[pt] A necessidade mundial de energia tem aumentado exponencialmente, no entanto, as reservas de combustíveis fósseis, além de produzirem sérios impactos ambientais, estão se esgotando ao longo dos anos. Por estas razões, muitos estudos vêm sendo feitos na busca de novas fontes renováveis de energia, como o reaproveitamento de resíduos de biomassa. Desta forma, o objetivo deste trabalho é estudar o processo de liquefação hidrotérmica (HTL) do bagaço de malte, gerado ao final do processo cervejeiro, para a produção de bio-óleo e biocarvão como potenciais combustíveis renováveis. A caracterização inicial da biomassa apresentou significativa quantidade de celulose e hemicelulose, alto teor de umidade e pequeno tamanho de partícula, sendo ideal para o processo. A HTL foi conduzida em um reator sob alta pressão em diferentes faixas de temperatura e tempos de residência. Uma modelagem cinética e termodinâmica foi realizada para a etapa inicial da liquefação, apresentando 62,08 kJ.mol−1 de energia de ativação e caráter endotérmico. Bio-óleo apresentou melhor rendimento, 18,2 por cento, a 300 C e 30 min, já o biocarvão atingiu 21,0 por cento de rendimento a 250 C e 5 min. A pequena diferença de valores, ao longo do tempo, comprovou que a maior produtividade ocorre sempre em 5 min, sendo este o tempo ótimo de reação. A análise do poder calorífico superior (PCS) demonstrou que altas temperaturas elevam a energia produzida. Em 5 min e a 300 C, melhores condições de operação, a HTL gerou um bio-óleo com PCS de 33,6 MJ.kg−1, sendo 27,8 por cento inferior a gasolina e um biocarvão com 26,7 MJ.kg−1, sendo 11,4 por cento superior ao carvão tradicional. Através das caracterizações finais, foi possível observar alta degradação da estrutura lignocelulósica da biomassa e identificar os compostos presentes no bio-óleo, indicando que os produtos da HTL apresentam alto potencial de utilização como combustíveis renováveis. / [en] The global energy needs have increased exponentially; however, fossil fuel reserves, in addition to producing serious environmental impacts, are running out over the years. For these reasons, many studies have been done in the search for new renewable energy sources, such as the reuse of biomass wastes. In this way, the purposes of this study are associated with the hydrothermal liquefaction process (HTL) of the malt bagasse, generated at the end of the brewing process, for the production of bio-oil and biochar as potential renewable fuels. The initial biomass characterization presented a significant amount of cellulose and hemicellulose, high moisture content and small particle size, ideal for the process. The HTL was conducted in a high pressure reactor in different temperature ranges and residence times. A kinetic and thermodynamic modeling was performed for the initial stage of liquefaction, presenting 62.08 kJ.mol−1 of activation energy and endothermic behavior. Bio-oil presented a better yield, 18.2 percent, at 300 C and 30 min, while the biochar reached 21.0 percent yield at 250 C and 5 min. The small distintion between values, over time, proved that the highest productivity always occurs at 5 min, which is the optimal reaction time. The higher heating value analysis (HHV) showed that high temperatures increase the energy produced. At 5 min and 300 C, better operating conditions, HTL generated a bio-oil with HHV of 33.6 MJ.kg−1, with 27.8 percent less than gasoline and a biochar with 26.7 MJ.kg−1, being 11.4 percent higher than traditional coal. Through the final characterization, it was possible to observe high degradation of the lignocellulosic structure of the biomass and to identify the compounds present in the bio-oil, indicating that the HTL products present high potential for use as renewable fuels.

[pt] A industrialização e a crescente preocupação com o meio ambiente geram, cada vez mais, a busca por fontes de energia que emitam menos gases efeito estufa. A biomassa, devido a sua grande ocorrência ao redor do mundo e a sua diversidade, é uma forte alternativa aos combustíveis fósseis. Sua gaseificação gera um combustível gasoso chamado syngas. A problemática no manejo dos resíduos sólidos urbanos (RSU) e a grande disponibilidade do bagaço de cana-de-açúcar no Brasil fizeram deles tipos de biomassa de interesse para este trabalho. Objetivou-se simular no MATLAB® a gaseificação cocorrente de biomassa com ar a partir de uma abordagem cinética. O modelo foi validado com dados da literatura e aplicado à simulação da co-gaseificação de RSU e bagaço de cana-de-açúcar, na qual a razão de co-gaseificação (RCG) representou a percentagem de RSU na biomassa de entrada. Um planejamento composto central com 3 fatores e 3 níveis foi realizado, resultando em 27 ensaios variando os fatores RCG, umidade da biomassa e razão de equivalência. Foram criados modelos polinomiais para a composição do syngas obtido, o PCI do syngas, a eficiência energética do processo e a soma das frações molares de CO e H2 em base úmida. Os modelos foram considerados robustos, com valores de R2 e R2 ajustado variando de 0,96082 a 0,99345 e 0,94007 a 0,98998, respectivamente. O impacto dos fatores escolhidos nas respostas foi analisado, e os modelos de eficiência energética e soma das frações molares de CO e H2 foram maximizados. O caso otimizado, com RCG 7,98 porcento, umidade 5,00 porcento e razão de equivalência 0,18, resultou em um syngas de composição 3,72 porcento H2O, 29,68 porcento CO, 7,87 porcento CO2, 19,07 porcento H2 e 0,80 porcento de CH4 em mol, correspondendo a um PCI de 6,56 MJ/Nm3 e uma eficiência energética de 37,66 porcento. Por fim, o processo demonstrou bom potencial para geração de um gás rico em CO e H2. / [en] Industrialization and growing environmental concern are increasingly leading to the search for energy sources that emit less greenhouse gases. Biomass, due to its great accessibility around the world and its diversity, is a strong alternative to fossil fuels. Its gasification produces a gaseous fuel called syngas. The urban solid waste (MSW) management problems and the wide availability of sugarcane bagasse in Brazil made them types of biomass of interest for this work. This work aimed to model biomass gasification in MATLAB ® for a downdraft gasifier and air as gasifying agent, using a kinetic approach. The model was validated with experimental and numerical data from the literature and was then applied to MSW and sugarcane bagasse co-gasification simulation, in which co-gasification ratio (CGR) represented MSW percentage in the incoming biomass. A central composite design of experiments with 3 factors and 3 levels was carried out, resulting in 27 tests varying CGR, biomass moisture and equivalence ratio. Polynomial models were created for syngas composition, syngas LHV, process energy efficiency and sum of CO and H2 molar fractions on a wet basis. The models were considered robust, with values of R2 and adjusted R2 ranging from 0,96082 to 0,99345 and 0,94007 to 0,98998, respectively. The impact of each chosen factor was investigated, and the energy efficiency and sum of CO and H2 molar fractions models were maximized. The optimized case, with CGR 7,98 percent, biomass moisture 5,00 percent and equivalence ratio 0,18, resulted in a syngas composition of 3,72 percent H2O, 29,68 percent CO, 7,87 percent CO2, 19,07 percent H2 and 0,80 percent CH4 in molar basis, corresponding to a LHV of 6,56 MJ/Nm3 and an energy efficiency of 37,66 percent. By the end, the process showed great potential to produce a syngas rich in CO and H2.

