Effect of methane slippage on an indirect internal reforming solid oxide fuel cell

Creation of an autothermal system by coupling an endothermic to an exothermic reaction demands matching the thermal requirements of the two reactions. The application studied here is the operation of a solid oxide fuel cell (SOFC) with both direct (DIR) and indirect (IIR) internal reforming of methane. Such internal reforming within a high-temperature fuel cell module can lead to an overall autothermal operation which simplifies the system design and increases efficiency. However, such coupling is not easy to achieve because of 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. Previous results have shown that the use of typical metal-based (e.g. Ni) IIR catalysts leads to full methane consumption but undesirable local cooling at the reformer entrance and the use of less active IIR catalysts (e.g. non-metals or diffusion limited nickel) leads to methane being carried-over into the SOFC anode (methane slippage). In order to evaluate performance in the latter case, a combined DIR and IIR SOFC steady-state model has been developed. Simulation results have shown that, lowering the IIR catalyst activity to prevent local cooling effects at the reformer entrance is not adequate, as the fast kinetics of the direct reforming reaction then lead to full methane conversion and steep temperature gradients in the first 10% of the fuel channel length. It is shown that the simultaneous reduction of the anode DIR reaction rate improves performance considerably. The system behaviour towards changes in current density, operating pressure, and flow configuration (counter-flow vs. co-flow) has been studied. Reduction of both DIR and IIR catalyst activity combined with a counter-flow operation leads to the best performance. System performance with an IIR oxide-based catalyst is also evaluated.     

Enhancing the Efficiency of SOFC‐Based Auxiliary Power Units by Intermediate Methanation

Fuel‐cell‐based auxiliary power units benefit from the high power density and fuel flexibility of solid oxide fuel cells (SOFCs), facilitating straightforward onboard fuel processing of diesel or jet fuel. The preferred method of producing the fuel gas is autothermal reforming, which to date has shown the best practical applicability. However, the resulting reformate is poor in methane, so that cell cooling is not supported by internal methane steam reforming. Accordingly, large flow rates of excess air are required to cool the stack. Hence, the power demand of the cathode air blower significantly limits the net electrical power output of the system and large cathode flow channels are required. The present work examines attempts to further increase the system efficiency in middle‐distillate‐fueled SOFC systems by decreasing the cathode air flow rates. The proposed concept is generally based on inducing endothermic methane steam reforming (MSR) inside the cells by augmenting the methane content in an upstream methanation step. Methanation, however, can only yield significant methane production rates if the reaction temperature is limited. Therefore, four process layouts are presented that include different cooling measures. Based on these setups, the general feasibility and the benefit of intermediate methanation are demonstrated.     

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.     

Development of a Combined Plasma-Matrix Reformer for Solid Oxide Fuel Cell Application

A novel plasma-matrix reformer (PMR) was suggested for methane conversion into hydrogen-rich fuel. To demonstrate the possibility of reforming performance, characteristics of product gas and CH₄ conversion were identified according to O₂/C ratio, water vapor supply, reformed gas recirculation, and water feed in the recirculation gas affecting energy conversion and hydrogen production. When the reformed gas recirculation and water feed to the recirculation pipe were performed at the same time, hydrogen production and energy conversion efficiency were superior compared to the conventional reforming method. The optimal operating conditions of the PMR were determined. The obtained high energy conversion efficiency and hydrogen selectivity indicated the applicability to solid oxide fuel cell stacks for residential power generation.     

SOFC fuelled by methane without coking: optimization of electrochemical performance

In recent years, fuel cell technology has attracted considerable attention from several fields of scientific research as fuel cells produce electric energy with high efficiency, emit little noise, and are non-polluting. Solid oxide fuel cells (SOFCs) are particularly important for stationary applications due to their high operating temperature (1,073–1,273 K). Methane appears to be a fuel of great interest for SOFC systems because it can be directly converted into hydrogen by direct internal reforming (DIR) within the SOFC anode. Unfortunately, internal steam reforming in SOFC leads to inhomogeneous temperature distributions which can result in mechanical failure of the cermet anode. Moreover this concept requires a large amount of steam in the fed gas. To avoid these problems, gradual internal reforming (GIR) can be used. GIR is based on local coupling between steam reforming and hydrogen oxidation. The steam required for the reforming reaction is obtained by the hydrogen oxidation. However, with GIR, Boudouard and cracking reactions can involve a risk of carbon formation. To cope with carbon formation a new cell configuration of SOFC electrolyte support was studied. This configuration combined a catalyst layer (0.1%Ir–CeO₂) with a classical anode, allowing GIR without coking. In order to optimise the process a SOFC model has been developed, using the CFD-Ace+ software package, and including a thin electrolyte. The impact of a thin electrolyte on previous conclusions has been assessed. As predicted, electrochemical performances are higher and carbon formation is always avoided. However a sharp decrease in the electrochemical performances appears at high current densities due to steam clogging.     

