Modeling of SOFC running on partially pre-reformed gas mixture

A two dimensional model is developed to study the transport and reaction processes in solid oxide fuel cells (SOFCs) fueled by partially pre-reformed gas mixture, considering the direct internal reforming (DIR) of methane and water gas shift (WGS) reaction in the porous anode of SOFC. Electrochemical oxidations of H₂ and CO fuels are both considered. The model consists of an electrochemical, a chemical model, and a computational fluid dynamics (CFD) model. Two chemical models are compared to examine their effects on SOFC modeling results. Different from the previous studies on hydrogen fueled SOFC, higher gas velocity is found to slightly decrease the performance of SOFC running on pre-reformed gas mixture, due to suppressed gas composition variation at a higher gas velocity. The current density distribution along the gas channels at an inlet temperature of 1173K is quite different from that at 1073K, as DIR reaction is facilitated at a higher temperature. It is also found that neglecting the electrochemical oxidation of CO can considerably underestimate the total current density of SOFC running on pre-reformed hydrocarbon fuels. An alternative method is proposed to numerically determine the open-circuit potential of SOFC running on hydrocarbon fuels. Electrochemical reactions are observed at open-circuit potentials.     

The effect of electrolyte type on performance of solid oxide fuel cells running on hydrocarbon fuels

A two-dimensional model is developed to simulate the performance of methane fueled solid oxide fuel cells (SOFCs), focusing on the effect of electrolyte type on SOFC performance. The model considers the heat and mass transfer, direct internal reforming (DIR) reaction, water gas shift reaction (WGSR), and electrochemical reactions in SOFCs. The electrochemical oxidation of CO in oxygen ion-conducting SOFC (O-SOFC) is considered. The present study reveals that the performance of H-SOFC is lower than that of O-SOFC at a high temperature or at a low operating potential, as electrochemical oxidation of CO in O-SOFC contributes to power generation. This finding is contrary to our common understanding that proton conducting SOFC (H-SOFC) always performs better than O-SOFC. However, at a high operating potential of 0.8 V or at a lower temperature, H-SOFC does exhibit better performance than O-SOFC due to its higher Nernst potential and higher ionic conductivity of the electrolyte. This indicates that the proton conductors can be good choices for SOFCs at intermediate temperature, even with hydrocarbons fuels. The results provide better understanding on how the electrolyte type influences the performance of SOFCs running on hydrocarbon fuels.     

A general electrolyte–electrode-assembly model for the performance characteristics of planar anode-supported solid oxide fuel cells

A general electrode–electrolyte-assembly (EEA) model has been developed, which is valid for different designs of solid oxide fuel cells (SOFCs) operating at different temperatures. In this study, it is applied to analyze the performance characteristics of planar anode-supported SOFCs. One of the novel features of the present model is its treatment of electrodes. An electrode in the present model is composed of two distinct layers referred to as the backing layer and the reaction zone layer. The other important feature of the present model is its flexibility in fuel, having taking into account the reforming and water–gas shift reactions in the anode. The coupled governing equations of species, charge and energy along with the constitutive equations in different layers of the cell are solved using finite volume method. The model can predict all forms of overpotentials and the predicted concentration overpotential is validated with measured data available in literature. It is found that in an anode-supported SOFC, the cathode overpotential is still the largest cell potential loss mechanism, followed by the anode overpotential at low current densities; however, the anode overpotential becomes dominant at high current densities. The cathode and electrolyte overpotentials are not negligible even though their thicknesses are negligible relative to the anode thickness. Even at low fuel utilizations, the anode concentration overpotential becomes significant when chemical reactions (reforming and water–gas shift) in the anode are not considered. A parametric study has also been carried out to examine the effect of various key operating and design parameters on the performance of an anode-supported planar SOFCs.     

