Modeling and simulation of the anode in direct ethanol fuels cells

Mathematical modeling has been extensively applied to the study and development of fuel cells. In this work, the objective is to characterize a mechanistic model for the anode of a direct ethanol fuel cell and perform appropriate simulations. The software Comsol Multiphysics (R) (and the Chemical Engineering Module) was used in this work. The software Comsol Multiphysics (R) is an interactive environment for modeling scientific and engineering applications using partial differential equations (PDEs). Based on the finite element method, it provides speed and accuracy for several applications. The mechanistic model developed here can supply details of the physical system, such as the concentration profiles of the components within the anode and the coverage of the adsorbed species on the electrode surface. Also, the anode overpotential-current relationship can be obtained. To validate the anode model presented in this paper, experimental data obtained with a single fuel cell operating with an ethanol solution at the anode were used. (C) 2008 Elsevier B.V. All rights reserved.

Thermodynamic analysis of direct steam reforming of ethanol in molten carbonate fuel cell

Fuel cell as MCFC (molten carbonate fuel cell) operate at high temperatures, and due to this issue, cogeneration processes may be performed, sending heat for own process or other purposes as steam generation in an industry. The use of ethanol for this purpose is one of the best options because this is a renewable and less environmentally offensive fuel, and cheaper than oil-derived hydrocarbons (in the case of Brazil). In the same country, because of technical, environmental and economic advantages, the use of ethanol by steam reforming process have been the most investigated process. The objective of this study is to show a thermodynamic analysis of steam reforming of ethanol, to determine the best thermodynamic conditions where are produced the highest volumes of products, making possible a higher production of energy, that is, a most-efficient use of resources. To attain this objective, mass and energy balances are performed. Equilibrium constants and advance degrees are calculated to get the best thermodynamic conditions to attain higher reforming efficiency and, hence, higher electric efficiency, using the Nernst equation. The advance degree of reforming increases when the operation temperature also increases and when the operation pressure decreases. But at atmospheric pressure (1 atm), the advance degree tends to the stability in temperatures above 700°C, that is, the volume of supplemental production of reforming products is very small for the high use of energy resources necessary. Reactants and products of the steam-reforming of ethanol that weren't used may be used for the reforming. The use of non-used ethanol is also suggested for heating of reactants before reforming. The results show the behavior of MCFC. The current density, at same tension, is higher at 700°C than other studied temperatures as 600 and 650°C. This fact occurs due to smaller use of hydrogen at lower temperatures that varies between 46.8 and 58.9% in temperatures between 600 and 700°C. The higher calculated current density is 280 mA/cm 2. The power density increases when the volume of ethanol to be used also increases due to higher production of hydrogen. The highest produced power at 190 mW/cm 2 is 99.8, 109.8 and 113.7 mW/cm2 for 873, 923 and 973K, respectively. The thermodynamic efficiency has the objective to show the connection among operational conditions and energetic factors, which are some parameters that describes a process of internal steam reforming of ethanol.

Voltammetric determination of ethyl acetate in ethanol fuel using a Fe 3+/Nafion®-coated glassy carbon electrode

A voltammetric method for the determination of ethyl acetate in ethanol fuel using a Fe3+/Nafion®-coated glassy carbon electrode (GCE) is proposed. The ethyl acetate present in the ethanol fuel was previously converted to acetohydroxamic acid via pretreatment with hydroxylamine chloride. The acetohydroxamic acid promptly reacted with the iron (III) present in the film, producing iron (III) acetohydroxamate, which presents a well-defined voltammetric peak current at -0.02 V. Optimization of the voltammetric parameters for the cyclic, linear sweep, square wave, and differential pulse modalities was carried out for this chemically-modified electrode. Square wave voltammetry afforded the best response for acetohydroxamic acid detection. The analytical curve for this species was linear from 9 to 100 μmol L 1 according to the following equation: ip (μA) = 0.27 + 2.55Cacetohydroxamic acid (μmol L 1), with linear correlation coefficient equal to 0.993. The technique presented limit of detection equal to 5.3 μmol L 1 and quantification limit of 17.6 μmol L 1. The proposed method was compared to the official method of ethyl acetate analysis (Gas Chromatography), and a satisfactory correlation was found between these techniques. © 2012 Elsevier Ltd. All rights reserved.

Preconcentration and determination of metal ions from fuel ethanol with a new 2,2'-dipyridylamine bonded silica

A silica surface chemically modified with [3-(2,2'-dipyridylamine) propyl] groups was prepared, characterized, and evaluated for its metal ion preconcentration in fuel ethanol. To our knowledge, we are the first authors who have reported the present modification on silica gel surface. The material was characterized using infrared spectra, scanning electronic microscopy, and 13C and 29Si solid-state NMR spectra. Batch and column experiments were conducted to investigate for metal ion removal from fuel ethanol. The results showed that the Langmuir model describes the sorption equilibrium data of the metal ions in a satisfactory way. From the Langmuir isotherms, the following maximum adsorption capacities (in mmolg -1) were determined: 1.81 for Fe(III), 1.75 for Cr(III), 1.30 for Cu(II), 1.25 for Co(II), 1.15 for Pb(II), 0.95 for Ni(II), and 0.87 for Zn(II). Thermodynamic functions, the change of free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) showed that the adsorption of metal ions onto Si-Pr-DPA was feasible, spontaneous, and endothermic. The sorption-desorption of the metal ions made possible the development of a preconcentration and quantification method of metal ions in fuel ethanol. © 2012 Elsevier Inc.