SOFC内部重整反应与电化学反应耦合机理

以经过预重整反应的混合气为原料的固体氧化物燃料电池（SOFC）内部,甲烷蒸气重整反应与电化学反应同时发生在阳极多孔介质中,二者受到不同的操作与设计参数的影响,对电池总体性能起着决定性作用。编制了三维数值模拟程序,对由多孔阳极层、气体流动管道、固体支撑平板构成的单个复合管道进行了研究。结果显示：重整反应主要发生在多孔材料靠近流动管道的薄层内,只有靠近管道入口处才能在较深处进行;电化学反应发生在多孔层与电解质的交界面处;重整反应生成的H2、CO扩散到多孔材料底部参加电化学反应;电化学反应生成的热量供重整反应使用。说明研究范围内,SOFC阳极复合通道具有较好的传热、传质性能,化学/电化学反应存在较好的耦合关系。     

1kW SOFC-CHP系统用催化燃烧耦合蒸汽重整反应器的实验研究

针对1 kW 固体氧化物燃料电池热电联供(SOFC-CHP)系统开发了集成催化燃烧、换热及蒸汽重整的反应器,搭建了性能评价系统,系统研究了燃烧侧气体组分及工艺参数对该反应器性能的影响规律。实验结果表明:在反应器燃烧侧气体入口温度为300℃、空燃比为10:1、电堆燃料利用率为65%、水碳比为3 的条件下,重整侧转化率达到73.6%,重整尾气中H₂ 含量为67.5%。电堆燃料利用率对重整反应转化效率影响较大,其值大于80%时,采用尾气燃烧的余热回收方式无法有效为蒸汽重整提供所需热量。在150~350℃范围内,降低燃烧侧气体入口温度对重整反应效率影响较小,建议采用尾气先换热再进行催化燃烧的流程设计,保证重整效率的前提下可有效提升系统热效率。空燃比的降低可小幅度提升重整效率,在保证电堆反应温度稳定的前提下,适当降低空燃比可减少空气压缩机的功耗,从而提升整个系统的效率。研究成果对SOFC-CHP 系统的优化和整体效率提升具有指导意义。     

Fuel processing in direct propane solid oxide fuel cell and carbon dioxide reforming of propane over Ni-YSZ

This work is aimed at understanding the reaction mechanism of propane internal reforming in the solid oxide fuel cell (SOFC). This mechanism is important for the design and operation of SOFC internal processing of hydrocarbons. An anode-supported SOFC unit with Ni-YSZ anode operating at 800 °C was tested with direct feeding of 5% propane. CO₂ reforming of propane was carried out in a reactor with Ni-YSZ catalyst to simulate internal propane processing in SOFC. The performance of this direct propane SOFC is stable. The C specie formed over the anode functional layer of SOFC can be completely removed. The major gas products of SOFC are H₂, CO, CH₄, C₂H₄ and CO₂. Pseudo-steady-state internal processing of propane in the anode catalytic layer of SOFC is associated with a CO₂/C₃H₈ molar ratio of about 1.26 and basically CO₂ reforming of propane. CO₂ dissociation to produce the O species to oxidize the C species from dehydrogenation and dissociation of propane and its fragments should be the major reaction during CO₂ reforming of propane.     

