Hydrogenation of nitrile butadiene rubber (NBR) has been carried out industrially for a number of years, producing a material with exceptional resilience to high temperatures and oxidative conditions. Current processes involve a batch reactor which is difficult to optimize further for larger scale production. A continuous process for this particular process is required in order to provide a large volume of production with consistent qualities. The integration of heat balance could be realized in a continuous process. A novel continuous process for hydrogenation of NBR has been developed in the present work. A multistage agitated contactor (MAC) was proposed as a gas liquid reactor for this process. Comprehensive hydrodynamic data have been acquired under various process conditions. The hydrodynamic behaviour under different operating variables such as stirring speed, liquid flow rate and gas flow rate has been understood through experimental study. It is found that an increase in stirring speed intensifies liquid backmixing while an increase liquid flow rate decreases liquid backmixing. The presence of gas flow helps in reducing liquid back mixing by two coupled effects: liquid entrainment effect due to a cocurrent operation manner and a strengthening effect of liquid flow rate due to its reduction of liquid hold-up. Contradictory conclusions regarding the effect of liquid viscosity on liquid backmixing in a MAC have been resolved through experimental investigation and computational fluid dynamics (CFD) simulations. It is shown that an increase in liquid velocity dampens turbulence which contributes to liquid phase backmixing within the reactor. The established hydrodynamic understanding of MACs in the present work widens its potential application for gas liquid process. Based on comprehensive understanding of the proposed reactor, a bench-scale prototype was designed and constructed in order to demonstrate hydrogenation performance. One more efficient catalyst for NBR hydrogenation, an osmium-based catalyst, was used in the present work. Hydrogenation degree of NBR in the continuous unit was investigated at operating conditions relevant to industrial applications. It is indicated from the experimental results that a desired hydrogenation degree of over 95% in 2.5% and 5% NBR solutions can be achieved at the conditions investigated. It is also shown that both system pressure and catalyst loading increase hydrogenation conversion. Mathematical modeling of the designed process was established by coupling the intrinsic catalytic hydrogenation from batch studies and flow behavior of the reactor. A cascade of stirred tanks with back flow (CTB) model was used to characterize the dynamic hydrogenation performance in a MAC. The comparison of experimental results and numerical prediction indicates that the established model could satisfactorily predict the hydrogenation in the designed process with consideration of approximately 30%-50% catalyst deactivated due to impurities and oxygen contamination in the polymer solution. A revised n CSTRs-in-series model was proposed to predict the hydrogenation degree at steady state and a good agreement was found when comparing the predicted results with the experimental data. A continuous process for hydrogenation at a pilot scale was designed based on the primary results from the bench scale process. A process with a capacity of 50 tons/year was targeted and the hydrogenation efficiency provided by the pilot scale unit has been estimated through the established reactor model.

Hydrogenated nitrile butadiene rubber (HNBR) which is known for its excellent elastomeric properties and mechanical retention properties after long time exposure to heat, oil and air is produced by the catalytic hydrogenation of nitrile butadiene rubber (NBR). Hydrogenation of NBR is carried out preferably in solution via homogeneous catalysis. As yet, it is being commercially produced in a semi-batch process where gaseous hydrogen continuously flows into a batch of reactant polymer. Several catalysts have been exploited successfully for the hydrogenation of NBR in organic solvents, which include palladium, rhodium, ruthenium, iridium and osmium complexes. Owing to the drawbacks of batch production (such as time taken for charging and discharging the reactants/products, heating and cooling, reactor clean up), and the huge demand for HNBR, a continuous process is proposed where potential time saving is possible in addition to the high turn over of the product. Numerical investigation of the HNBR production in a plug flow reactor and a continuous stirred tank reactor showed that a reactor with plug flow behavior would be economical and efficient. A static mixer (SM) reactor with open-curve blade internal geometry is designed based on the simulation and hydrodynamic results. The SM reactor was designed with 24 mixing elements, 3.81 cm ID and 90 cm length. The reactor has a jacket in which steam is used to heat the polymer solution. The hydrodynamics in the SM reactor (open-flat blade structure) with air-water system showed that plug flow could be achieved even under laminar flow conditions (Reh < 20). For a constant mean residence time, the Peclet number was varying such that it is 4.7 times the number of mixing elements (ne) used in the SM reactor. Empirical correlations were developed for gas hold up (εG) and overall mass transfer coefficient (KLa). The mass transfer experiments showed that high KLa, 4 to 6 times compared to that of the conventional reactors could be achieved in the SM reactor at particular operating conditions. Very important information on the Peclet