On-line mass spectrometry of the electro-oxidation of methanol in acidic media on tungsten carbide

The electro-oxidation of methanol at supported tungsten carbide (WC) nanoparticles in sulfuric acid solution was studied using cyclic voltammetry, potentiostatic measurements, and differential electrochemical mass spectroscopy (DEMS). The catalyst was prepared by a sonochemical method and characterized by X-ray diffraction. Over the WC catalyst, the oxidation of methanol (1 M in a sulfuric acid electrolyte) begins at a potential below 0.5 V/RHE during the anodic sweep. During potentiostatic measurements, a maximum current of 0.8 mA mg(-1) was obtained at 0.4 V. Measurements of DEMS showed that the methanol oxidation reaction over tungsten carbide produces CO2 (m/z=44); no methylformate (m/z=60) was detected. These results are discussed in the context of the continued search for alternative materials for the anode catalyst of direct methanol fuel cells.

On the open-circuit interaction between methanol and oxidized platinum electrodes

In the present work, results of the interaction between methanol and oxidized platinum surfaces as studied via transients of open-circuit potentials are presented. The surface oxidation before the exposure to interaction with 0.5 M methanol was performed at different polarization times at 1.4 V vs reversible hydrogen electrode (RHE). In spite of the small changes in the initial oxide content, the increase of the pre-polarization time induces a considerable increase of the time needed for the oxide consumption during its interaction with methanol. The influence of the identity of the chemisorbing anion on the transients was also investigated in the following media: 0.1 M HClO4, 0.5 M H2SO4, and 0.5 M H2SO4 + 0.1 mM Cl-. It was observed that the transient time increases with the energy of anion chemisorption and, more importantly, without a change in the shape of the transient, meaning that free platinum sites are available at the topmost layer all over the transient and not only in the potential region of small oxide `coverage`. The impact of the pre-polarization time and the effect of anion chemisorption on the transients are rationalized in terms of the presence of surface and subsurface oxygen driven by place exchange.

Triphenylmethane dyes, an alternative for mediated electronic transfer systems in glucose oxidase biofuel cells

The bioelectrochemical behavior of three triphenylmethane (TPM) dyes commonly used as pH indicators, and their application in mediated electron transfer systems for glucose oxidase bioanodes in biofuel cells was investigated. Bromophenol Blue, Bromothymol Blue, Bromocresol Green were compared bio-electrochemically against two widely used mediators, benzoquinone and ferrocene carboxy aldehyde. Biochemical studies were performed in terms of enzymatic oxidation, enzyme affinity, catalytic efficiency and co-factor regeneration. The different features of the TPM dyes as mediators are determined by the characteristics in the oxidation/reduction processes studied electrochemically. The reversibility of the oxidation/reduction processes was also established through the dependence of the voltammetric peaks with the sweep rates. All three dyes showed good performances compared to the FA and BQ when evaluated in a half enzymatic fuel cell. Potentiodynamic and power response experiments showed maxima power densities of 32.8 mu W cm(-2) for ferrocene carboxy aldehyde followed by similar values obtained for TPM dyes around 30 mu W cm(-2) using glucose and mediator concentrations of 10 mmol L(-1) and 1.0 mmol L(-1), respectively. Since no mediator consumption was observed during the bioelectrochemical process, and also good redox re-cycled processes were achieved, the use of triphenylmethane dyes is considered to be promising compared to other mediated systems used with glucose oxiclase bioanodes and/or biofuel cells. (C) 2011 Elsevier Inc. All rights reserved.

Stabilizing Nonstationary Electrochemical Time Series

Electrochemical systems are ideal working-horses for studying oscillatory dynamics. Experimentally obtained time series, however, are usually associated with a spontaneous drift in some uncontrollable parameter that triggers transitions among different oscillatory patterns, despite the fact that all controllable parameters are kept constant. Herein we present an empirical method to stabilize experimental potential time series. The method consists of applying a negative galvanodynamic sweep to compensate the spontaneous drift and was tested for the oscillatory electro-oxidation of methanol on platinum. For a wide range of applied currents, the base system presents spontaneous transitions from quasi-harmonic to mixed mode oscillations. Temporal patterns were stabilized by galvanodynamic sweeps at different rates. The procedure resulted in a considerable increase in the number of oscillatory cycles from 5 to 20 times, depending on the specific temporal pattern. The spontaneous drift has been associated with uncompensated oscillations, in which the coverage of some adsorbed species are not reestablished after one cycle; i.e., there is a net accumulation and/or depletion of adsorbed species during oscillations. We interpreted the rate of the galvanodynamic sweep in terms of the time scales of the poisoning processes that underlies the uncompensated oscillations and thus the spontaneous slow drift.

