Modelling of tubular-designed solid oxide fuel cell with indirect internal reforming operation fed by different primary fuels

Mathematical models of an indirect internal reforming solid oxide fuel cell (IIR-SOFC) fed by four different primary fuels, i.e., methane, biogas, methanol and ethanol, are developed based on steady-state, heterogeneous, two-dimensional and tubular-design SOFC models. The effect of fuel type on the thermal coupling between internal endothermic reforming with exothermic electrochemical reactions and system performance are determined. The simulation reveals that an IIR-SOFC fuelled by methanol provides the smoothest temperature gradient with high electrochemical efficiency. Furthermore, the content of CO₂ in biogas plays an important role on system performance since electrical efficiency is improved by the removal of some CO₂ from biogas but a larger temperature gradient is expected.Sensitivity analysis of three parameters, namely, a operating pressure, inlet steam to carbon (S:C) ratio and flow direction is then performed. By increasing the operating pressure up to 10 bar, the system efficiency increases and the temperature gradient can be minimized. The use of a high inlet S:C ratio reduces the cooling spot at the entrance of reformer channel but the electrical efficiency is considerably decreased. An IIR-SOFC with a counter-flow pattern (as based case) is compared with that with co-flow pattern (co-flow of air and fuel streams through fuel cell). The IIR-SOFC with co-flow pattern provides higher voltage and a smoother temperature gradient along the system due to superior matching between heat supplied from electrochemical reaction and heat required for steam reforming reaction; thus it is expected to be a better option for practical applications.     

Multi-physics modeling of a symmetric flat-tube solid oxide fuel cell with internal methane steam reforming

Methane is regarded as one of the ideal fuels for solid oxide fuel cells (SOFCs) due to its huge reserves and transportation properties. In this study, a 3D numerical model coupling with chemical reaction, electrochemical reaction, mass transfer, charge transfer, and heat transfer is developed to understand the heat and mass transfer processes of methane steam direct internal reforming based on double-sided cathodes (DSC) SOFC. After the model verification, the parametric simulations are performed to study the effects of operating voltage, inlet temperature, and steam to carbon (S/C) ratio on the performance of a DSC. It is found that the non-uniform distribution of flow rate among channels results in the non-uniform distribution of each physical field. Increasing the inlet temperature significantly enhances the performance of DSC, however, when the temperature is above 1073 K, the concentration loss and the temperature gradient of DSC increase, which is not conducive to the long-term operation of the DSC. In addition, we revealed the effect of the S/C ratios on the heat and mass transfer process. This study provides an insight into the heat and mass transfer process of SOFC with a mixture of steam and methane and operating conditions for enhancing the performance.     

Experimental investigation of temperature distribution of planar solid oxide fuel cell: Effects of gas flow,power generation,and direct internal reforming

The temperature distribution of an operating planar solid oxide fuel cell (SOFC) is experimentally investigated under direct internal reforming conditions. An in situ measurement is conducted using a cell holder and an infrared (IR) camera. The effects of the gas flow configuration, exothermic power generation reaction, and endothermic steam–methane reforming reaction are examined at a furnace temperature of 770 °C. The fuel flow and airflow are set to a coflow or counterflow configuration. The heat generation and absorption by the reactions are varied by tuning the average current density and the concentration of methane in the supplied fuel. The maximum value of the local temperature gradient along the cell tends to increase with increasing internal reforming ratio, regardless of the gas flow configuration. From the view point of a small temperature gradient, the counterflow configuration clearly shows better characteristics than that of the coflow, regardless of the internal reforming ratio.     