number, liquid hold were obtained from the hydrodynamic experiments conducted with the actual working fluids (hydrogen, polymer solutions) in the SM reactor. The superficial gas velocity had an adverse effect on both Peclet number and liquid hold up. The viscosity of the polymer solution also had a marginal negative effect on the Peclet number while a positive effect on the liquid hold up. The hydrogenation performance with the homogeneous catalyst OsHCl(CO)(O2)(PCy3)2 was performed in the continuous process with SM reactor. Complete hydrogenation of NBR was possible in a single pass. The effect of mean residence time, catalyst and polymer concentration on the final degree of hydrogenation was studied. The minimum catalyst required to achieve degree of hydrogenation over 97% was empirically found and an empirical correlation was developed for degree of hydrogenation as a function of operating conditions and parameters. Hydrogenation in the SM reactor is modeled by using plug flow with axial dispersion model that is coupled with the concentrations of carbon-carbon double bond, hydrogen and osmium catalyst. The model involves coupled, non-linear partial differential equations with different dimensionless parameters. The proposed model was verified with the experimental results obtained from the hydrogenation and hydrodynamic experiments. The model could satisfactorily predict the degree of hydrogenation obtained from experimental results at various operating conditions. In general, the designed continuous process with SM reactor performed well and was an effective method of manufacturing HNBR on a continuous basis. The designed system is amicable to the industrial operating conditions and promises to be highly efficient and economic process for production of HNBR.

Hydrogenated nitrile butadiene rubber (HNBR) which is known for its excellent elastomeric properties and mechanical retention properties after long time exposure to heat, oil and air is produced by the catalytic hydrogenation of nitrile butadiene rubber (NBR). Hydrogenation of NBR is carried out preferably in solution via homogeneous catalysis. As yet, it is being commercially produced in a semi-batch process where gaseous hydrogen continuously flows into a batch of reactant polymer. Several catalysts have been exploited successfully for the hydrogenation of NBR in organic solvents, which include palladium, rhodium, ruthenium, iridium and osmium complexes. Owing to the drawbacks of batch production (such as time taken for charging and discharging the reactants/products, heating and cooling, reactor clean up), and the huge demand for HNBR, a continuous process is proposed where potential time saving is possible in addition to the high turn over of the product. Numerical investigation of the HNBR production in a plug flow reactor and a continuous stirred tank reactor showed that a reactor with plug flow behavior would be economical and efficient. A static mixer (SM) reactor with open-curve blade internal geometry is designed based on the simulation and hydrodynamic results. The SM reactor was designed with 24 mixing elements, 3.81 cm ID and 90 cm length. The reactor has a jacket in which steam is used to heat the polymer solution. The hydrodynamics in the SM reactor (open-flat blade structure) with air-water system showed that plug flow could be achieved even under laminar flow conditions (Reh < 20). For a constant mean residence time, the Peclet number was varying such that it is 4.7 times the number of mixing elements (ne) used in the SM reactor. Empirical correlations were developed for gas hold up (εG) and overall mass transfer coefficient (KLa). The mass transfer experiments showed that high KLa, 4 to 6 times compared to that of the conventional reactors could be achieved in the SM reactor at particular operating conditions. Very important information on the Peclet number, liquid hold were obtained from the hydrodynamic experiments conducted with the actual working fluids (hydrogen, polymer solutions) in the SM reactor. The superficial gas velocity had an adverse effect on both Peclet number and liquid hold up. The viscosity of the polymer solution also had a marginal negative effect on the Peclet number while a positive effect on the liquid hold up. The hydrogenation performance with the homogeneous catalyst OsHCl(CO)(O2)(PCy3)2 was performed in the continuous process with SM reactor. Complete hydrogenation of NBR was possible in a single pass. The effect of mean residence time, catalyst and polymer concentration on the final degree of hydrogenation was studied. The minimum catalyst required to achieve degree of hydrogenation over 97% was empirically found and an empirical correlation was developed for degree of hydrogenation as a function of operating conditions and parameters. Hydrogenation in the SM reactor is modeled by using plug flow with axial dispersion model that is coupled with the concentrations of carbon-carbon double bond, hydrogen and osmium catalyst. The model involves coupled, non-linear partial differential equations with different dimensionless parameters. The proposed model was verified with the experimental results obtained from the hydrogenation and hydrodynamic experiments. The model could satisfactorily predict the degree of hydrogenation obtained from experimental results at various operating conditions. In general, the designed continuous process with SM reactor performed well and was an effective method of manufacturing HNBR on a continuous basis. The designed system is amicable to the industrial operating conditions and promises to be highly efficient and economic process for production of HNBR.

