ABSTRACT Cobalt and niobium oxide solids modified with alkaline earth metals (Mg, Ca, and Sr) were synthesized and characterized to compare the second element effect on the catalyst structural and chemical properties. The materials were prepared by co-precipitation of cobalt nitrate and niobium oxalate solutions using ammonium hydroxide as precipitating agent. The samples were characterized by XRD, SEM, Ra-man, BET, TPR, ammonia TPD and cyclohexane dehydrogenation reaction (CHD). Results showed that Mg, Ca or Sr addition changed cobalt niobate crystalline structure, leading to alkaline earth metal nio-bates with lower crystallinity. It was observed that Mg, Ca or Sr increased the solids acidity and changed cobalt niobate reduction behavior so that the lowest amount of metallic cobalt was obtained when Mg was incorporated. Modifiers also decreased cobalt niobate dehydrogenation activity. This effect was higher with Mg or Sr addition.

ABSTRACT The solid oxide fuel cells (SOFC) enable the efficient generation of clean energy, fitting the current requirements of the growing demand for electricity and for the environment preservation. When powered with biogas (from digesters of municipal wastes), the SOFCs also contribute to reduce the environmental impact of these wastes. The most suitable route to produce hydrogen inside SOFC from biogas is through dry reforming but the catalyst is easily deactivated by coke, because of the high amounts of carbon in the stream. A promising way to overcome this drawback is by adding a second metal to nickel-based catalysts. Aiming to obtain active, selective and stable catalysts for biogas dry reforming, solids based on nickel (15%) and copper (5%) supported on aluminum and magnesium oxide were studied in this work. Samples were prepared by impregnating the support with nickel and copper nitrate, followed by calcination at 500, 600 and 800 oC. It was noted that all solids were made of nickel oxide, nickel aluminate and magnesium aluminate but no copper compound was found. The specific surface areas did not changed with calcination temperature but the nickel oxide average particles size increased. The solids reducibility decreased with increasing temperature. All catalysts were active in methane dry reforming, leading to similar conversions but different selectivities to hydrogen and different activities in water gas shift reaction (WGSR). This behavior was assigned to different interactions between nickel and copper, at different calcination temperatures. All catalysts were active in WGSR, decreasing the hydrogen to carbon monoxide molar ratio and producing water. The catalyst calcined at 500 oC was the most promising one, leading to the highest hydrogen yield, besides the advantage of being produced at the lowest calcination temperature, requiring less energy in its preparation.

Abstract In this paper, a new way for γ-alumina synthesis was proposed, the raw material being aluminum powders obtained by high-energy milling of aluminum cans. This seems a good option for this metal recycling and energy saving, as well as hydrogen production. The materials were prepared by precipitation techniques, in which aluminum powders reacted with hydrochloric acid, giving aluminum chloride, which was subsequently transformed into aluminum hydroxide by reaction with ammonium hydroxide or sodium hydroxide as precipitant agents, and finally into γ-alumina by calcination. Results showed that the used preparation methods gave a γ-alumina structure, confirmed by XRD, with surface areas values (174 and 204 m2 g-1) close to those of a commercial γ-alumina Cyanamid Ketjen (180 m2 g-1) or an alumina prepared by a typical precipitation route (203 m2 g-1). Using sodium hydroxide as precipitant agent turned out to be more ecologically compatible since it did not release harmful environmental compounds.

ResumoOs processos enzimáticos que seguem o modelo cinético de Michaelis-Menten foram estudados a partir de diferentes propostas para descrever a etapa de inibição reversível. As propostas de inibição foram comparadas a partir de um processo genérico, onde as constantes cinéticas receberam valores unitários e o valor numérico da concentração de substrato foi dez (10) vezes superior ao valor numérico da concentração de enzima. Para cada proposta de modelo de inibição foram obtidas soluções numéricas a partir de sistema não linear de equações diferenciais ordinárias, gerando gráficos que apresentaram, separadamente, a variação das concentrações da enzima, dos complexos enzimáticos, do substrato e do produto da reação. Foi obtido um modelo, dentre as propostas avaliadas, com desempenho indicando comportamento similar ao verificado no modelo clássico de Michaelis-Menten, onde o complexo de reação é rapidamente formado e, ao longo do processo, decai até tender a zero. Em contrapartida, diferentemente do modelo clássico, na nova proposta de modelo o efeito de inibição começa em zero e, ao longo do processo, tende ao valor nominal da concentração inicial da enzima. Tais respostas mostraram-se válidas para valores distintos de concentração de enzima e de tempo de processo, mostrando robustez e indicando uma tendência do somatório do substrato e do produto atingir o valor nominal da concentração inicial do substrato ao longo do tempo de processamento.