Thermodynamic analysis of high‐temperature helium heated fuel reforming for hydrogen production

In order to take full advantage of the heat from high temperature gas cooled reactor, thermodynamic analysis of high‐temperature helium heated methane, ethanol and methanol steam reforming for hydrogen production based on the Gibbs principle of minimum free energy has been carried out using the software of Aspen Plus. Effects of the reaction temperature, pressure and water/carbon molar ratio on the process are evaluated. Results show that the effect of the pressure on methane reforming is small when the reaction temperature is over 900 °C. Methane/CO conversion and hydrogen production rate increase with the water/carbon molar ratio. However the thermal efficiency increases first to the maximum value of 61% and then decreases gradually. As to ethanol and methanol steam reforming, thermal efficiency is higher at lower reaction pressures. With an increase in water–carbon molar ratio, hydrogen production rate increases, but thermal efficiency decreases. Both of them increase with the reaction temperature first to the highest values and then decrease slowly. At optimum operation conditions, the conversion of both ethanol and methanol approaches 100%. For the ethanol and methanol reforming, their highest hydrogen production rate reaches, respectively, 88.69% and 99.39%, and their highest thermal efficiency approaches, respectively, 58.58% and 89.17%. With the gradient utilization of the high temperature helium heat, the overall heat efficiency of the system can reach 70.85% which is the highest in all existing system designs. Copyright © 2014 John Wiley & Sons, Ltd.     

Operational behavior and reforming kinetics over Ni/YSZ of a planar type pre-reformer for SOFC systems

At Forschungszentrum Jülich GmbH, a multi-component SOFC design based on planar stacks has been developed, in which all hot system components are scaled to a nominal SOFC stack power of 5 kW. To optimize the SOFC system it is necessary to investigate the effects of design and operating parameters on the system components like pre-reformer and afterburner. A special designed 5-layer planar type steam pre-reformer on basis of Ni/YSZ has been built and tested for operational behavior and kinetics of steam reforming with methane. This paper summarizes and discusses the experimental results on the global reaction kinetics of a Jülich planar pre-reformer in the temperature range between 350 °C and 620 °C at ambient pressure (1 bar). The species compositions of product gas at different feed compositions, flow rates and temperatures are determined by using gas-chromatographic methods and dew-point measurements. The reproducibility of experiments in the low temperature range (especially less than 430 °C) was only assured, when the catalyst has been reduced before every kinetic experiment. The proposed kinetic expression of Arrhenius type (second order with respect to mole fraction of methane and first order with respect to mole fraction of water) gives a good agreement with the experimental results of the methane steam reforming. It is general effective for different steam to carbon ratios. The temperature distribution in the pre-reformer and the loss of heat are also discussed.     

Mini CHP based on the electrochemical generator and impeded fluidized bed reactor for methane steam reforming

The paper presents a configuration of mini CHP with the methane reformer and planar solid oxide fuel cell (SOFC) stacks. This mini CHP may produce electricity and superheated steam as well as preheat air and methane for the reformer along with cathode air used in the SOFC stack as an oxidant. Moreover, the mathematical model for this power plant has been created. The thermochemical reactor with impeded fluidized bed for autothermal steam reforming of methane (reformer) considered as the basis for the synthesis gas (syngas) production to fuel SOFC stacks has been studied experimentally as well. A fraction of conversion products has been oxidized by the air fed to the upper region of the impeded fluidized bed in order to carry out the endothermic methane steam reforming in a 1:3 ratio as well as to preheat products of these reactions. Studies have shown that syngas containing 55% of hydrogen could be produced by this reactor. Basic dimensions of the reactor as well as flow rates of air, water and methane for the conversion of methane have been adjusted through mathematical modelling.The paper provides heat balances for the reformer, SOFC stack and waste heat boiler (WHB) intended for generating superheated water steam along with preheating air and methane for the reformer as well as the preheated cathode air. The balances have formed the basis for calculating the following values: the useful product fraction in the reformer; fraction of hydrogen oxidized at SOFC anode; gross electric efficiency; anode temperature; exothermic effect of syngas hydrogen oxidation by air oxygen; excess entropy along with the Gibbs free energy change at standard conditions; electromotive force (EMF) of the fuel cell; specific flow rate of the equivalent fuel for producing electric and heat energy. Calculations have shown that the temperature of hydrogen oxidation products at SOFC anode is 850 °C; gross electric efficiency is 61.0%; EMF of one fuel cell is 0.985 V; fraction of hydrogen oxidized at SOFC anode is 64.6%; specific flow rate of the equivalent fuel for producing electric energy is 0.16 kg of eq.f./(kW·h) while that for heat generation amounts to 44.7 kg of eq.f./(GJ). All specific parameters are in agreement with the results of other studies.     

