Modeling and simulation of the anode in direct ethanol fuels cells

Mathematical modeling has been extensively applied to the study and development of fuel cells. In this work, the objective is to characterize a mechanistic model for the anode of a direct ethanol fuel cell and perform appropriate simulations. The software Comsol Multiphysics (R) (and the Chemical Engineering Module) was used in this work. The software Comsol Multiphysics (R) is an interactive environment for modeling scientific and engineering applications using partial differential equations (PDEs). Based on the finite element method, it provides speed and accuracy for several applications. The mechanistic model developed here can supply details of the physical system, such as the concentration profiles of the components within the anode and the coverage of the adsorbed species on the electrode surface. Also, the anode overpotential-current relationship can be obtained. To validate the anode model presented in this paper, experimental data obtained with a single fuel cell operating with an ethanol solution at the anode were used. (C) 2008 Elsevier B.V. All rights reserved.

Nickel catalysts supported on ZrO2, Y2O3-stabilized ZrO2 and CaO-stabilized ZrO2 for the steam reforming of ethanol: Effect of the support and nickel load

Catalysts with various nickel loads were prepared on supports of ZrO2, ZrO2-Y2O3 and ZrO2-CaO, characterized by XRD and TPR and tested for activity in ethanol steam reforming. XRD of the supports identified the monoclinic crystalline phase in the ZrO2 and cubic phases in the ZrO2-Y2O3 and ZrO2-CaO supports. In the catalysts, the nickel impregnated on the supports was identified as the NiO phase. In the TPR analysis, peaks were observed showing the NiO phase having different interactions with the supports. In the catalytic tests, practically all the catalysts achieved 100% ethanol conversion, H-2 yield was near 70% and the gaseous concentrations of the other co-products varied in accordance with the equilibrium among them, affected principally by the supports. It was observed that when the ZrO2 was modified with Y2O3 and CaO, there were big changes in the CO and CO2 concentrations, which were attributed to the rise in the number of oxygen vacancies, permitting high-oxygen mobility and affecting the gaseous equilibrium. The liquid products analysis showed a low selectivity to liquid co-products during the reforming reactions. (c) 2007 Published by Elsevier B.V.

Production of hydrogen by ethanol steam reforming on Co/Al2O3 catalysts: Effect of addition of small quantities of noble metals

The catalytic performance of Co/Al2O3 catalysts promoted with small amounts noble metals (Pt, Pd, Ru, Ir) for steam reforming of ethanol (SRE) has been investigated. The catalysts were characterized by the energy dispersive X-ray, X-ray diffraction, BET surface area, X-ray absorption fine structure and temperature reduction programmed techniques. The results showed that the promoting effect of noble metals included a marked decrease of the reduction temperatures of both Co3O4 and cobalt surface species interacting with the support due to the hydrogen spillover effect, leading to a significant increase of the reducibilities of the promoted catalysts. The better catalytic performance for the ethanol steam reforming at 400 degrees C was obtained for the CoRu/Al2O3 catalyst, which presented an effluent gaseous mixture with the highest H, selectivity and the reasonable low CO formation. (C) 2007 Published by Elsevier B.V.

Hydrogen purification for fuel cell using CuO/CeO(2)-Al(2)O(3) catalyst

CuO/CeO(2), CuO/Al(2)O(3) and CuO/CeO(2)-Al(2)O(3) catalysts, with CuO loading varying from 1 to 5 wt.%, were prepared by the citrate method and applied to the preferential oxidation of carbon monoxide in a reaction medium containing large amounts of hydrogen (PROX-CO). The compounds were characterized ex situ by X-ray diffraction, specific surface area measurements, temperature-programmed reduction and temperature-programmed reduction of oxidized surfaces; XANES-PROX in situ experiments were also carried out to study the copper oxidation state under PROX-CO conditions. These analyses showed that in the reaction medium the Cu(0) is present as dispersed particles. On the ceria, these metallic particles are smaller and more finely dispersed, resulting in a stronger metal-support interaction than in CuO/Al(2)O(3) or CuO/CeO(2)-Al(2)O(3) catalysts, providing higher PROX-CO activity and better selectivity in the conversion of CO to CO(2) despite the greater BET area presented by samples supported on alumina. It is also shown that the lower CuO content, the higher metal dispersion and consequently the catalytic activity. The redox properties of the ceria support also contributed to catalytic performance. (C) 2010 Elsevier B.V. All rights reserved.

Potential oscillations in a proton exchange membrane fuel cell with a Pd-Pt/C anode

We report in this paper the occurrence of potential oscillations in a proton exchange membrane fuel cell (PEMFC) with a Pd-Pt/C anode, fed with H(2)/100 ppm CO, and operated at 30 degrees C. We demonstrate that the use of Pd-Pt/C anode enables the emergence of dynamic instabilities in a PEMFC. Oscillations are characterized by the presence of very high oscillation amplitude, ca. 0.8 V. which is almost twice that observed in a PEMFC with a Pt-Ru/C anode under similar conditions. The effects of the H(2)/CO flow rate and cell current density on the oscillatory dynamics were investigated and the mechanism rationalized in terms of the CO oxidation and adsorption processes. We also discuss the fundamental aspects concerning the operation of a PEMFC under oscillatory regime in terms of the benefit resulting from the higher average power output. (c) 2010 Elsevier B.V. All rights reserved.

