L'électrolyse en milieu oxydes fondus (MOE) peut être envisagée comme une nouvelle technologie de l’industrie sidérurgique pour la production de fer liquide sans émission de CO2. Dans ce concept, l'électrolyse est utilisée pour produire de l’oxygène gazeux et du fer liquide à des températures supérieures à 1810 K. Dans cette étude sont présentées les principales réactions électrochimiques lors de l’électrolyse en milieu fondu (MgO-Al2O3-SiO2). Une quantité importante de fer liquide a été produite lors d'électrolyses conduites pendant plusieurs heures. L'analyse MEB-EDS du dépôt a révélé un alliage de fer métallique quasi pur, uniquement contaminé par le matériau cathodique. Ce résultat traduit une sélectivité élevée du procédé électrolytique. L'étude de la réponse de l'électrolyte en fonction de la tension électrique et de la concentration de fer a révélé une limitation par la diffusion lors de l’électrolyse de bains de faibles concentrations en oxyde de fer, et à des potentiels inférieurs à 1,5 V. La demi-réaction de la cathode a été identifiée comme la réduction du fer ferreux en fer métallique. L’extrapolation des droites de Tafel sur les courbes courant-tension corrigées de la chute ohmique a conduit à des coefficients de transfert (de la réaction cathodique) proches à 0,6. L’ordre de réaction de réduction de FeII en Fe0 a été évalué autour de 1. L'analyse de la demi-réaction anodique dans les oxydes fondus à faible teneur en fer a montré que les premières espèces éctroactives sont les anions oxydes libres. Pour des tensions électriques croissantes, le transport des anions O2- libres devient limité et le transfert de charge est partiellement attribué à l’oxydation du fer ferreux. Au contraire, dans des mélanges d’oxydes fondus à concentrations élevées en fer, le transfert de charge est réalisé dans toute la gamme de tension par l'oxydation du fer ferreux. C’est seulement à haute tension, que l’oxydation des anions oxyde contribue au transfert des charges. Dans l'ensemble des compositions testées, aucune limitation du courant n’a été observée sur la réaction anodique / Molten oxide electrolysis (MOE) is an ambitious technique for the production of liquid iron by the use of renewable energies and thus lower CO2 emissions in the steel industry. In this concept, electrolysis is used to produce gaseous O2 and liquid iron metal at temperatures above 1810 K. In the experimental study presented here the key-parameters of the electrochemical reactions in a magnesio-aluminosilicate electrolyte and at the electrodes during MOE are investigated. A significant amount of liquid iron metal was produced during experiments of several hours. SEM-EDS analysis of the deposit revealed an alloy of iron metal and of the cathode material, which thereby indicates high process selectivity. Investigation of the electrolyte’s response in dependence of cell voltage and iron concentration inferred a diffusional limitation at low iron oxide concentrations at potentials below 1.5 V. The cathode half-reaction was identified as the reduction of ferrous iron to liquid iron metal. Using Tafel interpretation reaction-transfer coefficients close to 0.6 and an order of reaction around 1 were determined. The analysis of the anode half-reaction showed that in low iron bearing molten oxides, oxide anions were firstly oxidized into O2 gas. At high iron concentrations the charge transfer is conducted in the entire cell voltage range by the oxidation of ferrous iron. The participation of oxide anions in the charge transfer was only witnessed at high cell voltages. In the entire compositional range a limitation of the measured current due to the anode half reaction was not observed

