Autocatalysis in the open circuit interaction of alcohol molecules with oxidized Pt surfaces

We studied the open circuit interaction of methanol and ethanol with oxidized platinum electrodes using in situ infrared spectroscopy. For methanol, it was found that formic acid is the main species formed in the initial region of the transient and that the steep decrease of the open circuit potential coincides with an explosive increase in the CO(2) production, which is followed by an increase in the coverage of adsorbed CO. For ethanol, acetaldehyde was the main product detected and only traces of dissolved CO(2) and adsorbed CO were found after the steep potential decay. In both cases, the transients were interpreted in terms of (a) the emergence of sub-surface oxygen in the beginning of the transient, where the oxide content is high, and (b) the autocatalytic production of free platinum sites for lower oxide content during the steep decay of the open circuit potential.

Complex Oscillatory Response of a PEM Fuel Cell Fed with H(2)/CO and Oxygen

Oscillatory kinetics is commonly observed in the electrocatalytic oxidation of most species that can be used in fuel cell devices. Examples include formic acid, methanol, ethanol, ethylene glycol, and hydrogen/carbon monoxide mixtures, and most papers refer to half-cell experiments. We report in this paper the experimental investigation of the oscillatory dynamics in a proton exchange membrane (PEM) fuel cell at 30 degrees C. The system consists of a Pt/C cathode fed with oxygen and a PtRu (1:1)/C anode fed with H(2) mixed with 100 ppm of CO, and was studied at different cell currents and anode flow rates. Many different states including periodic and nonperiodic series were observed as a function of the cell current and the H(2)/CO flow rate. In general, aperiodic/chaotic states were favored at high currents and low flow rates. The dynamics was further characterized in terms of the relationship between the oscillation amplitude and the subsequent time required for the anode to get poisoned by carbon monoxide. Results are discussed in terms of the mechanistic aspects of the carbon monoxide adsorption and oxidation. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3463725] All rights reserved.

Effect of sugarcane harvesting systems on soil carbon stocks in Brazil: an examination of existing data

Agricultural management practices that promote net carbon (C) accumulation in the soil have been considered as an important potential mitigation option to combat global warming. The change in the sugarcane harvesting system, to one which incorporates C into the soil from crop residues, is the focus of this work. The main objective was to assess and discuss the changes in soil organic C stocks caused by the conversion of burnt to unburnt sugarcane harvesting systems in Brazil, when considering the main soils and climates associated with this crop. For this purpose, a dataset was obtained from a literature review of soils under sugarcane in Brazil. Although not necessarily from experimental studies, only paired comparisons were examined, and for each site the dominant soil type, topography and climate were similar. The results show a mean annual C accumulation rate of 1.5 Mg ha-1 year-1 for the surface to 30-cm depth (0.73 and 2.04 Mg ha-1 year-1 for sandy and clay soils, respectively) caused by the conversion from a burnt to an unburnt sugarcane harvesting system. The findings suggest that soil should be included in future studies related to life cycle assessment and C footprint of Brazilian sugarcane ethanol.

Determination of the geographical origin of Brazilian wines by isotope and mineral analysis

In the present research, we studied wines from three different south Brazilian winemaking regions with the purpose of differentiating them by geographical origin of the grapes. Brazil`s wide territory and climate diversity allow grape cultivation and winemaking in many regions of different and unique characteristics. The wine grape cultivation for winemaking concentrates in the South Region, mainly in the Serra GaA(0)cha, the mountain area of the state of Rio Grande do Sul, which is responsible for 90% of the domestic wine production. However, in recent years, two new production regions have developed: the Campanha, the plains to the south and the Serra do Sudeste, the hills to the southeast of the state. Analysis of isotopic ratios of (18)O/(16)O of wine water, (13)C/(12)C of ethanol, and of minerals were used to characterize wines from different regions. The isotope analysis of delta(18)O of wine water and minerals Mg and Rb were the most efficient to differentiate the regions. By using isotope and mineral analysis, and discrimination analysis, it was possible to classify the wines from south Brazil.

Biofuels and Sustainable Energy Development in Brazil

Through the assessment of three decades of the Alcohol Program in Brazil, the paper shows that adequate public policies regarding biomass production can deliver direct benefits like energy security improvement, foreign exchange savings, and local employment generation, reduced urban air pollution and avoided CO(2) emissions. Moreover, the paper shows that Brazilian produced ethanol has faced economies of scale, technical progress and productivity gains and is no longer dependent on subsidies to be competitive. The paper also examines the potential in Brazil for fostering other biofuels, namely biodiesel obtained from vegetable oils, as well as their implications on sustainable energy development. (C) 2011 Elsevier Ltd. All rights reserved.