Development of a technique for achieving an optimum BSFC for LAF engine

The reserves of gasoline and diesel fuels are ever decreasing, which plays an important role in the technological development of automobiles. Numerous countries, especially the United States, wish to slowly decrease their fuel dependence on other countries by producing in house renewable fuels like biodiesels or ethanol. Therefore, the new automobile engines have to successfully run on a variety of fuels without significant changes to their designs. The current study focuses on assessing the potential of ethanol fuels to improve the performance of 'flex-fuel SI engines,' which literally means 'engines that are flexible in their fuel requirement.' Another important area within spark ignition (SI) engine research is the implementation of new technologies like Variable Valve Timing (VVT) or Variable Compression Ratio (VCR) to improve engine performance. These technologies add more complexity to the original system by adding extra degrees of freedom. Therefore, the potential of these technologies has to be evaluated before they are installed in any SI engine. The current study focuses on evaluating the advantages and drawbacks of these technologies, primarily from an engine brake efficiency perspective. The results show a significant improvement in engine efficiency with the use of VVT and VCR together. Spark ignition engines always operate at a lower compression ratio as compared to compression ignition (CI) engines primarily due to knock constraints. Therefore, even if the use of a higher compression ratio would result in a significant improvement in SI engine efficiency, the engine may still operate at a lower compression ratio due to knock limitations. Ethanol fuels extend the knock limit making the use of higher compression ratios possible. Hence, the current study focuses on using VVT, VCR, and ethanol-gasoline blends to improve overall engine performance. The results show that these technologies promise definite engine performance improvements provided both their positive and negative potentials have been evaluated prior to installation.

A comparative study of GERIPA ethanol with other fuels

The GERIPA project aimed at generating renewable energy integrated with food production has led to a beneficial option for producing ethanol and electricity. Ethanol has economic, social and environmental potential. Considering just the first one, Brazil consumes 39 billion litres per year-L(D)/yr of diesel oil, 18% of it being imported. The Federal Government has a recovery programme for the soybean agribusiness aimed at soybean biodiesel (SBD) production in which a 10% addition to diesel has been proposed. This 10% involves producing 10.7 million L(SB)/d. Soybean bio-diesel production is not self-sustainable and such proposal could require an annual subsidy of up to US$1.33 billion. Soybean plantations would need about 10 to 12 times more land than is necessary for sugarcane plantations to produce the same equivalent thermal energy (ETE). Sixty-seven GERIPA projects (GP) producing 80,000 litres of ethanol per day (GP80) could be set up with the sum of US$1.33 billion; this would substitute current Brazilian biodiesel demand by 4.28%, adding the some value for each new subsidiary. Considering ETE, ethanol-GP cost would be 37% to 50% below that for a litre of SBD on account of its raw material (RM) and region. The diesel cycle`s thermal efficiency (eta(1)) yield is around 50% and that of the Otto cycle engine eta(1) is around 37%. The cost per km driven (CKD) by substituting SBD for ethanol-GP80 would thus indicate an 18% minimum and 59% maximum cost reduction for vehicle engines.

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.

Optimal fermentation conditions for maximizing the ethanol production by Kluyveromyces fragilis from cheese whey powder

Cheese whey powder (CWP) is an attractive raw material for ethanol production since it is a dried and concentrated form of CW and contains lactose in addition to nitrogen, phosphate and other essential nutrients. In the present work, deproteinized CWP was utilized as fermentation medium for ethanol production by Kluyveromyces fragilis. The individual and combined effects of initial lactose concentration (50-150 kg m(-3)), temperature (25-35 degrees C) and inoculum concentration (1-3 kg m(-3)) were investigated through a 2(3) full-factorial central composite design, and the optimal conditions for maximizing the ethanol production were determined. According to the statistical analysis, in the studied range of values, only the initial lactose concentration had a significant effect on ethanol production, resulting in higher product formation as the initial substrate concentration was increased. Assays with initial lactose concentration varying from 150 to 250 kg m(-3) were thus performed and revealed that the use of 200 kg m(-3) initial lactose concentration, inoculum concentration of 1 kg m(-3) and temperature of 35 degrees C were the best conditions for maximizing the ethanol production from CWP solution. Under these conditions, 80.95 kg m(-3) of ethanol was obtained after 44 h of fermentation. (C) 2011 Elsevier Ltd. All rights reserved.