New technologies, such as an efficient vapor-compression evaporator, a stationary lime kiln (SLK), and the MixAlco process, compelled us to re-evaluate methods for producing sugar from cane. These technologies allow more water and lime to be used, and they add more value to bagasse. Extracting and preserving the sugars, and lime pretreating the bagasse to enhance biodigestibility, all at the same time in a pile, was demonstrated to be unfeasible; therefore, sugar extraction must occur before lime treating the bagasse. Sugar extraction should occur countercurrently by lixiviation, where liquid moves in stages opposite to the soaked bagasse (megasse), which is conveyed by screw-press conveyors that gently squeeze the fiber in each stage, improving extraction. The performance of a pilot-scale screw-press conveyor was tested for dewatering capabilities and power consumption. The unoptimized equipment decreased megasse moisture from 96 to 89%. Simulation of the process suggested that eight stages are necessary to achieve 98% recovery from typical sugarcane. The cumulative power for the screw-press conveyor system was 17.0±2.1 hp•h/ton dry fiber. Thin raw juice preserved with lime for several months showed no sucrose degradation and no quality deterioration, except for reducing sugar destruction. The lime loading needed for 1-year preservation is 0.20 g Ca(OH)2/g sucrose. Shorter times require less lime. After preservation, the juice was carbonated and filtered, and the resulting sludge pelletized. Due to their high organic content, the pellets were too weak for calcination temperatures used in the SLK. The organics must be decreased prior to pelletization and sodium must be supplemented as a binding agent. Long-term lime pretreatment of bagasse showed two delignification phases: bulk (rapid) and residual (slow). These were modeled by two simultaneous first-order reactions. Treatments with air purging and higher temperatures (50 – 57oC) delignified more effectively, especially during the residual phase, thus yielding higher cellulase-enzyme digestibilities after 2 – 8 weeks of treatment. At temperatures > 60oC, pure oxygen purging is preferred. Fresh bagasse was of better quality than old bagasse. Treatment with NaOH yielded a larger bulk delignification phase than Ca(OH)2. Long-term lime pulping of bagasse was unsuitable for copy-quality paper, but it was appropriate for strawboard and other filler applications.

La biomasse lignocellulosique comprend les sous-produits agricoles et industriels pouvant être utilisés comme matière première dans des bioprocédés variés destinés à produire des molécules d'intérêt énergétique ou chimique. Ces ressources lignocellulosiques, peuvent notamment être fournies par l'industrie papetière qui est particulièrement adaptée pour les bio-raffineries modernes car elle est en capacité de produire en grande quantité un substrat ayant une faible teneur en lignine et sans composés inhibiteurs. La bagasse de canne à sucre est également un substrat prometteur par sa composition chimique simple et son abondance dans les pays tropicaux. Lors de l'utilisation de ces substrats, l'hydrolyse enzymatique constitue une étape cruciale permettant la transformation des fibres de cellulose en une source de carbone fermentescible. Si les aspects biochimiques de cette étape d'hydrolyse font l'objet de nombreuses recherches et de développements, les réactions sous haute teneur en matière sèche font apparaître des limitations physiques qui sont beaucoup moins étudiées et analysées mais constituent des verrous scientifiques et technologiques qui freinent actuellement l'utilisation de cette ressource abondante et durable. Ce travail s'inscrit dans ce contexte et propose l'étude de cette étape d'hydrolyse enzymatique de la lignocellulose en s'intéressant conjointement aux aspects biochimiques et physiques de façon à aller vers une compréhension et une maîtrise des transferts (de masse, de chaleur) dans les réactions à forte concentration en substrat. La stratégie adoptée a consisté à réaliser et analyser des réactions d'hydrolyse sous différentes conditions opératoires en travaillant dans un premier temps sur des concentrations intermédiaires (suspension semi-diluée), c'est-à-dire en introduisant, mais de façon limitée, les complexités dues aux interactions entre particules/fibres de lignocellulose. Les résultats obtenus sont ensuite utilisés pour élaborer une stratégie adaptée aux fortes concentrations. Les aspects physiques analysés sont essentiellement le comportement rhéologique du milieu réactionnel ainsi que la morpho-granulométrie des objets en suspension. Différentes métrologies, tant in-situ que ex-situ, ont été mises en œuvre et apportent des résultats complémentaires. Les études ont été menées sur un substrat de référence, le papier Whatman, et deux substrats à vocation industrielle: la pâte à papier et la bagasse de canne à sucre. La stratégie d'étude porte sur les aspects suivants: (i) le suivi de l'évolution des comportements rhéologiques et des propriétés morphologiques des suspensions au cours de l'hydrolyse, (ii) l'étude des mécanismes d'hydrolyse lors de la dégradation des substrats, (iii) l'étude de l'impact de la composition et de la structure des substrats sur les cinétiques de solubilisation et d'hydrolyse, (iv) la quantification de la contribution des différentes activités enzymatiques, seules ou en mélange par une approche physique multi-échelle et (v) le contrôle et l'optimisation des conditions d'alimentation dans un procédé discontinu alimenté (fed-batch) afin d'atteindre des conditions de milieu concentré. Les chapitres 1 et 2 de ce document sont consacrés à une étude bibliographique du sujet et à la présentation des matériels et méthodes mis en œuvre. Le troisième chapitre présente les résultats obtenus et leur analyse. Il est constitué de trois sections: tout d'abord une étude des propriétés des différents enzymes ou cocktail d'enzymes utilisés, des substrats retenus et des suspensions avec, notamment, la détermination des régimes semi-dilués et concentrés. Ensuite sont présentées et analysées les hydrolyses effectuées en milieu semi-dilué. Les mécanismes d'hydrolyse (fragmentation, solubilisation, hydratation et séparation des agglomérats) sont étudiés pour diverses concentrations et divers enzymes/cocktails. Enfin les résultats en milieu concentré sont présentés dans une dernière section. / Lignocellulosic biomass consists of several agriculture and industrial by-products that can be used as raw material for several bioprocesses to obtain range of products. Among lignocellulosic sources, the pulp & paper industry is appropriated for modern bio-refining thank to pulp with low lignin content and free of inhibitory compounds. Besides, sugarcane bagasse is a very promising feedstock because of its simple chemical composition and its abundancy especially in tropical