant en jeu une combinaison de l'ultrafiltration avec une chromatographie sur résine semble plus avantageux que celui mettant en jeu une évaporation sous vide combinée à une précipitation éthanolique. La démarche employée apporte également des réponses méthodologiques sur la démarche d'ACV appliquée aux procédés : l'importance de prendre en compte différentes méthodes de caractérisation, de tester la sensibilité de l'étude à l'unité fonctionnelle et aux hypothèses initiales ont été mises en avant. Enfin, dans le but de démontrer sa forte potentialité dans le domaine des procédés, l'ACV a été appliquée à certaines opérations unitaires. L'intérêt d'étudier l'influence des conditions opératoires des procédés sur les impacts environnementaux a été démontré. Par ailleurs, la nécessité de développer des outils de modélisation des procédés qui pourront être couplés à ceux de l'ACV afin d'intégrer pleinement les critères environnementaux au dimensionnement des procédés a été mis en avant. / The objective of this work was to evaluate the technical and environmental performance of a fractionation and purification process of hemicelluloses from wheat straw and bran. The approach used was first to assess the feasibility of the process on a pilot scale. This implied setting up twin-screw extrusion, concentration steps by ultrafiltration and a purification step by ion exchange chromatography. It was compared to a more traditional process where the extruded extract was treated by evaporation and ethanol precipitation. Study of the chemical composition of extracts and powders produced at each stage of the process, showed that the twin-screw extrusion gave lower yields than other extraction techniques, but had the advantage in terms of scale, continuity of the process and low water consumption. Furthermore, ultrafiltration is an interesting technique because it allows simultaneous purification and concentration of the extracts, and ion exchange chromatography proved to be an attractive solution for the removal of coloured compounds. In a second step, the life cycle assessment (LCA) methodology was applied to the process. This highlighted the strong environmental impact generated by some unit operations, and resulted in the identification of priorities to improve the process. Thus, the scenario involving a combination of ultrafiltration with ion exchange chromatography appears to be more advantageous than that involving vacuum evaporation combined with ethanol precipitation. The approach used also provides methodological answers for LCA applied to processes: the importance of taking into account different characterization methods, testing the sensitivity of the study to the functional unit, and reconsidering the initial assumptions, has been stressed. Finally, in order to demonstrate its high potential in the field of processes, LCA has been applied to some unit operations. The interest of studying the influence of process operating conditions on environmental impacts has been demonstrated. In addition, the need to develop tools for modelling processes that can be coupled to those of LCA in order to fully integrate environmental criteria into process design, has been highlighted.

Nas últimas décadas observou-se tanto o crescimento das preocupações ambientais e de sustentabilidade. Neste contexto, surgiu o conceito de biorrefinaria. No Brasil, uma das principais lavouras agroindustriais é a produção de cana-de-açúcar. A indústria sucroalcooleira já atua como um modelo de biorrefinaria tendo a possibilidade de produção de açúcar de etanol e ainda de energia elétrica. Contudo, existe grande potencialidade de produtos de originários de biomassa vegetal. Alguns exemplos das potencialidades são: (i) a utilização dos açúcares da fração polissacarídica para produção de etanol; (ii) produção de polpa e papel; (iii) produção de nanomateriais entre outras. Assim, este trabalho se propõe a buscar e aplicar tecnologias e processos voltados a utilização da cana-de-açúcar para a obtenção de produtos variados. O primeiro processo utilizado é a separação das frações casca e miolo da cana-de-açúcar: na casca existe uma baixa quantidade de células de armazenamento de açúcar e uma maior proporção de fibras estruturais ademais, da epiderme extrai-se a cera; na fração miolo concentra-se a maior parte do caldo rico em sacarose, pela elevada quantidade de células de parênquima. Visando elevar a concentração de sacarídeos para a produção de etanol estudou-se a realização de um processo hidrotérmico usando o próprio suco da cana-de-açúcar para a extração de açúcares da fração de hemiceluloses. Observou-se que para a reação hidrotérmica em meio neutro na faixa de temperaturas estudada (110 a 130°C) cerca de 95% dos sacarídeos são conservados. Contudo, nestas condições reacionais a preservação de massa de hemiceluloses também se mantém nesta faixa, assim verificou-se que o uso de um catalizador ácido permitiria uma conservação de sacarídeos similar e aceleraria a reação de remoção de hemiceluloses. Usando processos similares aos usados na indústria de papel e celulose obteve-se dois materiais celulósicos das frações casca e miolo de cana-de-açúcar com características físico-mecânicas diferenciadas. Apesar do maior teor de células de parênquima no miolo original, observou-se que o papel desta fração apresentou resultados promissores com propriedades similares ao de papeis comerciais. A partir destas polpas, obteve-se dois materiais celulósicos nanofibrilados distintos, sendo o material da casca dúctil e o de miolo mais rígido (maior módulo de Young) e ao mesmo tempo mais frágil (menor alongamento para a ruptura). Verificou-se ainda que a partir dessas polpas celulósicas pode-se produzir nanocristais de celulose II usando um processo de hidrólise e solubilização com ácido sulfúrico seguido de reprecipitação. Desenvolveu-se o processo de produção de nanocristais de celulose I usando água subcrítica associado ou não a CO2. Este processo tem o potencial de substituir a atual produção de nanocristais de celulose visto que neste utiliza-se somente água (com ou sem CO2) para promover a hidrólise em oposição ao método clássico que usa elevadas concentrações de ácido sulfúrico permitindo uma economia financeira e produzindo menor volume de resíduos. / In the last decades environmental concerns and sustainability have grown. In this context, the biorefinery concept arose. In Brazil, one of the leading agro-industrial crops is the production of sugarcane. The sugar industry is already a model of a biorefinery because of the possibility of producing ethanol, sugar and even electricity. However, plant biomass still has a great potential to produce new materials and chemicals. Some of the capabilities are: (i) the use of the sugars from the polysaccharide fraction aiming the ethanol production; (ii) the production of pulp and paper; (iii) production of nanomaterials, among others. This work aims to seek and apply technologies and processes to obtain different products from sugarcane. The first used is the separation of the rind and core fractions of sugarcane: in the rind there is a low amount of sugar storage cells and a higher proportion of structural fibers, and also wax from the epidermis; the core fraction concentrates the majority of the sucrose rich broth as consequence of the high quantity of parenchyma cells. In order to increase the concentration of saccharides a hydrothermal process was studied using the own juice of sugar cane to extract sugars from the hemicellulose fraction. It was observed that for the hydrothermal reaction in neutral medium in the temperature range studied (110 to 130 °C) of about 95% saccharides are conserved. However, in these reaction conditions the hemicellulose preservation is also kept in this range, so it was found that the use of an acid catalyst allow similar saccharides recovery and accelerate the hemicellulose removal. Using similar procedures to those of the pulp and paper industry two cellulosic materials with differentiated physical and mechanical characteristics were obtained from the rind and core fractions of sugarcane. Although most parenchyma content in the original core material, it was observed that this fraction showed promising results with properties similar to commercial papers. From these pulps, two different nanofibrillated cellulosic materials were obtained, being the rind material a ductile material and the core a rigid (higher Young\'s modulus) and brittle (lower elongation at break) one. It was also found that from these pulps cellulose II nanocrystals can be produced using a process of hydrolysis and solubilization with sulfuric acid followed by a reprecipitation process. The production of cellulose I nanocrystals through processes using subcritical water with or without CO2 were developed. These processes have the potential to replace the current nanocrystals production since only water is used (with or without CO2) to promote the hydrolysis, compared to the traditional method, which uses high concentrations of sulfuric acid, thus enabling economical saves and producing less amount of wastes.

L'objectif est la valorisation de biomolécules issues des eaux du procédé thermomécanique de fabrication de pâte à papier. La séparation des familles de biomolécules doit permettre de générer plusieurs fractions ayant un intérêt pour l'industrie cosmétique et phytosanitaire. Les terpènes, hémicelluloses, lignine et lignanes ont été identifiés dans ces eaux. Cependant, le choix s'est porté sur la valorisation de la lignine et des lignanes pour des raisons de sélectivité et de valeur ajoutée. La flottation et la filtration par membrane 150 kDa permettent d'effectuer une clarification par élimination de 100% des terpènes et de 59% des hémicelluloses. Le fractionnement de la lignine et des lignanes est effectué avec des membranes de 1 kDa et 300Da à pH 4 pour obtenir deux rétentats contenant respectivement 96% de lignine et 58% de lignanes par rapport aux polyphénols totaux. Une étude technico-économique de faisabilité de la filière de séparation est réalisée à l'échelle semi-industrielle . / This thesis work is part of a dynamic industrial ecology around the paper industry. The objective is the valorization of biomolecules coming from thermomechanical process waters of manufacture of paper pulp. The separation of biomolecule's families must allow generate several fractions having an interest for cosmetic and phytosanitary industry. Terpenes, hemicelluloses, lignin and lignans have been identified in these waters. However, the choice has worn on the valorization of lignin and lignans for reasons of selectivity and added value. Flotation and 150 kDa membrane filtration allow for clarification by removal of 100% of terpenes and 59% of hemicelluloses. Fractionation of the lignin and lignans is carried out with membranes of 1 kDa and 300 Da at pH 4 to obtain two retentates containing respectively 96% of lignin and 58% of lignans relative to the total polyphenols. A technical-economic study of feasibility of separation process is carried out on semi-industrial scale.