No description available.

O presente trabalho teve como objetivo o aproveitamento da matéria-prima residual óleo fúsel como fonte de baixo custo de álcool isoamílico para a síntese de ésteres com diferentes propriedades pela rota enzimática. Utilizou-se como proposta a esterificação do óleo fúsel com ácidos carboxílicos de diferentes tamanhos de cadeia carbônica mediada pela enzima lipase em processos descontínuo ou contínuo, visando obter produtos com propriedades aromáticas, emulsificantes e lubrificantes. A lipase selecionada de Rhizopus oryzae foi posteriormente imobilizada em diferentes suportes sílica-&beta;-ciclodextrina (SiO2- &beta;CD), sílica-hidroxietilcelulose (SiO2-HEC) ou co-polímero de estireno de divinilbenzeno (STY-DVB) e utilizada como biocatalisador para mediar as reações de esterificação do óleo fusel com os ácidos caprílico, láurico e oleico. Entre os suportes testados, apenas a sílica-hidroxietilcelulose (SiO2-HEC) apresentou resultados insatisfatórios em função da elevada afinidade desta matriz em adsorver a água formada como subproduto na reação de esterificação. Para cada par de óleo fúsel e ácido carboxílico, as condições adequadas para obtenção dos produtos alvos foram estabelecidas e os produtos resultantes analisados de acordo com a finalidade proposta. No caso do caprilato de isoamila, as condições reacionais foram determinadas por planejamento experimental, indicando que a formação do éster foi influenciada somente pela variável razão molar ao nível de 95% de confiança. O modelo matemático proposto permitiu prever as condições que favorecem o alcance de elevados rendimentos de formação do éster, sendo a reação maximizada (82% em 24 h) para meios reacionais constituídos de óleo fúsel e ácido caprílico na razão molar de 1:1,5 e temperatura de 45 ºC. O perfil sensorial do éster foi confirmado com auxílio do nariz eletrônico. Com relação ao laurato de isoamila foi possível estabelecer o processo em regime continuo utilizando a lipase de Rhizopus oryzae imobilizada em STY-DVB operando o sistema com concentrações elevadas do substrato que forneceu produtividades elevadas (1598,68 ± 135,79 &mu;mol g-1 min-1) do éster com excelente capacidade de dispersão de pigmentos que pode ser utilizado na formulação de cosméticos com rotulagem de produto natural. Finalmente, com relação ao éster oleato de isoamila, foi constatado limitado desempenho da lipase Rhizopus oryzae imobilizada em STY-DVB devido baixa atividade sintética deste biocatalisador para ácidos carboxílicos insaturados. Mesmo assim, foi possível obter produtividades volumétricas da ordem de 286, 20 ± 18,46 &mu;mol g-1 min-1, utilizando uma configuração de reator de leito empacotado em dois estágios acoplado a uma coluna extratora de água. As propriedades do produto formado atenderam as especificações recomendas para uso como biolubrificante. Desta forma, o presente projeto de tese demonstrou a potencialidade da aplicação do óleo fusel como fonte de baixo custo do álcool isoamílico na obtenção ésteres com propriedades adequadas para uso como aroma, emulsificante e lubrificante. O aproveitamento deste resíduo não somente