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

Fuel cell as molten carbonate fuel cell (MCFC) operates at high temperatures. Thus, cogeneration processes may be performed, generating heat for its own process or for other purposes of steam generation in the industry. The use of ethanol is one of the best options because this is a renewable and less environmentally offensive fuel, and is cheaper than oil-derived hydrocarbons, as in the case of Brazil. In that country, because of technical, environmental, and economic advantages, the use of ethanol by steam reforming process has 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 the highest volumes of products are produced, making possible a higher production of energy, that is, a more efficient use of resources. To attain this objective, mass and energy balances were performed. Equilibrium constants and advance degrees were calculated to get the best thermodynamic conditions to attain higher reforming efficiency and, hence, higher electric efficiency, using the Nernst equation. The advance degree (according to Castellan 1986, Fundamentos da Fisica/Quimica, Editora LTC, Rio de Janeiro, p. 529, in Portuguese) is a coefficient that indicates the evolution of a reaction, achieving a maximum value when all the reactants' content is used of reforming increases when the operation temperature also increases and when the operation pressure decreases. However, at atmospheric pressure (1 atm), the advance degree tends to stabilize in temperatures above 700 degrees C; that is, the volume of supplemental production of reforming products is very small with respect to high use of energy resources necessary. The use of unused ethanol is also suggested for heating of reactants before reforming. The results show the behavior of MCFC. The current density, at the same tension, is higher at 700 degrees C than other studied temperatures such as 600 and 650 degrees 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 degrees 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 powers at 190 mA/cm(2) are 99.8, 109.8, and 113.7 mW/cm(2) for 873, 923, and 973 K, respectively. The thermodynamic efficiency has the objective to show the connection among operational conditions and energetic factors, which are some parameters that describe a process of internal steam reforming of ethanol.

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.

Development of novel bioanodes for ethanol biofuel cell using PAMAM dendrimers as matrix for enzyme immobilization

This paper describes the preparation and application of a novel bioanode for use in ethanol/O(2) biofuel cells based upon immobilization of alcohol dehydrogenase (ADH) and polyamidoamine (PAMAM) dendrimers onto carbon cloth platforms. The power density measurements indicated a direct relationship between the amount of anchored ADH and the anode power values, which increased upon enzyme loading. The power density values ranged from 0.04 to 0.28 mW cm(-2), and the highest power density was achieved with the bioanode prepared with 28 U of ADH, which provided a power density of 0.28 mW cm(-2) at 0.3 V. The latter power output values were the maximum observed, even for higher enzyme concentrations. Stability of the bioanodes was quite satisfactory, since there was no appreciable reduction of enzymatic activity during the measurements. The method of bioanode preparation described here has proven to be very effective. The PAMAM dendrimer represents a friendly environment for the immobilization of enzymes, and it is stable and capable of generating high power density compared to other immobilization methods. (C) 2010 Elsevier B.V. All rights reserved.

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.

A novel electrocatalyst support with proton conductive properties for polymer electrolyte membrane fuel cell applications

The objective of this study is to graft the Surface of carbon black, by chemically introducing polymeric chains (Nafion (R) like) with proton-conducting properties. This procedure aims for a better interaction of the proton-conducting phase with the metallic catalyst particles, as well as hinders posterior support particle agglomeration. Also loss of active surface call be prevented. The proton conduction between the active electrocatalyst site and the Nafion (R) ionomer membrane should be enhanced, thus diminishing the ohmic drop ill the polymer electrolyte membrane fuel cell (PEMFC). PtRu nanoparticles were supported on different carbon materials by the impregnation method and direct reduction with ethylene glycol and characterized using amongst others FTIR, XRD and TEM. The screen printing technique was used to produce membrane electrode assemblies (MEA) for single cell tests in H(2)/air(PEMFC) and methanol operation (DMFC). In the PEMFC experiments, PtRu supported on grafted carbon shows 550 mW cm(-2) gmetal(-1) power density, which represents at least 78% improvement in performance, compared to the power density of commercial PtRu/C ETEK. The DMFC results of the grafted electrocatalyst achieve around 100% improvement. The polarization Curves results clearly show that the main Cause of the observed effect is the reduction in ohmic drop, caused by the grafted polymer. (C) 2009 Elsevier B.V. All rights reserved.