The effects of hydrogen sulfide on the polymer electrolyte membrane fuel cell anode catalyst: H(2)S-Pt/C interaction products

The performance of a polymer electrolyte membrane fuel cell (PEMFC) operating on a simulated hydrocarbon reformate is described. The anode feed stream consisted of 80% H(2),similar to 20% N(2), and 8 ppm hydrogen sulfide (H(2)S). Cell performance losses are calculated by evaluating cell potential reduction due to H(2)S contamination through lifetime tests. It is found that potential, or power, loss under this condition is a result of platinum surface contamination with elemental sulfur. Electrochemical mass spectroscopy (EMS) and electrochemical techniques are employed, in order to show that elemental sulfur is adsorbed onto platinum, and that sulfur dioxide is one of the oxidation products. Moreover, it is demonstrated that a possible approach for mitigating H(2)S poisoning on the PEMFC anode catalyst is to inject low levels of air into the H(2)S-contaminated anode feeding stream. (C) 2011 Elsevier B.V. All rights reserved.

Study of ethanol electro-oxidation in acid environment on Pt(3)Sn/C anode catalysts prepared by a modified polymeric precursor method under controlled synthesis conditions

A carbon-supported binary Pt(3)Sn catalyst has been prepared using a modified polymeric precursor method under controlled synthesis conditions This material was characterized using X-ray diffraction (XRD). and the results indicate that 23% (of a possible 25%) of Sn is alloyed with Pt, forming a dominant Pt(3)Sn phase. Transmission election microscopy (TEM) shows good dispersion of the electrocatalyst and small particle sizes (3 6 nm +/- 1 nm) The polarization curves for a direct ethanol fuel cell using Pt(3)Sn/C as the anode demonstrated Improved performance compared to that of a PtSn/C E-TEK. especially in the intrinsic resistance-controlled and mass transfer regions. This behavior is probably associated with the Pt(3)Sn phase. The maximum power density for the Pt(3)Sn/C electrocatalyst (58 mW cm(-2)) is nearly twice that of a PtSn/C E-TEK electrocatalyst (33 mW cm(-2)) This behavior is attributed to the presence of a mixed Pt(9)Sn and Pt(3)Sn alloy phase in the commercial catalysts (C) 2009 Elsevier B V All rights reserved

Effect of the catalyst composition in the Pt-x(Ru-Ir)(1-x)/C system on the electro-oxidation of methanol in acid media

The effect of variations in the composition for ternary catalysts of the type Pt-x(Ru-Ir)(1-x)/C on the methanol oxidation reaction in acid media for x values of 0.25, 0.50 and 0.75 is reported. The catalysts were prepared by the sol-gel method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), atomic absorption spectroscopy (AAS) and energy dispersive X-ray (EDX) analyses. The nanometric character (2.8-3.2 nm) of the sol-gel deposits was demonstrated by XRD and TEM while EDX and AAS analyses showed that the metallic ratio in the compounds was very near to the expected one. Cyclic voltammograms for methanol oxidation revealed that the reaction onset occur at less positive potentials in all the ternary catalysts tested here when compared to a Pt-0.75-Ru-0.25/C (E-Tek) commercial composite. Steady-state polarization experiments (Tafel plots) showed that the Pt-0.25(Ru-Ir)(0.75)/C catalyst is the more active one for methanol oxidation as revealed by the shift of the reaction onset towards lower potentials. In addition, constant potential electrolyses suggest that the addition of Ru and Ir to Pt decreases the poisoning effect of the strongly adsorbed species generated during methanol oxidation. Consequently, the Pt-0.25 (Ru-Ir)(0.75)/C Composite catalyst is a very promising one for practical applications. (c) 2007 Elsevier B.V. All rights reserved.

Strategic options development and analysis: the case of the brazilian railways

Judging by their success in Europe, Asia and North America, passenger and cargo railways are appreciated as the key to infrastructural development in Brazil. The issues are complex and steeped in uncertainty, as well as political and economic agendas, and a wide array of intersecting issues such as business and unionized interests, agricultural and industrial geographical spreads, as well as the emergence of alternative power sources. Not only are the issues systemic, but railway development itself always comes as a physical network structure. The situation under consideration, in other words, is systemic from both the soft and hard systems point of view, thus promising a rich context for systems studies. As an initial attempt in understanding the situation at hand, the research reported here applied the problem structuring approach known as Strategic Options Development and Analysis (SODA) in order to map and analyze issues facing the Brazilian railways. Strategic options for the future development of the railways were identified and analyzed, and ways forward for future research are proposed. In addition, the report serves as an initial knowledge base that can guide future systemic planning studies in the industry.