Orientador: Gustavo Ventorim / Resumo: O conceito de biorrefinaria surgiu do intuito de diminuir a dependência dos produtos oriundos do petróleo e seus consequentes problemas ambientais. Pesquisas buscam técnicas e materiais que substituam a matéria prima de origem fóssil por biomassa, agregando valor a produtos de origem renovável ou que anteriormente seriam descartados. A produção de combustíveis de 2ª geração (como bioetanol) possibilita o repasse de um custo razoável ao setor de transporte devido ao uso de matéria prima de baixo custo. A composição de forte associação entre celulose, hemicelulose e lignina exige uso de um método de pré-tratamento que atenue a interação entre os componentes da biomassa e facilite a conversão em bioprodutos. Este trabalho tem como objetivo estudar a combinação de pré-tratamentos, auto-hidrólise e polpação soda na obtenção de pasta celulósica a partir de cavacos de eucalipto. Esta polpa passa por processo de hidrólise ácida liberando açúcares que, na presença de microrganismos específicos (Saccharomyces cerevisiae) são fermentados a etanol. Cavacos de eucalipto pré-tratados por auto-hidrólise passaram por cozimentos soda em concentração de álcali ativo de 20%, 23% e 26%, estudando-se a influência da concentração de álcali no rendimento de produção de bioetanol. A polpação utilizando 20% de álcali ativo produziu rendimento de 130,30 L de etanol a partir de uma tonelada de cavacos, tendo maior impacto no rendimento que as polpações de 23% de álcali ativo, que foi responsável por um... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The concept of biorefinery appear from the idea of reducing dependence on petroleum products and their consequent environmental problems. Researches seek techniques and materials that substitute the feedstock of fossil origin for biomass, adding value to products of renewable origin or that would previously be discarded. The production of second-generation fuels (such as bioethanol) makes it possible to pass along a reasonable cost to the transportation sector due to low cost raw materials use. The strong association between cellulose, hemicellulose and lignin requires a pretreatment method that attenuates the interaction between biomass components and facilitates the conversion into bioproducts. It was studied the combination of, auto-hydrolysis and soda pulping (alkaline) pre-treatments to efficiently obtain cellulose must go through acid hydrolysis process. This pulp after being hydrolized liberates sugars that, in the presence of specific microorganisms (Saccharomyces cerevisiae), could be fermented to ethanol. Eucalyptus pretreated by auto-hydrolysis method were treated by soda pulping in active alkali concentration of 20%, 23%b and 26%, studying the influence of the alkali concentration on the yield of bioethanol. Pulping using 20% active alkali yielded 130,30L of ethanol from one ton of chips, which has better impact than the 23% active alkali pulping, which was responsible for a production of 118,8 L of ethanol and 26% active alkali pulping that produced 101,9L. All y... (Complete abstract click electronic access below) / Mestre

Les réserves de pétrole sont sur le déclin, les prix des ressources fossiles fluctuent et le CO 2 dégagé par leur consommation contribue inéluctablement au réchauffement climatique. Ce phénomène, conduit notre société vers l'utilisation accrue de biomasse pour la génération d'énergie, de composés chimiques et de matériaux. La réduction des déchets est considérée comme indissociable de cette transition énergétique et en opposition aux préjugés, l’accroissement des déchets organiques peut être bénéfique dans cette recherche de solutions alternatives. En effet, cela conduit à la génération de grandes quantités de matières qui peuvent représenter de potentielles ressources. De plus, changer le statut des déchets en coproduits pour la production de bioénergies n’entre pas en concurrence avec les filières alimentaires et cela constitue un des principaux enjeux des biotechnologies. Sous certaines conditions, les bioconversions anaérobies représentent des procédés d’ingénierie prometteurs pour accomplir le double enjeu de la valorisation des coproduits et de la production de molécules d’intérêt énergétique et chimique (biocarburants, chimie verte...). En revanche, l’innovation dans les biotechnologies blanches est nécessaire pour la production robuste, performante, rentable et environnementalement acceptable de biomolécules à partir de ressources renouvelables. Dans ce contexte, la société AFYREN a été pensée et créée pour répondre à ce défi mondial via sa technologie « tout en un », AFYNERIE, qui s’inspire de la nature et des sciences. L’objectif premier de ce travail de thèse, cœur du procédé AFYNERIE, était d’étudier les performances de microorganismes anaérobies, sous forme de souches pures ou de consortia pour la valorisation de substrats plus ou moins complexes via un processus de méthanogenèse avortée. Pour cela, il était nécessaire de considérer, déjà à l’échelle du laboratoire, une projection dans le monde industriel. Nous avons alors démontré les capacités de la diversité microbienne à produire des molécules plateformes à partir de coproduits agro-industriels