Co catalysts supported on SiO(2) and gamma-Al(2)O(3) applied to ethanol steam reforming: Effect of the solvent used in the catalyst preparation method

Cobalt catalysts were prepared on supports of SiO(2) and gamma-Al(2)O(3) by the impregnation method, using a solution of Co precursor in methanol. The samples were characterized by XRD, TPR, and Raman spectroscopy and tested in ethanol steam reforming. According to the XRD results, impregnation with the methanolic solution led to smaller metal crystallites than with aqueous solution, on the SiO(2) support. On gamma-Al(2)O(3), all the samples exhibited small crystallites, with either solvent, due to a higher Co-support interaction that inhibits the reduction of Co species. The TPR results were consistent with XRD results and the samples supported on gamma-Al(2)O(3) showed a lower degree of reduction. In the steam reforming of ethanol, catalysts supported on SiO(2) and prepared with the methanolic solution showed the best H(2), CO(2) and CO selectivity. Those supported on gamma-Al(2)O(3) showed lower H(2) selectivity. (C) 2011 Elsevier Ltd. All rights reserved.

CO preferential oxidation (CO-PROx) on La(1-x)Ce(x)NiO(3) perovskites

La(1-x)Ce(x)NiO(3) perovskites have been prepared, characterized by XRD. TPR and surface area and tested as catalysts for CO-PROx, with a feed of 2.5% CO, 5% O(2), 33% H(2) and N(2) to 100%. The samples exhibited an XRD pattern typical of the perovskite, with traces of NiO in the LaNiO(3) and La(0.95)Ce(0.05)NiO(3) samples, with some La(2)NiO(4) in the La(0.90)Ce(0.10)NiO(3) sample. All samples were active, but the perovskites with cerium showed good catalytic activity, demonstrating the promoter effect of cerium. The highest conversion of CO and H(2) was obtained with La(0.95)Ce(0.05)NiO(3), probably due to a synergy between Ni and Ce that enhanced O(2) mobility. (c) 2010 Elsevier B.V. All rights reserved.

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.

Mass transport effects in the borohydride oxidation reaction-Influence of the residence time on the reaction onset and faradaic efficiency

The borohydride oxidation reaction (BOR) was studied on Pt and Au electrodes by cyclic voltammetry in dilute alkaline borohydride solutions (0.1 M NaOH + 10(-3) mol L(-1) NaBH(4)). More specifically, the electrodes were considered as either Vulcan XC72-supported Pt or Au (noted as Pt/C and Au/C, respectively) active layers or smooth Pt or Au surfaces, the latter possibly being covered by a layer of (non-metalized) Vulcan XC72 carbon powder. The BOR onset potential and the number of electrons (n(e-)) exchanged per BH(4)(-) anion (faradaic efficiency) were investigated for these electrodes, to determine whether the residence time of reaction intermediates (at the electrode surface or inside the porous layer) does influence the overall reaction pathway/completion. For the carbon-supported platinum, n(e-) strongly depends on the thickness of the active layer. While thin (ca. 0.5 mu m-thick) Pt/C active layers yield n(e-) < 4, thick layers (approximately 3 mu m) yield n(e-)approximate to 8, which can be ascribed to the sufficient residence time of the molecules formed within the active layer (H(2), by heterogeneous hydrolysis, or BOR intermediates) enabling further (near-complete) oxidation. This puts into evidence that not only the nature of the electrocatalyst is important to reach high BOR efficiency, but also the structure/thickness of the active layer. The same trend applies for Au/C active layers and for smooth Pt or Au surfaces covered with a layer of (inactive) Vulcan XC72. In addition, the BOR onset usually shifts negative when the reaction intermediates are trapped, which suggests that some of the intermediates are more easily oxidized than BH(4)(-) itself; based on literature data, BH(3)OH(-) species is a likely candidate. (C) 2011 Elsevier B.V. All rights reserved.

Effects of starch gelatinization and oxidation on the rheological behavior of chitosan/starch blends

Chitosan/starchblends represent an interesting alternative for the preparation of biocompatible drug delivery systems, packing materials and edible films. This paper reports on the effects of starch gelatinization and oxidation on the rheological behavior of chitosan/starch blends. The results show that the modifications in the starch structure cause changes in G` (storage modulus) and G `` (lossmodulus) as a function of frequency. For chitosan/starch, G `` is higher than G`, showing a viscous behavior. However, for chitosan/gelatinized starch and chitosan/oxidized starch, an increase in the angular frequency promotes a modulus crossover at omega = 0.02 and 0.04 rad s(-1), respectively. The viscosity curves as a function of shear rate show that both modifications cause an increase in viscosity, and all blends show a non-Newtonian behavior. (C) 2011 Society of Chemical Industry

Anodic oxidation of wastewater containing the Reactive Orange 16 Dye using heavily boron-doped diamond electrodes