Methanol and ethanol electro-oxidation on Pt-SnO(2) and Pt-Ta(2)O(5) sol-gel-modified boron-doped diamond surfaces

The search for more efficient anode catalyst than platinum to be used in direct alcohol fuel cell systems is an important challenge. In this study, boron-doped diamond film surfaces were modified with Pt, Pt-SnO(2) and Pt-Ta(2)O(5) nano-crystalline deposits by the sol-gel method to study the methanol and ethanol electro-oxidation reactions in acidic medium. Electrochemical experiments carried out in steady-state conditions demonstrate that the addition of SnO(2) to Pt produces a very reactive electrocatalyst that possibly adsorbs and/or dissociate ethanol more efficiently than pure Pt changing the onset potential of the reaction by 190 mV toward less positive potentials. Furthermore, the addition of Ta(2)O(5) to Pt enhances the catalytic activity toward the methanol oxidation resulting in a negative shift of the onset potential of 170 mV. These synergic effects indicate that the addition of these co-catalysts inhibits the poisoning effect caused by strongly adsorbed intermediary species. Since the SnO(2) catalyst was more efficient for ethanol oxidation, it could probably facilitate the cleavage of the C-C bond of the adsorbed intermediate fragments of the reaction. (C) 2009 Elsevier B.V. All rights reserved.

Analysis of a molten carbonate fuel cell: cogeneration to produce electricity and cold water

The fuel cell is an emerging cogeneration technology that has been applied successfully in Japan, the USA and some countries in the European Union. This system performs direct conversion of the chemical energy of the oxidation of hydrogen from fuel with atmospheric oxygen into direct current electricity and waste heat via an electrochemical process relying on the use of different electrolytes (phosphoric acid, molten carbonate and solid oxide, depending on operating temperature). This technology permits the recovery of waste heat, available from 200 degreesC up to 1000 degreesC depending on the electrolyte technology, which can be used in the production of steam, hot or cold water, or hot or cold air, depending on the associated recuperation equipment. In this paper, an energy, exergy and economic analysis of a fuel cell cogeneration system (FCCS) is presented. The FCCS is applied in a segment of the tertiary sector to show that it is a feasible alternative for rational decentralized energy production under Brazilian conditions. The technoeconomic analysis shows a global efficiency or fuel utilization efficiency of 86%. Analysis shows that the exergy losses in the fuel cell unit and the absorption refrigeration system are significant. Furthermore, the payback period estimated is about 3 and 5 years for investments in fuel cells of 1000 and 1500 US$/kW, respectively. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

A solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica for differential pulse adsorptive stripping analysis of nickel in ethanol fuel

A solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica (SiAt-SPCPE) was applied to Ni2+ determination in commercial ethanol fuel samples. The proposed method comprised four steps: (1) Ni2+ preconcentration at open circuit potential directly in the ethanol fuel sample, (2) transference of the electrode to an electrochemical cell containing DMG, (3) differential pulse voltammogram registering and (4) surface regeneration by polishing the electrode. The proposed method combines the high Ni2+ adsorption capacity presented by 2-aminothiazole organofunctionalized silica with the electrochemical properties of the Ni(DMG)2 complex, whose electrochemical reduction provides the analytical signal.All experimental parameters involved in the proposed method were optimized. Using a preconcentration time of 20 min, it was obtained a linear range from 7.5 x 10(-9) to 1.0 x 10(-6) mol L-1 with detection limit of 2.0 x 10(-9) mol L-1. Recovery values between 96.5 and 102.4% were obtained for commercial samples spiked with 1.0 mu mol L-1 Ni2+ and the developed electrode was totally stable in ethanolic solutions. The contents of Ni2+ found in the commercial samples using the proposed method were compared to those obtained by graphite furnace atomic absorption spectroscopy by using the F- and t-test. Neither the F- nor t-values exceeded the critical values at 95% confidence level, confirming that there are not statistical differences between the results obtained by both methods. These results indicate that the developed electrode can be successfully employed to reliable Ni2+ determination in commercial ethanol fuel samples without any sample pretreatment or dilution step. (c) 2006 Elsevier B.V. All rights reserved.