A comparative study of the electrogeneration of hydrogen peroxide using Vulcan and Printex carbon supports

A comparative study of two different conductive carbon-black pigments, Vulcan XC-72 R and Printex L6, for the electrogeneration of hydrogen peroxide (H(2)O(2)) by reducing dissolved oxygen in an alkaline solution was performed. The materials were physically characterized by X-ray diffraction (XRD), Fourier transform infrared attenuated total reflection (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). XRD shows the presence of SO(2) and ATR-FTIR technique indicates a difference in NO and SO(2) functional groups between the two carbon pigments. XPS indicated presence of SO and NO and more oxygenated acid species on Printex L6. A rotating ring-disk electrode was used for electrochemical analysis of the oxygen reduction reaction (ORR). The results showed that the Printex L6 was better than Vulcan XC-72 R for H(2)O(2) production. Results also indicate that the number of electrons transferred in the ORR for Printex L6 and Vulcan XC-72 R were 2.2 and 2.9, respectively, while the percentages of H(2)O(2) formed were 88% and 51%. Scanning electrochemistry microscopy images confirmed the higher amount of H(2)O(2) formed in the Printex L6 pigment. Printex L6 was shown to be a more promising for H(2)O(2) production than Vulcan XC-72 R, while the latter was shown to have more potential for fuel cells. (C) 2011 Elsevier Ltd. All rights reserved.

Fermentation of Groundnut Shell Enzymatic Hydrolysate for Fuel Ethanol Production by Free and Sorghum Stalks Immobilized Cells of Pichia stipitis NCIM 3498

Groundnut shell (GS), after separation of pod, is readily available as a potential feedstock for production of fermentable sugars. The substrate was delignified with sodium sulfite. The delignified substrate released 670 mg/g of sugars after enzymatic hydrolysis (50 degrees C, 120 rpm, 50 hrs) using commercial cellulases (Dyadic Xylanase PLUS, Dyadic Inc. USA). The groundnut shell enzymatic hydrolysate (45.6 g/L reducing sugars) was fermented for ethanol production with free and sorghum stalks immobilized cells of Pichia stipitis NCIM 3498 under submerged cultivation conditions. Immobilization of yeast cells on sorghum stalks were confirmed by scanning electron microscopy (SEM). A maximum of ethanol production (17.83 g/L, yield 0.44 g/g and 20.45 g/L, yield 0.47 g/g) was observed with free and immobilized cells of P. stipitis respectively in batch fermentation conditions. Recycling of immobilized cells showed a stable ethanol production (20.45 g/L, yield 0.47 g/g) up to 5 batches followed by a gradual downfall in subsequent cycles.

The Influence of Initial Xylose Concentration, Agitation, and Aeration on Ethanol Production by Pichia stipitis from Rice Straw Hemicellulosic Hydrolysate

Rice straw hemicellulosic hydrolysate was used as fermentation medium for ethanol production by Pichia stipitis NRRL Y-7124. Shaking bath experiments were initially performed aiming to establish the best initial xylose concentration to be used in this bioconversion process. In the sequence, assays were carried out under different agitation (100 to 200 rpm) and aeration ((V) under bar (flask)/V(medium) ratio varying from 2.5 to 5.0) conditions, and the influence of these variables on the fermentative parameters values (ethanol yield factor, Y(P/S); cell yield factor, Y(X/S); and ethanol volumetric productivity, Q(P)) was investigated through a 2(2) full-factorial design. Initial xylose concentration of about 50 g/l was the most suitable for the development of this process, since the yeast was able to convert substrate in product with high efficiency. The factorial design assays showed a strong influence of both process variables in all the evaluated responses. The agitation and aeration increase caused a deviation in the yeast metabolism from ethanol to biomass production. The best results (Y(P/S) = 0.37 g/g and Q(P) = 0.39 g/l. h) were found when the lowest aeration (2.5 V(flask)/V(medium) ratio) and highest agitation (200 rpm) levels were employed. Under this condition, a process efficiency of 72.5% was achieved. These results demonstrated that the establishment of adequate conditions of aeration is of great relevance to improve the ethanol production from xylose by Pichia stipitis, using rice straw hemicellulosic hydrolysate as fermentation medium.

