The performance of a phosphoric acid fuel cell reactor, (PAFC), with n-hexadecane, C16H34, canola biodiesel, soybean biodiesel and petroleum diesel fuel has been investigated. Fifteen-hour steady-state operation was achieved with each of the diesel fuels. This is the first extensive study reported in the literature in which n-hexadecane is used directly as the fuel. It is also the first study of a fuel cell operated with petroleum diesel fuel. Identification of steady-state conditions (temperature = 190oC, molar ratio of fuel to water = 414) is significant because it demonstrates that stable fuel cell operation is technically feasible when operating a PAFC with diesel fuels. Degradation in fuel cell performance was observed prior to reaching steady-state. The degradation was attributed to a carbonaceous material forming on the surface of the anode. After treating the anode with water the fuel cell performance recovered. However, the fuel cell performance degraded again prior to obtaining another steady-state operation. Several consistent observations suggested that the carbonaceous material formed from the diesel fuels might be a reaction intermediate necessary for steady-state operation. Finally, the experiments indicated that water in the phosphoric acid electrolyte could be used as the water required for the anodic reaction. The water formed at the cathode could provide the replacement water for the electrolyte, thereby eliminating the need to provide a water feed system for the fuel cell.

Magister Scientiae - MSc (Chemistry) / The anode catalyst is one of the important parts of the direct alcohol fuel cell (DAFC); it is responsible for the alcohol oxidation reaction (AOR) takes place at the anode side. Pd has been reported to have good alcohol oxidation reactions and good stability in alkaline solution. Better stability and activity has been reported for Pd alloyed catalysts when compared to Pd. Choosing a suitable alcohol also has an effect on the activity and stability of the catalyst. This study investigates the best catalyst with better AOR and the best stability and also looks at the better alcohol to use between glycerol and ethanol for the five in-house catalysts (20% Pd, PdNi, PdNiO, PdMn3O4 and PdMn3O4NiO on multi walled carbon nanotubes) using cyclic voltammetry (CV), linear sweep voltammetry (LSV), electrochemical impedance spectrometry (EIS) and chronoamperometry. HR-TEM and XRD techniques were used to determine the particle size and average particle size, respectively while EDS used to determine elemental composition and ICP was used to determine catalyst loading. It was observed from LSV that PdNiO was the most active catalyst for both ethanol and glycerol oxidation, and it was the most stable in ethanol while PdMn3O4 proved to be the most stable catalyst in glycerol observed using chronoamperometry. The best alcohol in this study was reported to be glycerol having given the highest current densities for all the inhouse catalysts compared to ethanol observed using LSV. From XRD and HR-TEM studies, particle sizes were in the range of 0.97 and 2.69 nm for XRD 3.44 and 7.20 nm for HR-TEM with a little agglomeration for PdMn3O4 and PdMn3O4NiO.