Comparative analysis between a PEM fuel cell and an internal combustion engine driving an electricity generator: Technical, economical and ecological aspects

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

Poly(2,5-bibenzimidazole) Membranes: Physico-Chemical Characterization Focused on Fuel Cell Applications

Membranes of Poly(2,5-benzimidazole) (ABPBI), prepared by polycondensation in polyphosphoric acid, were characterized from the fuel cell application point of view: mechanical properties of the membranes for different acid doping levels, thermal stability, permeability for the different gases/vapors susceptible of use in the cell (hydrogen, oxygen, methanol and ethanol), electro-osmotic water drag coefficient, oxidation stability to hydroxyl radicals, phosphoric acid leaching rate and, finally, in-plane membrane conductivity. ABPBI membranes presented an excellent thermal stability, above 500 degrees C in oxygen, suitable mechanical properties for high phosphoric acid doping levels, a low methanol and ethanol limiting permeation currents, and oxygen permeability compared to Nafion membranes, and a low phosphoric acid leaching rate when exposed to water vapor. On the contrary, hydrogen permeation current was higher than that of Nafion, and the chemical stability was very limited. Membrane conductivity achieved 0.07 S cm(-1) after equilibration with a humid environment. Fuel cell tests showed reasonable good performances, with a maximum power peak of 170 mW cm(-2) for H-2/air at 170 degrees C operating under a humidified hydrogen stream, 39.9 mW cm(-2) for CH3OH/O-2 at 200 degrees C for a methanol/water weight ratio of 1: 2, and 31.5 mW cm(-2) for CH3CH2OH/O-2 at the same conditions than for methanol. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.014207jes] All rights reserved.

Microfluidic microbial fuel cell fabrication and rapid screening of electrochemically microbes

The demand for novel renewable energy sources, together with the new findings on bacterial electron transport mechanisms and the progress in microbial fuel cell design, have raised a noticeable interest in microbial power generation. Microbial fuel cell (MFC) is an electrochemical device that converts organic substrates into electricity via catalytic conversion by microorganism. It has represented a continuously growing research field during the past few years. The great advantage of this device is the direct conversion of the substrate into electricity and in the future, MFC may be linked to municipal waste streams or sources of agricultural and animal waste, providing a sustainable system for waste treatment and energy production. However, these novel green technologies have not yet been used for practical applications due to their low power outputs and challenges associated with scale-up, so in-depth studies are highly necessary to significantly improve and optimize the device working conditions. For the time being, the micro-scale MFCs show great potential in the rapid screening of electrochemically active microbes. This thesis presents how it will be possible to optimize the properties and design of the micro-size microbial fuel cell for maximum efficiency by understanding the MFC system. So it will involve designing, building and testing a miniature microbial fuel cell using a new species of microorganisms that promises high efficiency and long lifetime. The new device offer unique advantages of fast start-up, high sensitivity and superior microfluidic control over the measured microenvironment, which makes them good candidates for rapid screening of electrode materials, bacterial strains and growth media. It will be made in the Centre of Hybrid Biodevices (Faculty of Physical Sciences and Engineering, University of Southampton) from polymer materials like PDMS. The eventual aim is to develop a system with the optimum combination of microorganism, ion exchange membrane and growth medium. After fabricating the cell, different bacteria and plankton species will be grown in the device and the microbial fuel cell characterized for open circuit voltage and power. It will also use photo-sensitive organisms and characterize the power produced by the device in response to optical illumination.