Made available in DSpace on 2015-01-26T13:21:17Z (GMT). No. of bitstreams: 0 Previous issue date: 2014-06-26Bitstream added on 2015-01-26T13:30:46Z : No. of bitstreams: 1 000801981.pdf: 983064 bytes, checksum: 453874979a1b747ca1d5c8ade2e5e0aa (MD5) / No presente trabalho, investigaram-se os efeitos dos íons alcalinos Na+, Li+ substituídos pelo íon H+ e Na+ nos centros relacionados ao alumínio que é uma impureza encontrada naturalmente nas matrizes de quartzo natural. Foram realizadas medidas de absorção óptica na região do visível e do ultravioleta, assim como medidas no infravermelho de amostras de quartzo natural que passaram ou não pelo processo de eletrodifusão. Foi investigado um efeito de escurecimento no quartzo citrino quando este é exposto ao sol, correlacionando com os centros estudados no presente trabalho, [AlO4/H], [Li-OH] e [Na-OH], identificáveis na região do infravermelho e os centros [AlO4]0 e E’ identificáveis no espectro de absorção óptica. A existência desses centros, chamados de centros de impurezas, é facilitada pela presença de um canal estrutural no quartzo, o qual permite a entrada de íons substitucionais como Al3+ e intersticiais Na+, Li+ e H+ junto a cadeia cristalina do quartzo. As amostras foram submetidas à radiação gama de dose aproximada a 20kGy, o resultado foi analisado com base nos centros estudados e os efeitos da eletrodifusão foram analisados por espectroscopia na região do UV-Vis e Infravermelho. A análise infravermelha indicou que a eletrodifusão de hidrogênio no quartzo citrino e hialino foi bem sucedida, uma vez que observa-se um incremento no centro [AlO4/H]0 e um decréscimo no centro [Li-OH], localizado na banda em 3484cm-1. A interação entre a radiação gama e o quartzo faz com que os centros relacionados à presença de hidrogênio com o alumínio aumentem, pois, a radiação ao excitar os átomos da rede do quartzo acaba por afetar diretamente os centros cujo compensador de carga são os átomos alcalinos Li+,Na+ e K+ do centro [AlO4/M]0, havendo então a compensação por átomos de hidrogênio, formando então mais centros [AlO4/H]0. O aparecimento das bandas em 430 ... / In the present study, we investigated the effects of alkali ions Na+ , Li+ replaced by ion H+ and Na+ in the center related to the aluminum that is a found naturally in motrices natural quartz. Measurements of optical absorption in the visible and ultraviolet region and measures infrared samples of natural quartz that have passed or not by electrodiffusion process were performed. An effect of browning in citrine quartz was investigated when exposed to the sun , correlating with the centers studied in this work, [ AlO4/H]0 , [ Li-OH ] and [Na-OH] , identifiable in the infrared region in the centers [AlO4]0 and E’ that are identifiable in the optical absorption spectrum. The existence of such centers, centers called impurities is facilitated by the presence of a structural channel quartz, which allows the entry of ions such as substitutional Al3+ substitutional and interstitial as Na+, Li+ and H+ along the crystal quartz chain . The samples were submitted to gamma radiation dose of approximately 20kGy , the outcome was analyzed based on the centers and the effects of electrodiffusion were analyzed by spectroscopy, UV- Vis and IR region. Infrared analysis indicated that the hydrogen electrodiffusion in citrine and hyaline quartz was successful , since there is an increase in the center [AlO4/H]0 and a decrease in the [Li-OH] , located in the band at 3484cm -1. The interaction between gamma radiation and quartz causes the centers related to the presence of hydrogen with aluminum increase , because the radiation to excite the atoms of the quartz network ultimately directly affect the centers whose compesator load are the alkali atoms Li+ , Na+ and K+ center [AlO4/M]0 , then there is compensation for hydrogen atoms , thus forming more centers [AlO4/H]0 . The appearance of bands at 430 and 620 nm associated to the center [AlO4]0 in the citrine and hyaline quatz after irradiation, enables us to state that ...