réels en mode stérile puis non stérile. Cette étude s’est appuyée en parallèle sur la caractérisation et la dynamique des populations microbiennes mises en jeu. Ensuite, l’accumulation des métabolites, à la fois inhibiteurs et d’intérêt, dans les milieux fermentaires en mode discontinu et avec des rendements compétitifs, a débouché sur la nécessité de surpasser ces limitations par le passage à un mode continu. Pour ce faire, un procédé d’extraction biocompatible des synthons issus de l’opération de fermentation a été mise en œuvre selon différents mode de réalisations. Ce couplage des opérations unitaires, sous forme de fermentation extractive, a livré des résultats prometteurs tout en étant bâtit dans un cadre de bioraffinerie et d’écologie industrielle qui tend vers le « zéro déchet ». Enfin, à l’inverse des autres technologies émergentes, pour se placer dans une approche de drop-in, la biologie et la chimie ont été associées. Le but a été d’illustrer la multipotence des acides gras volatils (AGVs) en termes d’applications industrielles et de réaliser la preuve de concept de la transformation de la biomasse non alimentaire en biomolécules d’intérêt énergétique et chimique. Ces travaux ont permis de soulever les points clés du changement d’échelle du procédé AFYNERIE et d’entrevoir des perspectives tant fondamentales qu’appliquées. Cette brique technologique, de par sa philosophie multi-intrants/multi-produits, couplant fermentation-extraction-synthèse, permet d’initier la transition au stade pilote d’un procédé innovant compatible avec une future économie biosourcée. / Fossil oil reserves are decreasing, oil prices are fluctuating, and the CO 2 released by oil consumption contributes to global warming. These are driving our society towards increased use of biomass for energy, chemical compounds and other materials. Minimizing waste has been seen as a concern associated with alternative energy efforts. Contrary to expectation, increasing organic waste can be beneficial for alternative energy efforts, because it would result in large amounts of organic resources that can be potential raw materials. Moreover, using waste as a resource for bioenergy production does not compete with human or animal food or agricultural surfaces, and that is one of the greatest challenges facing biotechnology. Using waste as a resource for biomolecule production would thus be an interesting approach to reducing waste in the environment and producing renewable materials. Under specific conditions, detrital biomass can be converted into biomolecules of interest by microorganisms. Anaerobic fermentation techniques represent promising engineering processes for accomplishing the dual goals of waste reduction and renewable biomolecule production for biofuel and green chemistry markets. On the other hand, innovative fermentation processes are necessary for the strong, successful, cost-effective and eco-friendly production of bulk chemicals from renewable resources. In this context, AFYREN company was thought and founded to answer this world challenge through its “all in one” technology, AFYNERIE, which is inspired from the nature and sciences. The first objective of this thesis, heart of the AFYNERIE process, was to study the performances of anaerobic microorganisms, in the form of pure strains or of consortia for the valorization of more or less complex substrata via a process of failed methanogenesis. For that purpose, it was necessary to consider, already at the laboratory scale, a projection in the industrial world. Then, we demonstrated the capacities of the microbial diversity to produce platform molecules from real agro-industrial by-products in sterile and then non sterile mode. This study leaned in parallel on the characterization and the dynamics of involved microbial populations. Then, the accumulation of metabolites, which are at the same time inhibitory and of interest, in fermentative media in batch mode and with competitive yields, resulted in the necessity of surpassing these limitations by the passage in a continuous mode. To do this, a process consisted of a biocompatible extraction of synthons stemming from the operation of fermentation was implemented according to different mode of realizations. This coupling of single operations, in the form of extractive fermentation, delivered promising results while builds in a frame of biorefinery and industrial ecology which tightens towards a “zero waste”. Finally, contrary to the other emergent technologies, to take place in a drop-in approach, biology and chemistry were associated. The purpose was to illustrate the versatility of volatile fatty acids (VFAs) in terms of industrial applications and to realize the proof of concept of the transformation of the non-food biomass in biomolecules of energy and chemical interest. These works allowed to underline key points of the scale-up of AFYNERIE process and to glimpse perspectives fundamental as well as applied perspectives. This technological brick, due to its multi-inputs / multi-products philosophy, coupling fermentation-extraction-synthesis, allows to introduce the transition to the pilot stage of an innovative process compatible with a future biobased economy.