SummaryEnzymatic processes that follow the kinetic model of Micahelis-Merten had been studied taking as reference different proposals to describe the reversible inhibition phase. Inhibition proposals were compared based on a generic process. In this process, the kinetic constants received unitary values and the numeric value of the substrate concentration was ten (10) times higher than the numeric value of enzyme concentration. Numeric solutions based on a non-linear system of ordinary differential equations were obtained for each proposal of the inhibition model, resulting in a graphic representing, separately, the variation of enzyme concentrations, enzymatic complexes, substrate and product reaction. One model was obtained, among the evaluated proposals, with performance indicating behavior similar to the classical Michaelis-Menten model, where the reaction complex is rapidly formed and, along the process, decay tending to zero. However, differently from the classic model, in the proposed new model the inhibition process starts at zero and, during the process, tends to the nominal value of the initial enzymatic concentration. Such responses were shown to be valid for different values of enzyme concentration and processing time, showing robustness and indicating that the sum of the substrate and the product tends to reach the nominal value of the initial concentration of the substrate along the processing time.

A fermentação sourdough para a produção de pães é fortemente motivada por seus efeitos benéficos quanto ao sabor, textura, vida de prateleira e pelas propriedades nutricionais dos produtos obtidos. Nesta pesquisa, estudou-se a aplicação dos micro-organismos Kluyveromyces marxianus, Dekkera bruxellensis e Lactobacillus plantarum como culturas starters alternativas na produção de pães. A partir de sete ensaios resultantes de um delineamento de mistura simplex-centroide, foram realizadas nos pães análises sensorial e instrumental. Observou-se que pães produzidos com L. plantarum apresentaram menor volume específico, enquanto que a mistura entre K. marxianus e L. plantarum exerceu influência positiva, possibilitando obter produtos de maior volume específico. A análise sensorial demonstrou a boa aceitabilidade para os pães produzidos com a mistura entre D. bruxellensis e K. marxianus e para a mistura entre os três micro-organismos. Os resultados deste trabalho demonstram a possibilidade do uso de culturas starters definidas para a fermentação sourdough, que é tradicionalmente obtida sem controle de processo.

The sourdough fermentation in bread making is strongly motivated due to its beneficial aspects on flavor, texture, shelf life, and the nutritional properties of the obtained products. In this research, the yeasts Kluyveromyces marxianus and Dekkera bruxellensis, and the bacterium Lactobacillus plantarum were used as alternative starter cultures in bread making. Experimental designs generated from simplex-centroid mixture were used in the sensorial analyses of breads. Results have shown that bread obtained with pure cultures of L. plantarum presented the smallest specific volume, while the mixture of K. marxianus and L. plantarum positively influenced the formation of good specific volume of products. Sensorial analysis showed good acceptability for breads obtained with D. bruxellensis and K. marxianus mixture, as well as for the mixture of the three microorganisms. The results obtained in this research suggest the possibility of using defined starter cultures for sourdough fermentation, which is traditionally carried out without any process controls.

No processo em um único estágio com a adição simultânea de β-galactosidase e de cultura lática, foram avaliadas a conversão da lactose, o tempo de processamento, a viscosidade e a sinérese. A fermentação foi promovida por cultura láctica, contendo dois micro-organismos probióticos, Bifidobacterium animalis e Lactobacillus acidophilus, associados aos micro-organismos característicos do iogurte. Foi utilizado um preparado enzimático contendoβ-galactosidases obtidas de Kluyveromyces lactis e de Aspergillus niger. Os efeitos da concentração inicial de lactose, concentração de enzima e tempo de adição da enzima foram avaliados por meio de um planejamento experimental (2³ ensaios mais três pontos centrais). As seguintes condições foram estabelecidas: concentração inicial de lactose de 91 g L-1, concentração de enzima de 0.5 g L-1 e adição da enzima no início da fermentação. Nessas condições, um decréscimo no tempo de processamento (de 4,55 h para 3,68 h) e um incremento na conversão de lactose (de 15,2% para 97,9%) foram observados em relação à fermentação sem a adição da enzima, sem alterações prejudiciais em algumas propriedades físicas do iogurte (viscosidade, e sinérese).

In a single-stage process with the simultaneous addition of β-galactosidase and lactic culture, the lactose conversion, the processing time, viscosity and syneresis were evaluated. Fermentation was promoted by lactic culture containing two probiotic microorganisms, Bifidobacterium animalis and Lactobacillus acidophilus, associated with the typical microorganisms of yogurt. An enzymatic preparation containing β-galactosidases from Kluyveromyces lactis and Aspergillus niger was used. A central composite design (2³ trials plus three central points) was proposed in order to evaluate the effects of initial lactose concentration, enzyme concentration and the time of addition of the enzyme. The following conditions were established: initial lactose concentration of 91 g L-1, enzyme concentration of 0.5 g L-1 and enzyme addition at the beginning of fermentation. In these conditions, a decrease in processing time (from 4.55 to 3.68 h) and an increase in lactose conversion (from 15.2 to 97.9%) were observed in relation to the fermentation without enzyme addition, and no detrimental changes in some physical properties of yogurt (viscosity, and syneresis).