abstract: CubeSats are a newly emerging, low-cost, rapid development platform for space exploration research. They are small spacecraft with a mass and volume of up to 12 kg and 12,000 cm3, respectively. To date, CubeSats have only been flown in Low Earth Orbit (LEO), though a large number are currently being designed to be dropped off by a mother ship on Earth escape trajectories intended for Lunar and Martian flyby missions. Advancements in propulsion technologies now enable these spacecraft to achieve capture orbits around the moon and Mars, providing a wealth of scientific data at low-cost. However, the mass, volume and launch constraints of CubeSats severely limit viable propulsion options. We present an innovative propulsion solution using energy generated by onboard photovoltaic panels to electrolyze water, thus producing combustible hydrogen and oxygen for low-thrust applications. Water has a high storage density allowing for sufficient fuel within volume constraints. Its high enthalpy of formation provides more fuel that translates into increased ∆V and vastly reduced risk for the launch vehicle. This innovative technology poses significant challenges including the design and operation of electrolyzers at ultra-cold temperatures, the efficient separation of the resultant hydrogen and oxygen gases from liquid water in a microgravity environment, as well as the effective utilization of thrust to produce desired trajectories. Analysis of the gas combustion and flow through the nozzle using both theoretical equations and finite-volume CFD modeling suggests an expected specific impulse of 360 s. Preliminary results from AGI's Satellite Toolkit (STK) indicate that the ΔV produced by the system for an 8kg CubeSat with 6kg of propellant in a LEO orbit (370 km altitude) is sufficient for an earth escape trajectory, lunar capture orbit or even a Mars capture orbit. These results suggest a promising pathway for an in-depth study supported by laboratory experiments to characterize the strengths and weaknesses of the proposed concept. / Dissertation/Thesis / Masters Thesis Aerospace Engineering 2015

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Agradecemos a compreensão on 2017-10-11T13:19:14Z (GMT) / Submitted by Elisa Fonseca Horta null (elisafhort@hotmail.com) on 2017-10-18T23:17:23Z No. of bitstreams: 1 Dissertação Elisa Fonseca Horta.pdf: 1848190 bytes, checksum: a5ac9a5af484d749ce6cad8c93ccd0be (MD5) / Approved for entry into archive by Luiz Galeffi (luizgaleffi@gmail.com) on 2017-10-23T13:08:05Z (GMT) No. of bitstreams: 1 horta_ef_me_rcla.pdf: 1848190 bytes, checksum: a5ac9a5af484d749ce6cad8c93ccd0be (MD5) / Made available in DSpace on 2017-10-23T13:08:05Z (GMT). No. of bitstreams: 1 horta_ef_me_rcla.pdf: 1848190 bytes, checksum: a5ac9a5af484d749ce6cad8c93ccd0be (MD5) Previous issue date: 2017-09-05 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A degradação anaeróbia é um processo biológico que a partir de uma fonte de carbono gera biogás. Dessa forma, este estudo visou compreender a influência do campo elétrico (ação de cargas elétricas) na degradação anaeróbia da glicose e na geração de biogás em reatores em batelada. Experimentos iniciais foram realizados para determinar as condições ideais de operação (concentração da fonte de carbono e tipo de inóculo). Foram utilizados 4 concentrações de glicose (0,67; 1,00; 2,00 e 10,00g/l) e 3 concentrações de acetato de sódio (0,50; 1,00 e 2,00g/l) para 4 inóculos provenientes de reatores de fluxo ascendente ( 2 de abatedouro de aves, 1 de estação de tratamento de esgoto e uma mistura dos outros 3 lodos). Foram elaborados experimentos com dois meios de cultivo diferentes a fim de identificar o meio nutricional ideal para a geração de metano, meio PYG (genérico para crescimento microbiano) e meio Del Nery (específico para metanogênicas). A próxima etapa foi operar reatores anaeróbios em batelada sob influência do campo elétrico, com utilização de placas paralelas e fonte elétrica com regulagem de tensão, nas condições determinadas pelos experimentos iniciais. As voltagens testadas foram: natural (sem interferência); aterrado (0,0V); 1,5V; 2,0V; 2,5V e 3,0V. As gerações mais elevadas de metano foram observadas para um dos inóculos provenientes do tratamento de águas residuárias de avicultura; a concentração de 2,00 g/l de glicose e o meio PYG. Em todos os reatores com voltagem induzida (de 1,5V a 3,0V) houve eletrólise da água. O reator de 1,5V foi o que obteve os melhores resultados na geração de biogás, apresentando aumento de 200% na geração de metano em comparação com o reator natural, e na remoção da DQO (demanda química de oxigênio), que foi de 93,96% da concentração inicial dos ensaios (5,00g/l). Concluiu-se que o campo elétrico teve influência positiva na degradação anaeróbia para a condição de 1,5V. / The anaerobic degradation process turns a carbon source into biogas. Thus, this study aims to understand the influence of the electric field (action of electric charges) on the anaerobic degradation of glucose and on the generation of biogas in batch reactors. Initial experiments were performed to determine the ideal operating conditions (carbon source concentration and inoculum type). Four concentrations of glucose (0.67, 1.00, 2.00 and 10.00 g/l) and 3 concentrations of sodium acetate (0.50, 1.00 and 2.00 g/l) were used for 4 inoculum from upflow reactors (2 from poultry slaughterhouse, 1 from sewage treatment plant and a mixture of the other 3 sludge). Experiments were carried out with two different culture media in order to identify the ideal nutritional medium for the generation of methane, PYG medium (generic for microbial growth) and Del Nery medium (specific for methanogenic). The next step was to operate anaerobic reactors in batch under the influence of the electric field, using parallel plates and an electric source with voltage regulation, under the conditions determined by the initial experiments. The tested voltages were: natural (no interference); grounded (0,0V); 1.5V; 2.0V; 2.5V and 3.0V. Higher generations of methane were observed using one of the inoculum sourced from poultry wastewater; the concentration of 2.00 g/l glucose and the PYG medium. In all reactors with induced voltage (from 1.5V to 3.0V) there was electrolysis of the water. The 1.5V reactor obtained the best results in the biogas generation, presenting a 200% increase in the methane generation in comparison to the natural reactor and in the removal of COD (Chemical Oxygen Demand), which was 93,96% of the initial assay concentration (5.00 g/l). In conclusion, the electric field had a positive influence on the anaerobic degradation for the 1.5V condition.