countries. In the bioconversion of lignocellulose, enzymatic hydrolysis is a crucial step that allows the transformation of cellulosic and hemicellulosic fibers into fermentable carbon sources. The lack of knowledge about physical limitations and hydrolysis mechanisms, especially at high dry matter content, stands as the main barrier which forbids the scale-up of bio-refinery processes. Thus, the efficient and sustainable use of lignocellulosic resources is currently a major challenge and need to be investigated. In this context, this PhD focused on the enzymatic hydrolysis of lignocellulose by both physical and biochemical approaches. The strategy consisted in carrying out and in analyzing the hydrolysis reactions under different operating conditions with semi-dilute suspensions. Then, obtained results were used to develop a hydrolysis strategy for concentrated suspensions. Different methodologies, in- and ex-situ analyses, were implemented and provided complementary results. From physical approach, analyses consisted in rheological behavior of suspensions as well as the morpho-granulometry of particles. The study was carried out on a reference substrate, Whatman paper, and on two industrial substrates, paper pulp and sugarcane bagasse. The strategy aimed to investigate different stakes: (i) evolution of rheological behaviors and the morphological properties of suspensions, (ii) hydrolysis mechanisms during the degradation of substrates, (iii) impact of substrate composition and structure on solubilization and hydrolysis kinetics, (iv) quantification of the contribution of single enzyme and enzyme mixture activities by multi-scale physical approaches and (v) control and optimization of feeding parameters for fed-batch process in order to access to concentrated suspension. Chapters 1 and 2 of this document are devoted to a research bibliographic and presentation of materials and methods. The third chapter presents obtained results and discussion in three sections. The first one is a study of the properties of different enzymes and substrates, in particular, the determination of semi-dilute and concentrated regime. Subsequently the enzymatic hydrolysis at semi-dilute regime is presented to highlight the hydrolysis mechanisms (fragmentation, solubilization, solvation and agglomerate separation) in relationship with enzyme mixtures and dosages. Finally, results in concentrated regime are discussed in the final section.

Thesis (MScEng)--Stellenbosch University, 2012 / ENGLISH ABSTRACT: Through many years of research, a number of production schemes have been developed for converting lignocellulosic biomass into transport fuels. These technologies have been assessed through a number of techno-economic studies for application in a particular context in terms of the technical and economic feasibility. However, previous studies using these methods have tended to lack vigour in various aspects. Either the energy efficiency of the processes were not maximised through adequate heat integration, or a competing technology which existed was not considered. From an economic perspective, the financial models would often lack the vigour to account for the risk and uncertainty that is inherent in the market prices of the commodities. This phenomenon is especially relevant for the biofuel industry that faces the full fledge of uncertainties experienced by the agricultural sector and the energy sector. Furthermore, from an environmental perspective, the techno-economic studies had often ignored the environmental impacts that are associated with biofuel production. Thus, a comparative study could have favoured an option due to its economic feasibility, while it could have had serious environmental consequences. The aim of this study was to address these issues in a South African context, where biofuels could be produced from sugarcane bagasse. The first step would be to modify an existing simulation model for a bioethanol scenario that operates with a Separate Hydrolysis and Fermentation (SHF process) configuration into a second processing scenario that operates with a Simultaneous Saccharification and Fermentation (SSF process) configuration using reliable experimental data. The second step was to ensure that the maximum energy efficiency of each scenario was realised by carrying out pinch point analysis as a heat integration step. In contrast to these biological models is the thermochemical model that converts bagasse to gasoline and diesel via gasification, Fischer-Tropsch synthesis and refining (GFT process). While there were no significant advances in technology concerning this type of process, the energy efficiency was to be maximised with pinch point analysis. The GFT process obtained the highest energy efficiency of 50.6%. Without the affects of pinch point technology, the efficiency dropped to 46%, which thus emphasises the importance of heat integration. The SSF had an efficiency of 42.8%, which was superior to that of the SHF at 39.3%. This resulted from a higher conversion of biomass to ethanol in the SSF scenario. Comparing the SHF model to an identical model found in literature that did not have pinch point retrofits, this study showed lower efficiency. This arose because the previous study did not account for the energy demands of the cold utility systems such as the cooling tower operation, which has been shown in this study to account for 40% of the electrical energy needs. The economic viability of all three processes was assessed with Monte Carlo Simulations to account for the risks that the fluctuations in commodity prices and financial indices pose. This was accomplished by projecting the fluctuations of these parameters from samples of a historical database that has been transformed into a probability distribution function. The consequences were measured in terms of the Net Present Value (NPV) and Internal Rate of Return (IRR) for a large number of simulations. The results of these variables were aggregated and were then assessed by testing the probability that the NPV<0, and that the IRR recedes below the interest rate of 12.64%. The investment was thus deemed unfeasible if these probabilities were greater than 20%. Both biological models were deemed profitable in terms of this standard. The probabilities were 13% for the SSF and 14% for the SHF. The GFT process however was deemed completely unfeasible because the probability that the NPV<0 was 78%. Given that the GFT process had the highest energy efficiency, this result arises mainly because the capital investment of 140,000USD/MWHHV of biomass energy input is to enormous for any payback to be expected. The environmental footprint of each process was measured using Life Cycle Assessments (LCAs). LCAs are a scientifically intricate way of quantifying and qualifying the effects of a product or process within a specified boundary. The impacts are