Enzyme-catalyzed biofuel cells would be a great alternative to current battery technology, as they are clean, safe, and capable of using diverse and abundant renewable biomass with high energy densities, at mild reaction conditions. However, currently, three largest technical challenges for emerging enzymatic fuel cell technologies are incomplete oxidation of most fuels, limited power output, and short lifetime of the cell. Synthetic pathway biotransformation is a technology of assembling a number of enzymes coenzymes for producing low-value biocommodities. In this work, it was applied to generate bioelectricity for the first time. Non-natural enzymatic pathways were developed to utilize maltodextrin and glucose in enzymatic fuel cells. Three immobilization approaches were compared for preparing enzyme electrodes. Thermostable enzymes from thermophiles were cloned and expressed for improving the lifetime and stability of the cell. To further increase the power output, non-immobilized enzyme system was demonstrated to have higher power densities compared to those using immobilized enzyme system, due to better mass transfer and retained native enzyme activities. With the progress on pathway development and power density/stability improvement in enzymatic fuel cells, a high energy density sugar-powered enzymatic fuel cell was demonstrated. The enzymatic pathway consisting of 13 thermostable enzymes enabled the complete oxidation of glucose units in maltodextrin to generate 24 electrons, suggesting a high energy density of such enzymatic fuel cell (300 Wh/kg), which was several folds higher than that of a lithium-ion battery. Maximum power density was 0.74 mW/cm2 at 50 deg C and 20 mM fuel concentration, which was sufficient to power a digital clock or a LED light. These results suggest that enzymatic fuel cells via synthetic pathway biotransformation could achieve high energy density, high power density and increased lifetime. Future efforts should be focused on further increasing power density and enzyme stability in order to make enzymatic fuel cells commercially applicable. / Ph. D.

No description available.

O presente projeto avaliou uma célula combustível microbiana (CCM) composta de um reator combinado (anaeróbio e aeróbio), operada em fluxo contínuo com tempo de detenção hidráulico de 12 horas, alimentada com esgoto sintético (487 \'+ OU -\' 115 mg DQO/L) e esgoto sanitário (631 \'+ OU -\' 213 mg DQO/L). A estabilidade da CCM variou conforme as características do substrato aplicado. A eficiência de remoção de DQO ficou em 61 \'+ OU -\' 17; 67 \'+ OU -\' 26%, para esgoto sintético e sanitário respectivamente. Em média tensão obtida com o esgoto sintético foi de 76 mV com picos - 112,5 e 409 mV, enquanto que com o esgoto sanitário foi possível obter 52,1 mV na média e pico de geração em 325 mV. A potência variou de 10-150 mW/\'M POT.2\' com resistências entre 50-650 \'ômega\'. A geração de energia elétrica não apresentou relação linear com a DQO consumida em nenhum dos casos. A aplicação de barras de grafite como eletrodos se mostrou satisfatória na condução da corrente elétrica, o fator limitante foi a transferência de massa, principalmente a transferência de prótons do anodo para o catodo e a difusão de oxigênio para o anodo. Contudo os resultados obtidos demonstraram que é possível gerar eletricidade e, simultaneamente, tratar esgoto sanitário. / This project evaluated a microbial fuel cell (MFC) consisting of combined reactor (anaerobic and aerobic), operated in continuous flow with hydraulic detention time of 12 hours, fed with synthetic wastewater (487 \'+ OR -\' 115 mg COD/L) and wastewater (631 \'+ OR -\' 213 mg COD/L). The stability of the CCM varied according to the characteristics of the substrate applied. The efficiency of COD removal was at 61 \'+ OR -\' 17; 67 \'+ OR -\' 26 for synthetic wastewater and sawage respectively. On a average voltage obtained with synthetic wastewater was 76 mV with peaks - 112.5 and 409 mV, while the wastewater was obtained 52.1 mV on average peaks generation at 325 power was varied from 10-150 mW/\'M POT.2\' with resistances between 50-650 \'ômega\'. The power generation showed no liner relationship with the COD consumed in any case. The application of graphite rods as electrodes were satisfactory in the conduction of electrical of protons from the anode to the cathode and the diffusion of oxygen to the anode. However the results showed that it is possible to generate electricity while simultaneously treating sewage.