Certains procédés d'électrolyse industriels, comme ceux de production de fluor et d'aluminium, génèrent du gaz sur des électrodes peu mouillées par l'électrolyte. Dans ces procédés, la convection est en grande partie induite par le mouvement des bulles. Le temps de résidence du gaz n'étant pas maitrisé, la modélisation de ces électrolyses se heurte à de nombreux défis. Ce travail propose un état des connaissances nécessaires à la modélisation de ce type de cellules. Après avoir mis au point une méthode permettant de réaliser des électrodes fortement hydrophobes, nous avons étudié le dégagement gazeux que celles-ci produisent. Nous avons observé que les bulles qui s'y forment croissent par coalescence et ce phénomène affecte la vitesse de croissance et la taille au détachement. Par la suite, nous avons démontré qu'en localisant le dépôt hydrophobe il est possible d'obtenir une population de bulles dont le nombre, la taille et la position sont maitrisés. Nous avons constaté que l'émission acoustique est un outil efficace pour mesurer, sans observation visuelle, la taille et la vitesse d'ascension des bulles produites par électrolyse. La fréquence la plus énergétique du spectre des salves d'émission acoustique des cellules d'électrolyse produisant du gaz permet, quand la fraction volumique de gaz est faible, de mesurer la taille de toutes les bulles dans la cellule. Quand les bulles sont nombreuses et denses, cette même fréquence est liée aux dimensions de la cellule, à la densité de courant, à la taille des bulles et à la fraction volumique en gaz dans le panache. Nous avons proposé une explication à cette observation basée sur l'hypothèse d'un couplage acoustique des bulles. En l'absence d'agitation vigoureuse, l'activité acoustique d'une cellule d'électrolyse produisant des bulles traduit l'importance du transport de matière aux électrodes. La mesure de la répartition de la densité de courant par la méthode des électrodes segmentées dans une cellule en convection libre a été réalisée. Cette étude a été menée dans le but de tester un outil de simulation numérique des cellules d'électrolyse produisant du gaz. L'effet de la mouillabilité de l'électrode sur la répartition du courant a été évalué. / Molten salts electrochemical processes, like fluorine and aluminium production processes produce bubbles on electrodes slightly wetted by an electrolyte. In those cells, the electrolyte convection is mainly induced by the motion of bubbles. Then, the residence time of gas is not under control and the modelling of such electrolysis still faces many challenges. This work begins with a collection of the information required to model gas-producing cells. We developed an electrochemical composite coating technique to achieve the production of highly hydrophobic electrodes. Then we studied the gas evolution obtained with these electrodes, we observed that coalescences determines the bubbles growth rate and sizes at detachment. When the hydrophobic deposit is local, it is possible to obtain a bubble population whose number, size and position are controlled. We found that the acoustic emission is an effective tool to measure the size and rising speed of bubbles produced by electrolysis without having to observe them visually. When the volume fraction of gas is low, the most energetic frequency of the spectrum of acoustic emission bursts allows measuring the size of all bubbles in the cell. When bubbles are numerous, the most energetic frequency of the acoustic emission spectrum is related to the dimensions of the cell, current density, sizes of the bubbles and gas volume fraction in the plume. We have proposed an explanation for this observation based on the assumption of an acoustic coupling of the bubbles. When bubbles are produced, the acoustic activity of an electrolysis cell is correlated with the mass transport at electrodes. We propose a set of measurements of the distribution of current density at the electrodes in a cell with electrolyte free convection. These measurements have been carried out to benchmark a numerical simulation tool. The effect of the wettability of the electrode on the current distribution was evaluated.