Modeling of a SOFC fuelled by methane: From direct internal reforming to gradual internal reforming

Natural gas appears to be a fuel of great interest for SOFC systems. The principal component of natural gas is methane, which can be converted into hydrogen by direct or gradual internal reforming (DIR or GIR) within the SOFC anode. However, DIR requires a large amount of steam to produce hydrogen. If the injected mixture contains very small quantities of steam, GIR is then obtained. With GIR, the risk of carbon formation is even greater. This paper proposes a model and simulation, using the CFD-Ace software package, of the behaviour of a tubular SOFC using GIR and a comparison between utilization in DIR and GIR. A thermal study is included in the model and a detailed thermodynamic analysis is carried out to predict the carbon formation boundary for SOFCs fuelled by methane. Thermodynamic equilibrium calculations taking into account Boudouard and methane cracking reactions allowed us to investigate the occurrence of carbon formation. Simulations were used to calculate the distributions of partial pressures for all the gas species (CH₄, H₂, CO, CO₂, H₂O), current densities and potentials in both electronic and ionic phases within the anode part (i.e., gas channel and cermet anode). The simulations indicate that there is no decrease in electrochemical performance if GIR is used rather than DIR. A thermal study appears to confirm that the cooling effect due to the endothermic reforming reaction is eliminated in GIR, but the thermodynamic study indicates that carbon formation can be suspected for x_H2O/x_CH4 ratios lower than one.     

Catalytic aspects of the steam reforming of hydrocarbons in internal reforming fuel cells

Steam reforming of hydrocarbons such as natural gas is an attractive method of producing the hydrogen fuel gas required by fuel cells. It may be carried out external to the fuel cell or internally. The two types of fuel cell in which internal reforming is most appropriate are the molten carbonate (MCFC), operating at ca. 650°C and the solid oxide (SOFC) which currently operates above 800°C. At such temperatures, the heat liberated by the electrochemical reactions within the cell can be utilised by the endothermic steam reforming reaction. This paper reviews some of the catalytic aspects of internal reforming in these two types of cell. In the MCFC the major catalyst issue is that of long term activity in the presence of a corrosive alkaline environment produced by the cell's electrolyte. In Europe, this is being addressed by British Gas and others, in a programme part-funded by the European Commission. In this programme, potential catalysts for the direct internal reforming MCFC were evaluated in ‘out-of-cell’ tests. This has led to the demonstration of a 1 kW proof-of-concept DIR-MCFC stack and the start of a European ‘Advanced DIR-MCFC’ project. For the SOFC, it has been shown that state-of-the-art nickel cermet anodes can provide sufficient activity for steam reforming without the need for additional catalyst. However, anode degradation may occur when steam reforming is carried out for long periods. New anode materials could therefore offer significant benefits.     

Development of a novel test system for in situ catalytic, electrocatalytic and electrochemical studies of internal fuel reforming in solid oxide fuel cells

A test system based around a thin‐walled extruded solid electrolyte tubular reactor has been developed, which enables the fuel reforming catalysis and surface chemistry occurring within solid oxide fuel cells and the electrochemical performance of the fuel cell to be studied under genuine operating conditions. It permits simultaneous monitoring of the catalytic chemistry and the cell performance, allowing direct correlation between the fuel cell performance and the reforming characteristics of the anode, as well as enabling the influence of drawing current on the catalysis and surface reaction pathways to be studied. Temperature‐programmed reaction measurements can be carried out on anodes in an actual SOFC, and have been used to investigate the reduction characteristics of different anode formulations, methane activation and methane steam reforming, and to evaluate the nature and level of carbon deposition on the anode during reforming. This revised version was published online in July 2006 with corrections to the Cover Date.     

Residential Solid Oxide Fuel Cell Generator Fuelled by Ethanol: Cell,Stack and System Modelling with a Preliminary Experiment

The flexibility and feasibility of a 5 kW SOFC generator designed for natural gas (NG) and fuelled by a non‐conventional liquid fuel such as ethanol is analysed. A complete generator model is implemented to predict and determine the main criticalities when ethanol fuel is adoperated. The main balance‐of‐plant (BoP) units considered are the reformer, the recirculation system based on an ejector, the tubular cells bundles constituting the stack unit, the after‐burner zone and the air blower. The electrical and global efficiencies achieved at nominal operating conditions show how ethanol maintains generator performance good, while only slightly reducing the system AC efficiency from 48% (achieved by NG) to 45%. The effectiveness and flexibility of the recirculation system when changing the fuel is also verified since a safe steam‐to‐carbon ratio (STCR) is established after the fuel is switched from NG ethanol. The stack thermal management is analysed in detail and related to the system performances, showing how a high endothermic fuel reforming reaction is required to maintain the overall system efficiency. A preliminary experiment with ethanol feeding the Siemens generator is finally presented. The system response to the new fuel is monitored by several measured parameters and the system regulation is explained.     