assessed on a range of environmental issues, such as Global Warming, Acidification, Eutrophication and Human toxicity. Furthermore, if the project under concern has multiple output products, then the impacts are distributed between the output products in proportion to the revenue that each generates. The impacts were either relative to the flow of feedstock, which was 600MW of bagasse, or to the functional unit, which was the amount of fuel required to power a standard vehicle for a distance of 1 kilometre. In either case, the GFT scenario was the least burdening on the environmental. This was expected because the GFT process had the highest energy efficiency and the process itself lacked the use of processing chemicals. Relative to the feedstock flow, the SSF was the most environmentally burdening scenario due to the intensive use of processing chemicals. Relative to the functional unit, the SHF was the most severe due to its low energy efficiency. Thus, the following conclusions were drawn from the study:  The GFT is the most energy and environmentally efficient process, but it showed no sign of economic feasibility. iv  There is no significant difference in the economic and environmental evaluation of the SSF and SHF process, even though the SSF is considered to be a newer and more efficient process. The major cause of this is because the setup of the SSF model was not optimised. / AFRIKAANSE OPSOMMING: Deur baie jare van navorsing is ‘n aantal produksie-skemas vir die omskakeling van lignosellulose biomassa na vloeibarebrandstof ontwikkel. Hierdie tegnologië is geassesseer ten opsigte van die tegniese en ekonomiese haalbaarheid deur middel van tegno-ekonomiese studies in bepaalde tekste. Tog het hierdie vorige studies besliste beperkings gehad. Of die energie-doeltreffendheid van die proses is nie gemaksimeer deur voldoende hitte-integrasie nie, of 'n mededingende tegnologie wat bestaan is nie oorweeg nie. Vanuit 'n ekonomiese perspektief, was die finansiële modelle dikwels nie die omvattend genoeg om rekening te hou met die risiko en onsekerheid wat inherent is in die markpryse van die kommoditeite nie. Hierdie verskynsel is veral relevant vir die biobrandstof bedryf wat die volle omvang van onsekerhede ervaar waaraan die landbousektor en die energiesektoronderhewig is. Verder het die tegno-ekonomiese studies dikwels die omgewingsimpakte wat verband hou met biobrandstofproduksie geïgnoreer. Dus kon ‘n opsie deur die ekonomiese haalbaarheid bevoordeel word, ten spyte van die ernstige omgewingsimpakte wat dit kon inhou. Die doel van hierdie studie was om hierdie kwessies aan te spreek in 'n Suid-Afrikaanse konteks, waar biobrandstof uit suikerriet bagasse geproduseer kan word. Die eerste stap was om 'n bestaande simulasiemodel vir 'n bio-scenario wat met Afsonderlike Hidroliese en Fermentasie (SHF proses) stappe werk, te modifiseer vir 'n tweede verwerking scenario wat met 'n gelyktydige Versuikering en Fermentasie (SSF proses) konfigurasie werk. Die verandering is gedoen deur die gebruik van betroubare eksperimentele data. Die tweede stap was om te verseker dat elke scenario die maksimum energie-doeltreffendheid het, deur 'n hitte-integrasie stap, wat gebruik maak van “pinch-point” analise. In teenstelling met hierdie biologiese modelle, is daar die thermochemiese roete waar petrol en diesel van bagasse vervaardig word via vergassing, Fischer-Tropsch-sintese en rafinering (GFT proses). Daar was geen betekenisvolle vooruitgang in tegnologie vir hierdie proses nie, maar die energie-doeltreffendheid is gemaksimeer word deur energie-integrasie. Die GFT proses toon die hoogste energie-doeltreffendheid van 50,6%. Sonder die invloed van energie-integrasie het die doeltreffendheid gedaal tot 46%, wat dus die belangrikheid van hitte-integrasie beklemtoon. Die SSF het 'n effektiwiteit van 42,8% gehad, wat beter was as dié 39,3% van die SHF opsie. Hierdie hoër effektiwiteit wasas gevolg van die hoër omskakeling van biomassa na etanol in die SSF scenario. Die energie doeltreffendheid vir die SHF-model was laer as met 'n identiese model (sonder energie-integrasie) wat in die literatuur gevind wat is. Dit het ontstaan omdat die vorige studie nie 'n volledig voorsiening gemaak het met die energie-eise van die verkillingstelselsnie, wat tot 40% van die elektriese energie behoeftes kan uitmaak. Die ekonomiese lewensvatbaarheid van al drie prosesse is bepaal met Monte Carlo simulasies om die risiko's wat die fluktuasies in kommoditeitspryse en finansiële indekse inhou, in berekening te bring. Hierdie is bereik deur die projeksie van die fluktuasies van hierdie parameters aan die hand van 'n historiese databasis wat omskep is in 'n waarskynlikheid verspreiding funksie. Die gevolge is gemeet in terme van die netto huidige waarde (NHW) en Interne Opbrengskoers (IOK) vir 'n groot aantal simulasies. Die resultate van hierdie veranderlikes is saamgevoeg en daarna, deur die toets van die waarskynlikheid dat die NPV <0, en dat die IRR laer as die rentekoers van 12,64% daal, beoordeel. Die belegging is dus nie realiseerbaar geag as die waarskynlikhede meer as 20% was nie. Beide biologieseprosesse kan as winsgewend beskou word in terme van bostaande norme. Die waarskynlikhede was 13% vir die SSF en 14% vir die SHF. Aangesien die NHW van die GFT-proses onder 0 met ‘n waarskynlikheid van 78% is, is die opsie as nie-winsgewend beskou. Gegewe dat die GFT-proses die hoogste energie-doeltreffendheid het, is die resultaat hoofsaaklik omdat die kapitale belegging van 140,000 USD / MWHHV-biomassa energie-inset te groot is, om enige terugbetaling te verwag. Die omgewingsvoetspoor van elke proses is bepaal deur die gebruik van Lewens Siklus Analises (“Life Cycle Assessments”) (LCAS). LCAS is 'n wetenskaplike metodeom die effek van ‘n produk of proses binne bepaalde grense beide kwalitatief en kwantitatief te bepaal. Die impakte word beoordeel vir 'n verskeidenheid van omgewingskwessies, soos aardverwarming, versuring, eutrofikasie en menslike toksisiteit. Voorts, indien die projek onder die saak verskeie afvoer produkte het, word die impakte tussen die afvoer produkte verdeel, in verhouding tot die inkomste wat elkeen genereer. Die impak was met of relatief tot die vloei van roumateriaal (600MW van bagasse), of tot die funksionele eenheid, wat die hoeveelheid van brandstof is om 'n standaard voertuig aan te dryf oor 'n afstand van 1 kilometer. In al die gevalle het die GFT scenario die laagste belading op die omgewing geplaas. Hierdie is te verwagte omdat die GFT proses die hoogste energie-doeltreffendheid het en die proses self nie enige addisionele chemikalieë vereis nie. Relatief tot die roumateriaal vloei, het die SSF die grootse belading op die omgewing geplaas as gevolg van die intensiewe gebruik van verwerkte chemikalieë. Relatief tot die funksionele eenheid, was die SHF die swakste as gevolg van sy lae energie-doeltreffendheid.