Orientador: Edson Tomaz / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-15T13:26:06Z (GMT). No. of bitstreams: 1 Baroni_Paula_M.pdf: 2153923 bytes, checksum: 0d73b228cc0146200966eb10e60b81f4 (MD5) Previous issue date: 2010 / Resumo: A degradação de poluentes por biodegradação é um dos processos mais econômicos para o tratamento de compostos orgânicos. Na presença de substâncias tóxicas e recalcitrantes, entretanto, o processo biológico não é capaz de promover a degradação ou pode despender um tempo considerável para que a concentração requerida de um poluente seja alcançada. Os processos eletroquímicos foto-assistidos são uma alternativa ao tratamento de poluentes persistentes, possibilitando inclusive sua completa mineralização, devido à formação de radicais com alto poder de oxidação. O resultado positivo deste processo em diversos estudos levou à realização este trabalho, que tem como objetivo verificar a degradação de fenol em uma escala piloto. Foram utilizados quatro reatores tubulares em série, com área superficial interna de 0,18 m2 cada, revestidos com TiO2/RuO2 (70 %/30 %), que é o catalisador e anodo do sistema. No interior do reator apresenta-se o catodo, uma rede cilíndrica de titânio expandido a uma distância de 3 mm do anodo. Concentricamente ao catodo há um tubo de quartzo, dentro do qual a lâmpada ultravioleta permanece protegida. Os ensaios foram realizados em um volume de 80 L de uma solução de fenol de 100 mg.L-1 e 0,08 mol.L-1 de eletrólito suporte (K2SO4), avaliando-se a degradação de fenol, de carbono orgânico total e a formação dos intermediários de oxidação hidroquinona e benzoquinona, tendo como variáveis independentes no planejamento experimental a densidade de corrente, a vazão e o pH inicial. A densidade de corrente foi a variável mais significativa, sendo que a maior densidade utilizada (95 mA.cm-2) promoveu a melhor degradação, reduzindo 73 % da carga orgânica total e 99 % de fenol. Entretanto, a menor densidade de corrente garantiu maior eficiência energética ao processo. O ensaio com melhor desempenho (40 mA.cm-2; pH = 4,21; vazão = 3650 L.h-1) degradou 61 % de carbono orgânico total e 99 % de fenol, consumindo 2072 kWh por quilograma de carbono orgânico degradado e 1047 kWh por quilograma de fenol degradado, evidenciando a necessidade de otimização do processo. Alguns ensaios utilizando cloreto de sódio como eletrólito para a geração de cloro ativo no meio reacional não mostraram vantagens em relação ao uso de sulfato de potássio (K2SO4) / Abstract: The biodegradation of pollutants is one of the most economical types of treatment of organic wastewater. In the presence of toxic and recalcitrant compounds, however, the biological processes don't promote degradation or may spend considerable time to reach the required concentration of a pollutant. The photo-assisted electrochemical processes are an alternative treatment for recalcitrant pollutants, enabling their complete mineralization, due to the formation of radicals with high oxidation power. This process showed positive outcome for phenol degradation in several studies on laboratory scale, so this work aims to verify its efficiency in a pilot scale. It was used four tubular reactors in series, with inner surface area of 0.18 m2 each one, coated with an oxide layer composed of TiO2 / RuO2 (70% / 30%), which are the system's catalyst and also anode. Inside the reactor is the cathode, a cylindrical screen of expanded titanium, in a distance of 3 mm from the anode. Concentrically to the cathode is a quartz tube, within which the ultraviolet lamp remains protected. The experiments were carried out in 80 L of a 100 mg.L-1 phenol solution and 0.08 mol.L-1 of supporting electrolyte (K2SO4). In the experimental design, the dependent variables were the degradation of phenol, total organic carbon and the formation of the intermediates, hydroquinone and benzoquinone. The effects of current density, flow rate and initial pH on the degradation rate were investigated. The