A sustainable and low-cost system, namely a photo-bioelectrochemical system (photo-BES), based on the natural blueprint of photosynthetic microorganisms was studied. The aim of this research work is to improve the efficiency of electron transfer of the microorganisms for bioelectricity generation. The first strategy adopted was the evaluation of the exoelectrogenic activity of oxygenic photosynthetic cyanobaterium, Synechococcus elongatus PCC 7942, in biophotovoltaic (BPV) platforms through a comparative performance analysis of bioanode materials. The second approach involved improving the performance of anoxygenic photosynthetic bacterium, Rhodopseudomonas palustris ATCC® 17001™, by varying the ratio of nitrogen to carbon sources (N:C) to maximise both biohydrogen production and exoelectrogenesis for conversion into bioelectricity in photosynthetic microbial fuel cells (photoMFCs). A linear correlation was obtained between average surface roughness/surface area and maximum power density of ITO-coated and graphene/ITO-coated substrates. Graphene/ITO-coated PET bioanodes produced the highest maximum power output of 29±4 μW m-2 in a single chamber BPV device due to improved biofilm formation and improved electrochemical activity. XG Leaf®, also known as graphene paper, helped to bridge the shortcomings of carbon fibres in terms of wettability. The most hydrophilic, 240 μm thick graphene paper, produced the highest maximum power output of 393±20 μW m-2 in a membrane electrode assembly (MEA)-type BPV device, mainly due to reduced electrochemical polarisation. A proof of concept study compared the performance of screen-printed graphene onto a membrane separator against 3D-printed bioanodes coated with carbon nanotubes. One mm thick 3D-printed bioanode was better performing as its structures promoted a much denser biofilm with extensive fibrous extracellular matrix. Using a ratio of N:C=0.20 resulted in higher biohydrogen production and higher exoelectrogenic activity, generating a maximum power output of 361±157 mW m-2 and 2.39±0.13 mW m-2, respectively. This study provided additional insight in improving the electron transfer efficiency, which could be used to further optimise photo-BESs as part of future research and development for sustainable technologies.

Apresenta-se neste trabalho a aplicação de turbogeradores instalados em usinas de açúcar e etanol como alternativa eficiente de complementaridade do sistema energético brasileiro e contribuição à utilização de recursos renováveis, além de fazer abordagem aos sistemas de cogeração para este tipo de aplicação. A biomassa da cana-de-açúcar dispõe de um potencial energético significativo e o trabalho visa abordar os recursos para transformação da energia química contida neste combustível em energias térmica e elétrica, úteis para o processo industrial das usinas de açúcar e etanol. Também são explorados os métodos de dimensionamento das termelétricas a vapor que operam em conjunto com o processo fabril destas indústrias. Adicionalmente são avaliados métodos para favorecer a eficiência energética dos projetos de cogeração nas indústrias sucroalcooleiras a fim de elevar o potencial de geração de bioeletricidade e contribuir com a rentabilidade global da usina por meio da comercialização desta energia. / This work presents the application of turbine generator sets installed in sugar and ethanol mills as an efficient alternative of complement of the Brazilian power system and contribution to the use of renewable resources, besides to cogeneration systems approach for this kind of application. The sugar cane biomass has a great energetic potential and the work aims to mention the transformation of the chemical energy contained in this fuel into thermal and electrical energy, useful for the sugar and ethanol industrial process. The design criteria of steam power plant operating together with the process of these industries are also explored. Additionally methods to improve the efficiency of the cogeneration projects in sugar and ethanol mills to increase the power generation potential are evaluated, contributing to the global profitability of the mill through the commercialization of this energy.