Ce travail de thèse porte sur l'extraction et la caractérisation mécanique des fibres de canne à sucre. A partir de la bagasse de canne à sucre, résidu fibreux de l'industrie sucrière, des techniques d'extractions sont mises en place afin d'extraire des fibres techniques, dont l'analyse des propriétés chimiques et physico-mécaniques définira par la suite, les domaines d'application textile possibles. Les fibres de canne obtenues ont d'abord été étudiées d'un point de vue physique et morphologique, à partir de mesures et d'observations de leurs sections et de leurs profils. Ainsi, l'analyse de la distribution en diamètre et en longueur des fibres ont été étudiés avec l'établissement de paramètres de centrage barbe et hauteur (longueur pondérée à la masse), ont permis de déterminer leurs tailles moyennes, leurs finesses et leurs dispersions tout en vérifiant l'effet des conditions de traitement. Ont ainsi été obtenus différents types de fibres, présentant des propriétés mécaniques (en flexion et en traction) variées en relation avec les changements de structure dus à l'extraction. Les performances mécaniques de ces fibres restent comparables aux autres fibres naturelles, confirmant ainsi leur potentiel textile. Une première piste de valorisation de ces fibres a été envisagée lors de la fabrication d'un fil de canne à sucre. Des essais de filature ont ainsi été menés sur micro-filature, en 100% fibres de canne mais aussi en mélange 30-70% coton/bagasse. Enfin, une introduction à l'approche environnementale basée sur l'analyse de cycle de vie, a été succinctement abordée, ouvrant le champ à d'autres études. Les résultats montrent que le potentiel textile de la canne à sucre est quantifiable, et que ses fibres extractibles, sont comparables à d'autres fibres naturelles non conventionnelles utilisés dans le domaine textile.

A produção de biocombustíveis de segunda geração está entre os temas mais pesquisados atualmente. Entre estes, a obtenção de etanol a partir de bagaço de cana-de-açúcar é de grande interesse nacional, considerando-se a abundância desta matéria-prima no país e a possibilidade de incremento na produção deste álcool sem necessidade de expansão da área plantada. Sob o ponto de vista de produção industrial, no entanto, é fundamental o desenvolvimento de trabalhos visando ao estudo de alternativas de processos e biorreatores susceptíveis de ampliação de escala. Estratégias como sacarificação e fermentação/cofermentação simultâneas (SSF/SSCF) têm sido estudadas e têm como vantagens a intensificação do processo pela redução do custo de investimento e minimização de problemas de inibição de enzimas por produtos. No entanto, neste caso, geralmente o uso de condições não otimizadas (temperatura) para cada passo biológico é desvantajoso. Com o objetivo de superar essa desvantagem, avaliou-se o uso de reatores de coluna interconectados para a produção de etanol a partir de bagaço de cana-de-açúcar empregando células de Scheffersomyces shehatae imobilizadas em alginato de cálcio em sistema SSCF. O bagaço foi previamente pré-tratado por processo alcalino e alcalino assistido por cavitação hidrodinâmica. Experimentos em SSCF em batelada foram realizados usando duas colunas interconectadas. Uma delas (para hidrólise) foi mantida a 50ºC e carregada com bagaço pré-tratado e a outra coluna (para fermentação) foi mantida a 30°C e carregada com células imobilizadas. Meio contendo preparação comercial de celulases e nutrientes para o micro-organismo foi recirculado entre as colunas. Os efeitos da vazão de recirculação e carga enzimática foram avaliados usando planejamento estatístico como ferramenta. Dados iniciais de hidrólise enzimática em reator de coluna mostraram elevada taxa de reação no início do processo, com redução desta ao longo da hidrólise devido à recalcitrância crescente do material residual à ação enzimática. Os resultados obtidos no planejamento estatístico mostraram que a carga enzimática foi a variável mais influente no processo, embora a vazão de recirculação e a interação entre as variáveis também tenham apresentado efeitos significativos. As condições selecionadas corresponderam a uma vazão de recirculação de 14 mL/min e carga enzimática de 15 FPU/g e os experimentos nestas condições resultaram em valores de fator de rendimento (Yp/s) de 0,493 g/g, produtividade volumétrica de 0,469 g.L-1.h-1 e eficiência de 96,58%. Além disso, nestas condições, 70,72±1,32 % da celulose presente inicialmente no material e 56,37±0,76 % da hemicelulose foram hidrolisadas. O sistema mostrouse adequado para realização do processo SSCF, com potencial para ser utilizado para intensificação da produção de etanol 2G em biorrefinarias. / Currently, the production of second generation biofuels is one of the most researched topics. Among these, the ethanol obtained from sugarcane bagasse is of great national interest, considering the abundance of this raw material in the country and the possibility of increasing the production of this alcohol without the need of expanding the crop area. From viewpoint of industrial production, however, the development of studies of process alternatives and bioreactors adequate for scale up is fundamental. Strategies as saccharification and simultaneous fermentation/cofermentation (SSF/SSCF) have been studied and have as advantages the intensification of the process by reducing the cost of investment and minimizing problems of inhibition of enzymes by hydrolysis products. However, in this case, generally the use of non-optimized conditions (temperature) for each biological step is disadvantageous. In order to overcome this drawback, the use of interconnected column reactors for the production of ethanol from sugarcane bagasse was evaluated using calcium alginate immobilized cells of Scheffersomyces shehatae in SSCF system. The bagasse was previously pretreated by alkaline and hydrodynamic cavitation-assisted alkaline process. Batch experiments of SSCF were performed using two interconnected columns. One of them (for hydrolysis) was kept at 50 ° C and loaded with pre-treated bagasse and the other column (for fermentation) was kept at 30 ° C and loaded with immobilized cells. Medium containing comercial preparation of cellulases and nutrients for the microorganism was recirculated between the columns. The effects of recirculation flow and enzymatic loading were evaluated using statistical design as a tool. Initial data on enzymatic hydrolysis in a column reactor showed a high reaction rate at the beginning of the process, with a reduction in the hydrolysis rate along the process due to the increasing recalcitrance of the residual material to the enzymatic action. The results obtained in the statistical design showed that enzymatic loading was the most influential variable in the process, although the recirculation flow rate and the interaction between the variables also had significant effects. The selected conditions corresponded to a recirculation flow rate of 14 mL/min and enzyme loading of 15 FPU/g and the experiments carried out under these conditions resulted in yield factor (Yp/s) values of 0.493 g/g, volumetric productivity of 0.469 gL- 1.h-1 and fermentation efficiency of 96.58%. Moreover, under these conditions, 70.72±1.32 % of the cellulose initially present in the material and 56.37±0.76 % of the hemicellulose were hydrolyzed. The system proved to be adequate to perform the SSCF process, with potential to be used to intensify the production of 2G ethanol in biorefineries.