current density was the most significant variable and the highest density used (95 mA.cm-2) provided better degradation, reducing 73% of total organic carbon and 99% of phenol. However, the lower current density brought greater energy efficiency to the process. The best performance (40 mA.cm-2, pH = 4.21, F = 3650 L.h-1) degraded 61% of total organic carbon and 99% of phenol, consuming 2072 kWh per kilogram of organic carbon degraded and 1047 kWh per kilogram of phenol degraded, indicating the need for process optimization. Some tests using sodium chloride as electrolyte for the generation of active chlorine in the reaction, showed no advantages over the use of potassium sulphate (K2SO4) / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

Orientador: Ennio Peres da Silva / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-20T23:54:00Z (GMT). No. of bitstreams: 1 Pinto_CristianodaSilva_D.pdf: 3399884 bytes, checksum: 5b999382e246b0d2ebdb93de6389fb2c (MD5) Previous issue date: 2012 / Resumo: Diversas estratégias têm sido propostas para a introdução do hidrogênio na economia, especificamente no setor de transportes para se reduzir impactos ambientais em comparação com os combustíveis convencionais. Uma das estratégias implica na utilização de Hidrano (misturas de hidrogênio e Gás Natural Veicular), fazendo uso da infraestrutura de postos de GNV e dos veículos já existentes convertidos para uso de GNV. Dessa forma custos e prazos são reduzidos, tornando a introdução do hidrogênio mais promissora economicamente. Esta tese verifica se o hidrogênio pode ser imediatamente introduzido no mercado energético brasileiro através do Hidrano, com frações molares de hidrogênio de 10%, 20% e 30%. O hidrogênio será gerado através da eletrólise da água nos postos de GNV. Foram então determinados os custos do hidrogênio, os preços e a competitividade do Hidrano de forma a atender o perfil de vendas de um posto de porte médio nos Estados de São Paulo e Rio de Janeiro. O preço do Hidrano ao consumidor depende principalmente do preço de seu maior constituinte, o GNV, vendido na época a 1,308 R$/m3 no Estado de São Paulo e a 1,662 R$/m3 no Estado do Rio de Janeiro. O preço do Hidrano ao consumidor varia entre 1,474 R$/m3 e 2,047 R$/m3, dependendo de sua composição e da região. Em vista de sua competitividade em relação aos outros combustíveis automotivos, o Hidrano 10 apresenta bom potencial de introdução no mercado, inclusive do ponto de vista econômico. A competitividade entre os combustíveis no Estado de São Paulo é de 0,280 R$/km para a gasolina, 0,259 R$/km para o etanol, 0,111 R$/km para o GNV, 0,129 R$/km para o Hidrano 10 com tarifação do Grupo B3 e 0,125 R$/km para o Hidrano 10 com tarifação do Grupo A4 Convencional. No Estado do Rio de Janeiro a competitividade é de 0,300 R$/km para a gasolina, 0,311 R$/km para o etanol, 0,141 R$/km para o GNV, 0,161 R$/km para o Hidrano 10 com tarifação do Grupo B3 e 0,157 R$/km para o Hidrano 10 com tarifação do A4 Convencional. Também foram estimados os impactos dessa proposta em termos energéticos e ambientais. Há redução de emissões de CO2 e CO. As emissões de THC serão possivelmente reduzidas e as de NOx aumentadas. A proposta do Hidrano permite às concessionárias de energia elétrica entrarem no mercado de combustíveis veiculares e aumentar suas vendas. Ao mesmo tempo as concessionárias de gás natural terão reduzidas as vendas de GNV no curto prazo, o que deverá ser revertido no médio e longo prazos com os ganhos de rendimento trazidos pelo Hidrano aos veículos / Abstract: Several strategies have been proposed to introduce hydrogen in the economy specifically in the transport sector in order to reduce environmental impacts of conventional fuels. One of the strategies implies in adding hydrogen to compressed natural gas (HCNG), making use of the existing refueling stations and natural gas fleet. Thus the costs and time for the introduction of hydrogen in the economy will be reduced. This thesis verifies whether