Atmospheric impacts of the life cycle emissions of fuel ethanol in Brazil: based on chemical exergy

An assessment is made of the atmospheric emissions from the life cycle of fuel ethanol coupled with the cogeneration of electricity from sugarcane in Brazil. The total exergy loss from the most quantitative relevant atmospheric emission substances produced by the life cycle of fuel ethanol is 3.26E+05 kJ/t of C(2)H(5)OH, Compared with the chemical exergy of 1 t of ethanol (calculated as 34.56E + 06 kJ). the exergy loss from the life cycle`s atmospheric emission represents 1.11% of the product`s exergy. The activity that most contributes to atmospheric emission chemical exergy losses is the harvesting of sugarcane through the methane emitted in burning. Suggestions for improved environmental quality and greater efficiency of the life cycle of fuel ethanol with cogenerated energy are: harvesting the sugarcane without burning, renewable fuels should be used in tractors, trucks and buses instead of fossil fuel and the transportation of products and input should be logistically optimized. (C) 2009 Elsevier Ltd. All rights reserved.

Lifecycle assessment of fuel ethanol from sugarcane in Brazil

This paper presents the lifecycle assessment (LCA) of fuel ethanol, as 100% of the vehicle fuel, from sugarcane in Brazil. The functional unit is 10,000 km run in an urban area by a car with a 1,600-cm(3) engine running on fuel hydrated ethanol, and the resulting reference flow is 1,000 kg of ethanol. The product system includes agricultural and industrial activities, distribution, cogeneration of electricity and steam, ethanol use during car driving, and industrial by-products recycling to irrigate sugarcane fields. The use of sugarcane by the ethanol agribusiness is one of the foremost financial resources for the economy of the Brazilian rural area, which occupies extensive areas and provides far-reaching potentials for renewable fuel production. But, there are environmental impacts during the fuel ethanol lifecycle, which this paper intents to analyze, including addressing the main activities responsible for such impacts and indicating some suggestions to minimize the impacts. This study is classified as an applied quantitative research, and the technical procedure to achieve the exploratory goal is based on bibliographic revision, documental research, primary data collection, and study cases at sugarcane farms and fuel ethanol industries in the northeast of SA o pound Paulo State, Brazil. The methodological structure for this LCA study is in agreement with the International Standardization Organization, and the method used is the Environmental Design of Industrial Products. The lifecycle impact assessment (LCIA) covers the following emission-related impact categories: global warming, ozone formation, acidification, nutrient enrichment, ecotoxicity, and human toxicity. The results of the fuel ethanol LCI demonstrate that even though alcohol is considered a renewable fuel because it comes from biomass (sugarcane), it uses a high quantity and diversity of nonrenewable resources over its lifecycle. The input of renewable resources is also high mainly because of the water consumption in the industrial phases, due to the sugarcane washing process. During the lifecycle of alcohol, there is a surplus of electric energy due to the cogeneration activity. Another focus point is the quantity of emissions to the atmosphere and the diversity of the substances emitted. Harvesting is the unit process that contributes most to global warming. For photochemical ozone formation, harvesting is also the activity with the strongest contributions due to the burning in harvesting and the emissions from using diesel fuel. The acidification impact potential is mostly due to the NOx emitted by the combustion of ethanol during use, on account of the sulfuric acid use in the industrial process and because of the NOx emitted by the burning in harvesting. The main consequence of the intensive use of fertilizers to the field is the high nutrient enrichment impact potential associated with this activity. The main contributions to the ecotoxicity impact potential come from chemical applications during crop growth. The activity that presents the highest impact potential for human toxicity (HT) via air and via soil is harvesting. Via water, HT potential is high in harvesting due to lubricant use on the machines. The normalization results indicate that nutrient enrichment, acidification, and human toxicity via air and via water are the most significant impact potentials for the lifecycle of fuel ethanol. The fuel ethanol lifecycle contributes negatively to all the impact potentials analyzed: global warming, ozone formation, acidification, nutrient enrichment, ecotoxicity, and human toxicity. Concerning energy consumption, it consumes less energy than its own production largely because of the electricity cogeneration system, but this process is highly dependent on water. The main causes for the biggest impact potential indicated by the normalization is the nutrient application, the burning in harvesting and the use of diesel fuel. The recommendations for the ethanol lifecycle are: harvesting the sugarcane without burning; more environmentally benign agricultural practices; renewable fuel rather than diesel; not washing sugarcane and implementing water recycling systems during the industrial processing; and improving the system of gases emissions control during the use of ethanol in cars, mainly for NOx. Other studies on the fuel ethanol from sugarcane may analyze in more details the social aspects, the biodiversity, and the land use impact.