Com o objetivo de avaliar a substituição da FDN do bagaço de cana-de-açúcar in natura (BIN) pela FDN da casca de soja (CS) em dietas com alta proporção de concentrado para cordeiros confinados, foram realizados três experimentos: desempenho animal (Experimento I), digestibilidade dos nutrientes no trato digestivo total (Experimento II) e comportamento ingestivo (Experimento III). O Experimento I consistiu de um arranjo fatorial, onde foram utilizados 60 cordeiros da raça Santa Inês (peso vivo de 16,4 ± 0,3 kg e idade de 67 ± 2 ) dias em um delineamento experimental de blocos casualizados com 5 tratamentos e seis repetições. Os tratamentos utilizados foram: 100C (100% de concentrado), BIN14 (95% de concentrado e 5% de BIN), BIN18 (90% de concentrado e 10% de BIN), CS14 (92% de concentrado e 8% de CS) e CS18 (88% de concentrado e 12% de CS). As dietas foram formuladas para serem isoprotéicas e os teores de BIN e CS ajustados para que os valores de FDN fossem os mesmos entre as dietas BIN14 e CS14 (14%) e entre as dietas BIN18 e CS18 (18%). As dietas contendo CS proporcionaram maior (P=0,07) ganho de peso diário do que as dietas contendo BIN e os cordeiros alimentados com a dieta 100C apresentaram menor (P=0,09) consumo de matéria seca por peso metabóico do que os alimentados com as dietas que continham alguma fonte de fibra (BIN ou CS). Não foi observada diferença (P>0,10) na conversão alimentar. Observou-se uma interação (P<0,07) (Teor x Fonte) para o rendimento de carcaça quente e fria, onde as dietas com 14% FDN apresentaram desempenhos semelhantes, porém, a CS foi superior ao BIN nas dietas contendo 18% FDN. No Experimento II, foram utilizados cinco borregos da raça Santa Inês (35,6 kg PV e com idade de 5,5 meses) em um delineamento em quadrado latino 5 x 5. Os tratamentos utilizados foram os mesmos do Experimento I. As dietas que continham alguma das fontes de fibra promoveram maiores (P<0,05) consumos de matéria seca (MS), matéria orgânica (MO) e da FDN que a dieta 100C. Além disso, foi observado efeito das fontes de fibra sobre o consumo de FDN (P<0,025) e na digestibilidade dos nutrientes (P<0,001), onde a CS promoveu maior digestibilidade da MS, MO e da FDN que o BIN. No Experimento III, foram utilizados os mesmos animais e o mesmo delineamento experimental do Experimento I. As dietas contendo alguma das fontes de fibra promoveram maiores (P<0,05) tempos de ingestão, ruminação e mastigação (minutos/dia e minutos/g de FDN) que a dieta 100C. Ao se comparar as fontes de FDN, verificou-se que o BIN proporcionou maior (P<0,0001) atividade de ruminação que a CS (minutos/dia e minutos/g de FDN). Os teores de FDN interagiram com as fontes nos tempos despendidos para ingestão (P<0,002) e na atividade de mastigação (P<0,03) em minutos/dia e minutos/g de FDN, sendo que o BIN apresentou maiores resultados que a CS em ambos os teores (14 ou 18% FDN). A CS proporcionou melhores ganhos de peso e digestibilidade aparente dos nutrientes do que o BIN, apesar dos resultados indicarem que a FDN da CS possui apenas 14% da efetividade física do BIN. Entretanto, o BIN estimulou a ruminação e mastigação de cordeiros recebendo dietas com alta proporção de concentrado. / Three trials were conduced to evaluate the replacement of sugar cane bagasse (SB) by soybean hulls (SH) as NDF source on lambs fed a high grain feedlot diet. A performance trial (Trial I) with 60 Santa Ines ram lambs (16.4 kg BW and 67 days old), was conduced on a factorial arrangement, in a complete randomized block design, with 5 treatments and six replications. The treatments were: 100C (all concentrate diet), SB14 (95% concentrate and 5% SB), SB18 (90% concentrate and 10% SB), SH14 (92% concentrate and 8% SH) and SH18 (88% concentrate and 12% SH). Diets were isoproteic, and the levels of NDF were adjusted to be 14% (SB14 and SH14) or 18% (SB18 and SH18) for both NDF sources. Animals on SH diets had higher ADG (P=0.07) than animals on SB. 100C diet decreased (P=0.09) dry matter intake (PV 0.75 ) compared to diets containing fiber sources (SB or SH). There was no difference (P>0.10) on feed conversion. An interaction (P<0.07) among NDF source and level was observed for the hot and cold carcasses yields. SH at 18% NDF had higher carcasses yields than SB at the same NDF level. On digestibilty trial (Trial II), five Santa Ines ram lambs (35.6 kg BW and 172 days old), were used in a 5 x 5 Latin square design. Experimental treatments were the same as those used on Trial I. Diets with fiber sources (SH or SB) increased (P<0.05) dry matter (DM), organic matter (OM) and NDF intakes compared to 100C diet. NDF intake (P<0.025) and nutrient digestibilities (P<0.001) were affected by fiber sources, with improved DM, OM and NDF digestibilities for SH treatments compared to SB. During the Trial I a behavioral evaluation (Trial III) was performed. Diets containing fiber sources had an increased (P<0.05) eating, ruminating and chewing times (minutes/day and minutes/g NDF) compared to 100C diet. SB increased (P<0.0001) the rumination activity in relation to SH (minutes/day and minutes/g NDF). There were interactions of NDF levels and sources for time spent feeding (P<0.002) and chewing activities (P<0.03) (minutes/day and minutes/g NDF), where higher for SB in both NDF levels (14 or 18%). SH resulted in higher weight gain and nutrient digestibilities than SB, although, the results indicate that NDF from SH has only 14% of physical effectiveness of SB. However, SB improved rumination and chewing activities when lambs were fed high grain diets.