Apresenta-se neste trabalho a aplicação de turbogeradores instalados em usinas de açúcar e etanol como alternativa eficiente de complementaridade do sistema energético brasileiro e contribuição à utilização de recursos renováveis, além de fazer abordagem aos sistemas de cogeração para este tipo de aplicação. A biomassa da cana-de-açúcar dispõe de um potencial energético significativo e o trabalho visa abordar os recursos para transformação da energia química contida neste combustível em energias térmica e elétrica, úteis para o processo industrial das usinas de açúcar e etanol. Também são explorados os métodos de dimensionamento das termelétricas a vapor que operam em conjunto com o processo fabril destas indústrias. Adicionalmente são avaliados métodos para favorecer a eficiência energética dos projetos de cogeração nas indústrias sucroalcooleiras a fim de elevar o potencial de geração de bioeletricidade e contribuir com a rentabilidade global da usina por meio da comercialização desta energia. / This work presents the application of turbine generator sets installed in sugar and ethanol mills as an efficient alternative of complement of the Brazilian power system and contribution to the use of renewable resources, besides to cogeneration systems approach for this kind of application. The sugar cane biomass has a great energetic potential and the work aims to mention the transformation of the chemical energy contained in this fuel into thermal and electrical energy, useful for the sugar and ethanol industrial process. The design criteria of steam power plant operating together with the process of these industries are also explored. Additionally methods to improve the efficiency of the cogeneration projects in sugar and ethanol mills to increase the power generation potential are evaluated, contributing to the global profitability of the mill through the commercialization of this energy.

O presente projeto avaliou uma célula combustível microbiana (CCM) composta de um reator combinado (anaeróbio e aeróbio), operada em fluxo contínuo com tempo de detenção hidráulico de 12 horas, alimentada com esgoto sintético (487 \'+ OU -\' 115 mg DQO/L) e esgoto sanitário (631 \'+ OU -\' 213 mg DQO/L). A estabilidade da CCM variou conforme as características do substrato aplicado. A eficiência de remoção de DQO ficou em 61 \'+ OU -\' 17; 67 \'+ OU -\' 26%, para esgoto sintético e sanitário respectivamente. Em média tensão obtida com o esgoto sintético foi de 76 mV com picos - 112,5 e 409 mV, enquanto que com o esgoto sanitário foi possível obter 52,1 mV na média e pico de geração em 325 mV. A potência variou de 10-150 mW/\'M POT.2\' com resistências entre 50-650 \'ômega\'. A geração de energia elétrica não apresentou relação linear com a DQO consumida em nenhum dos casos. A aplicação de barras de grafite como eletrodos se mostrou satisfatória na condução da corrente elétrica, o fator limitante foi a transferência de massa, principalmente a transferência de prótons do anodo para o catodo e a difusão de oxigênio para o anodo. Contudo os resultados obtidos demonstraram que é possível gerar eletricidade e, simultaneamente, tratar esgoto sanitário. / This project evaluated a microbial fuel cell (MFC) consisting of combined reactor (anaerobic and aerobic), operated in continuous flow with hydraulic detention time of 12 hours, fed with synthetic wastewater (487 \'+ OR -\' 115 mg COD/L) and wastewater (631 \'+ OR -\' 213 mg COD/L). The stability of the CCM varied according to the characteristics of the substrate applied. The efficiency of COD removal was at 61 \'+ OR -\' 17; 67 \'+ OR -\' 26 for synthetic wastewater and sawage respectively. On a average voltage obtained with synthetic wastewater was 76 mV with peaks - 112.5 and 409 mV, while the wastewater was obtained 52.1 mV on average peaks generation at 325 power was varied from 10-150 mW/\'M POT.2\' with resistances between 50-650 \'ômega\'. The power generation showed no liner relationship with the COD consumed in any case. The application of graphite rods as electrodes were satisfactory in the conduction of electrical of protons from the anode to the cathode and the diffusion of oxygen to the anode. However the results showed that it is possible to generate electricity while simultaneously treating sewage.

