Selection of appropriate fuel processor for biogas-fuelled SOFC system

The performance of biogas-fed solid oxide fuel cell (SOFC) systems utilizing different reforming agents (steam, air and combined air/steam) has been investigated via thermodynamic analysis to determine the most suitable feed. The boundary of carbon formation was first calculated to specify the minimum amount of each reforming agent necessary to avoid carbon formation. The SOFC performance (electrical efficiency and power density) was determined at different biogas compositions and reforming agent:biogas ratios. The SOFC performance is better when the methane content in the biogas is higher. Steam is considered to be the most suitable reforming agent in this study as the steam-fed SOFC offers much higher power density than the air-fed SOFC although its electrical efficiency is slightly lower. When steam is added in the air-fed SOFC as in the case of the co-fed SOFC, the power density can be improved but the electrical efficiency becomes lower compared with the case of the air-fed SOFC. Finally, in order to improve the electrical efficiency of the steam-fed SOFC, the biogas split option was proposed. It was found that a higher electrical efficiency can be achieved. In addition, although the power density is lowered by this operation, the value is still higher than the case of the air-fed SOFC.     

Modeling of CO2 gasification of carbon for integration with solid oxide fuel cells

This modeling study focuses on gasification of carbon by CO₂ in a minimally fluidized bed containing a solid oxide fuel cell (SOFC). Kinetic parameters for a five‐step reaction mechanism characterizing the Boudouard reaction (C + CO₂ → 2CO) were determined thermogravimetrically at 1 atm from 973 to 1273 K. Experimentally determined kinetic parameters are employed in a transport model that predicts velocities and gas concentration profiles established in the carbon bed as a consequence of convection, diffusion, and heterogeneous reaction. The model is used to simulate the effect of an imbedded SOFC, in contact with the carbon bed. Although the model does not assume particular I‐V characteristics for the fuel cell, it indicates that current densities in the practical range of 100–1000 mA/cm² can be supported. Results show that temperature strongly affects the current density, whereas CO₂ flow rate has only a weak effect. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Biodiesel formulations as fuel for internally reforming solid oxide fuel cell

Biodiesel (alkyl ester of rapeseed oil) is prepared using various, methyl, ethyl and butyl alcohols through the transesterification process. Sodium hydroxide and sulfuric acid are used as catalyst for methyl alcohol, ethyl alcohol and butyl alcohol respectively. Biodiesel-water formulations are formulated using water and emulsifiers like sodium lauryl sulphate (SLS) and SPAN 80 in a high shear mixer. The formulations are tested at 800 °C as fuel for internal reforming in solid oxide fuel cells (SOFCs). The formulations based on methyl and butyl esters require the use of emulsifiers to prepare stable emulsions, while ethyl esters are able to form stable emulsions without emulsifiers. The decrease in the biodiesel concentration of formulation does not have any effect on the power density of the ethyl ester formulation. Fuel cells fuelled with 20% formulations lasted longer than 50% formulations in all the formulations tested as result of increase in steam carbon ratio resulting in effective removal of carbon deposited on the anode surface. Butyl ester formulations exhibited the worst performance in both types of formulation tests. The best performance was exhibited by 20% ethyl formulation in terms of life of the cell but 50% methyl ester formulations exhibit the highest power density.     

Solid oxide fuel cells with YSZ-BNO Bi-layer electrolyte film deposited by magnetron sputtering