O mundo se depara atualmente com a perspectiva de um significativo aumento na demanda por etanol combustível. O bagaço de cana está entre os maiores subprodutos agroindustriais no Brasil, sendo uma das alternativas na utilização para a produção do etanol de segunda geração. A degradação do bagaço de cana requer a ação de muitas enzimas diferentes que são reguladas transcripcionalmente. Considerando-se que o custo de celulases e hemicelulases contribuem substancialmente no preço do bioetanol, novos estudos visando o entendimento da eficiência e produtividade de celulases são de grande importância. Para entender como melhorar coquetéis de enzimas que podem hidrolizar o bagaço de cana-de-açúcar pré-tratado, uitlizou-se um experimento de genômica para investigar-se quais genes e vias são transcripcionalmente moduladas durante o crescimento de A. niger em bagaço de cana-de-açúcar explodido. Neste trabalho foram identificados genes que codificam celulases e hemicelulases com aumento da expresão durante o crescimento em bagaço de cana-de-açúcar explodido. Foi também realizada a determinação do acúmulo de mRNA de diversos genes que codificam transportadores para verificar se estes eram induzidos por xilose e por depedência de glicose. Foram identificados 18 genes que corresponde a 58% de celulases preditas em A. niger e 21 genes que correponde a 58% de hemicelulases preditas em A. niger os quias foram altamente expressos durante o crescimento em bagaço de cana-de-açúcar explodido. Foi investigado também o papel central realizado pelas proteínas quinases e fosfatases não essenciais (NPKs e NPPs, respectivamente) quando em presença de celulose como fonte de carbono, no sensoriamento do estado energético e na subsequente via de sinalização no fungo filamentoso modelo Aspergillus nidulans. O estudo com A. nidulans identificou 11 quinases e 7 fosfatases não essências, NPKs e NPPs, respectivamente, envolvidas na produção de celulases e em alguns casos, na produção também de hemicelulases. O envolvimento destas NPKs identificadas na resposta induzida por avicel e na desrepressão foram acessados pela análise do transcriptoma da cepa selvagem e por microscopia de fluorescência através da cepa de fusão CreA::GFP expressa no selvagem e no background dos mutantes de NPKs. A ausência das quinases snfA e schA reduziu dramaticamente a resposta transcricional induzida por celulose incluindo a expressão de enzimas hidrolíticas e transportadores, enquanto que a ausência de snfA resultou em uma quase completa modulação gênica induzida por celulose. O mecanismo pelo qual essas duas quinases controlam a transcrição gênica foi identificado, onde os dois mutantes de quinases foram capazes de desbloquear o CreA mediante a repressão catabólica do carbono (CCR), sob condições de desrepressão, como em baixa presença de carbono ou crescimento em celulose. Desta forma, este trabalho abriu novas possibilidades para o entendimento da sacarificação do bagaço de cana-de-açúcar por hidrolases de A. niger e para a construção de coquetéis de enzimas mais eficientes para a obtenção do etanol de segunda geração. Também possibilitou a identificação de muitas quinases e fosfatases envolvidas no sensoriamento do carbono e do estado energético, as quais demonstraram papéis sobrespostos e distintos de snfA e schA na regulação da desrepressão de CreA e na produção de enzimas hidrolíticas em A. nidulans. / The world today is faced with the prospect of a significant increase in demand for fuel ethanol. Sugarcane bagasse is among the largest agro-industrial by-products in Brazil, one of the alternatives in use for the production of second generation ethanol. Degradation of sugarcane bagasse requires the action of many different enzymes which are transcriptionally regulated. Considering that the costs of cellulases and hemicellulases contribute substantially to the price of bioethanol, new studies aimed at understanding and improving cellulase efficiency and productivity are of paramount importance. To understand how to improve enzymatic cocktails that can hydrolyze pretreated sugarcane bagasse, we used a genomics approach to investigate which genes and pathways are transcriptionally modulated during growth of A. niger on steam-exploded sugarcane bagasse. We also sought to determine whether the mRNA accumulation of several steam-exploded sugarcane bagasseinduced genes encoding putative transporters is induced by xylose and dependent on glucose. We identified 18 genes that corresponds to 58% of A. niger predicted cellulases and 21 genes that correspond to 58% of A. niger predicted hemicellulases, that were highly expressed during growth on sugarcane bagasse. The central role performed by nonessential protein kinases (NPK) and phosphatases (NPP) when grown on cellulose as a sole carbon source, in the sensing energetic status and the subsequent signalling pathways was assessed in the model filamentous fungus Aspergillus nidulans. This study identified multiple kinases and phosphatases (NPKs and NPPs, respectively) involved in the sensing of carbon or energetic status, while demonstrating the overlapping and distinct roles of snfA and schA in the regulation of CreA derepression and hydrolytic enzyme production in A.nidulans. The involvement of the identified NPKs in avicel-induced responses and CreA derepression was assessed by genome-wide transcriptomics and fluorescent microscopy of a CreA::GFP fusion proteinexpressed in the wild-type and NPK-deficient mutant backgrounds. The absence of either the schA or snfA kinase dramatically reduced cellulose-induced transcriptional responses including the expression of hydrolytic enzymes and transporters, while the absence snfA resulted in a near complete loss of wild-typecellulose-induced gene modulation. The mechanism by which these two NPKs controlled gene transcription was identified, as neither of NPK-deficient mutants were able to unlock CreA-mediated carbon catabolite repression, under derepressing conditions, such as carbon starvation or growth on cellulose. Our presently reported work opens new possibilities for understanding sugarcane biomass saccharification by A. niger hydrolases and for the construction of more efficient enzymatic cocktails for second-generation bioethanol. This work also enable the identification of multiple kinases and phosphatases involved in the sensing of carbon or energetic status, while demonstrating the overlapping and distinct roles of snfA and schA in the regulation of CreA derepression and hydrolytic enzyme production in A.nidulans.