L'adoption d'une méthodologie est cruciale pour la conception de procédés chimiques optimaux. L'optimisation multi-objective de modèles rigoureux en est un exemple, jouissant d'une application extensive dans la littérature. Cette méthode retourne un ensemble de solutions, dit de Pareto, présentant un compromis optimal entre les fonctions objectives. Ceci est suivi par une étape de sélection d'une solution d'intérêt répondant à des critères définis. Cette méthodologie s'appliquait, dans le cadre de cette thèse, à deux procédés. Le premier consistait en une distillerie d'éthanol à partir de la canne à sucre, combinée à un système de cogénération et de combustion à partir de la biomasse de canne à sucre. Le deuxième contenait en plus un système d'hydrolyse enzymatique de cette biomasse. Notre première contribution traitait de la construction d'une procédure pour la modélisation, simulation, intégration thermique et évaluation du coût des équipements. La deuxième contribution traitait de l'analyse des résultats réalisée à travers un suivi de variables mesurées, une fragmentation de la courbe de Pareto, une hiérarchisation des variables de décision et une comparaison avec la littérature. La dernière contribution traitait de l'étape de sélection qui s'est réalisée à travers une évaluation économique des solutions, sous des scénarii différents, avec la Valeur Nette Présente comme critère de sélection. En conclusion, cette thèse constitue une première application intégrale de la méthodologie proposée. Elle représente, de par ses contributions, un tremplin pour des applications futures à des procédés chimiques ou biochimiques, plus spécialement pour la canne à sucre / The use of a systematic methodology is crucial for the design of optimal chemical processes, namely bio-processes. Multi-objective optimization of rigorous process models is therein a prime example, with extensive use in literature. This method yields a Pareto set of optimal compromise solutions, from which one optimal solution is chosen based on specific criteria. This methodology was applied, in the course of this thesis, to two studied processes. The first consisted in a distillery converting sugarcane to ethanol, combined with a sugarcane biomass combustion and power cogeneration system. The second contained an additional biomass hydrolysis system. Our first contribution deals with the construction of an organized procedure for the modeling, simulation, heat integration and equipment and capital cost estimation of chemical processes. The second contribution deals with the analysis of the optimization results through a tracking of measured variables, the fragmentation of the Pareto curve, an ordering of optimization variables, and a comparisons with literature results. The final realization deals with the selection step realized through an economic evaluation of optimal solutions for various scenarios, with the Net Present Value as the selection criterion. In conclusion, this thesis constitutes a first integral application of the said methodology. It sets, through its contributions, a stepping stone for future application in the field of chemical and biochemical processes, namely for sugarcane processes

Nessa pesquisa foram testadas tanto CCM com membranas e sem membranas que tinham por característica reproduzir sistemas de tratamento de esgoto sanitário. A etapa experimental desse trabalho foi dividida entre o Brasil (ensaios com CCM sem a MTP e utilizando esgoto sanitário) e Portugal (ensaios com CCM tradicionais de uma e duas câmaras, utilizando água residuária sintética e a bactéria Lactobacillus pentosus). A execução em dois locais diferentes resultou em um maior aprofundamento e desenvolvimento da pesquisa. As CCM foram avaliadas principalmente quanto ao potencial elétrico e eficiência da degradação de compostos orgânicos (esgoto sanitário e água residuária sintética). Para os dados obtidos no Brasil, as três configurações apresentaram maior diferença na potência em função do modo de operação. A operação intermitente apresentou a maior potência (11 mW/m2) para a CCM cilíndrica de fluxo ascendente, enquanto que operação continua a maior potência (4,2 mW/m2) foi obtida para a CCM retangular de fluxo horizontal, a qual também apresentava uma maior facilidade na manutenção quanto aos eletrodos (adição/remoção). A CCM cúbica de fluxo ascendente devido a sua concepção simples demandava um sistema complementar para o aumento da remoção de DQO. Apesar da baixa potência mensurada para os ensaios realizados no Brasil há de se pontuar que os mesmos foram obtidos para reatores sem membranas e utilizando o esgoto sanitário, o qual apresentou grande sazonalidade. Para a etapa realizada em Portugal, foi possível realizar quinze diferentes ensaios e mais um ensaio específico de crescimento. A maior potência (10,37 mW/m2) foi obtida para CCM de câmara dupla operada de modo contínuo para um tempo de detenção hidráulico (TDH) de 20 horas. A maior potência obtida para a CCM de câmara única foi de 5,53 mW/m2 quando houve a adição do extrato de levedura (função teórica de mediador). A potência da CCM, na maioria das vezes, esteve relacionada à proporção de sólidos voláteis e totais, SV/ST, quantidade de bactérias, pH, características de operação e por fim a configuração da CCM. O ensaio de crescimento revelou a correlação da potência em função da quantidade de bactérias inseridas da massa do biofilme (SV) e mostra-se como uma ferramenta na avaliação da potência das CCM. / In this research were tested MFC with membranes and without membrane that aimed to reproduce the characteristics of sewage treatment systems. The experimental phase of this work was divided between Brazil (MFC membrane-less using sewage) and Portugal (MFC tests with traditional single and dual chamber, using synthetic wastewater and Lactobacillus pentosus bacteria). The performance in two different locations resulted in a further deepening and development of research. The MFC were evaluated primarily on the electric potential and efficiency of degradation of organic compounds (sewage and synthetic wastewater). For data obtained in Brazil, the three patterns showed greater difference in power as a function of the operating mode. The intermittent operation showed the highest power (11 mW/m2) for the MFC cylindrical upflow, while operation continues the increased power (4.2 mW/m2) was obtained for the rectangular horizontal flow CCM, which also had an easier maintenance as the electrodes (addition/removal). The upflow cubic MFC because of its simple design required a complementary system to increase the COD removal. Despite the low power measured for tests conducted in Brazil there to point out that they were obtained for reactors without membranes and using the sanitary sewer, which showed a high seasonality. To step held in Portugal, was possible fifteen different tests and more individual test growth. The higher power (10.37 mW/m2) was obtained for MFC dual chamber continuously operated for a hydraulic retention time (HRT) of 20 hours. The greater potency obtained for the single chamber MFC was 5.53 mW/m2 when there was the addition of yeast extract (theoretical mediator function). The potency of MFC, most often been related to the proportion of total solids and volatile, VS/TS, the amount of bacteria, pH, operating characteristics, and finally the configuration of the MFC. The growth assay revealed the correlation power as a function of the quantity of bacterial biofilm mass inserted (VS) and shows up as a tool in assessing the potency of the MFC.