Simulation analysis of a system combining solid oxide and polymer electrolyte fuel cells

We evaluated the performance of system combining a solid oxide fuel cell (SOFC) stack and a polymer electrolyte fuel cell (PEFC) stack by a numerical simulation. We assume that tubular-type SOFCs are used in the SOFC stack. The electrical efficiency of the SOFC–PEFC system increases with increasing oxygen utilization rate in the SOFC stack. This is because the amount of exhaust heat of the SOFC stack used to raise the temperature of air supplied to it decreases as its oxygen utilization rate increases and because that used effectively as the reaction heat of the steam reforming reaction of methane in the stack reformer increases. The electrical efficiency of the SOFC–PEFC system at 190 kW ac is 59% (LHV), which is equal to that of the SOFC-gas turbine combined system at 1014 kW ac.     

Methane membrane steam reforming: Heat duty assessment

Membrane reactors are an innovative technology with huge application potentialities for equilibrium limited endothermic reactions. Assembling a membrane selective to a reaction product avoids the equilibrium conditions to be achieved, supporting the reactions at lower operating temperatures. Taking as an example the natural gas steam reforming, a methane conversion around 98% can be reached imposing an operating temperature of 823 K, much lower than that of the traditional process. In the present paper, a stringent analysis of heat power requirement needed to carry out the natural gas steam reforming process by applying a membrane reactor is made. The simulations allows to understand how the main operating parameters (inlet temperature, inlet methane flow-rate, steam to carbon ratio, ratio between sweeping steam and inlet methane, operating reaction pressure) influence the total heat power required by the process, divided among power contributions for the reaction heat duty, reactant steam and permeation steam generation and preheating. Moreover, the specific thermal energy per mole of pure H₂ is computed and assessed. Optimizing the operating conditions set, a specific thermal energy per mole of pure hydrogen of 92.3 kWh kmol⁻¹ is obtained corresponding to a total thermal power of 687.4 kW required to convert, in a single membrane reactor, a methane flow-rate of 2 kmol h⁻¹ (GHSV = 9.590 h⁻¹) with a conversion around 98%.     

3D modeling of anode-supported planar SOFC with internal reforming of methane

Deposition of carbon on conventional anode catalysts and formation of large temperature gradients along the cell are the main barriers for implementing internal reforming in solid oxide fuel cell (SOFC) systems. Mathematical modeling is an essential tool to evaluate the effectiveness of the strategies to overcome these problems. In the present work, a three-dimensional model for a planar internal reforming SOFC is developed. A co-flow system with no pre-reforming, methane fuel utilization of 75%, voltage of 0.7 V and current density of 0.65 A cm⁻² was used as the base case. The distributions of both temperature and gas composition through the gas channels and PEN (positive electrode/electrolyte/negative electrode) structure were studied using the developed model. The results identified the most susceptible areas for carbon formation and thermal stress according to the methane to steam ratio and temperature gradients, respectively. The effects of changing the inlet gas composition through recycling were also investigated. Recycling of the anode exhaust gas, at an optimum level of 60% for the conditions studied, has the potential to significantly decrease the temperature gradients and reduce the carbon formation at the anode, while maintaining a high current density.     