Bi-layer electrolyte films of Zr_0.84Y_0.16O_1.92 (YSZ)- 0.79Bi₂O₃-0.21Nb₂O₅ (BNO) were deposited by RF magnetron sputtering on NiO-SDC anode substrates. The stoichiometry of the BNO electrolyte film was found strongly dependent on the ratio of Ar and O₂ during sputtering, and the BNO film deposited at a mixture of 31 sccm Ar and 7 sccm O₂ appeared to be the closest to the target composition. When deposited at 300 °C and subsequently annealed at 700 °C, the BNO electrolyte emerged to be crack free and dense with some scattering closed pores. The XRD patterns of the film are indexed to the cubic Fm m structure of Bi₃NbO₇. The as-deposited film was well-crystalline and consisted of fine grains and random orientation microstructures. For electrolyte thicknesses of approximately 4.0 μm YSZ and 1.5 μm BNO layers, the open circuit voltage (OCV) and the maximum power density of the single cell with Ag cathode read respectively 0.94 V and 10 mW/cm² at 600 °C. These OCV values are lower than the expected theoretical value due to the high partial electronic conductivity.     

The impact of carbon formation on Ni-YSZ anodes from biomass gasification model tars operating in dry conditions

The combination of solid oxide fuel cells (SOFCs) and biomass gasification has the potential to become an attractive technology for the production of clean and renewable energy. However the impact of tars, formed during biomass gasification, on the performance and durability of SOFC anodes has not been well established experimentally. This paper reports on an experimental study of the effects of carbon formation on the anodes of SOFC button cells from synthetic model tars arising from the gasification of biomass material. Furthermore the paper evaluates appropriate model tars to study the effects of typical biomass gasification tars on SOFC operation. The anode material used in this work was a 60:40 wt.% NiO/YSZ cermet, which was tested in a 15% H₂ gas mixture containing a concentration of 15 g/Nm³ of different biomass gasification model tars. Model tars included benzene and toluene representing the simplest and most predominant of biomass gasification tars, and a tar mix consisting of higher molecular weight tars such as naphthalene, pyrene, and phenol. It was found that carbon formation in dry conditions significantly damaged the anode of the fuel cell resulting in decreased cell performance and excessive anode polarization resistances. The higher reactivity of benzene compared to other model tars led to higher levels of carbon formation on reduced Ni-O catalysts. Different types of carbon were formed depending on the operating temperature of the SOFC.     

Modelling of an indirect internal reforming solid oxide fuel cell

Creation of an autothermal system by coupling an endothermic to an exothermic reaction demands the matching of the thermal requirements of the two reactions. The application under study is a solid oxide fuel cell (SOFC) with indirect internal reforming (IIR) of methane, whereby the endothermic steam reforming reaction is thermally coupled to the exothermic oxidation reactions. A steady-state model of an IIR-SOFC has been developed to study the mismatch between the thermal load associated with the rate of steam reforming at typical SOFC temperatures and the local amount of heat available from the fuel cell reactions. Results have shown a local cooling effect, undesirable for ceramic fuel cells, close to the reformer entrance. The system behaviour towards changes in catalyst activity, fuel inlet temperature, current density, and operating pressure has been studied. Increasing the operating pressure is shown to be an effective way of reducing both the local cooling caused by the reforming reactions and the overall temperature increase across the cell. Simulations for both counter-flow and co-flow configurations have been performed and compared.     

Catalytic performance of Ni/CeO2/Al2O3 modified with noble metals in steam gasification of biomass

In the steam gasification of biomass, the additive effect of noble metals such as Pt, Pd, Rh and Ru to the Ni/CeO₂/Al₂O₃ catalyst was investigated. Among these noble metals, the addition of Pt was most effective even when the loading amount of added Pt was as small as 0.01 wt.%. In addition, the catalyst characterization suggests the formation of the Pt–Ni alloy over the Pt/Ni/CeO₂/Al₂O₃.     

Development of Ni catalysts for tar removal by steam gasification of biomass

Catalytic performance of Ni/CeO₂/Al₂O₃ catalysts prepared by a co-impregnation and a sequential impregnation method in steam gasification of real biomass (cedar wood) was investigated. Especially, Ni/CeO₂/Al₂O₃ catalysts prepared by the co-impregnation method exhibited higher performance than Ni/Al₂O₃ and Ni/CeO₂/Al₂O₃ prepared by the sequential impregnation method, and the catalysts gave lower yields of coke and tar, and higher yields of gaseous products. The Ni/CeO₂/Al₂O₃ catalysts were characterized by thermogravimetric analysis, temperature-programmed reduction with H₂, transmission electron microscopy and extended X-ray absorption fine structure, and the results suggested that the interaction between Ni and CeO₂ became stronger by the co-impregnation method than that by sequential method. Judging from both results of catalytic performance and catalyst characterization, it is found that the intimate interaction between Ni and CeO₂ can play very important role on the steam gasification of biomass.     