O mercado brasileiro de eletricidade enfrentou nos últimos anos, crises de abastecimento, devido ao maior crescimento da demanda em relação à oferta. Derivado da falta de investimentos em infraestrutura e da concentração da matriz energética em hidroeletricidade, esse cenário pode ser minimizado pela bioeletricidade cogerada a partir do bagaço da cana. Porém, a efetiva exploração de seu potencial, depende das usinas reconhecerem-na como produto viável e lucrativo. Nesse sentido, o objetivo deste estudo foi caracterizar a comercialização de bioeletricidade no ACL e compará-la com o ACR identificando ameaças, oportunidades, pontos fortes e fracos de cada um. Realizou-se entrevistas com gestores: de quatro usinas sucroenergéticas, da distribuidora de energia local e de um consumidor livre. Utilizando-se a análise SWOT e PEST e as técnicas de análise de conteúdo e correspondência os dados foram trabalhados. Os resultados indicaram que a principal vantagem do ACR é a segurança quanto ao preço da energia e a desvantagem é a inflexibilidade do contrato aliado a altas penalidades. O ponto forte relevante do ACL é a flexibilidade na definição de prazo, preço e quantidade e a fraqueza é a volatilidade do preço. Devido a essas características os agentes tendem a atuar nos dois mercados, adotando como estrutura de governança principal o mercado e as formas híbridas em segundo plano. Constatou-se ainda a necessidade da atuação governamental como incentivador de fontes renováveis e provedor de soluções para entraves como a conexão a rede de transmissão, fraqueza dos dois mercados, e a falta de um ambiente adequado de comercialização. / In recent years, the Brazilian electricity market has gone through provision crises, due to the greater increase in demand with regard to supplies. Resulting from the lack of infrastructural investments and the concentration of the energy matrix in hydroelectricity, this scenario can be minimized by the bioelectricity coproduced based on sugar cane pulp. However, the effective exploration of its potential depends on sugar cane mills acknowledging it as a viable and profitable product. This research aimed to characterize bioelectricity commerce in a Free Contracting Environment (ACL) and compare it with a Regulated Contracting Environment (ACR), identifying the threats, opportunities, strong and weak points of each. Interviews were held with managers: of four sugar-electricity mills, the local energy distributor and a free consumer. Data were processed using SWOT and PEST analysis, as well as content and correspondence analysis techniques. The results indicated that the main advantage of ACR is security about energy prices, while the disadvantage is the contracts lack of flexibility, in combination with high penalties. The relevant strong point of ACL is the flexibility to define term, price and quantity, and the weakness is price volatility. Due to these characteristics, agents tend to act in both markets, adopting the market as the main governance structure and hybrid forms at a secondary level. Government action is needed to encourage renewable energy sources and provide solutions to bottlenecks like connection with the transmission network, weakness of both markets and lack of an adequate trading environment.