Performance analysis and temperature gradient of solid oxide fuel cell stacks operated with bio-oil sorption-enhanced steam reforming

A high temperature gradient within a solid oxide fuel cell (SOFC) stack is considered a major challenge in SOFC operations. This study investigates the effects of the key parameters on SOFC system efficiency and temperature gradient within a SOFC stack. A 40-cell SOFC stack integrated with a bio-oil sorption-enhanced steam reformer is simulated using MATLAB and DETCHEM. When the air-to-fuel ratio and steam-to-fuel ratio increase, the stack average temperature and temperature gradient decrease. However, a decrease in the stack temperature steadily reduces the system efficiency owing to the tradeoff between the stack performance and thermal balance between heat recovered and consumed by the system. With an increase in the bio-oil flow rate, the system efficiency decreases because of the lower resident time for the electrochemical reaction. This is not, however, beneficial to the maximum temperature gradient. To minimize the temperature gradient of the SOFC stack, a decrease in the bio-oil flow rate is the most effective way. The maximum temperature gradient can be reduced to 14.6 K cm⁻¹ with the stack and system efficiency of 76.58 and 65.18%, respectively, when the SOFC system is operated at an air-to-fuel ratio of 8, steam-to-fuel ratio of 6, and bio-oil flow rate of 0.0041 mol s⁻¹.     

Modeling of SOFC with indirect internal reforming operation: Comparison of conventional packed-bed and catalytic coated-wall internal reformer

In the present work, mathematical models of indirect internal reforming solid oxide fuel cells (IIR-SOFC) fueled by methane were developed to analyze the thermal coupling of an internal endothermic reforming with exothermic electrochemical reactions and determine the system performance. The models are based on steady-state, heterogeneous, two-dimensional reformer and annular design SOFC models. Two types of internal reformer i.e. conventional packed-bed and catalytic coated-wall reformers were considered here. The simulations indicated that IIR-SOFC with packed-bed internal reformer leads to the rapid methane consumption and undesirable local cooling at the entrance of internal reformer due to the mismatch between thermal load associated with rapid reforming rate and local amount of heat available from electrochemical reactions. The simulation then revealed that IIR-SOFC with coated-wall internal reformer provides smoother methane conversion with significant lower local cooling at the entrance of internal reformer.     

Thermodynamic performance comparison of SOFC-MGT-CCHP systems coupled with two different solar methane steam reforming processes

Multi-energy complementary distributed energy system integrated with renewable energy is at the forefront of energy sustainable development and is an important way to achieve energy conservation and emission reduction. A comparative analysis of solid oxide fuel cell (SOFC)-micro gas turbine (MGT)-combined cooling, heating and power (CCHP) systems coupled with two solar methane steam reforming processes is presented in terms of energy, exergy, environmental and economic performances in this paper. The first is to couple with the traditional solar methane steam reforming process. Then the produced hydrogen-rich syngas is directly sent into the SOFC anode to produce electricity. The second is to couple with the medium-temperature solar methane membrane separation and reforming process. The produced pure hydrogen enters the SOFC anode to generate electricity, and the remaining small amount of fuel gas enters the afterburner to increase the exhaust gas enthalpy. Both systems transfer the low-grade solar energy to high-grade hydrogen, and then orderly release energy in the systems. The research results show that the solar thermochemical efficiency, energy efficiency and exergy efficiency of the second system reach 52.20%, 77.97% and 57.29%, respectively, 19.05%, 7.51% and 3.63% higher than those of the first system, respectively. Exergy analysis results indicate that both the solar heat collection process and the SOFC electrochemical process have larger exergy destruction. The levelized cost of products of the first system is about 0.0735$/h that is lower than that of the second system. And these two new systems have less environmental impact, with specific CO₂ emissions of 236.98 g/kWh and 249.89 g/kWh, respectively.     

Exergy analysis of hydrogen production via steam methane reforming

The performance of hydrogen production via steam methane reforming (SMR) is evaluated using exergy analysis, with emphasis on exergy flows, destruction, waste, and efficiencies. A steam methane reformer model was developed using a chemical equilibrium model with detailed heat integration. A base-case system was evaluated using operating parameters from published literature. Reformer operating parameters were varied to illustrate their influence on system performance. The calculated thermal and exergy efficiencies of the base-case system are lower than those reported in literature. The majority of the exergy destruction occurs due to the high irreversibility of chemical reactions and heat transfer. A significant amount of exergy is wasted in the exhaust stream. The variation of reformer operating parameters illustrated an inverse relationship between hydrogen yield and the amount of methane required by the system. The results of this investigation demonstrate the utility of exergy analysis and provide guidance for where research and development in hydrogen production via SMR should be focused.     