Low-temperature gasification of a woody biomass under a nickel-loaded brown coal char

Catalytic gasification of a woody biomass, Japanese cypress, was investigated under a prepared nickel-loaded brown coal (LY-Ni) char in a two-stage fixed-bed reactor. The nickel-loaded brown coal was prepared by ion-exchange method with a nickel loading rate of 8.3 wt.%. Nickel species dispersed well in the brown coal, and the LY-Ni char via devolatilization at 600 °C showed a great porous property with a specific surface area of 382 m² g^− 1.The LY-Ni char was confirmed to be quite active for the Japanese cypress volatiles gasification at a relatively low-temperature range from 450 to 650 °C. For example, at 550 °C, 16.6 times hydrogen gas and 6.3 times total gases were yielded from the catalytic steam gasification of Japanese cypress volatiles under the LY-Ni char, compared with the case of non-catalyst. The biomass tar decomposition showed a dependence on catalyst temperatures. When the catalyst temperature was higher than 500 °C, Japanese cypress tar converted much efficiently, high gas yields and high carbon balances were obtained.     

Integrated methane decomposition and solid oxide fuel cell for efficient electrical power generation and carbon capture

This work proposes the application of methane decomposition (MD) as a fuel processor to replace methane steam reforming (MSR) for hydrogen production for a methane-fuelled solid oxide fuel cell (SOFC) system. In this work, comparison between the MD–SOFC and the MSR–SOFC was performed in terms of SOFC performances and economic analysis to demonstrate a benefit of using MD as a fuel processor. Energy analysis of SOFC system was evaluated based on thermally self-sufficient condition where no external energy is required for the system. Although the MD–SOFC system offers lower electrical efficiency than that of the MSR–SOFC as solid carbon is generated without being further combusted to generate energy; however, the MD–SOFC stack can be operated at higher power density due to high purity of hydrogen supplied to the fuel cell, resulting in smaller size of the system when compared to the MSR–SOFC. Moreover, the MD–SOFC system is less complicated than that of the MSR–SOFC as the CCS facility is not necessary to be included to reduce CO₂ emission. Economic analysis demonstrated that the SOFC system with MD is more competitive than the conventional system with MSR when considering the valuable by-products of solid carbon even with the low-valued carbon black. It is suggested that the success of this proposed SOFC system with MD relies on the technology development on cogeneration of hydrogen and valuable carbon products.     

Isothermal models for anode-supported tubular solid oxide fuel cells

Modeling of solid oxide fuel cells (SOFCs) has gained considerable significance in recent years. A detailed phenomenological model for SOFC can be used to understand performance limitations, optimization, in situ diagnostics and control. In this paper, we study the transport and various electrochemical phenomena in an anode-supported tubular SOFC using a steady-state model. In particular, we discuss the importance of modeling different phenomena vis-a-vis their impact on the prediction capability of the model. It is observed that even a reasonably simple model can be sufficiently predictive in a particular operating range. As the operating range of the cell is increased, the predictive capability of a model validated in a narrow range cannot be guarantied. It has also been observed that neglecting momentum conservation in the model for a tubular SOFC can affect the predictive capability of the model at higher overpotentials. An extensively validated model is used to study the percentage conversion of oxygen and oxygen concentration profile within a cell at different operating conditions. All of the simulation studies are supported by experimental data that spans a wide range of operation in terms of the DC polarization, reactant flow rates and operating temperatures.     