Assessing land availability to produce biomass for energy: The case of Brazilian charcoal for steel making

The paper discusses the availability of biomass in Brazil to supply charcoal to the steel industry on the bases of an initial global assessment of land potentially available for plantations and of Brazilian data that allows refining the assessment and specifying the issue of practical availability. Technical potentials are first assessed through a series of simple rules against direct competition with agriculture, forests and protected areas, and of quantitative criteria, whether geo-climatic (rainfall), demographic (population density) or legal (reserves). Institutional, social and economic factors are then identified and discussed so as to account for the practical availability of Brazilian biomass through six criteria. The ranking of nine Brazilian States according to these criteria brings out the necessary trade-offs in the selection of land for plantations that would efficiently supply charcoal to the steel industry. (C) 2008 Elsevier Ltd. All rights reserved.

A novel use for sugarcane bagasse hemicellulosic fraction: Xylitol enzymatic production

The excess of sugarcane bagasse (SCB) from the sugar-alcohol industry is considered a by-product with great potential for many bioproducts production. This work had as objective to verify the performance of sugarcane bagasse hemicellulosic hydrolysate (SCBHH) as source of sugars for enzymatic or in vitro xylitol production. For this purpose, xylitol enzymatic production was evaluated using different concentrations of treated SCBHH in the commercial reaction media. The weak acid hydrolysis of SCB provided a hydrolysate with 18 g L(-1) and 6 g L(-1) of xylose and glucose, respectively. Considering the reactions, changes at xylose xylitol conversion efficiency and volumetric productivity in xylitol were not observed for the control experiment and using 20 and 40% v.v (1) of SCBHH in the reaction media. The conversion efficiency achieved 100% in all the experiments tested. The results showed that treated SCBHH is suitable as xylose and glucose source for the enzymatic xylitol production and that this process has potential as an alternative for traditional xylitol production ways. (C) 2011 Published by Elsevier Ltd.

Role of Glycerol Addition on Xylose-to-Xylitol Bioconversion by Candida guilliermondii

The effect of glycerol on xylose-to-xylitol bioconversion by Candida guilliermondii was evaluated by its addition (0.7 and 6.5 g/l) to semidefined media (xylose as a substrate). The glycerol concentrations were chosen based on the amounts produced during previous studies on xylitol production by C. guilliermondii. Medium without glycerol addition (control) and medium containing glycerol (53 g/l) in substitution to xylose were also evaluated. According to the results, the addition of 0.7 g/l glycerol to the fermentation medium favored not only the yield (Y (P/S) = 0.78 g/g) but also the xylitol productivity (Q (P) = 1.13 g/l/h). During the xylose-to-xylitol bioconversion, the formation of byproducts (glycerol and ethanol) was observed for all conditions employed. In relation to the cellular growth, glycerol as the only carbon source for C. guilliermondii was better than xylose or xylose and glycerol mixtures, resulting in a maximum cellular concentration (5.34 g/l).

Influence of temperature on continuous high gravity brewing with yeasts immobilized on spent grains

Flavor compounds` formation and fermentative parameters of continuous high gravity brewing with yeasts immobilized on spent grains were evaluated at three different temperatures (7, 10 and 15 degrees C). The assays were performed in a bubble column reactor at constant dilution rate (0.05 h(-1)) and total gas flow rate (240 ml/min of CO(2) and 10 ml/min of air), with high-gravity all-malt wort (15 degrees Plato). The results revealed that as the fermentation temperature was increased from 7 to 15 degrees C, the apparent and real degrees of fermentation, rate of extract consumption, ethanol volumetric productivity and consumption of free amino nitrogen (FAN) increased. In addition, beer produced at 15 degrees C presented a higher alcohols to esters ratio (2.2-2.4:1) similar to the optimum values described in the literature. It was thus concluded that primary high-gravity (15 degrees Plato) all-malt wort fermentation by continuous process with yeasts immobilized on spent grains, can be carried out with a good performance at 15 degrees C.

Fermentation of cellulosic hydrolysates obtained by enzymatic saccharification of sugarcane bagasse pretreated by hydrothermal processing

This work aims to evaluate the fermentability of cellulosic hydrolysates obtained by enzymatic saccharification of sugarcane bagasse pretreated by hydrothermal processing using Candida guilliermondii FTI 20037 yeast. The inoculum was obtained from yeast culture in a medium containing glucose as a carbon source supplemented with rice bran extract, CaCl(2)center dot 2H(2)O and (NH(4))(2)SO(4) in 50 mL Erlenmeyer flasks, containing 20 mL of medium, initial 5.5 pH under agitation of an orbital shaker (200 rpm) at 30A degrees C for 24 h. The cellulosic hydrolysates, prior to being used as a fermentation medium, were autoclaved for 15 min at 0.5 atm and supplemented with the same nutrients employed for the inoculum, except the glucose, using the same conditions for the inoculum, but with a period of 48 h. Preliminary results showed the highest consumption of glucose (97%) for all the hydrolysates, at 28 h of fermentation. The highest concentration of ethanol (20.5 g/L) was found in the procedure of sugarcane bagasse pretreated by hydrothermal processing (195A degrees C/10 min in 20 L reactor) and delignificated with NaOH 1.0% (w/v), 100A degrees C, 1 h in 500 mL stainless steel ampoules immersed in an oil bath.