Detailed Multi‐dimensional Modeling of Direct Internal Reforming Solid Oxide Fuel Cells

Fuel flexibility is a significant advantage of solid oxide fuel cells (SOFCs) and can be attributed to their high operating temperature. Here we consider a direct internal reforming solid oxide fuel cell setup in which a separate fuel reformer is not required. We construct a multidimensional, detailed model of a planar solid oxide fuel cell, where mass transport in the fuel channel is modeled using the Stefan‐Maxwell model, whereas the mass transport within the porous electrodes is simulated using the Dusty‐Gas model. The resulting highly nonlinear model is built into COMSOL Multiphysics, a commercial computational fluid dynamics software, and is validated against experimental data from the literature. A number of parametric studies is performed to obtain insights on the direct internal reforming solid oxide fuel cell system behavior and efficiency, to aid the design procedure. It is shown that internal reforming results in temperature drop close to the inlet and that the direct internal reforming solid oxide fuel cell performance can be enhanced by increasing the operating temperature. It is also observed that decreases in the inlet temperature result in smoother temperature profiles and in the formation of reduced thermal gradients. Furthermore, the direct internal reforming solid oxide fuel cell performance was found to be affected by the thickness of the electrochemically‐active anode catalyst layer, although not always substantially, due to the counter‐balancing behavior of the activation and ohmic overpotentials.     

Performance Research on a Methane Compact Reformer Integrated with Catalytic Combustion

A multichannel reformer integrated with catalytic combustion was investigated for methane steam reforming to produce hydrogen. In this system, the main portion of the required heat was supplied by methane oxidation in the catalytic combustor located on two sides of the reformer. In the compact multichannel reactor, the methane conversion rate is high enough compared to the equilibrium values at different temperatures. The performance of the multichannel reformer was investigated under various operating conditions, such as the reformer temperature and the feed stream ratios in both the reformer and the catalytic combustor. The best feed flow rate ratio of reforming to combustion ranged from 1.3 to 1.5, with > 95 % methane conversion. It is anticipated that this multichannel reformer can generate enough hydrogen for a 30‐W fuel cell system, due to its small volume.     

SOFC中低浓度干甲烷在Ni/YSZ阳极上的反应

固体氧化物燃料电池(SOFC)趋向于直接使用甲烷天然气为燃料,确定甲烷在固体氧化物燃料电池阳极发生的化学与电化学反应非常重要.以Ni/YSZ为阳极、YSZ板做电解质、LSM为阴极,用涂浆法制作电解质支撑的电池,研究低浓度干甲烷在固体氧化物燃料电池中的反应.改变甲烷浓度、电池工作温度、电解质厚度,用在线色谱测量不同电流密度下,阳极出口气体产生速率.根据阳极出口气体产生速率变化,分析干甲烷在阳极的反应变化.通过氧消耗计算和转移电子数的分析,说明甲烷在电池阳极发生不同类型的反应.电流密度小时,甲烷发生部分氧化反应.电流密度大时,发生氢氧化和CO氧化,部分甲烷发生总反应为完全氧化的反应.部分甲烷发生完全氧化反应的同时,部分甲烷仍发生部分氧化反应,但其反应速率随电流密度增加逐渐降低.甲烷浓度和试验温度增加,甲烷开始发生完全氧化的电流密度增加.     

Effect of Anode off‐gas Recycling on Reforming of Natural Gas for Solid Oxide Fuel Cell Systems

The effect of anode off‐gas recycling (AOGR) on the characteristic performance of a natural gas reformer equipped with a precious metal catalyst is investigated experimentally. The reformer is operated both with synthetic AOGR gas and in steam reforming (SR) conditions. The characteristic performance in SR and AOGR mode are compared with equilibrium, and it is found that equilibrium is more readily achieved in AOGR mode. The reformer is used for extended periods of time (100–1,000 h) in conditions where carbon formation is thermodynamically possible to measure any changes in characteristic performance. No significant change in the performance is observed due to carbon formation or catalyst deactivation. The reformer could be successfully implemented in a 10 kW SOFC system with an anode off‐gas recycling loop.     