Forecasting fuel ethanol consumption in Brazil by time series models: 2006-2012

This article analysed scenarios for Brazilian consumption of ethanol for the period 2006 to 2012. The results show that if the country`s GDP sustains a 4.6% a year growth, domestic consumption of fuel ethanol could increase to 25.16 billion liters in this period, which is a volume relatively close to the forecasted gasoline consumption of 31 billion liters. At a lower GDP growth of 1.22% a year, gasoline consumption would be reduced and domestic ethanol consumption in Brazil would be no higher than 18.32 billion liters. Contrary to the current situation, forecasts indicated that hydrated ethanol consumption could become much higher than anhydrous consumption in Brazil. The former is being consumed in cars moved exclusively by ethanol and flex-fuel cars, successfully introduced in the country at 2003. Flex cars allow Brazilian consumers to choose between gasoline and hydrated ethanol and immediately switch to whichever fuel presents the most favourable relative price.

Catalytic oxidation of ethanol on gold electrode in alkaline media

This work presents a study of the catalytic oxidation of ethanol on polycrystalline gold electrode in alkaline media. The investigation was carried out by means of chronoamperometry, cyclic voltammetry, and in situ FTIR spectroscopy. The main goal was to investigate the early stages of ethanol electrooxidation, namely at fairly low potentials (E = 600 mV vs. RHE) and for moderate reaction times (t < 300 s). Chronoamperometric experiments show a current increase accompanying the increasing in the ethanol concentration up to about 2 M and then a slight decrease at 3 M. Adsorbed CO has been observed as early as about 200 mV vs. RHE and indicates that the cleavage of the C-C bond might occur, probably to a small extent, at very low overpotentials during ethanol adsorption on gold surface. The amount of dissolved acetate ions produced during the chronoamperomentry was followed by the asymmetric stretching band at 1558 cm(-1) as a function of time, and found to increase linearly with time up to 300 s. This allowed estimating the reaction order of acetate formation with respect to ethanol concentration.

Net greenhouse gas fluxes in Brazilian ethanol production systems

Biofuels are both a promising solution to global warming mitigation and a potential contributor to the problem. Several life cycle assessments of bioethanol have been conducted to address these questions. We performed a synthesis of the available data on Brazilian ethanol production focusing on greenhouse gas (GHG) emissions and carbon (C) sinks in the agricultural and industrial phases. Emissions of carbon dioxide (CO(2)) from fossil fuels, methane (CH(4)) and nitrous oxide (N(2)O) from sources commonly included in C footprints, such as fossil fuel usage, biomass burning, nitrogen fertilizer application, liming and litter decomposition were accounted for. In addition, black carbon (BC) emissions from burning biomass and soil C sequestration were included in the balance. Most of the annual emissions per hectare are in the agricultural phase, both in the burned system (2209 out of a total of 2398 kg C(eq)), and in the unburned system (559 out of 748 kg C(eq)). Although nitrogen fertilizer emissions are large, 111 kg C(eq) ha-1 yr-1, the largest single source of emissions is biomass burning in the manual harvest system, with a large amount of both GHG (196 kg C(eq) ha-1 yr-1). and BC (1536 kg C(eq) ha-1 yr-1). Besides avoiding emissions from biomass burning, harvesting sugarcane mechanically without burning tends to increase soil C stocks, providing a C sink of 1500 kg C ha-1 yr-1 in the 30 cm layer. The data show a C output: input ratio of 1.4 for ethanol produced under the conventionally burned and manual harvest compared with 6.5 for the mechanized harvest without burning, signifying the importance of conservation agricultural systems in bioethanol feedstock production.