Comparison between two methane reforming models applied to a quasi-two-dimensional planar solid oxide fuel cell model

Up to recently 2-D solid oxide fuel cell (SOFC) modelling efforts were based on global kinetic approaches for the methane steam reforming and water gas shift reactions (WGS) or thermodynamic equilibrium. Lately detailed models for elementary heterogeneous chemical kinetics of reforming (HCR) over Ni–YSZ anode became available in literature. Both approaches were employed in a quasi 2-D model of a planar high temperature electrolyte supported (ESC) SOFC and simulations were carried out for three different fuel gas compositions: pre-reformed natural gas (high CH₄ content), and two different biomass derived producer gases (low CH₄ content). The results show that the HCR predicts much slower reforming rates which leads to a more evenly distributed solid temperature but smaller power output and thus electrical efficiency. The two models result into predictions that differ greatly if high methane content fuels are used and for such cases the decision upon the modelling scheme to follow should be based on experimental investigations.     

Thermodynamic analysis of ITSOFC hybrid system for polygenerations

Solid oxide fuel cell (SOFC) is an energy conversion device that produces electricity directly from fossil fuels through electrochemical reactions. Intermediate and low temperature SOFCs (IT/LT, 300–800 °C SOFCs) are the main strains of the world SOFC R&D now. The exhaust gas of SOFC has high value in use. So SOFC is often integrated into a hybrid system with other power systems. Research shows that the electrical efficiency and the total efficiency of a hybrid system can be about 60% and 80% higher than an independent one. In this paper, the performance of intermediate temperature SOFC hybrid system was analyzed. Based on presenting a steady-state mathematical model of ITSOFC, the steady-state model of each designed system was presented. Results show that a hybrid system can achieve high efficiency. The results of this research can be useful in design and application for polygenerations integrated by SOFCs.     

Thermodynamic modeling of direct internal reforming solid oxide fuel cells operating with syngas

In this paper a direct internal reforming solid oxide fuel cell (DIR-SOFC) is modeled thermodynamically from the energy point of view. Syngas produced from a gasification process is selected as a fuel for the SOFC. The modeling consists of several steps. First, equilibrium gas composition at the fuel channel exit is derived in terms mass flow rate of fuel inlet, fuel utilization ratio, recirculation ratio and extents of steam reforming and water–gas shift reaction. Second, air utilization ratio is determined according to the cooling necessity of the cell. Finally, terminal voltage, power output and electrical efficiency of the cell are calculated. Then, the model is validated with experimental data taken from the literature. The methodology proposed is applied to an intermediate temperature, anode-supported planar SOFC operating with a typical gas produced from a pyrolysis process. For parametric analysis, the effects of recirculation ratio and fuel utilization ratio are investigated. The results show that recirculation ratio does not have a significant effect for low current density conditions. At higher current densities, increasing the recirculation ratio decreases the power output and electrical efficiency of the cell. The results also show that the selection of the fuel utilization ratio is very critical. High fuel utilization ratio conditions result in low power output and air utilization ratio but higher electrical efficiency of the cell.     

Thermal field under the effect of the chemical reaction of a direct internal reforming solid oxide fuel cell DIR-SOFC

The effects of direct internal reforming in a fuel cell solid oxide (SOFC) on thermal fields are studied by mathematical modeling. This study presents the thermal fields of a standard fuel cell (Ni-YSZ/YSZ/LSM) anode supported. This study is also made in the perpendicular plane at the flow of gases. The fuel cell is powered by air and fuel, CH₄, H₂, CO₂, CO and H₂O hence the birth of the phenomenon of direct internal reforming (DIR-SOFC). It is based on reforming chemical reactions, steam reforming reaction and water–gas shift reaction. The main purpose of this work is the visualization of temperature fields under the influence of global chemical reactions and the confirmation of the thermal behavior of this chemical reaction. The thermal fields are obtained by a computer program (FORTRAN).     

Internal reforming of hydrocarbon fuels in tubular solid oxide fuel cells

The application of heterogeneous catalysis has an important role to play in the successful commercial development of solid oxide fuel cell (SOFC) technology. In this paper, we present an SOFC that combines a catalyst layer with a conventional anode, allowing internal reforming via partial oxidation (POX) of fuels such as methane, propane, butane, biomass gas, etc., without coking and yielding stable power output. The catalyst layer is fabricated on the anode simply by catalyst support coating and reforming catalyst impregnation. The composition and microstructure of catalyst support layer as well as the catalyst composition was easily tailored to meet the demand of in situ reforming. The usage of catalyst layer as an integrated part of the traditional SOFC will provide a simple low-cost power-generating system at substantially higher fuel efficiency and faster start-ups, and may accelerate the application of SOFCs through the direct use of hydrocarbon fuels.     