With greenhouse gas emissions (of which CO2 is the major component) being a major environmental concern, mitigation of those emissions is becoming increasingly imperative. The ability to use a fast growing, photosynthetic organism like microalgae that can survive primarily on nutrients such as sunlight and air (with increased CO2 levels) makes it a desirable agent for CO2 sequestration. The primary goal of this project is the engineering of the sequestration of CO2 using the cultivation of the microalgae species <i>Chlorella vulgaris</i>. Secondary goals of the project are the exploration and development of valuable by-products of the cultivation and the determination of whether utilizing microalgae to capture CO2 could be integrated economically into an industrial facility.<p> The batch growth kinetics of the photosynthetic algal species <i>C. vulgaris</i> were investigated using a well-mixed stirred bioreactor. The growth rate was found to increase as the dissolved CO2 increased to 150 mg/L (10% CO2 by volume in the gas), but fell dramatically at higher concentrations. Increasing the radiant flux also increased growth rate. With a radiant flux of 32.3 mW falling directly on the 500 mL culture media, the growth rate reached up to 3.6 mg of cells/L-h. Both pH variation (5.5 - 7.0) and mass transfer rate of CO2 (KLa between 6 h-1 and 17 h-1) had little effect on growth rate.<p> The operation of continuously stirred tank bioreactors (CSTBs) at minimum cost is a major concern for operators. In this work, a CSTB design strategy is presented where impeller stirring speed and aeration rate are optimized to meet the oxygen demand of growing cells, simultaneously minimizing the capital and operating cost. The effect of microbial species, ions in the culture medium, impeller style, as well as changing CSTB size and biomass input density on the optimum operating conditions, is examined. A study of the effects of various parameters on the CSTB design is shown.<p> Using the kinetic data collected in the batch growth study, a novel external loop airlift photobioreactor (ELAPB) was designed and tested. A model was developed for <i>C. vulgaris</i> growth in the ELAPB that incorporated growth behaviour, light attenuation, mass transfer, and fluid dynamics. The model predicts biomass accumulation, light penetration, and transient CO2 concentrations, and compares predictions to experimental data for radiant fluxes of 0.075 1.15 W/m2 and 0 20% CO2 enrichment of feed air, with a 10% average error. The effect of radiant flux and CO2 concentration is presented with discussion of radial and vertical profiles along the column. For a fed-batch culture at a biomass density of 170 mg/L, the penetration of the radiant flux was found to decrease by 50% within the first 1 cm, and 75% at 2 cm. Theoretical optimum growth conditions are determined to be 0.30 W/m2 and 6% CO2 enrichment of inlet feed air.<p> The algal culture was observed to be a workable electron acceptor in a cathodic half cell. A net potential difference of 70 mV was achieved between the growing <i>C. vulgaris</i> culture acting as a cathode and a 0.02 M potassium ferrocyanide anodic half cell. Surge current and power levels of 1.0 µA/mg of cell dry weight and 2.7 mW/m2 of cathode surface area were measured between these two half cells. The recently developed photosynthetic cathode was also coupled to a fermentative anode to produce a completely microbial fuel cell. Loading effects and the effect of changing culture conditions on fuel cell operation are reported. The maximum power output measured was 0.95 mW/ m2 at 90 V and 5000 ohms. A significant increase in this output is achieved with the addition of supplemental glucose to the anodic half cell and the enrichment of the feed air bubbled into the cathodic half cell with 10% CO2.<p> Two economic feasibility studies were performed on the integration of ELAPBs into an industrial facility. These integration studies operated the ELAPBs continuously as biocathodes in coupled microbial fuel cells (MFCs) that capture CO2 from an existing 130 million L/yr bioethanol plant, while generating electrical power and yielding oil for biodiesel to provide operational revenue to offset costs. The anodes for the coupled MFCs are the existing yeast batch fermentors, and the CO2 to be sequestered comes from the existing bioethanol production. Two different design schemes were evaluated, in both cases the maximum profit was achieved with the maximum number of tall columns operated in parallel. The first design evaluated a batch bioethanol facility with off-site oil processing, and the economic feasibility is demonstrated by the positive Net Present Worth achieved over the 20 year life of the plant, at a 10% rate of return on investment. The second design, for a continuous bioethanol operation, processes both oil and algae biomass on-site, but the economics of this second process are only positive (Internal Rate of Return 9.93%.) if the government provides financial assistance in the form of generous carbon credits (a speculative $100 per tonne of CO2 not yet attained) and a 25% capital equipment grant.