Ethanol production by a new pentose-fermenting yeast strain, Scheffersomyces stipitis UFMG-IMH 43.2, isolated from the Brazilian forest

The ability of a recently isolated Scheffersomyces stipitis strain (UFMG-IMH 43.2) to produce ethanol from xylose was evaluated. For the assays, a hemicellulosic hydrolysate produced by dilute acid hydrolysis of sugarcane bagasse was used as the fermentation medium. Initially, the necessity of adding nutrients (MgSO(4).7H(2)O, yeast extract and/or urea) to this medium was verified, and the yeast extract supplementation favoured ethanol production by the yeast. Then, in a second stage, assays under different initial xylose and cell concentrations, supplemented or not with yeast extract, were performed. All these three variables showed significant (p < 0.05) influence on ethanol production. The best results (ethanol yield and productivity of 0.19 g/g and 0.13 g/l/h, respectively) were obtained using the hydrolysate containing an initial xylose concentration of 30 g/l, supplemented with 5.0 g/l yeast extract and inoculated with an initial cell concentration of 2.0 g/l. S. stipitis UFMG-IMH 43.2 was demonstrated to be a yeast strain with potential for use in xylose conversion to ethanol. The establishment of the best fermentation conditions was also proved to be of great importance to increasing the product formation by this yeast strain. These findings open up new perspectives for the establishment of a feasible technology for ethanol production from hemicellulosic hydrolysates. Copyright (C) 2011 John Wiley & Sons, Ltd.

Ethanol production process from banana fruit and its lignocellulosic residues: Energy analysis

Tropical countries, such as Brazil and Colombia, have the possibility of using agricultural lands for growing biomass to produce bio-fuels such as biodiesel and ethanol. This study applies an energy analysis to the production process of anhydrous ethanol obtained from the hydrolysis of starch and cellulosic and hemicellulosic material present in the banana fruit and its residual biomass. Four different production routes were analyzed: acid hydrolysis of amylaceous material (banana pulp and banana fruit) and enzymatic hydrolysis of lignocellulosic material (flower stalk and banana skin). The analysis considered banana plant cultivation, feedstock transport, hydrolysis, fermentation, distillation, dehydration, residue treatment and utility plant. The best indexes were obtained for amylaceous material for which mass performance varied from 346.5 L/t to 388.7 L/t, Net Energy Value (NEV) ranged from 9.86 MJ/L to 9.94 MJ/L and the energy ratio was 1.9 MJ/MJ. For lignocellulosic materials, the figures were less favorable: mass performance varied from 86.1 to 123.5 L/t, NEV from 5.24 10 8.79 MJ/L and energy ratio from 1.3 to 1.6 MJ/MJ. The analysis showed, however, that both processes can be considered energetically feasible. (C) 2010 Elsevier Ltd. All rights reserved.

Obtaining and selection of hexokinases-less strains of Saccharomyces cerevisiae for production of ethanol and fructose from sucrose

Saccharomyces cerevisiae hexokinase-less strains were produced to study the production of ethanol and fructose from sucrose. These strains do not have the hexokinases A and B. Twenty-three double-mutant strains were produced, and then, three were selected for presenting a smaller growth in yeast extract-peptone-fructose. In fermentations with a medium containing sucrose (180.3 g L-1) and with cell recycles, simulating industrial conditions, the capacity of these mutant yeasts in inverting sucrose and fermenting only glucose was well characterized. Besides that, we could also see their great tolerance to the stresses of fermentative recycles, where fructose production (until 90 g L-1) and ethanol production (until 42.3 g L-1) occurred in cycles of 12 h, in which hexokinase-less yeasts performed high growth (51.2% of wet biomass) and viability rates (77% of viable cells) after nine consecutive cycles.