Paper-structured catalyst for the steam reforming of biodiesel fuel

Architectonics of the paper-structured catalyst for the application to the biofuel reformer or direct internal reforming SOFC (DIRSOFC) was studied. Inorganic fiber network, “paper”, composed of yttria-stabilized zirconia (YSZ) fiber (Zf), alumina fiber (Af) and inorganic binder (Al₂O₃ sol (As) or ZrO₂ sol (Zs) or CeO₂ sol (Cs)) was prepared by a simple paper-making process. Then, the catalytic activities of the Ni and Ni–MgO loaded papers called “paper-structured catalysts (PSCs)” for the steam reforming of biodiesel fuels (BDFs) were evaluated. Ni–MgO loaded PSC using Cs as an inorganic binder, Ni–MgO/ZfAfCs, exhibited excellent performance over Ru/γAl₂O₃ catalyst beads. Formation of light hydrocarbons, especially C₂H₄, was eliminated and water–gas shift reaction was more promoted compared to the catalyst beads.     

Developing fuel map to predict the effect of fuel composition on the maximum voltage of solid oxide fuel cells

A thermodynamic model is developed to determine the fuels that would yield an identical maximum cell voltage (MCV) for solid oxide fuel cells (SOFCs) at a given operating condition. These fuels make a continuous curve in the ternary coordinate system. A fuel map is established by developing the continuous fuel curves for different MCVs at the same operating condition and representing them in the carbon-hydrogen-oxygen (C-H-O) ternary diagram. Using the fuel map, the effect of the composition of a fuel containing carbon, hydrogen, oxygen, and inert gas atoms on the MCV of SOFCs can be easily studied. In addition to the effect of the fuel composition, the graphical representation of fuel maps can be applied to study the effect of the fuel processors on the MCV of SOFCs. As a general result, among fuels that can be directly utilized in SOFCs, at the same temperature and pressure, the one located at the intersection of the H-C axis and the carbon deposition boundary (CDB) curve in the C-H-O ternary diagram, provides the highest MCV for SOFCs. The results also show that for the fuels that cannot be directly utilized in SOFC, the steam reforming fuel processor always yields a higher MCV than the autothermal reforming or the partial oxidation fuel processors at the same inlet fuel temperature.     

Steam reforming behavior of methanol using paper-structured catalysts: Experimental and computational fluid dynamic analysis

Copper–zinc oxide (Cu/ZnO) catalyst powders were impregnated into paper-structured composites (catalyst paper) using a papermaking process. The paper-structured catalyst was subjected to the methanol steam reforming (MSR) process and exhibited excellent performance compared with those achieved by pellet-type or powdered catalyst. The catalyst paper demonstrated a relatively stable gas flow as compared to catalyst pellets. Furthermore, the MSR process was simulated by computational fluid dynamic (CFD) analysis, and the heat conductivity influence of the catalyst layer was investigated. Higher heat conductivity contributed to both higher methanol conversion and lower carbon monoxide concentration; localization of heat and chemical species such as hydrogen and carbon dioxide were improved, resulting in suppression of reverse water–gas shift reaction. The CFD analysis was applied to the design of a catalyst layer in which a suitable shape was suggested, where carbon monoxide formation was further suppressed without a decrease in the methanol conversion.     

A CFD-based model of a planar SOFC for anode flow field design

This study presents a 3D CFD model of a planar SOFC with internal reforming for anode flow field design. The developed model reflects the influence of various factors on fuel cell performance including flow field design and kinetics of chemical and electrochemical reactions. The case study illustrates applications of the CFD model for planar SOFC with different anode flow field designs. Simulation results indicate the importance of the anode flow field design for planar SOFCs. The model is useful for optimization of fuel cell design and operating conditions.     