Implications for Using Biogas as a Fuel Source for Solid Oxide Fuel Cells: Internal Dry Reforming in a Small Tubular Solid Oxide Fuel Cell

The feasibility of operating a solid oxide fuel cell (SOFC) on biogas has been studied over a wide compositional range of biogas, using a small tubular solid oxide fuel cell system operating at 850 °C. It is possible to run the SOFC on biogas, even at remarkably low levels of methane, at which conventional heat engines would not work. The power output varies with methane content, with maximum power production occurring at 45% methane, corresponding to maximal production of H₂ and CO through internal dry reforming. Direct electrocatalytic oxidation of methane does not contribute to the power output of the cell. At higher methane contents methane decomposition becomes significant, leading to increased H₂ production, and hence transiently higher power production, and deleterious carbon deposition and thus eventual cell deactivation.     

Modeling of transport, chemical and electrochemical phenomena in a cathode-supported SOFC

This paper investigates the performance of a planar cathode-supported solid oxide fuel cell (SOFC) with composite electrodes using a detailed numerical model. The methane reforming reaction is included in the model and takes place mostly in the porous, thin anode at the high operating temperature of 800-1000^°C. A single computational domain comprises the fuel and air channels and the electrodes-electrolyte assembly eliminating the need for internal boundary conditions. The equations governing transport and chemical and electrochemical processes for mass, momentum, chemical and charged species and energy are solved using Star-CD augmented by subroutines written in-house. The operating cell voltage is determined by the potential difference between the cathode and the anode, whose potentials are fixed. Results of temperature, chemical species, current density and electric potential distribution for a co-flow configuration are shown and discussed. It is found that the sub-cooling effect observed in anode-supported cells is almost ameliorated, making the cathode-supported cell favorable from the viewpoint of material stability.     

Analysis of a proton-conducting SOFC with direct internal reforming

This paper presents a performance analysis of a planar SOFC (solid oxide fuel cell) with proton-conducting electrolyte (SOFC-H⁺). The SOFC-H⁺ is fueled by methane and operated under direct internal reforming and isothermal conditions. A one-dimensional steady-state model coupled with a detailed electrochemical model is employed to investigate the distribution of gas composition within fuel and air channels and all the electrochemical-related variables. The current–voltage characteristics of SOFC-H⁺ are analyzed and the result shows that the operation of SOFC-H⁺ at 0.7 V gives a good compromise on power density and fuel utilization. However, high CO content at fuel channel is observed at this condition and this may hinder the SOFC-H⁺ performance by reducing catalyst activity. The effect of key cell operating parameters, i.e., steam to carbon ratio, temperature, pressure, and water content in oxidant, on the performance of SOFC-H⁺ and the content of CO is also presented in this study.     

Model‐based optimization of hydrogen generation by methane steam reforming in autothermal packed‐bed membrane reformer

An autothermal membrane reformer comprising two separated compartments, a methane oxidation catalytic bed and a methane steam reforming bed, which hosts hydrogen separation membranes, is optimized for hydrogen production by steam reforming of methane to power a polymer electrolyte membrane fuel cell (PEMFC) stack. Capitalizing on recent experimental demonstrations of hydrogen production in such a reactor, we develop here an appropriate model, validate it with experimental data and then use it for the hydrogen generation optimization in terms of the reformer efficiency and power output. The optimized reformer, with adequate hydrogen separation area, optimized exothermic‐to‐endothermic feed ratio and reduced heat losses, is shown to be capable to fuel kW‐range PEMFC stacks, with a methane‐to‐hydrogen conversion efficiency of up to 0.8. This is expected to provide an overall methane‐to‐electric power efficiency of a combined reformer‐fuel cell unit of ～0.5. Recycling of steam reforming effluent to the oxidation bed for combustion of unreacted and unseparated compounds is expected to provide an additional efficiency gain. © 2010 American Institute of Chemical Engineers AIChE J, 2011