Cobalt catalysts derived from hydrotalcite-type precursors applied to steam reforming of ethanol

Catalysts derived from Co/Mg/Al hydrotalcite-type precursors modified with La and Ce were characterized by XANES and tested in ethanol steam reforming. The reaction data showed that, with a molar ratio of water: ethanol = 3:1 in the feed, addition of Ce and La favored acetaldehyde production. Increasing the water content (water:ethanol = 5:1) decreased the acetaldehyde formation by favoring the adsorption of water molecules on these samples, enhancing the acetaldehyde conversion. (C) 2011 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.

Effects of adding La and Ce to hydrotalcite-type Ni/Mg/Al catalyst precursors on ethanol steam reforming reactions

Catalyst precursors composed of Ni/Mg/Al oxides with added La and Ce were tested in ethanol steam reforming (ESR) reactions. La and Ce were added by anion-exchange. The oxides were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES) analysis. The catalyst precursors consist of a mixture of oxides, with the nickel in the form of NiO strongly interacting with the support Mg/Al. The XPS analysis showed a lanthanum-support interaction, but no interaction of Ce species with the support. The reaction data obtained with the active catalysts showed that the addition of Ce and La resulted in better H(2) production at 550 degrees C. The CeNi catalyst provided the higher ethanol conversion, with lower acetaldehyde production, possibly clue to a favoring of water adsorption on the weakly interacting clusters of CeO(2) on the surface. (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.

Valorization of an Industrial Organosolv-Sugarcane Bagasse Lignin: Characterization and Use as a Matrix in Biobased Composites Reinforced With Sisal Fibers

In the present study, the main focus was the characterization and application of the by-product lignin isolated through an industrial organosolv acid hydrolysis process from sugarcane bagasse, aiming at the production of bioethanol. The sugarcane lignin was characterized and used to prepare phenolic-type resins. The analysis confirmed that the industrial sugarcane lignin is of HGS type, with a high proportion of the less substituted aromatic ring p-hydroxyphenyl units, which favors further reaction with formaldehyde. The lignin-formaldehyde resins were used to produce biobased composites reinforced with different proportions of randomly distributed sisal fibers. The presence of lignin moieties in both the fiber and matrix increases their mutual affinity, as confirmed by SEM images, which showed good adhesion at the biocomposite fiber/matrix interface. This in turn allowed good load transference from the matrix to the fiber, leading to biobased composites with good impact strength (near 500 J m(-1) for a 40 wt% sisal fiber-reinforced composite). The study demonstrates that sugarcane bagasse lignin obtained from a bioethanol plant can be used without excessive purification in the preparation of lignocellulosic fiber-reinforced biobased composites displaying high mechanical properties. Biotechnol. Bioeng. 2010;107: 612-621. (C) 2010 Wiley Periodicals, Inc.

Carbon dioxide reforming of ethanol over Ni/Y(2)O(3)-ZrO(2) catalysts

Supported nickel catalysts of composition Ni/Y(2)O(3)-ZrO(2) were synthesized in one step by the polymerization method and compared with a nickel catalyst prepared by wet impregnation. Stronger interactions were observed in the formed catalysts between NiO species and the oxygen vacancies of the Y(2)O(3)-ZrO(2) in the catalysts made by polymerization, and these were attributed to less agglomeration of the NiO during the synthesis of the catalysts in one step. The dry reforming of ethanol was catalyzed with a maximum CO(2) conversion of 61% on the 5NiYZ catalyst at 800 degrees C, representing a better response than for the catalyst of the same composition prepared by wet impregnation. (C) 2009 Published by Elsevier B.V.

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.

Synthesis, Characterization, and Electrocatalytic Activity toward Methanol Oxidation of Carbon-Supported Pt(x)-(RuO(2)-M)(1-x) Composite Ternary Catalysts (M = CeO(2), MoO(3), or PbO(x))

Carbon-supported platinum is commonly used as an anode electrocatalyst in low-temperature fuel cells fueled with methanol. The cost of Pt and the limited world supply are significant barriers for the widespread use of this type of fuel cell. Moreover, Pt used as anode material is readily poisoned by carbon monoxide produced as a byproduct of the alcohol oxidation. Although improvements in the catalytic performance for methanol oxidation were attained using Pt-Ru alloys, the state-of-the-art Pt-Ru catalyst needs further improvement because of relatively low catalytic activity and the high cost of noble Pt and Ru. For these reasons, the development of highly efficient ternary platinum-based catalysts is an important challenge. Thus, various compositions of ternary Pt(x)-(RuO(2)-M)(1-x)/C composites (M = CeO(2), MoO(3), or PbO(x)) were developed and further investigated as catalysts for the methanol electro-oxidation reaction. The characterization carried out by X-ray diffraction, energy-dispersive X-ray analysis, transmission electron microscopy, X-ray photoelectron spectroscopy, and cyclic voltammetry point out that the different metallic oxides were successfully deposited on the Pt/C, producing small and well-controlled nanoparticles in the range of 2.8-4.2 nm. Electrochemical experiments demonstrated that the Pt(0.50)(RuO(2)-CeO(2))(0.50)/C composite displays the higher catalytic activity toward the methanol oxidation reaction (lowest onset potential of 207 mV and current densities taken at 450 mV, which are 140 times higher than those at commercial Pt/C), followed by the Pt(0.75)(RuO(2)-MoO(3))(0.25)/C composite. In addition, both of these composites produced low quantities of formic acid and formaldehyde when compared to a commercially available Pt(0.75)-Ru(0.25)/C composite (from E-Tek, Inc.), suggesting that the oxidation of methanol occurs mainly by a pathway that produces CO(2) forming the intermediary CO(ads).