Boron-doped diamond (BDD) films grown on the titanium substrate were used to study the electrochemical degradation of Reactive Orange (RO) 16 Dye. The films were produced by hot filament chemical vapor deposition (HFCVD) technique using two different boron concentrations. The growth parameters were controlled to obtain heavily doped diamond films. They were named as E1 and E2 electrodes, with acceptor concentrations of 4.0 and 8.0 x 10(21) atoms cm(-3), respectively. The boron levels were evaluated from Mott-Schottky plots also corroborated by Raman`s spectra, which characterized the film quality as well as its physical property. Scanning Electron Microscopy showed well-defined microcrystalline grain morphologies with crystal orientation mixtures of (1 1 1) and (1 00). The electrode efficiencies were studied from the advanced oxidation process (AOP) to degrade electrochemically the Reactive Orange 16 azo-dye (RO16). The results were analyzed by UV/VIS spectroscopy, total organic carbon (TOC) and high-performance liquid chromatography (HPLC) techniques. From UV/VIS spectra the highest doped electrode (E2) showed the best efficiency for both, the aromaticity reduction and the azo group fracture. These tendencies were confirmed by the TOC and chromatographic measurements. Besides, the results showed a direct relationship among the BDD morphology, physical property, and its performance during the degradation process. (C) 2011 Elsevier B.V. All rights reserved.

Light-Induced Oxidation of Unsaturated Lipids as Sensitized by Flavins

Triplet-excited riboflavin ((3)RF*) was found by laser flash photolysis to be quenched by polyunsaturated fatty acid methyl esters in tert-butanol/water (7:3, v/v) in a second-order reaction with k similar to 3.0 x 10(5) L mol(-1) s(-1) at 25 degrees C for methyl linoleate and 3.1 x 10(6) L mol(-1) s(-1), with Delta H double dagger = 22.6 kJ mol(-1) and Delta S double dagger = -62.3 J K(-1) mol(-1), for methyl linolenate in acetonitrile/water (8:2, v/v). For methyl oleate, k was <10(4) L mol(-1) s(-1). For comparison, beta-casein was found to have a rate constant k similar to 4.9 x 10(8) L mol(-1) s(-1). Singlet-excited flavin was not quenched by the esters as evidenced by insensitivity of steady-state fluorescence to their presence. Density functional theory (DFT) calculations showed that electron transfer from unsaturated fatty acid esters to triplet-excited flavins is endergonic, while a formal hydrogen atom transfer is exergonic (Delta G(HAT)degrees = -114.3, -151.2, and -151.2 kJ mol(-1) for oleate, linoleate, and linolenate, respectively, in acetonitrile). The reaction is driven by acidity of the lipid cation radical for which a pK(a) similar to -0.12 was estimated by DFT calculations. Absence of electrochemical activity in acetonitrile during cyclic voltammetry up to 2.0 V versus NHE confirmed that Delta G(ET)degrees > 0 for electron transfer. Interaction of methyl esters with (3)RF* is considered as initiation of the radical chain, which is subsequently propagated by combination reactions with residual oxygen. In this respect, carbon-centered and alkoxyl radicals were detected using the spin trapping technique in combination with electron paramagnetic resonance spectroscopy. Moreover, quenching of 3RF* yields, directly or indirectly, radical species which are capable of initiating oxidation in unsaturated fatty acid methyl esters. Still, deactivation of triplet-excited flavins by lipid derivatives was slower than by proteins (factor up to 10(4)), which react preferentially by electron transfer. Depending on the reaction environment in biological systems (including food), protein radicals are expected to interfere in the mechanism of light-induced lipid oxidation.

Photo-assisted electrochemical degradation of real textile wastewater

In the present study, photo-assisted electrochemical degradation of real textile wastewater was performed. Degradation assays were performed at constant current (40 mA cm(-2)) in a combined electro/photochemical flow-cell using a Ti/Ru(0.3)Ti(0.7)O(2) DSA(R) type electrode. The results show that the method is capable of removing color and chemical oxygen demand (COD) from the effluent. Additionally, the effect of initial pH and type of supporting electrolyte (Na(2)SO(4) or NaCl) was investigated. The principal figures of merit used in this study were COD removal and color removal (605 nm). The results show that up to 72% color and up to 59% COD removal in 120 min is possible under the operating conditions employed. Studies of the phytotoxicity of the wastewater before and after the photo-assisted degradation assays are also presented and the results demonstrate that the toxicity of the effluent is dependent on the length of electrolysis time and the treatment procedure employed.

Fuel ethanol price drivers in the Atlantic basin : Brazil & the U.S. traders perspectives

Como a oportunidade de exportação de etanol combustível é muito recente, o agronegócio carece de literatura para formação de gestores e estrategistas. Este trabalho tem como objetivo descrever o mecanismo de formação de preços de etanol tanto no Brasil como nos Estados Unidos da America. Decupei as variáveis que impactam na formação de preços, custo de produção de etanol de cana-de-açúcar, custo da logística e desidratação no Caribe, custo do etanol de milho e fiz algumas análises de cenários de formação de preços das principais variáveis e consegui organizar este conhecimento em um gráfico que contém no eixo superior preço do etanol hidratado na usina no Brasil e no eixo inferior o preço do bushel de milho em Chicago cujas interceções nas retas da taxa do dólar e do preço do gás natural, fornecem no eixo Y o preço do produto no porto de Nova York, ficando uma visualização simples das possibilidades da janela de exportação. A metodologia permite assumir diferentes cenários de oferta, demanda e preços e estabelecer diferentes estratégias de comercialização.