The roles of xylan and lignin in oxalic acid pretreated corncob during separate enzymatic hydrolysis and ethanol fermentation

High yields of hemicellulosic and cellulosic sugars are critical in obtaining economical conversion of agricultural residues to ethanol. To optimize pretreatment conditions, we evaluated oxalic acid loading rates, treatment temperatures and times in a 2(3) full factorial design. Response-surface analysis revealed an optimal oxalic acid pretreatment condition to release sugar from the cob of Zea mays L ssp. and for Pichia stipitis CBS 6054. To ferment the residual cellulosic sugars to ethanol following enzymatic hydrolysis, highest saccharification and fermentation yields were obtained following pretreatment at 180 degrees C for 50 min with 0.024 g oxalic acid/g substrate. Under these conditions, only 7.5% hemicellulose remained in the pretreated substrate. The rate of cellulose degradation was significantly less than that of hemicellulose and its hydrolysis was not as extensive. Subsequent enzymatic saccharification of the residual cellulose was strongly affected by the pretreatment condition with cellulose hydrolysis ranging between 26.0% and 76.2%. The residual xylan/lignin ratio ranged from 0.31 to 1.85 depending on the pretreatment condition. Fermentable sugar and ethanol were maximal at the lowest ratio of xylan/lignin and at high glucan contents. The model predicts optimal condition of oxalic acid pretreatment at 168 degrees C, 74 min and 0.027 g/g of oxalic acid. From these findings, we surmised that low residual xylan was critical in obtaining maximal glucose yields from saccharification. Published by Elsevier Ltd.

Simultaneous saccharification and ethanol fermentation of oxalic acid pretreated corncob assessed with response surface methodology

Response surface methodology was used to evaluate optimal time, temperature and oxalic acid concentration for simultaneous saccharification and fermentation (SSF) of corncob particles by Pichia stipitis CBS 6054. Fifteen different conditions for pretreatment were examined in a 2(3) full factorial design with six axial points. Temperatures ranged from 132 to 180 degrees C, time from 10 to 90 min and oxalic acid loadings from 0.01 to 0.038 g/g solids. Separate maxima were found for enzymatic saccharification and hemicellulose fermentation, respectively, with the condition for maximum saccharification being significantly more severe. Ethanol production was affected by reaction temperature more than by oxalic acid and reaction time over the ranges examined. The effect of reaction temperature was significant at a 95% confidence level in its effect on ethanol production. Oxalic acid and reaction time were statistically significant at the 90% level. The highest ethanol concentration (20 g/l) was obtained after 48 h with an ethanol volumetric production rate of 0.42 g ethanol l(-1) h(-1). The ethanol yield after SSF with P. stipitis was significantly higher than predicted by sequential saccharification and fermentation of substrate pretreated under the same condition. This was attributed to the secretion of beta-glucosidase by P. stipitis. During SSF, free extracellular beta-glucosidase activity was 1.30 pNPG U/g with P. stipitis, while saccharification without the yeast was 0.66 pNPG U/g. Published by Elsevier Ltd.

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.

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.

Combined production of sugar, ethanol and electricity: Thermoeconomic and environmental analysis and optimization

Many works have shown the potential of the Brazilian sugarcane industry as an electricity supplier. However, few studies have studied how this potential could be achieved without jeopardizing the production of sugar and ethanol. Also, the impact of modifications in the cogeneration plant on the costs of production of sugar and ethanol has not been evaluated. This paper presents an approach to the problem of exergy optimization of cogeneration systems in sugarcane mills. A general model to the sugar and ethanol production processes is developed based on data supplied by a real plant, and an exergy analysis is performed. A discussion is made about the variables that most affect the performance of the processes. Then, a procedure is presented to evaluate modifications in the cogeneration system and in the process, and their impact on the production costs of sugar, ethanol and electricity. Furthermore, a discussion on the renewability of processes is made based on an exergy index of renewability. As a general conclusion, besides adding a new revenue to the mill, the generation of excess electricity improves the exergo-environmental performance of the mill as a whole. (C) 2010 Elsevier Ltd. All rights reserved.

Competitiveness of Brazilian sugarcane ethanol compared to US corn ethanol

Corn ethanol produced in the US and sugarcane ethanol produced in Brazil are the world`s leading sources of biofuel. Current US biofuel policies create both incentives and constraints for the import of ethanol from Brazil and together with the cost competitiveness and greenhouse gas intensity of sugarcane ethanol compared to corn ethanol will determine the extent of these imports. This study analyzes the supply-side determinants of cost competitiveness and compares the greenhouse gas intensity of corn ethanol and sugarcane ethanol delivered to US ports. We find that while the cost of sugarcane ethanol production in Brazil is lower than that of corn ethanol in the US, the inclusion of transportation costs for the former and co-product credits for the latter changes their relative competitiveness. We also find that the relative cost of ethanol in the US and Brazil is highly sensitive to the prevailing exchange rate and prices of feedstocks. At an exchange rate of US$1=R$2.15 the cost of corn ethanol is 15% lower than the delivered cost of sugarcane ethanol at a US port. Sugarcane ethanol has lower GHG emissions than corn ethanol but a price of over $113 per ton of CO(2) is needed to affect competitiveness. (C) 2010 Elsevier Ltd. All rights reserved.