A presente pesquisa foi desenvolvida para avaliar as potencialidades das células de combustível como tecnologia em si, inclusive os beneficios econômicos que se podem ter por meio do suprimento de energia elétrica se comparada com o aproveitamento da mesma por meio da rede pública. Além de uma parte descritiva do estado de arte da tecnologia, a presente dissertação foi focada em duas partes: a primeira trata de um estudo experimental onde uma célula, a membrana polimérica, foi conectada a um inversor, permitindo assim de fornecer energia elétrica na rede pública. Na segunda parte foi realizada uma avaliação engenhero-econômica com uma Célula de Combustível de Ácido Fosfórico para o aproveitamento da energia elétrica com cogeração de calor para as condições de mercado brasileiro. O primeiro estudo mostrou como seja possível abastecer uma célula (neste caso alimentada por hidrogênio) para fornecer continuamente energia elétrica na rede, onde necessário ou onde seja impossível para o usuário se conectar a rede pública. O segundo estudo, por sua vez, mostrou que atualmente a células de combustível de média temperatura de Ácido Fosfórico (PAFC) não é uma tecnologia ainda madura e que é viável economicamente somente em aplicações de nicho, por exemplo setores indústriais eletro-intensivos e com necessidade de energia termica também. Todavia, projeções futuras baseadas em curvas de aprendizados e a queda do preço do gás natural mostram como a expansão da tecnologia e a possibilidade de acessar um combustível barato podem abrir futuro para a PAFC mundialmente. / This Masters dissertation aims to study technical potentialities of Fuel Cell technology, including the economical benefits that can provide compared with public grid as well. Thus, the dissertation has been focused in two main parts: the first concerns in an experimental approach to supply electrical power to the public grid using a Polymer Electrolyte Membrane Fuel Cell (PEMFC), while the second one presents a global (from an engineering and economic point-of-view) assessment of a Phosphoric Acid Fuel Cell (PAFC) for the co-generation of heat with electrical energy in Brazil. The first study has been accomplished connecting a PEMFC with a power inverter to the public grid. It has been proved experimentally that Fuel Cell is an alternative device that, as long as fuel is fed, may provide electrical energy continuously and more efficiently than traditional devices. The second study has been focused in the so-called Phosphoric Acid Fuel Cell (PAFC) that, being a Medium Temperature Fuel Cell, beyond to supply electrical energy, may be used for co-generation of thermal energy. Through this study it has been showed that, at the current state-of-art, PAFC is is not already a mature technology and it becomes economically viable only for niche market applications, represented by the industrial sectors with high base load power and continuous thermal energy demand. However, accumulated knowledge expressed by learning curve and natural gas shock price caused by possible LNG supplying and shale gas recovery are the two main factors that may turn investment in PAFC profitable worldwide.

A presente pesquisa foi desenvolvida para avaliar as potencialidades das células de combustível como tecnologia em si, inclusive os beneficios econômicos que se podem ter por meio do suprimento de energia elétrica se comparada com o aproveitamento da mesma por meio da rede pública. Além de uma parte descritiva do estado de arte da tecnologia, a presente dissertação foi focada em duas partes: a primeira trata de um estudo experimental onde uma célula, a membrana polimérica, foi conectada a um inversor, permitindo assim de fornecer energia elétrica na rede pública. Na segunda parte foi realizada uma avaliação engenhero-econômica com uma Célula de Combustível de Ácido Fosfórico para o aproveitamento da energia elétrica com cogeração de calor para as condições de mercado brasileiro. O primeiro estudo mostrou como seja possível abastecer uma célula (neste caso alimentada por hidrogênio) para fornecer continuamente energia elétrica na rede, onde necessário ou onde seja impossível para o usuário se conectar a rede pública. O segundo estudo, por sua vez, mostrou que atualmente a células de combustível de média temperatura de Ácido Fosfórico (PAFC) não é uma tecnologia ainda madura e que é viável economicamente somente em aplicações de nicho, por exemplo setores indústriais eletro-intensivos e com necessidade de energia termica também. Todavia, projeções futuras baseadas em curvas de aprendizados e a queda do preço do gás natural mostram como a expansão da tecnologia e a possibilidade de acessar um combustível barato podem abrir futuro para a PAFC mundialmente. / This Masters dissertation aims to study technical potentialities of Fuel Cell technology, including the economical benefits that can provide compared with public grid as well. Thus, the dissertation has been focused in two main parts: the first concerns in an experimental approach to supply electrical power to the public grid using a Polymer Electrolyte Membrane Fuel Cell (PEMFC), while the second one presents a global (from an engineering and economic point-of-view) assessment of a Phosphoric Acid Fuel Cell (PAFC) for the co-generation of heat with electrical energy in Brazil. The first study has been accomplished connecting a PEMFC with a power inverter to the public grid. It has been proved experimentally that Fuel Cell is an alternative device that, as long as fuel is fed, may provide electrical energy continuously and more efficiently than traditional devices. The second study has been focused in the so-called Phosphoric Acid Fuel Cell (PAFC) that, being a Medium Temperature Fuel Cell, beyond to supply electrical energy, may be used for co-generation of thermal energy. Through this study it has been showed that, at the current state-of-art, PAFC is is not already a mature technology and it becomes economically viable only for niche market applications, represented by the industrial sectors with high base load power and continuous thermal energy demand. However, accumulated knowledge expressed by learning curve and natural gas shock price caused by possible LNG supplying and shale gas recovery are the two main factors that may turn investment in PAFC profitable worldwide.