Performance of tubular Solid Oxide Fuel Cell at reduced temperature and cathode porosity

The effect of decreasing the inlet temperature and the cathode porosity of tubular Solid Oxide Fuel Cell (SOFC) with one air channel and one fuel channel is investigated using Computational Fluid Dynamics (CFD) approach. The CFD model was developed using Fluent SOFC to simulate the electrochemical effects. The cathode and the anode of the cell were resolved in the model and the convection and conduction heat transfer modes were included. The results of the CFD model are presented at inlet temperatures of 700 °C, 600 °C and 500 °C and with cathode porosity of 30%, 20% and 10%. It was found that the Fluent-based SOFC model is an effective tool for analyzing the complex and highly interactive three-dimensional electrical, thermal, and fluid flow fields associated with the SOFCs. It is found that the SOFC can operate in the intermediate temperature range and with low porosity cathodes more efficient than at high temperatures given that the transport properties of the cathode, anode and the electrolyte can be kept the same.     

Operation of solid oxide fuel cells on glycerol fuel: A thermodynamic analysis using the Gibbs free energy minimization approach

Solid oxide fuel cells (SOFCs) are very flexible, unlike other fuel cells. In principle, SOFCs can operate on almost any fuel. Currently much effort is invested in the development of SOFCs for portable applications operating directly on liquid fuels such as methanol and ethanol rather than hydrogen. However, there are very few publications dealing with the direct use of glycerol in SOFCs for portable systems. A recently published study shows that the performance achieved for an SOFC fueled by pure glycerol is quite interesting even when there is a thick electrolyte membrane, indicating that glycerol is a promising fuel for portable applications. For this reason a thermodynamic analysis for SOFCs operating directly on glycerol fuel is performed in the present study. The Gibbs energy minimization method computes the equilibrium compositions of the anode gas mixture, carbon deposition boundaries and electromotive forces (EMFs) as a function of fuel utilization and temperature. Moreover, the minimum amounts of H₂O, CO₂ (direct internal reforming case) and air (partial oxidation case) to be added to glycerol in the feedstock to avoid carbon deposition at the open circuit voltage (OCV) are calculated. Finally, a thermodynamic analysis is performed, taking into account the experimental conditions employed in a previous study. Experimental observations concerning carbon deposition in an SOFC operating on glycerol can be explained by the theoretical analysis developed in the present study. Additionally, the effect of mixed electronic-ionic conduction of the electrolyte on carbon deposition at the anode is discussed based on the thermodynamic analysis of the C-O system.     

Detailed kinetic modelling of the T-POX reforming process using a reactor network approach

Solid-oxide fuel cells (SOFCs) are particularly attractive since they offer clean and efficient decentralized electricity generation and can be incorporated into hybrid systems with CHP capabilities. However, small scale SOFC systems operated with hydrocarbon fuels require external reforming. A very promising reforming technology involves partial oxidation (POX) in an inert porous material (T-POX reformer). The present work provides extensive numerical simulation of a prototype T-POX reformer operating with methane. Computations are performed using a reactor network approach incorporating full detailed chemistry and results are successfully compared against experimentally determined hydrocarbon species data. Computational results are further used to identify the elementary kinetic pathways for hydrocarbon fuel partial oxidation, molecular growth and pollutant formation as well as to identify optimum reformer operating conditions.     

Recent progress in integration of reforming catalyst on metal-supported SOFC for hydrocarbon and logistic fuels

The metal-supported solid oxide fuel cell (MS-SOFC) is of current research interest in the clean energy field due to its high performance, quick start-up, thermal cycle stability, and lower raw material cost compared to the conventional cermet-based SOFC. To efficiently operate a MS-SOFC using complex hydrocarbon and logistic fuels, it is required to introduce an internal reforming catalyst within the anode metal scaffold. This review article discusses some examples of the performance of MS-SOFCs under hydrocarbon and logistic fuels with and without an additional reforming catalyst. We also discuss the performance improvement of conventional cermet-based SOFCs by adding reforming catalysts via the infiltration method. This information can be directly applied to future MS-SOFC applications. Furthermore, this review article proposes possible novel methods such as direct precursor infiltration, catalyst-anode premixing, and atomic layer deposition methods to introduce the reforming catalyst into a MS-SOFC for improving its initial electrochemical performance and long-term stability under hydrocarbon and logistics fuel.     