Carbon supported electrocatalysts prepared by the sol-gel method and their utilization for the oxidation of methanol in acid media

One of the key objectives in fuel-cell technology is to improve the performance of the anode catalyst for the alcohol oxidation and reduce Pt loading. Here, we show the use of six different electrocatalysts synthesized by the sol -gel method on carbon powder to promote the oxidation of methanol in acid media. The catalysts Pt-PbO(x) and Pt-(RuO(2)-PbO(x)) with 10% of catalyst load exhibited significantly enhanced catalytic activity toward the methanol oxidation reaction as compared to Pt-(RuO(2))/C and Pt/C electrodes. Cyclic voltammetry studies showed that the electrocatalysts Pt-PbO(x)/C and Pt-(RuO(2)-PbO(x))/C started the oxidation process at extremely low potentials and that they represent a good novelty to oxidize methanol. Furthermore, quasi-stationary polarization experiments and cronoamperometry studies showed the good performance of the Pt-PbO(x), Pt-(RuO(2)-PbO(x))/C and Pt-(RuO(2)-IrO(2))/C catalysts during the oxidation process. Thus, the addition of metallic Pt and PbO(x) onto high-area carbon powder, by the sol -gel route, constitutes an interesting way to prepare anodes with high catalytic activity for further applications in direct methanol fuel cell systems.

Solvent assisted decomposition of the tetrahedral intermediate of the transesterification reaction to biodiesel production. A density functional study

B3LYP/6-31 + G(d) calculations were employed to investigate the mechanism of the transesterification reaction between a model monoglyceride and the methoxide and ethoxide anions. The gas-phase results reveal that both reactions have essentially the same activation energy (5.9 kcal mol(-1)) for decomposition of the key tetrahedral intermediate. Solvent effects were included by means of both microsolvation and the polarizable continuum solvation model CPCM. Both solvent approaches reduce the activation energy, however, only the microsolvation model is able to introduce some differentiation between methanol and ethanol, yielding a lower activation energy for decomposition of the tetrahedral intermediate in the reaction with methanol (1.1 kcal mol(-1)) than for the corresponding reaction with ethanol (2.8 kcal mol(-1)), in line with experimental evidences. Analysis of the individual energy components within the CPCM approach reveals that electrostatic interactions are the main contribution to stabilization of the transition state. (C) 2009 Elsevier Ltd. 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.

Competitividade dos biocombustíveis no Brasil: uma comparação entre os principais biocombustíveis etanol e biodisel

As preocupações mundiais com o aquecimento global e os efeitos nocivos da utilização de combustíveis fósseis têm fomentado a busca por novos modelos energéticos, baseados em fontes limpas e renováveis, com destaque para os biocombustíveis. Sem menos importância, o esgotamento das reservas mundiais de matérias-primas fósseis, somado às instabilidades geopolíticas nas principais regiões produtoras, impulsionam, cada vez mais, o desenvolvimento destes novos modelos. Neste cenário, o Brasil tem papel de destaque. Líder mundial na produção e consumo de etanol à base de cana-de-açúcar, o país iniciou, em 2005, a inclusão de mais uma fonte de energia renovável em sua matriz energética: a mistura do biodiesel no diesel mineral. O presente trabalho tem como objetivo analisar a competitividade dos principais biocombustíveis brasileiros: o etanol e o biodiesel. Em primeiro lugar, estes produtos foram analisados quanto às suas principais características; em segundo, avaliou-se a competitividade econômica destes combustíveis frente a seus produtos substitutos diretos derivados do petróleo. Finalmente, foram analisados os benefícios (tangíveis e intangíveis) inerentes à utilização dos biocombustíveis, e como estes intangíveis deveriam ser precificados, como forma de atribuir um prêmio aos benefícios que trazem ao meio-ambiente e à sociedade. Esta dissertação pretende servir de base para uma avaliação mais profunda da real competitividade econômica dos biocombustíveis frente aos combustíveis derivados do petróleo, além de colocar em cheque as principais análises atuais e críticas sobre a utilização destes produtos. Além disso, o presente trabalho visa avaliar o potencial e as limitações da produção dos biocombustíveis no Brasil.

Estudo prospectivo da internacionalização do etanol combustível.