retira um composto indesejado do meio ambiente, mas também permite a geração de diferentes produtos de interesse industrial, constituindo-se, assim, em um forte apelo ambiental. / The aim of the present work was to investigate the feasibility of using fusel oil as a source of low cost feedstock based on isoamyl alcohol for the synthesis of esters with different properties by enzymatic route. For this, it was proposed to perform the esterification reaction of fusel oil with carboxylic acids with different sizes of carbonic chain mediated by the enzyme lipase under batch or continuous runs, in order to obtain products with aromatic, emulsifying and lubricant properties. Rhizopus oryzae lipase immobilized on different supports silica-&beta;-cyclodextrin (SiO2-&beta;CD), silica-hydroxyethylcellulose (SiO2- HEC) or co-polymer of styrene divinylbenzene (STY-DVB) were chosen as biocatalysts to mediate the esterification reactions of fusel oil with caprylic, lauric and oleic acids. Among the supports tested, only the silica hydroxyethylcellulose (SiO2-HEC) provided unsatisfactory results due to its high affinity to adsorb the water generated as byproduct. For each pair of fusel oil and carboxylic acid, appropriate conditions for obtaining the target product were established, and the resulting product further analyzed according to its proposed use. In the case of isoamyl caprylate, reaction conditions were determined by factorial design, indicating that the ester formation was influenced only by the molar ratio at 95% of confidence level. The proposed mathematical model allowed predicting the conditions that favor the achievement of high yields of ester formation, being maximized (82% in 24 h) with substrate consisting of fusel oil and caprylic acid at molar ratio of 1:1.5 and temperature of 45°C. The sensory profile of the ester was confirmed with help of the electronic nose. With respect to isoamyl laurate it was possible to establish a stable process under continuous flow using Rhizopus oryzae lipase immobilized on STY-DVB feeding the reactor with high substrate concentrations, providing high ester productivity (1598.68 ± 135.79 g-1 &mu;mol min-1) with excellent dispensability of pigments that can be used in cosmetic formulation label as natural product. Finally, with regards to the isoamyl oleate, the performance of Rhizopus oryzae lipase immobilized on STY-DVB was limited due to its low activity towards unsaturated carboxylic acids. Still, it was possible to obtain volumetric productivity of about 286. 20 ± 18.46 &mu;mol g-1 min-1 using two-stage packed bed reactor coupled with a water column extraction. The properties of the formed product meet the specifications recommend for use as biolubricant. In this way, this work demonstrated the feasibility of applying the fusel oil as a source of low-cost isoamyl alcohol to obtain esters with appropriate properties for use as flavor, emulsifier or lubricant. The use of this waste material not only removes unwanted compounds from the environment, but also allows the generation of different products of industrial interest, thus having a strong environmental appeal.

