Reduction kinetics of NiO-YSZ composite for application in solid oxide fuel cell

A porous nickel-8 mol% yttria stabilized zirconia (Ni-8YSZ) composite, used as anode for solid oxide fuel cell, was obtained by reduction of NiO-8YSZ cermet. The first goal was the evaluation of the temperature effect of powder processing by thermogravimetry. In addition, the influence of porosity in the reduction kinetic of the sample sintered at 1450 A degrees C was evaluated. The final porosity produced in NiO-8YSZ composite by pore former was 30.4 and 37.9 vol.%, respectively, for 10 and 15 mass% of corn starch. The sample with 15 mass% of corn starch promotes a reduction rate almost twice higher than sample with 10 mass% of corn starch. The porosity introduced by the reduction of NiO was 23 vol.%.

Investigation of the CO tolerance mechanism at several Pt-based bimetallic anode electrocatalysts in a PEM fuel cell

The electrocatalysis of CO tolerance of Pt/C, PtRu/C, PtFe/C, PtMo/C, and PtW/C at a PEM fuel cell anode has been investigated using single cell polarization and online electrochemical mass spectrometry (EMS) measurements, and cyclic voltammetry, X-ray diffraction (XRD), in situ X-ray absorption near edge structure (XANES) analyses of the electrocatalysts. For all bimetallic electrocatalysts, which presented higher CO tolerance, EMS results have shown that the production of CO(2) start at lower hydrogen electrode overpotentials as compared to Pt/C, confirming the occurrence of the so-called bifunctional mechanism. On the other hand, XANES results indicate an increase in the Pt 5d-band vacancies for the bimetallic catalysts, particulary for PtFe/C, this leading to a weakening of the Pt-CO bond, helping to increase the CO tolerance (the so-called electronic effect). For PtMo/C and PtRu/C supplied with H(2)/CO, the formation of CO(2) is observed even when the cell is at open circuit, confirming some elimination of CO by a chemical process, most probably the water gas shift reaction. (C) 2008 Elsevier Ltd. All rights reserved.

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.

In Bio-Fuel We Trust

In bio-fuel we trust. Or do we? In this chapter, ethnographic material from Sweden is used to discuss ways sin which trust may influence the choice of bio-fuel for heating purposes. The meaning and substance of trust or distrust, as well as the very conditions for trust, are elaborated on in relation to solar and bio-pellet systems, district heating with bio-fuel, and traditional fireplaces. An important conclusion of this chapter is that the degree to which people perceive others as being like themselves or not tends to be decisive for whether these others are to be trusted, and therefore worth listening to. The context and situation in which a certain heating system is being chosen does not only involve trust in individuals, however, but in companies and the authorities, as well as in the arterfacts themselves. An example is given on how distrust of district heating companies led house owners to reject an offer of district heating despite the comfort and environmental benefit this could have provided. it is shown how this distrust might be resolved by making the rhythm of households and sitrict heating companies more in step with one another. The strong emotional attachment to and deep-felt trust in the traditional fireplace is also analysed, and a question is put forward as to whether these feelings could be transferred to modern bio-pellet stoves. Finally, our great and assured trust in bio-fuel as a main solution to global climate change is shortly commented upon and partly questioned.