Operation viability and performance of solid oxide fuel cell fuelled by different feeds

The performances of solid oxide fuel cells (SOFCs) fed by different types of feed, i.e. biogas, biogas-reformed feed, methane-reformed feed and pure hydrogen, are simulated in this work. Maximum temperature gradient and maximum cell temperature are regarded as indicators for operation viability investigation whereas power density and electrical efficiency are considered as performance indicators. The change in operating parameters, i.e. excess air, fuel feed rate and operating voltage, affects both the performance and operation viability of SOFC, and therefore, these operating parameters should be carefully selected to obtain best possible power density and reasonable temperature and temperature gradient. Pure hydrogen feed offers the highest SOFC performance among the other feeds. Extremely high excess air is required for SOFC fed by biogas to become operation viable and, in addition, its power density is much lower than those of SOFCs fed by the other feeds. Methane-reformed feed offers higher power density than biogas-reformed feed since H₂ concentration of the former one is higher.     

Modeling the temperature field in the reforming anode of a button-shaped solid oxide fuel cell

A model predicting the temperature field in the porous reforming anode of a solid oxide fuel cell is presented herein. The model is based on mass, momentum, and heat balances of a chemically reacting mixture of gases within the porous matrix of the anode. The important novel characteristic of the model is the consideration of the both internal reforming and electrochemical reactions in the bulk of the porous anode. The electronic and ionic currents in the anodes are calculated utilizing the solution of the Poisson equations for the electric potentials in the porous medium. The transfer current density is described by the Butler–Volmer equation.The model is applied to investigate the temperature field and the reactive flow in button-shaped fuel cells with uniform and graded (multi-layer) anodes composed of Ni and YSZ particles with methane/water vapor mixture used as the fuel. The maximum temperature difference between the hot and cold spots of the anodes is found to reach up to 200 K. The results indicate that the generation of Joule heating caused by the current passing through the anode and the activation losses are the dominating heat sources compared to the gas-water shift and electrochemical reactions.     

Development of La(CrCoFeNi)O3 system perovskites as interconnect and cathode materials for solid oxide fuel cells

The purpose of this research is to develop interconnect and cathode materials for use in solid oxide fuel cells (SOFCs) which demonstrate desired properties of outstanding sintering properties, high electrical conductivity, and excellent chemical stability at high temperatures. Five different perovskite oxides of lanthanum in combination with chromium, iron, cobalt and nickel oxides powders, i.e. LaCr_0.7Co_0.1Fe_0.1Ni_0.1O₃(LCr7CFN), LaCo_0.7Cr_0.1Fe_0.1 Ni_0.1O₃(LCo7CFN), LaFe_0.7Cr_0.1Co_0.1Ni_0.1O₃(LFe7CCN), LaNi_0.7Cr_0.1Co_0.1Fe_0.1O₃(LNi7CCF), and LaCr_0.25Co_0.25Fe_0.25Ni_0.25O₃(LCCFN), were synthesized through the Pechini method. XRD results show that all materials are in single phase, either rhombohedral or orthorhombic crystal structure. The resulting powders were able to be sintered to a high relative density at a temperature of 1400 °C for 2 h in air. The electrical conductivity of the sintered sample was measured and evaluated from 300 °C to 800 °C. The LCCFN sample appears to have the best combination of sintering property (approximate 94% relative density) and electrical conductivity (88.13 Scm⁻¹ at 800 °C).     

Effects of controlling parameters on production of hydrogen by catalytic steam gasification of biomass at low temperatures

Low temperature catalytic steam gasification of biomass is being investigated around the world as an environmentally friendly alternative to the existing techniques for hydrogen production. The aim of the present investigation was to gain a fundamental understanding about the catalytic steam gasification of some species under low temperature conditions. The research, in particular, focused on the role and relative importance of controlling parameters, such as reaction temperature and the heating rate on the composition of the products. It was found that higher temperatures and steam flow rates increased the gas yield. A relatively low reaction temperature of 600 °C and a high steam content of about 90% showed the strongest tendency for maximising the hydrogen production.     