Ce sujet de thèse fait partie d’un projet européen visant à développer l’utilisation de la lumière solaire pour créer des produits à haute valeur ajoutée en utilisant la photochimie catalytique. Dans ce contexte, la synthèse de nanophotocatalyseurs est essentielle car les caractéristiques des nanomatériaux doit être maîtrisées pour optimiser l'efficacité de la réaction. Les méthodes de synthèses utilisant les fluides supercritiques (haute pression / haute température) se sont révélés être des procédés de choix pour de tels développements. Combinés à l’utilisation de microréacteurs, il est alors possible d’accéder à un contrôle fin des propriétés du matériau, notamment celles de surface. Les objectifs de ce projet sont de (i) développer des procédés de synthèse permettant de concevoir de nouveaux nanophotocatalyseurs basés sur l’oxyde de titane et des nanoparticules de semi-conducteurs de nitrures, en particulier GaN/TiO2 et GaxIn1-xN/TiO2, (ii) de tester l’efficacité photocatalytique de ces matériaux sur plusieurs réactions photochimiques modèles (oxydation des thiols, trifluorométhylation, conversion des amines en imines), à la fois en réacteur fermé et en réacteurs photochimiques sous flux et (iii) d’étudier les options de changement d’échelle pour améliorer les taux de production de ces nanophotocatalyseurs. / This PhD thesis is part of a larger European ITN project (Photo4Future) dealing with improvement of the use of sun light for making valuable products through new heterogeneous catalytic photochemical processes. In this context, the synthesis of nanophotocatalysts is essential since their characteristics must be controlled to optimize the process efficiency towards the desired products. Supercritical fluids synthesis approaches (high pressure / high temperature) have proven to be promising for such developments. Combined to microreactors, it is then possible to reach a precise control of material properties, including surfaces. The objectives of this project are (i) to develop synthetic methods for designing new nanophotocatalysts based on titania and nitrides quantum dots, in particular GaN/TiO2 and GaxIn1-xN/TiO2, (ii) to test their photocatalytics efficiency on several model photochemical reactions (oxidation of thiols, trifluoromethylation and amine to imine conversion), both in batch mode and using continuous flow photochemical reactors and (iii) to investigate the scale-up options for increasing the production rates of such nanophotocatalysts.

Apesar do crescimento nas exportações de açúcar, a conjuntura atual do setor sucroalcooleiro e a instabilidade do mercado externo têm feito com que as usinas busquem mais competitividade. A Tecnologia da Informação (TI) tem participação nesta busca, visto que, hoje, é impossível uma empresa apresentar um gerenciamento integrado eficaz sem a utilização de sistemas informatizados. Alguns desses sistemas, os ERP, têm se desenvolvido muito nos últimos anos, chegando, por exemplo, a ponto de possuírem módulos específicos para determinados tipos de empresas. Um dos desenvolvedores desses sistemas criou módulos específicos para o Planejamento e Controle da Produção (PCP) em indústrias de processo contínuo. Os conceitos envolvidos em tais módulos são apresentados nesta dissertação e comparados com os módulos tradicionais de Planejamento e Controle de Produção. Depois do embasamento conceitual, e da apresentação dos processos industriais de uma determinada usina de açúcar e álcool, é desenvolvida a configuração de tais módulo, para análise da compatibilidade desses ao processo produtivo da usina. / In spite of the growth in the sugar exports, the current situation of the sector responsible for the production of sugar and alcohol, as well as the instability of the external market, responsible for the fact that sugar and alcohol mills are looking for an increase competitiveness. The Information Technology (IT) has a great degree of participation in this search for competitiveness, because it is impossible for a company to introduce an effective integrated management network without the utilization of computerized systems. Some of these systems, called Enterprise Resources Planning, have developed remarkably in the last years, reaching, for instance, the point of having their own specific modules for certain industry types. One of the developers of these systems developed specific modules for the production planning and control in industries of continuous process. The concepts involved in such modules are introduced in this dissertation, and compared with the traditional modules of production planning and control. Basic concepts are introduced at first, then the industrial processes of a plant are explained, and the modeling of such company is presented for the analysis of the compatibility of the modules to the productive process of the plant.