Effect of hemicellulose and lignin on enzymatic hydrolysis of cellulose from brewer`s spent grain

Enzymatic hydrolysis of brewer`s spent grain in three different forms: original (untreated), pretreated by dilute acid (cellulignin), and pretreated by a sequence of dilute acid and dilute alkali (cellulose pulp), was studied to verify the effect of hemicellulose and lignin on cellulose conversion into glucose. The hydrolysis was carried out using a commercial cellulase concentrate (Celluclast 1.5 L) in an enzyme/substrate ratio of 45 FPU/g, 2% (w/v) substrate concentration, 45 degrees C for 96 h. According to the results, the cellulose hydrolysis was affected by the presence of hemicellulose and/or lignin in the sample. The cellulose conversion ratio (defined as glucose yield + cellobiose yield) from cellulignin was 3.5-times higher than that from untreated sample, whereas from cellulose pulp such value was 4-times higher, correspondent to 91.8% (glucose yield of 85.6%). This best result was probably due to the strong modification in the material structure caused by the hemicellulose and lignin removal from the sample. As a consequence, the cellulose fibers were separated being more susceptible to the enzymatic attack. It was concluded that the lower the hemicellulose and lignin contents in the sample, the higher the efficiency of cellulose hydrolysis. (C) 2007 Elsevier Inc. All rights reserved.

Identification of the biodiesel source using an electronic nose

Biodiesel is an important new alternative fuel. The feedstock used and the process employed determines whether it fulfills the required specifications. In this work, an identification method is proposed using an electronic nose (e-nose). Four samples of biodiesel from different sources and one of petrodiesel were analyzed and well-recognized by the e-nose. Both pure biodiesel and B20 blends were studied. Furthermore, an innovative semiquantitative method is proposed on the basis of the smellprints correlated by a feed-forward artificial neural network. The results have demonstrated that the e-nose can be used to identify the biodiesel source and as a preliminary quantitative assay in place of expensive equipment.

Extraction of manganese peroxidase produced by Lentinula edodes

Lentinula edodes, commonly called shiitake, is considered a choice edible mushroom with exotic taste and medicinal quality. L. edodes grows very well and produces a range of enzymes when cultivated on eucalyptus residues. Development of appropriate experimental procedures for recovery and determination of enzymes became a widely important cash crop. In this work, enzymes produced by L. edodes were extracted using different pH buffer and determined regarding peroxidases and proteases. Lignin peroxidase (LiP) was not detected in the extracts based on veratryl alcohol or azure B oxidation. Proteases were very low while Mn-peroxidases (MnP) predominated. The optimal pH for MnP recovery was 5.0, under agitation at 25 degrees C. The oxidation of phenol red decreased after dark-colored small compounds or ions were eliminated by dialysis. The extract of L. edodes contained components of high molecular weight, such as proteases or high polyphenol, that could be involved in the LiP inactivation. L. edodes sample previously submitted to dialysis was also joined to UP of Phanerochaete chrysosporium and a total inhibition of UP was observed. (C) 2007 Elsevier Ltd. All rights reserved.

Clarification of a wheat straw-derived medium with ion-exchange resins for xylitol crystallization

BACKGROUND: Xylitol bioproduction from lignocellulosic residues comprises hydrolysis of the hemicellulose, detoxification of the hydrolysate, bioconversion of the xylose, and recovery of xylitol from the fermented hydrolysate. There are relatively few reports on xylitol recovery from fermented media. In the present study, ion-exchange resins were used to clarify a fermented wheat straw hemicellulosic hydrolysate, which was then vacuum-concentrated and submitted to cooling in the presence of ethanol for xylitol crystallization. RESULTS: Sequential adsorption into two anion-exchange resins (A-860S and A-500PS) promoted considerable reductions in the content of soluble by-products (up to 97.5%) and in medium coloration (99.5%). Vacuum concentration led to a dark-colored viscous solution that inhibited xylitol crystallization. This inhibition could be overcome by mixing the concentrated medium with a commercial xylitol solution. Such a strategy led to xylitol crystals with up to 95.9% purity. The crystallization yield (43.5%) was close to that observed when using commercial xylitol solution (51.4%). CONCLUSION: The experimental data demonstrate the feasibility of using ion-exchange resins followed by cooling in the presence of ethanol as a strategy to promote the fast recovery and purification of xylitol from hemicellulose-derived fermentation media. (c) 2008 Society of Chemical Industry.

Optimisation of environmental gas cleaning routes for solid wastes cogeneration systems - Part I - Analysis of waste incineration steam cycle

Research of advanced technologies for energy generation contemplates a series of alternatives that are introduced both in the investigation of new energy sources and in the improvement and/or development of new components and systems. Even though significant reductions are observed in the amount of emissions, the proposed alternatives require the use of exhaust gases cleaning systems. The results of environmental analyses based on two configurations proposed for urban waste incineration are presented in this paper; the annexation of integer (Boolean) variables to the environomic model makes it possible to define the best gas cleaning routes based on exergetic cost minimisation criteria. In this first part, the results for steam cogeneration system analysis associated with the incineration of municipal solid wastes (MSW) is presented. (c) 2007 Elsevier Ltd. All rights reserved.