hydrogen can be immediately introduced into the Brazilian energy market by means of HCNG, containing mole fractions of 10%, 20% and 30% of hydrogen, employed as fuel for conventional vehicles adapted to CNG. Hydrogen will be generated by water electrolysis in the CNG station. Then the cost of hydrogen and the prices and competitiveness of HCNG were determined to meet the sales profile of a midsize gas station in the states of Sao Paulo and Rio de Janeiro. The final price of HCNG depends mainly on the price of its major constituent, CNG, sold at that time for 1,308 R$/m3 in the State of São Paulo and for 1,662 R$/m3 in the State of Rio de Janeiro. The price of HCNG to the consumer varies between 1,474 R$/m3 e 2,047 R$/m3, depending on its composition and the region. In view of its competitiveness compared to other automotive fuels, HCNG 10 (CNG with 10% molar fraction of hydrogen) shows good potential for marketing. The competitiveness among fuels in the State of Sao Paulo is 0,280 R$/km for gasoline, 0,259 R$/km for ethanol, 0,111 R$/km for CNG, 0,129 R$/km for HCNG 10 with power tariff B3 and 0,125 R$/km for HCNG 10 with power tariff A4 Conventional. In the State of Rio de Janeiro the competitiveness is 0,300 R$/km for gasoline, 0,311 R$/km for ethanol, 0,141 R$/km for CNG, 0,161 R$/km for HCNG 10 with power tariff B3 and 0,157 R$/km for HCNG 10 with power tariff A4 Conventional. The energy and environmental impacts of this proposal were also estimated. There is a reduction of CO2 and CO emissions. THC emissions are likely to be reduced and NOx are likely to increase. The proposal of introducing HCNG allows electric utilities to enter the market for vehicular fuels and increase their sales. At the same time, natural gas utilities will have the sales of CNG reduced in the short term, although this trend may be reversed in the medium and long terms with performance gains brought by HCNG to vehicles / Doutorado / Planejamento de Sistemas Energeticos / Doutor em Planejamento de Sistemas Energéticos

This thesis concerns the design, implementation and operation of a hydrogen energy storage facility that has been added to an existing renewable energy system at West Beacon Farm, Leicestershire, UK. The hydrogen system consists of an electrolyser, a pressurised gas store and fuel cells. At times of surplus electrical supply, the electrolyser converts electrical energy into chemical energy in the form of hydrogen. This hydrogen is stored until there is a shortage of electrical energy to power the loads on the system, at which point it is reconverted back to electricity by the process of reverse-electrolysis that takes place within a fuel cell. The renewable energy sources, supplying electrical power to domestic and office loads at the site, are photovoltaic, wind and micro-hydroelectric. This work is being carried out through a project, conceived and overseen by the author, known as the Hydrogen and Renewables Integration (HARI) project. The purpose of this study is to demonstrate and gain experience in the integration of hydrogen energy storage with renewable energy systems and, most importantly, to develop software models that could be used for the design of future systems of this type in a range of applications. Effective models have been created and verified against the real-world operation of the system. These models have been largely completed, although some minor details remain unfinished as the are dependant upon studies linked to this one which are yet to be concluded. Subject to some fine tuning that this would entail, then, the models can be used to design a stand-alone, integrated hydrogen and renewable energy system, where only the load profile and weather conditions of a site are known. Significant practical experience has been gained through the design, installation and two years' of operation of the system. Many important insights have been obtained in relation to the integration of the system and the design and operation of its components.