Esta dissertação tem como objetivo elaborar cenários para a internacionalização do etanol combustível através da metodologia da prospectiva estratégica. Após a descrição da história do desenvolvimento do etanol combustível na matriz energética brasileira, descreveram-se, além do atual mercado de etanol no Brasil e no Mundo, os principais aspectos que influenciarão no desenvolvimento de sua comercialização como commodity internacional. Para isto, é aplicada a metodologia de prospecção de cenários para a utilização do etanol no âmbito mundial. Para os cenários identificados, após a revisão das literaturas teórica e empírica sobre o tema, é elaborado um estudo que descreve estratégias de internacionalização possíveis para Petrobras Biocombustível S.A., subsidiária da Petrobras Petróleo Brasileiro S.A, responsável pelos negócios de etanol da companhia, tanto no Brasil quanto no exterior.

Subsídios para a gestão dos planos de aplicação de vinhaça (PAV): um estudo de caso da região de Piracicaba

Concomitantemente à produção de etanol, a partir da fermentação de diferentes matérias-primas (cana-de-açúcar, beterraba, milho, trigo, batata, mandioca), produz-se a vinhaça. A vinhaça da cana-de-açúcar é gerada na proporção média de 12 litros para cada litro de etanol. O Brasil é o maior produtor mundial de cana-de-açúcar (570 milhões de toneladas, em 2009) com a produção de 27 bilhões de litros/ano de etanol, no ciclo 2009/2010, basicamente para fins carburantes, e, portanto, a quantidade de vinhaça produzida é da ordem de 320 bilhões de litros/ano. Dentre as possíveis soluções para a destinação da vinhaça, tais como: concentração, tratamento químico e biológico ou produção de biomassa, é sua aplicação no solo a forma mais usual de disposição. No entanto, sua aplicação no solo não pode ser excessiva nem indiscriminada, sob pena de comprometer o ambiente e a rentabilidade agrícola e industrial da unidade sucroalcooleira. A necessidade de medidas de controle sobre a aplicação de vinhaça no solo do Estado de São Paulo, que concentra a produção de 60% do etanol produzido no Brasil, levou à elaboração da Norma Técnica P4.231, em 2005. A constatação do cumprimento dos itens desta Norma é uma das ações do agente fiscalizador, no monitoramento da geração e destinação da vinhaça pelos empreendimentos produtores de etanol. Os itens 5.7.1 e 5.7.2, desta Norma, tornam obrigatório o encaminhamento à CETESB (Companhia Ambiental do Estado de São Paulo), para fins de acompanhamento e fiscalização, até o dia 02 de abril de cada ano, o PAV (Plano de Aplicação de Vinhaça). Com o intuito de proporcionar melhor entendimento da Norma P4.231, contribuir para otimização de sua aplicabilidade e melhoria e perceber a realidade prática da aplicação da vinhaça, foram analisados PAVs protocolados na Agência Ambiental de Piracicaba, licenças concedidas, processos de licenciamento e realizadas vistorias a campo. Conclui-se que a Norma P4.231 representa um avanço no gerenciamento do uso da vinhaça no Estado de São Paulo, por disciplinar a disposição de vinhaça no solo, tornando obrigatórios: demarcações de áreas protegidas e núcleos populacionais, caracterização de solo e da vinhaça, doses máximas a serem aplicadas, estudos da geologia e hidrogeologia locais, monitoramento das águas subterrâneas, impermeabilização de tanques e dutos. Estabelece critérios a serem obedecidos por lei, e todos são condutas de boas práticas de proteção ao meio, que repercutem em maior rentabilidade agrícola e industrial. A Norma P4.231 é bem elaborada, complexa e extensa, o que a torna de difícil execução. Para facilitar sua aplicabilidade, sugere-se o estabelecimento de um cronograma de prioridades: impermeabilização dos tanques e dutos, drenos testemunha com funcionamento otimizado e boa caracterização do que está sendo aplicado, se vinhaça pura ou se misturada a águas residuárias. Das oito empresas deste estudo, apenas quatro (as maiores) vêm protocolando os PAVs com regularidade, desde 2005. As informações apresentadas foram incompletas e, em alguns casos, precárias. Mesmo com lacunas, os dados fornecidos, desde o início da obrigatoriedade do PAV, foram de utilidade para esboçar o perfil da atividade sucroalcooleira na região estudada.

Uso de operações estruturadas para financiamento de projetos no setor sucroenergético brasileiro

O setor sucroenergético brasileiro passou por um intenso ciclo de crescimento nos últimos anos. Ainda assim, a demanda de etanol no país continua a superar a capacidade de produção, principalmente devido ao sucesso dos carros flex-fuel. As usinas voltaram também a atenção à bioeletricidade, aos alcoolquímicos e a diversos outros subprodutos e coprodutos do processo de produção de açúcar e etanol. Por estes motivos, se faz necessária a realização de maiores investimentos em ampliação e modernização das atuais usinas, e no aumento do número de unidades de produção. Para que tais investimentos sejam realizados da maneira mais eficiente, é necessário conhecer todas as opções de linhas de crédito disponíveis. Uma delas, pouco usada e com bons resultados é a Structured Project Finance. O presente trabalho tem como objetivo discutir o modelo de Structured Project Finance e apresentá-lo como uma possível alternativa de financiamento de projetos de usinas de açúcar e etanol no Brasil. Sua principal contribuição é apresentar uma alternativa de financiamento que agregue mais valor ao negócio.