From polyarylated cycloparaphenylenes to carbon nanotube segments and metallo N 4-macrocycles as fuel cell catalysts

In this work the synthesis of polyarylated cycloparaphenylenes (CPPs) is described in order to form structurally defined carbon nanotube (CNT) segments by the Scholl reaction. Therefore, polyphenylene macrocycles in different sizes and substitution patterns were synthesized. The influence of the ring-strain on the oxidative cyclodehydrogenation of these macrocycles towards CNT segments was investigated. It was demonstrated that a selective solution based bottom-up synthesis of CNT segments could be accomplished, having polyarylated CPPs, sufficient in size and with the right substituents at the critical positions. These findings mark an important step towards the bottom-up synthesis of length- and diameter defined ultrashort CNTsrnIn the second part of this work, novel non-precious metal catalysts (NPMCs) based on phenanthroline-indole macrocycles were synthesized and their electrocatalytic performance in the cathodic oxygen reduction was investigated. It could be demonstrated that all catalysts contributed to the direct 4-electron reduction of oxygen to water in alkaline media and a superior long-term stability was observed. Since these NPMCs are not heat pre-treated, the catalytically active site was structurally well-defined, allowing the investigation of the structure-property relationship. Moreover, it could be shown that these novel NPMCs act as efficient ORR catalysts and could replace the expensive and scarce platinum in fuel cell applications.rn

Biobutanol as Fuel for Direct Alcohol Fuel Cells-Investigation of Sn-Modified Pt Catalyst for Butanol Electro-oxidation

Direct alcohol fuel cells (DAFCs) mostly use low molecular weight alcohols such as methanol and ethanol as fuels. However, short-chain alcohol molecules have a relative high membrane crossover rate in DAFCs and a low energy density. Long chain alcohols such as butanol have a higher energy density, as well as a lower membrane crossover rate compared to methanol and ethanol. Although a significant number of studies have been dedicated to low molecular weight alcohols in DAFCs, very few studies are available for longer chain alcohols such as butanol. A significant development in the production of biobutanol and its proposed application as an alternative fuel to gasoline in the past decade makes butanol an interesting candidate fuel for fuel cells. Different butanol isomers were compared in this study on various Pt and PtSn bimetallic catalysts for their electro-oxidation activities in acidic media. Clear distinctive behaviors were observed for each of the different butanol isomers using cyclic voltammetry (CV), indicating a difference in activity and the mechanism of oxidation. The voltammograms of both n-butanol and iso-butanol showed similar characteristic features, indicating a similar reaction mechanism, whereas 2-butanol showed completely different features; for example, it did not show any indication of poisoning. Ter-butanol was found to be inactive for oxidation on Pt. In situ FTIR and CV analysis showed that OHads was essential for the oxidation of primary butanol isomers which only forms at high potentials on Pt. In order to enhance the water oxidation and produce OHads at lower potentials, Pt was modified by the oxophilic metal Sn and the bimetallic PtSn was studied for the oxidation of butanol isomers. A significant enhancement in the oxidation of the 1° butanol isomers was observed on addition of Sn to the Pt, resulting in an oxidation peak at a potential ∼520 mV lower than that found on pure Pt. The higher activity of PtSn was attributed to the bifunctional mechanism on PtSn catalyst. The positive influence of Sn was also confirmed in the PtSn nanoparticle catalyst prepared by the modification of commercial Pt/C nanoparticle and a higher activity was observed for PtSn (3:1) composition. The temperature-dependent data showed that the activation energy for butanol oxidation reaction over PtSn/C is lower than that over Pt/C.

Comparison of direct immunofluorescence, conventional cell culture and polymerase chain reaction techniques for detecting respiratory syncytial virus in nasopharyngeal aspirates from infants

A total of 316 samples of nasopharyngeal aspirate from infants up to two years of age with acute respiratory-tract illnesses were processed for detection of respiratory syncytial virus (RSV) using three different techniques: viral isolation, direct immunofluorescence, and PCR. Of the samples, 36 (11.4%) were positive for RSV, considering the three techniques. PCR was the most sensitive technique, providing positive findings in 35/316 (11.1%) of the samples, followed by direct immunofluorescence (25/316, 7.9%) and viral isolation (20/315, 6.3%) (p < 0.001). A sample was positive by immunofluorescence and negative by PCR, and 11 (31.4%) were positive only by RT-PCR. We conclude that RT-PCR is more sensitive than IF and viral isolation to detect RSV in nasopharyngeal aspirate specimens in newborn and infants.