Two main subjects are addressed in this study. The ability of a bright red material with metallic behaviour to be used as a visible light photocatalyst for hydrogen evolution and the feasibility of visible light photocatalytic water splitting using Z-schemes constituted from different kinds of photocatalysts and materials used as mediators. Strontium niobate (Sr₁₋ₓNbO₃) is an A-site deficient perovskite with intense red colour. It is an unusual material that displays both metallic type conduction and- as we present- photocatalytic activity. Specifically, photocatalytic visible light hydrogen production with oxalic acid as a sacrificial reagent is achieved from this material even without the need for a co-catalyst or other alteration. This photocatalytic activity is screened with time and related to different parameters that might influence it, like crystal structure, surface area and surface chemistry. The crystal structure of strontium niobate is A site stoichiometry dependant and the materials acquires a cubic symmetry for Sr≤ 0.92 and orthorhombic for 0.92≤ Sr≤ 0.97. The change of crystal structure from cubic to orthorhombic symmetry seems to have a negative effect on the photocatalytic activity, as the NbO₆ octahedra become distorted and unfavourable for d-orbital overlapping. The highest photocatalytic activity is exhibited at the turning point of one structure to the other. Increase in the photocatalytic activity is also exhibited by enlarging the surface area through ball milling, nevertheless, a clear trend for surface area effect on activity is not obtained among samples with different Sr content. Additionally, an enrichment of Sr on the surface of strontium niobate is observed by XPS, which apart from the fact that seems to be a governing factor improving stability it is also considered a key point for the exhibited photocatalytic activity altogether. Full water splitting under visible light from Z-schemes is studied by fabricating three general categories of systems. These three different categories depend on the mediator used to fabricate the Z-schemes and are: redox couple Z-schemes (with Fe⁺³/Fe⁺²), solid mediator Z-schemes (with GO) and no mediator Z-schemes. The materials used as photocatalysts for the fabrication of the Z-schemes are: Sr₀.₉₂NbO₃ for hydrogen production and both WO₃ and BiVO₄ independently for oxygen production. The photocatalytic activity for water splitting is evaluated in production of hydrogen and oxygen with time and the ratio of their production rates is frequently checked to see whether the ideal hydrogen to oxygen 2:1 is achieved. The general idea acquired from the results of all the three types of systems is that, water splitting with Z-schemes is a complicated process and in most cases governed by many subreactions. More specifically, in all cases of redox couple Z-schemes we got hydrogen to oxygen ratio imbalances and with the most prominent one being the lack of hydrogen production. Thankful is the fact that a certain type of system, the one consisting of WO₃ as oxygen photocatalyst and Fe⁺² as initial mediator species gives results very close to the ideal one and with a high degree of reproducibility indicating this way the probable formation of a Z-scheme that has overcome more of the imbalances. In between the two other categories, solid mediator and no mediator Z-schemes, subreactions seem to be the governing factor hence imbalances are always present. A case study in the no mediator Z-schemes on an attempt to investigate sources of imbalances, reveals that a big source of imbalance is most probably from the trapping of protons from WO₃.

A sustainable solution for meeting the energy demands at our planet is by utilizing wind-, solar-, wave-, thermal-, biomass- and hydroelectric power. These renewable and CO2 emission-free energy sources are highly variable in terms of spatial and temporal availability over the Earth, introducing the need for an appropriate method of storing and carrying energy. Hydrogen has gained significant attention as an energy storage- and carrier media because of the high energy density that is exploited within the ‘power-to-gas’ process chain. A robust way of producing sustainable hydrogen is via electrochemical water splitting. In this work the search for new heterogeneous catalyst materials with the aim of increasing energy efficiency in water splitting has involved methods of both electrochemical water splitting and chemical water oxidation. Some 21 compounds including metal- oxides, oxofluorides, oxochlorides, hydroxide and metals have been evaluated as catalysts. Two of these were synthesized directly onto conductive backbones by hydrothermal methods. Dedicated electrochemical cells were constructed for appropriate analysis of reactions, with one cell simulating an upscale unit accounting for realistic large scale applications; in this cell gaseous products are quantified by use of mass spectrometry. Parameters such as real time faradaic efficiency, production of H2 and O2 in relation to power input or overpotentials, Tafel slopes, exchange current density and electrochemical active surface area as well as turnover numbers and turnover frequencies have been evaluated. Solubility, possible side reactions, the role of the oxidation state of catalytically active elements and the nature of the outermost active surface layer of the catalyst are discussed. It was concluded that metal oxides are less efficient than metal based catalysts, both in terms of energy efficiency and in terms of electrode preparation methods intended for long time operation. The most efficient material was Ni-Fe hydroxide electrodeposited onto Ni metal foam as conductive backbone. Among the other catalysts, Co3Sb4O6F6 was of particular interest because the compound incorporate a metalloid (Sb) and redox inert F and yet show pronounced catalytic performance. In addition, performance of materials in water splitting catalysis has been discussed on the basis of results from electron microscopy, solubility experiments and X-ray diffraction data.