Estudos in situ comumente são conduzidos com pequeno número de animais, existindo poucos trabalhos enfocando o impacto da variabilidade animal sobre seus resultados. O objetivo deste estudo foi explorar o efeito da variabilidade animal sobre as taxas fracionais de degradação (kd) de MS, FDN, FDA e CEL de forragens. Foi conduzido experimento utilizando trinta novilhos Nelore portadores de cânula ruminal (372 ± 16,02 kg P.V.). Dieta 1, todos os animais receberam dieta contendo 100% feno de Coast-cross + sal mineral, ambos ad libitum. Na Dieta 2, todos os animais receberam dieta com 88% de bagaço de cana in natura, 8% de farelo de soja, 2,8% de premix mineral e 1,2% de uréia. Em ambos os períodos foram incubadas amostras de feno de Coast-cross (Fc) (7,31% PB; 78,24% FDN; 40,92% FDA), bagaço de cana-de-açuçar (BAG) (3,04% PB; 90,31% FDN; 69,36% FDA) e feno Tifton-85 (Ft) (13,32% PB; 73,27% FDN; 39,29% FDA) em sacos de poliamida (10 cm x 20 cm; 30 ± 10 &mu;m porosidade) nos tempos 0, 12, 24, 48, 72 e 144 h. Os sacos foram suspensos no saco ventral do rúmen em ordem reversa e removidos simultaneamente no tempo zero. Os teores de MS, FDN, FDA e lignina nos resíduos foram determinados por química líquida e a CEL foi calculada por subtração do teor de lignina da fração do FDA. A cinética de degradação ruminal de MS, FDN, FDA e CEL foram calculadas de acordo com o modelo não linear Y(t) = a + b (1 - e(-kd × t) ); onde t >= 0. As atividades de comportamento ingestivo (ingestão, ruminação, ingestão de água e ócio) foram registradas em intervalos de 10 minutos durante 24 horas. Análise de Componentes Principais foi utilizada para determinar a correlação entre substratos; Análise Fatorial para caracterizar a população de animais (P<0,05); Análise de Agrupamento e Contrastes Multivariados para compor grupos dentro da população (P<0,01) e Análise de Correlação Canônica para determinar correlação entre kd e comportamento ingestivo (P<0,01). Simulação entre número de animais e coeficiente de variação (CV) foi realizada na tentativa de estimar a quantidade adequada de repetições para estes estudos. As médias de kd para MS, FDN, FDA e CEL foram: 3,26; 3,29; 3,44 e 3,54 para Fc; 3,74; 3,88; 4,07 e 4,49 para Ft; e 2,67; 2,68; 2,58 e 2,65 para BAG respectivamente. Foram compostos três níveis de kd para Fc e Ft (alto, médio e baixo) e quatro para BAG (alto, médio alto, médio baixo e baixo). O CV é adequado para mensuração da precisão do ensaio, sendo mais indicado o índice de variação (IV). Em ambas as fases, para todos os substratos, não houve correlação entre kd e comportamento ingestivo. As diferentes correlações de kd entre substratos para as duas fases, demonstra a influência da dieta ofertada sobre o kd. O estudo da variabilidade e o IV indicam que o número de animais é dependente do substrato avaliado, porém o estudo da variabilidade demonstra que os indivíduos que compõe este número são distintos entre dietas. / In situ studies are general carried out with a few number of animals and there are few trials that inquire the impact of animal variability on these results. The aim of this study was to investigate the effect of animal population variability on fractional disappearance rate (kd) of DM, NDF, ADF and cellulose (CEL). Experiment using thirty ruminally canullated Nellore bulls (372 ± 16.02 kg BW) was carried over. In phase 1, all animals received 100% Coast-cross hay with mineral mix ad libitum. In period 2, all animals received a diet containing 88% sugarcane bagasse, 8% soybean meal, 2.8% mineral mix and 1.2% urea (DM basis). In both trials, representative samples of Coast-cross hay (CCH - 7.31% CP, 78.24% NDF, 40.92% ADF), sugarcane bagasse (BAG - 3.04% CP, 90.31% NDF, 69.36% ADF) and Tifton-85 hay (TH - 13.32% CP, 73.27% NDF, 39.29% ADF) were incubated in polyamide-bags (10 cm × 20 cm; 30 ± 10 &mu;m pore size) for 0, 12, 24, 48, 72, and 144 h. Bags were suspended in the rumen ventral sac before at feeding in reverse order and removed simultaneously at time zero. Residual DM, NDF, ADF, and lignin were determined by wet chemistry. Cellulose (CEL) was calculated as ADF minus lignin. Ruminal degradation kinetics of DM, NDF, ADF, and CEL were calculated using a nonlinear model Y(t) = a + b (1 - e(-kd × t) ); where t >= 0. Feeding behavior parameters (eating, ruminating, water drinking and idling) were recorded every 10 minutes during 24 h. Principal component analysis was used to determine correlation of variables among substrates. Factorial Analysis was used to characterize animal population (P<0.05), Cluster with Multivariate Contrasts (P<0.01) to analyze differences in kd groups and Multivariate Canonical correlation analysis (P<0.05) to correlate kd with feeding behavior parameters. A simulation with number of animals was done against coefficient of variation (CV) to determinate optimum number of animals in an in situ assay. The kd (average) of DM, NDF, ADF, and CEL were: 3.26, 3.29, 3.44 and 3.54 for CCH; 3.74, 3.88, 4.07 and 4.49 for TH; and 2.67, 2.68, 2.58 and 2.65 for BAG, respectively. There was no correlation among substrates in both periods. Were found three groups of kd for CCH and TH (high, medium and low) and four groups for BAG (high, medium-high, medium, and low). CV is not adequate to measure experimental precision, instead it, variation index is indicated (VI). In both incubations phases, there was no relationship between feeding behavior and kd, for all incubated forages sources. The kd correlations among substrates between two incubation phases were different, indicating influence of the diet on kd. Variability investigation and VI parameter indicate that the number of animals necessary in these trials is affected by the substrate incubated. However, the variability investigation suggests that probably different animals compose this number.