Thermodynamic analysis for a solid oxide fuel cell with direct internal reforming fueled by ethanol

In the present study, a detailed thermodynamic analysis is carried out to provide useful information for the operation of solid oxide fuel cells (SOFC) with direct internal reforming (DIR) fueled by ethanol. Equilibrium calculations are performed to find the ranges of inlet steam/ethanol (H₂O/EtOH) ratio where carbon formation is thermodynamically unfavorable in the temperature range of 500-1500 K. Two types of fuel cell electrolytes, i.e., oxygen-conducting, and hydrogen-conducting electrolytes, are considered. The key parameters determining the boundary of carbon formation are temperature, type of solid electrolyte and extent of the electrochemical reaction of hydrogen. The minimum H₂O/EtOH ratio for which the carbon formation is thermodynamically unfavored decreases with increasing temperature. The hydrogen-conducting electrolyte is found to be impractical for use, due to the tendency for carbon formation. With a higher extent of the electrochemical reaction of hydrogen, a higher value of the H₂O/EtOH ratio is required for the hydrogen-conducting electrolyte, whereas a smaller value is required for the oxygen-conducting electrolyte. This difference is due mainly to the water formed by the electrochemical reaction at the electrodes.     

A medium entropy cathode with enhanced chromium resistance for solid oxide fuel cells

Perovskite type SrCo_0.9Ta_0.1O_3-δ (SCT91) cathode exhibits high activity for oxygen reduction reactions, but the instability in Cr-containing atmosphere restricts its application in intermediate temperature solid oxide fuel cells (IT-SOFCs). In this study, a B-site medium-entropy SrCo_0.5Fe_0.2Ti_0.1Ta_0.1Nb_0.1O_3-δ (SCFTTN52111) cathode is proposed and investigated as a potential Cr-tolerance cathode. The electrochemical activity of pristine SCT91 cathode degrades rapidly in the presence of volatile chromium species. In contrast, SCFTTN52111 performs very stable. Chromium vapors prefer to react with segregated SrO species rather than Co₃O₄ precipitates_. Significant secondary phases of SrCrO₄ and Co₃O₄ are detected on SCT91 electrode, while only trace by-products are found on medium-entropy cathode. The better Cr tolerance is closely related to the enhanced structural stability by medium-entropy engineering and reduced surface Sr segregations. This work sheds light on the development of robust cathodes for IT-SOFCs through rational design of configuration entropy.     

Thermodynamic modeling of the power plant based on the SOFC with internal steam reforming of methane

Mathematical model based on the thermodynamic modeling of gaseous mixtures is developed for SOFC with internal steam reforming of methane. Macroscopic porous-electrode theory, including non-linear kinetics and gas-phase diffusion, is used to calculate the reforming reaction and the concentration polarization. Provided the data concerning properties and costs of materials the model is fit for wide range of parametric analysis of thermodynamic cycles including SOFC.     

Analysis of a solid oxide fuel cell system for combined heat and power applications under non-nominal conditions

In this paper, a model for a solid oxide fuel cell (SOFC) system for decentralized electricity production is developed and studied. The proposed system, operated on natural gas, consists of a planar anode supported fuel cell section and a balance of plant (BoP) which includes gases supply, a fuel processor, a heat management system, an after-burner and a power conditioning system. A reference case is defined and evaluated taking into account the state of the art of the technology and the related technical constrains. Electrical and thermal efficiency of the system, for non-reference conditions are evaluated. In particular, the effect of the deviation from the reference conditions of fuel utilization, gas temperature spring in fuel cell stack, anode off-gas recirculation rate, air inlet temperature and external pre-reforming reaction extent is analyzed. The present study revealed to be a powerful tool for evaluating the SOFC system performance under a wide range of operation and paves the way for defining control strategies in order to maintain high system efficiency under part-load operations.