Este trabalho mostra uma aplicação de conceitos de produção enxuta em uma empresa de processo contínuo. Existe uma percepção por parte de algumas destas empresas de que, sendo de fluxo contínuo, elas se adequam mais aos princípios da produção em massa, não sendo portanto aplicáveis a elas os conceitos de produção enxuta. Também existe a crença, igualmente questionável, de que elas já são enxutas por natureza, devido ao elevado nível de automação com pouca manipulação e movimentações discretas. Este trabalho mostra que isso nem sempre é verdade e que uma empresa de processo contínuo pode se beneficiar consideravelmente da aplicação de conceitos de manufatura enxuta. É apresentada aqui uma revisão bibliográfica das principais ferramentas e conceitos de produção enxuta. Também é apresentado um caso já documentado na literatura técnica de aplicação destes conceitos em uma empresa química de processo contínuo. A seguir é mostrado o caso de aplicação de produção enxuta conduzida pelo autor em uma empresa de grande porte do setor termoplástico no estado de São Paulo, que tem características de processo contínuo. São também apresentados os resultados desta aplicação, evidenciando os ganhos obtidos como redução de 21% no indicador de refugo e 14% no tempo médio de set up, e algumas considerações sobre aplicação de produção enxuta em empresas desta natureza. / This paper shows a application of the concepts of lean production in a continuous process company. There is a misconception from some companies\' part that because they have continuous process, they fit more the mass production principles, therefore it is not valid to them the concept of lean production. There is also the belief, questionable as well, that they are naturally lean, due to the high level of automation with little handling and discret movements. This paper shows that this is not true and that continuous process company can benefit considerably from the application of the lean production concepts. It is presented here a bibliography review of the main tools and concepts of lean production. It is also presented a documented case of the application of these concepts in a chemical industry with continuous process. Next, the case of the application of lean production is showed, conducted by the author in a big company of termoplastic in the state of São Paulo that presents the characteristics of continuous process. The results of this application is presented, enfasizing the results obtained, it was obtained 21% of reduction in the screp indicator and 14% in the midium time of the set up and also some comments about the application of the lean production in these kinds of companies.

O objetivo deste trabalho foi desenvolver um processo efetivo de síntese enzimática de biodiesel em reator de leito fixo, conectados em série, a partir de óleos vegetais operando em modo contínuo. Para o desenvolvimento do projeto, foram selecionados óleos vegetais de baixo impacto na cadeia alimentícia, tais como óleos de babaçu, macaúba e coco que apresentam composição predominantemente láurica (35-47%). A enzima selecionada para condução dos experimentos foi a lipase microbiana de Burkholderia cepacia imobilizada covalentemente em matriz híbrida sílica-PVA com comprovada eficiência na síntese de biodiesel a partir de diferentes matérias-primas lipídicas. Todos os experimentos foram efetuados na ausência de solventes a 50?C utilizando etanol como doador do grupo acila. Foram testados reatores de leito fixo (um estágio) e em série (dois estágios). A etapa inicial do trabalho consistiu em testes de desempenho do reator (um estágio) verificando a influência das propriedades dos óleos vegetais no rendimento do processo e atividade do biocatalisador. Apesar do biocatalisador ter apresentado elevado tempo de meia- vida > 373 h, nas condições testadas, independente do óleo usado a concentração máxima de ésteres esperada não foi alcançada (68,2%) limitando os rendimentos para valores máximos de 87,5%. Para contornar as restrições identificadas foi adotada uma configuração de reator de leito fixo dois estágios incorporando uma coluna recheada com resina catiônica (Lewatit GF 202) para adsorção do glicerol formado como subproduto. O desempenho do reator foi avaliado para substratos constituídos de óleos láuricos na razão molar óleo: etanol de 1:12, definindo os limites de operação em termos de vazão do substrato. Foi quantificado o desempenho do sistema para 4 diferentes vazões volumétricas correspondendo a tempos espaciais entre 7 a 17h e determinadas para cada condição a influência do tempo espacial na concentração de ésteres de etila formados, rendimentos de transesterificação e produtividade. O funcionamento do sistema foi comprovado quantitativamente para tempos espaciais no reator de 14h, fornecendo rendimentos de transesterificação médios de 95,9 ± 4,1% e valores médios de produtividade de 41,5 ± 1,5 mg.g-1.h-1. As amostras de biodiesel purificadas apresentaram viscosidade cinemática média de 5,5 ± 0,3 mm2.s-1, valor que atende a norma americana ASTM (D6751) e