Elbesparing med pelletkaminer och solvärme i direktelvärmda småhus

The aim of this study was to investigate how electricallyheated houses can be converted to using wood pellet and solarheating. There are a large number of wood pellet stoves on themarket. Many stoves have a water jacket, which gives anopportunity to distribute the heat to domestic hot water and aradiator heating system. Three typical Swedish houses with electric resistanceheating have been studied. Fourteen different system conceptsusing wood pellet stoves and solar heating systems have beenevaluated. The systems and the houses have been simulated indetail using TRNSYS. The houses have been divided in up to 10different zones and heat transfer by air circulation throughdoorways and open doors have been simulated. The pellet stoveswere simulated using a recently developed TRNSYS component,which models the start- and stop phases, emissions and thedynamic behaviour of the stoves. The model also calculates theCO-emissions. Simulations were made with one stove without awater jacket and two stoves with different fractions of thegenerated heat distributed in the water circuit. Simulations show that the electricity savings using a pelletstove are greatly affected by the house plan, the systemchoice, if the internal doors are open or closed and thedesired level of comfort. Installing a stove with awater-jacket connected to a radiator system and a hot waterstorage has the advantage that heat can be transferred todomestic hot water and be distributed to other rooms. Suchsystems lead to greater electricity savings, especially inhouses having a traditional layout. It was found that not allrooms needed radiators and that it was more effective in mostcases t use a stove with a higher fraction of the heatdistributed by the water circuit. The economic investigation shows that installing a woodpellet stove without a water jacket gives the lowest totalenergy- and capital costs in the house with an open plan (fortoday's energy prices and the simulated comfort criteria). Inthe houses with a traditional layout a pellet stove givesslightly higher costs than the reference house having onlyelectrical resistance heating due to the fact that less heatingcan be replaced. The concepts including stoves with a waterjacket all give higher costs than the reference system, but theconcept closest to be economical is a system with a bufferstore, a stove with a high fraction of the heat distributed bythe water circuit, a new water radiator heating system and asolar collector. Losses from stoves can be divided into: flue gas lossesincluding leakage air flow when the stove is not in operation;losses during start and stop phases; and losses due to a highair factor. An increased efficiency of the stoves is importantboth from a private economical point of view, but also from theperspective that there can be a lack of bio fuel in the nearfuture also in Sweden. From this point of view it is alsoimportant to utilize as much solar heat as possible. Theutilization of solar heat is low in the simulated systems,depending on the lack of space for a large buffer store. The simulations have shown that the annual efficiency ismuch lower that the nominal efficiency at full power. Thesimulations have also shown that changing the control principlefor the stove can improve efficiency and reduce theCO-emissions. Today's most common control principle for stovesis the on/off control, which results in many starts and stopsand thereby high CO-emissions. A more advanced control varyingthe heating rate from maximum to minimum to keep a constantroom temperature reduces the number of starts and stops andthereby the emissions. Also the efficiency can be higher withsuch a control, and the room temperature will be kept at a moreconstant temperature providing a higher comfort.

On equilibrium prices in continuous time

We combine general equilibrium theory and théorie générale of stochastic processes to derive structural results about equilibrium state prices.

Essays on international prices and the subjacent market structure

Esta tese utiliza a informação contida em preços internacionais para identificar parâmetros de modelos de comércio sob competição imperfeita, desta forma permitindo inferência sobre o comportamento das exportações, sobre os ganhos de troca da abertura comercial e sobre a variedade de bens produzidos domesticamente. Em primeiro lugar, investigamos o repasse cambial, no longo prazo, para os preços praticados por exportadores brasileiros. O foco no longo prazo permite controlar os efeitos da rigidez de preço no curto prazo, de maneira que o repasse incompleto evidencie competição imperfeita com preços flexíveis. Em segundo lugar, calculamos os ganhos de troca de novas variedades de bens importados baseando-nos em estimativas para as elasticidades de substituição desagregadas. Finalmente, qualificamos a ênfase da literatura de comércio em ganhos de eficiência no lugar de ganhos de variedade, demonstrando que a variedade de bens produzidos domesticamente se amplia após aberturas comerciais desde que as firmas tenham uma margem de decisão em bens intermediários ou na qualificação da mão de obra.

Os impactos da agroenergia no mercado de terras: dinâmica de preço e elasticidade de uso

Este trabalho tem como objetivo construir um referencial teórico que auxilie no entendimento de como a Agroenergia poderá impactar o mercado de terras no Brasil. Posteriormente, analisar os reflexos desta nova conjuntura no coeficiente de elasticidade de uso da terra, para a cultura da cana-de-açúcar, no Estado de São Paulo, após a introdução dos veículos flex-fuel no mercado brasileiro. Os aspectos relacionados ao mercado de terras, suas definições e características de uso, têm sido objeto de estudo de muitos pensadores e economistas, desde o final do século XIX. Motivado por esta afirmação, procurou-se realizar uma revisão de literatura para entender as diferentes linhas do pensamento econômico em relação às principais variáveis que compõem a formação de preço e a dinâmica do mercado de terras. Segundo a teoria neoclássica, o valor da terra está intrinsecamente associado à sua capacidade de produção. Aliado a esta característica, também é fundamental entender os atributos da terra como ativo real, seja na expectativa de ganhos de capital ou reserva de valor. Com o intuito de contribuir para esta discussão, foi proposto um fluxograma, que identificou como as variáveis deveriam se correlacionar e impactar na formação do preço das terras agrícolas. É possível afirmar que, no curto prazo, a Agroenergia impactará o valor das terras agrícolas, via preço das commodities, características de ativo real, especialmente na aposta de ganhos de capital e devido ao aumento das políticas governamentais relacionados à produção de biocombustíveis. Em relação ao coeficiente de elasticidade da área de cana-de-açúcar, em São Paulo, em relação a expectativa de preço da tonelada equivalente de ATR, para o açúcar e o etanol, observou-se que a cultura de cana-de-açúcar se tornou mais sensível às variações no preço da tonelada de ATR, expandindo a área cultivada com uma menor variação na expectativa de preço, após a introdução dos veículos flex-fuel no mercado nacional.