Brazil and the USA: rethinking the future of ethanol for stronger mutual wns

A produção de etanol e a dominação da indústria, historicamente, tem sido uma fonte de discórdia para seus dois principais produtores. Os EUA com seu etanol de milho e o Brasil com sua etanol de cana, são os dois maiores produtores mundiais de etanol (1º EUA; 2º Brasil) e tem competido pela participação de mercado mundial há décadas. A partir de Dezembro de 2011, os EUA levantaram as tarifas e os subsídios que foram instalados para proteger sua indústria de etanol, o que muda o campo de jogo da produção mundial de etanol para o futuro. Atualmente em todo o mundo, o etanol é usado em uma proporção muito menor comparativamente a outros combustíveis. Esta pesquisa analisa o nível potencial de colaboração entre os EUA e o Brasil, facilitando um diálogo entre os stakeholders em etanol. A pesquisa consiste principalmente de conversas e entrevistas, com base em um conjunto de perguntas destinadas a inspirar conversas detalhadas e expansivas sobre os temas de relações Brasil-EUA e etanol. Esta pesquisa mostra que o etanol celulósico, que é também conhecido como etanol de segunda geração, oferece mais oportunidades de parceria entre os EUA e o Brasil, como há mais oportunidades para pesquisa e desenvolvimento em conjunto e transferência de tecnologia nesta área. Enquanto o etanol de cana no Brasil ainda é uma indústria próspera e crescente, o milho e a cana são muito diferentes geneticamente para aplicar as mesmas inovações exatas de um etanol de primeira geração, por outro. As semelhanças entre os processos de fermentação e destilação entre as matérias-primas utilizadas nos EUA e no Brasil para o etanol de segunda geração torna o investimento conjunto nesta área mais sensível. De segunda geração é uma resposta para a questão "alimentos versus combustíveis". Esta pesquisa aplica o modelo de co-opetição como um quadro de parceria entre os EUA e o Brasil em etanol celulósico. A pesquisa mostra que enquanto o etanol pode não ser um forte concorrente com o petróleo no futuro imediato, ele tem melhores perspectivas de ser desenvolvido como um complemento ao petróleo, em vez de um substituto. Como os EUA e o Brasil tem culturas de misturar etanol com petróleo, algo da estrutura para isso já está em vigor, a relação de complementaridade seria fortalecido através de uma política de governo clara e de longo prazo. A pesquisa sugere que apenas através desta colaboração, com toda a partilha de conhecimentos técnicos e estratégias econômicas e de desenvolvimento, o etanol celulósico será um commodity negociado mundialmente e uma alternativa viável a outros combustíveis. As entrevistas com os interessados em que esta pesquisa se baseia foram feitas ao longo de 2012. Como a indústria de etanol é muito dinâmica, certos eventos podem ter ocorrido desde esse tempo para modificar ou melhorar alguns dos argumentos apresentados.

How to indirectly assess transaction costs to evaluate market integration: evidence from the international ethanol market

Mercados são instituições criadas para facilitar uma atividade de comercialização. Isto é possível porque um mercado é constituído por instituições que foram desenhadas para reduzir os custos de transação associados a este processo de troca. A partir dessas duas ideias, esta tese possui três objetivos principais. (i) Analisar por que a literatura de análise de cointegração tem mensurado estes custos de forma imprecisa. A principal razão é certa confusão entre os conceitos de custos de transação, de transporte e de comercialização. (ii) Propor um procedimento para mensurar indiretamente os custos de transação de mercado variáveis combinando os modelos de cointegração com mudança de regime e a estrutura teórica oferecidas pela Nova Economia Institucional. Este procedimento é aplicado para quantificar quanto custa comercializar etanol no mercado internacional usando suas atuais instituições. (iii) Por fim, usando os mesmos modelos e a mesma estrutura teórica, esta dissertação contesta a hipótese de que já existe um mercado internacional de etanol bem desenvolvido, tal qual a literatura tem assumido. De forma semelhante, também é avaliada a hipótese de que a remoção das barreiras comerciais norte-americanas para o etanol brasileiro seria uma condição suficiente para o desenvolvimento deste mercado internacional. Os testes aplicados rejeitam ambas as hipóteses.

Business process in supply chain integration in sugar and ethanol industry

This article presents the application of a diagnosis method in a Brazilian company from the sugar and ethanol industry to identify the level of supply chain integration. The diagnosis method is based on Cooper, Lambert and Pagh reference model for SCM. The method involves nine referential axes established from the eighth key business processes of the reference model.

On the temperature stability of extracellular hemoglobin of Glossoscolex paulistus, at different oxidation states: SAXS and DLS studies

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