a brasileira pela resolução ANP n°14/2012. A lipase imobilizada em SiO2-PVA foi estável quanto à suas características morfológicas e catalíticas revelando tempo médio de meia-vida (t1/2) superior a 500 h. O emprego da configuração de reatores de leito fixo (PBR) em duplo estágio pode elevar os níveis de rendimento de transesterificação, aumentar a produtividade de biodiesel, por consequência reduzir o custo global do processo. As características globais do desempenho do sistema contínuo proposto torna atrativa a continuidade dos estudos em escala ampliada de processo. / The aim of this study was to develop an effective enzymatic continuous process to obtain biodiesel from vegetable oils in two-stage packed bed reactors. For this, non- edible vegetable oils (babassu, macaw palm and coconut) having predominant lauric acid (35-47%) composition were assessed. The selected enzyme was the microbial lipase from Burkholderia cepacia covalent immobilized on hybrid matrix silica-PVA (SiO2-PVA) which showed already satisfactory performance in the biodiesel synthesis from different lipid feedstocks. All experiments were carried out in solvent free system at 50°C using ethanol as acyl acceptor. Packed bed reactors (simple and two-stages) were tested. Preliminary work was focused on the determination of the influence of the properties of the vegetable oils on the process yield and biocatalyst activity using simple packed bed reactor. Under the conditions used, the biocatalyst was found to have high half-life time > 373 h and independent of the used oil the maximum concentration expected esters was not reached (68.2%) limiting the maximum yield to 87.5%. To overcome such constraints a two-stage packed bed reactor incorporating a column with cationic resins (Lewatit GF 202) to remove the glycerol formed as by-product was proposed. The reactor performance was evaluated for substrates consisting of lauric oils at molar ratio of oil-to-ethanol of 1:12, determining its operation limits in terms of substrate flow rate. The system performance was quantified for four different flow rates corresponded to spatial times from 7 to 17 h. For each condition, the influence of spatial times in the ethyl esters formation, transesterification yields and productivities were determined. The reactor operation was demonstrated for spatial time of 14 h, attaining transesterification yields of 95.9 ? 4.1% and productivities of 41.5 ? 1.5 mg.g-1.h-1.The immobilized lipase on SiO2-PVA was found to be stable regarding its morphological and catalytic characteristics, showing half-life time (t1/2) higher than 500 h. Biodiesel purified samples showed average kinematic viscosity of 5.5 ± 0.3 mm2.s-1, value that meets the criteria established by the American National Standard ASTM (D6751) and Brazilian ANP resolution No. 14/2012. Therefore, the continuous packed-bed reactor connected in series and glycerol separation system has a great potential for achieving high level of transesterification yields, raising biodiesel productivity, consequently decreasing industrial process cost. The performance characteristics of the proposed continuous system made attractive to develop further studies aiming at scaling up the process.

The purpose of the experiment was to investigate the effect of fruit flavor compounds on biogas production from fruit wastes. The flavor compounds from different fruits were selected and synthetic medium was used throughout the experiment. The experiment was carried out both in batch and continuous process using thermophilic inoculums obtained from Söbacken waste management plant. The inhibitors were added at three different concentrations 0.05g/L, 0.5g/L and 5g/L respectively and were carried out in triplicates for batch cultivation.The result from batch cultivation showed that hexanal, (E)-2-hexanal, myrcene and octanol showed inhibitory activity. Hexanal, (E)-2-hexanal, myrcene, and octanol decreased biogas production by factor of 316.8%, 434.22%, 329.68% and 433.61% at concentration of 5g/L. Continuous experiment was carried out on Automatic Methane Potential Test System AMPTS II. Eight reactors, each with inhibitor compounds were used with a retention time of 30 days and an organic loading rate of 3g VS/day. The inhibitor concentration was increased from 0.5g/L to 5g/L and for some compounds up to 10g/L. During cultivation, several factors were measured periodically such as pH, total biogas production, biogas composition, FOS/TAC and VFA.The inhibitory effect was clearly shown at concentration higher than 0.5g/L. Addition of 5g/L hexanal, nonanal, (E)-2-hexanal, α-pinene , car-3-ene, myrcene and octanol resulted in reduction of biogas production by 81.2%, 4.67%, 50.74%, 7.06%, 24.01%, 31.84% and 52.85% respectively. When compared to batch process, continuous process required higher concentration of flavor compounds to reduce biogas production. This might be due to adaptation of cells towards toxic compounds during continuous process. / Program: Master of Science with a major in Resource Recovery-Industrial Biotechnology