Reinsurance in Brazil: what happened to prices?

Neste estudo investigamos a mudança no Brasil de um mercado fechado monopolista de resseguros para um mercado aberto. O foco tem sido sobre os prêmios, como a queda nos preços foi um dos benefícios mais antecipados da nova estrutura do mercado. Para comparar os preços de resseguro entre mercados o Índice Combinado foi usado. Ao comparar o Brasil ao Resto do Mundo, Índices Combinados significativamente menores foram observados para 2001 - 2007. No período 2008 - 2010, após a abertura, parece ter sido uma convergência dos Índices Combinados com os níveis no mundo. Confirma que os preços de resseguro eram altos no passado, e que ocorreu uma queda nos preços desde a abertura. No entanto estas conclusões devem ser tratados com alguma precaução uma vez que apenas 2,5 anos de experiência está disponível desde a abertura do mercado e outros fatores podem ter influenciado a evolução dos preços observados.

Preços de etanol no Brasil : uma análise espacial

A introdução da tecnologia flex-fuel resultou em um expressivo aumento do consumo de etanol no Brasil, tornando-o principal concorrente da gasolina nos postos de combustíveis. Apesar disso, diferentemente da gasolina, a oferta de etanol sofre com a sazonalidade da safra de cana de açúcar, mostrando-se insuficiente para atender a demanda, incorrendo em altos preços nos períodos de entressafra. Além destes fatores, a expansão do uso de etanol como combustível enfrenta a ausência de políticas públicas claras que incentivem o mercado, assim como uma estrutura logística que permita o escoamento do produto a baixos custos. O presente trabalho buscou demonstrar como se comportam espacialmente os preços de etanol e gasolina no Brasil. Observou-se que os preços de etanol combustível ao consumidor foram menores quanto mais próximos das regiões produtoras e maiores conforme se distanciam, até se tornarem desvantajosos para o consumidor de alguns estados na medida em que a paridade de preços frente à gasolina supera o limite técnico de 70%. Observou-se também que a sazonalidade distinta das duas regiões produtoras do país define padrões sazonais de áreas que predominantemente consomem etanol ou gasolina, conforme a paridade de 70%. Este resultado indica que a necessidade de estoques e fluxos de produtos depende não apenas das condições logísticas, mas também da combinação da sazonalidade das regiões produtoras. Por fim, intencionou-se entender como e em que proporção os preços ao produtor do estado de São Paulo relacionam-se com os preços ao consumidor de outras regiões do país. Este estudo demonstrou que a velocidade de transmissão dos preços não está relacionada com a distância e que fatores logísticos e características específicas de cada mercado são os principais determinantes do comportamento dos preços ao consumidor em relação às alterações nos preços ao produtor do estado de São Paulo.

Using common features to understand the behavior of metal-commodity prices and forecast them at different horizons

The objective of this article is to study (understand and forecast) spot metal price levels and changes at monthly, quarterly, and annual horizons. The data to be used consists of metal-commodity prices in a monthly frequency from 1957 to 2012 from the International Financial Statistics of the IMF on individual metal series. We will also employ the (relatively large) list of co-variates used in Welch and Goyal (2008) and in Hong and Yogo (2009) , which are available for download. Regarding short- and long-run comovement, we will apply the techniques and the tests proposed in the common-feature literature to build parsimonious VARs, which possibly entail quasi-structural relationships between different commodity prices and/or between a given commodity price and its potential demand determinants. These parsimonious VARs will be later used as forecasting models to be combined to yield metal-commodity prices optimal forecasts. Regarding out-of-sample forecasts, we will use a variety of models (linear and non-linear, single equation and multivariate) and a variety of co-variates to forecast the returns and prices of metal commodities. With the forecasts of a large number of models (N large) and a large number of time periods (T large), we will apply the techniques put forth by the common-feature literature on forecast combinations. The main contribution of this paper is to understand the short-run dynamics of metal prices. We show theoretically that there must be a positive correlation between metal-price variation and industrial-production variation if metal supply is held fixed in the short run when demand is optimally chosen taking into account optimal production for the industrial sector. This is simply a consequence of the derived-demand model for cost-minimizing firms. Our empirical evidence fully supports this theoretical result, with overwhelming evidence that cycles in metal prices are synchronized with those in industrial production. This evidence is stronger regarding the global economy but holds as well for the U.S. economy to a lesser degree. Regarding forecasting, we show that models incorporating (short-run) commoncycle restrictions perform better than unrestricted models, with an important role for industrial production as a predictor for metal-price variation. Still, in most cases, forecast combination techniques outperform individual models.