Simulation of SOFC performance using a modified exchange current density for pre-reformed methane-based fuels

Numerical simulations can be used to visualize and better understand various distributions such as gas concentration and temperature in solid oxide fuel cells (SOFCs) under realistic operating conditions. However, pre-existing models generally utilize an anode exchange current density equation which is valid for humidified hydrogen fuels – an unrealistic case for SOFCs, which are generally fueled by hydrocarbons. Here, we focus on developing a new, modified exchange current density equation, leading to an improved numerical analysis model for SOFC anode kinetics. As such, we experimentally determine the exchange current density of SOFC anodes fueled by fully pre-reformed methane. The results are used to derive a new phenomenological anode exchange current density equation. This modified equation is then combined with computational fluid dynamics (CFD) to simulate the performance parameters of a three-dimensional electrolyte-supported SOFC. The new modified exchange current density equation for methane-based fuels reproduces the I–V characteristics and temperature distribution significantly better than the previous models using humidified hydrogen fuel. Better simulations of SOFC performance under realistic operating conditions are crucial for the prediction and prevention of e.g. fuel starvation and thermal stresses.     

Life cycle environmental impact comparison of solid oxide fuel cells fueled by natural gas,hydrogen, ammonia and methanol for combined heat and power generation

This study aims to provide a comprehensive environmental life cycle assessment of heat and power production through solid oxide fuel cells (SOFCs) fueled by various chemical feeds namely; natural gas, hydrogen, ammonia and methanol. The life cycle assessment (LCA) includes the complete phases from raw material extraction or chemical fuel synthesis to consumption in the electrochemical reaction as a cradle-to-grave approach. The LCA study is performed using GaBi software, where the selected impact assessment methodology is ReCiPe 1.08. The selected environmental impact categories are climate change, fossil depletion, human toxicity, water depletion, particulate matter formation, and photochemical oxidant formation. The production pathways of the feed gases are selected based on the mature technologies as well as emerging water electrolysis via wind electricity. Natural gas is extracted from the wells and processed in the processing plant to be fed to SOFC. Hydrogen is generated by steam methane reforming method using the natural gas in the plant. Methanol is also produced by steam methane reforming and methanol synthesis reaction. Ammonia is synthesized using the hydrogen obtained from steam methane reforming and combined with nitrogen from air in a Haber-Bosch plant. Both hydrogen and ammonia are also produced via wind energy-driven decentralized electrolysis in order to emphasize the cleaner fuel production. The results of this study show that feeding SOFC systems with carbon-free fuels eliminates the greenhouse gas emissions during operation, however additional steps required for natural gas to hydrogen, ammonia and methanol conversion, make the complete process more environmentally problematic. However, if hydrogen and ammonia are produced from renewable sources such as wind-based electricity, the environmental impacts reduce significantly, yielding about 0.05 and 0.16 kg CO₂ eq., respectively, per kWh electricity generation from SOFC.     

Numerical modeling of SOFCs operating on biogas from biodigesters

In this study, numerical predictions of SOFCs performance operating on biogas are performed in order to evaluate the potential use of biogas produced from different organic sources processed in biodigesters as the fuel for SOFCs. The SOFC performance is predicted numerically by using a fully three-dimensional non-commercial CFD code called DREAM-SOFC. The analysis mainly focuses on the effect of biogas composition on the fuel cell performance. Different biogas compositions are used as the fuel supplied to the SOFC and the concentration of the species in the biogas are those measured by means of a gas chromatography system of the biogas produced in biodigesters installed at University of Guanajuato. Particularly, the biogas produced from water lily and cactus was evaluated as potential fuel for SOFCs. It was observed that the SOFC performance is higher when biogas from water lily is supplied to the SOFC when compared with biogas from cactus.