Fluxo de potência ótimo reativo via método da função lagrangiana barreira modificada

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Electrocatalysis of oxidation of hydrogen on platinum ordered intermetallic phases: Kinetic and mechanistic studies

An experimentally based kinetic and mechanistic study of the hydrogen oxidation reaction (HOR) on platinum and platinum ordered intermetallic materials in acid medium is presented. RDE kinetic data were re-evaluated and complemented by Tafel plots obtained from chronoamperometric measurements. Among the materials evaluated, PtSb and PtSn exhibited markedly improved kinetic current densities and exchange current densities, compared to Pt in the same experimental conditions. It is proposed that the intermetallic phase enhanced the adsorptive characteristic of the surface sites and, as a consequence, improved the kinetics of the adsorption steps (Tafel or Heyrovsky) of the mechanism involved. (c) 2006 Published by Elsevier B.V.

Hydrogen oxidation on ordered intermetallic electrodes covered with CO

This describes an experimental evaluation of the electrocatalytic activity of the hydrogen oxidation reaction on electrodes of platinum and the ordered intermetallic phases PtSb and PtSn, on which CO has previously been deposited. The experiments were carried out in perchloric acid solution and the analysis based on steady-state polarization curves and Tafel plots derived from chronoamperometric data. Both intermetallics, PtSb and PtSn, performed better than Pt towards the HOR, when their surface was deliberately covered with CO. It is suggested that the intermetallic surfaces have a lower affinity for CO molecules, causing a lower CO coverage on these surfaces, and/or a weaker surface-CO interaction, compared to Pt under the same conditions. (C) 2007 Elsevier B.V. All rights reserved.

Esquemas alternativos para o passo de parametrização do método da continuação baseados em parâmetros físicos

O método de fluxo de carga convencional é considerado inadequado para se obter o ponto de máximo carregamento (PMC) de sistemas de potência, devido à singularidade da matriz Jacobiana neste ponto. Os métodos da continuação são ferramentas eficientes para a solução deste tipo de problema, visto que técnicas de parametrização podem ser utilizadas para evitar a singularidade da matriz Jacobiana. Neste trabalho, novas opções para a etapa de parametrização do método da continuação são apresentadas. Mostra-se que variáveis com claro significado físico podem ser utilizadas na etapa de parametrização. As seguintes variáveis foram testadas: perda total de potência ativa e reativa, potência ativa e reativa na barra de referência, potência reativa das barras de geração, e as perdas de potência ativa e reativa nas linhas de transmissão (LT). Além de facilitar a implementação computacional do método de continuação, as técnicas de parametrização apresentadas simplificam a definição matemática e o entendimento do método por parte de engenheiros de potência, visto que os métodos de continuação existentes na literatura sempre utilizam técnicas de parametrização complexas, e de interpretação puramente geométrica. Resultados obtidos com a nova metodologia para os sistemas testes do IEEE (14, 30, 57 e 118 barras) mostram que as características de convergência do método de fluxo de carga convencional são melhoradas na região do PMC. Além disso, durante o traçado das curvas PV, as diversas técnicas de parametrização podem ser comutadas entre si possibilitando o cálculo de todos os pontos da curva com um número reduzido de iterações. Diversos testes são realizados para proporcionar a comparação do desempenho dos esquemas de parametrização propostos.

Determinação do ponto de máximo carregamento de sistemas de potência utilizando o fluxo de carga desacoplado rápido parametrizado

Os métodos de fluxo de carga por Newton-Raphson e fluxo de carga desacoplado rápido convencionais são considerados inadequados para a obtenção do ponto de máximo carregamento de sistemas de potência, devido à problemas de mal-condicionamento neste ponto crítico e na sua vizinhança. Neste ponto a matriz Jacobiana do método de Newton-Raphson torna-se singular e considera-se que não são mais válidas as hipóteses de desacoplamento P-V e Q-teta utilizadas para a formulação do método fluxo de carga desacoplado rápido. No entanto, mostra-se neste trabalho, que com pequenas modificações, as versões XB e BX do fluxo de carga desacoplado rápido tornam-se adequadas para a obtenção do ponto de máximo carregamento. Estas novas versões modificadas são comparadas entre si com o intuito de explicitar suas características, assim como da influência da atuação dos limites de geração de potência reativa e de tap's de transformadores. Os resultados obtidos para os sistemas testes do IEEE (14, 30, 57 e 118 barras) mostram que as características de convergência das versões originais são preservadas. Além disso, durante o traçado das curvas PV, os diversos métodos podem ser comutados entre si possibilitando o cálculo de todos os pontos da curva com um número reduzido de iterações.

Artificial neural networks for load flow and external equivalents studies

In this paper an artificial neural network (ANN) based methodology is proposed for (a) solving the basic load flow, (b) solving the load flow considering the reactive power limits of generation (PV) buses, (c) determining a good quality load flow starting point for ill-conditioned systems, and (d) computing static external equivalent circuits. An analysis of the input data required as well as the ANN architecture is presented. A multilayer perceptron trained with the Levenberg-Marquardt second order method is used. The proposed methodology was tested with the IEEE 30- and 57-bus, and an ill-conditioned 11-bus system. Normal operating conditions (base case) and several contingency situations including different load and generation scenarios have been considered. Simulation results show the excellent performance of the ANN for solving problems (a)-(d). (C) 2010 Elsevier B.V. All rights reserved.