Thermodynamic analysis of hydrogen production via sorption-enhanced steam methane reforming in a new class of variable volume batch-membrane reactor

Combined reaction–separation processes are a widely explored method to produce hydrogen from endothermic steam reforming of hydrocarbon feedstock at a reduced reaction temperature and with fewer unit operation steps, both of which are key requirements for energy efficient, distributed hydrogen production. This work introduces a new class of variable volume batch reactors for production of hydrogen from catalytic steam reforming of methane that operates in a cycle similar to that of an internal combustion engine. It incorporates a CO₂ adsorbent and a selectively permeable hydrogen membrane for in situ removal of the two major products of the reversible steam methane reforming reaction. Thermodynamic analysis is employed to define an envelope of ideal reactor performance and to explore the tradeoff between thermal efficiency and hydrogen yield density with respect to critical operating parameters, including sorbent mass, steam to methane ratio and fraction of product gas recycled. Particular attention is paid to contrasting the variable volume batch-membrane reactor approach to a conventional fixed bed reaction–separation approach. The results indicates that the proposed reactor is a viable option for low temperature distributed production of hydrogen from methane, the primary component of natural gas feedstock, motivating a detailed study of reaction/adsorption kinetics and heat/mass transfer effects.     

CFD study of heat and mass transfer in ethanol steam reforming in a catalytic membrane reactor

This work shows the analysis of ethanol steam reforming process within a catalytic membrane reactor. A 2-D non-isothermal CFD model was developed using Comsol Multiphysics, based on previous experimentally validated isothermal model. A comprehensive heat and mass transfer study was carried out utilizing the model. Operating conditions such as liquid hourly space velocity (LHSV) (3.77–37.7 h^?1), temperature (673–823 K), reaction side pressure (4–10 bar) and permeate side sweep gas flow pattern were discussed. A temperature gradient along the reactor was observed from the model and a “cold spot” was seen at the reactor entrance area, which is unfavorable for the highly endothermic ethanol steam reforming process. By changing the sweep gas pattern to counter-current, the “cold spot” appears to be smaller with a reduced temperature drop. By studying the individual reaction rates, reverse methane steam reforming (methanation) was observed, caused by the low temperature in the “cold spot”. Optimal operating conditions were found to be under LHSV = 37.7 h^?1 and counter-current sweep gas conditions.     

Steam reforming on Ni-samaria-doped ceria cermet anode for practical size solid oxide fuel cell at intermediate temperatures

Direct internal and external reforming operations on Ni-samaria-doped ceria (SDC) anode with the practical size solid oxide fuel cell (SOFC) at intermediate temperatures from 600 to 750 °C are carried out to reveal the reforming activities and the electrochemical activities, being compared with the hydrogen-fueled power generation. The cell performance with direct internal and external steam reforming of methane and their limiting current densities were almost the same irrespective of the progress of reaction in the methane reformate at 700 and 750 °C. The durability test for 5.5 h at 750 °C with direct internal reforming operation confirmed that the cell performance did not deteriorate. The operation temperature of the cell controlled the reforming activities on the anode, and the large size electrode gave rise to high conversion due to the slow space velocity of the steam reforming. Direct internal steam reforming attained sufficient level of conversion for SOFC power generation with methane at 700 and 750 °C on the large Ni-SDC cermet anode.     

Is steam addition necessary for the landfill gas fueled solid oxide fuel cells?

Landfill gas in Hong Kong – a mixture of about 50% (by volume) CH₄ and 50% CO₂ – can be utilized for power generation in a solid oxide fuel cell (SOFC). Conventional way of utilizing CH₄ in a SOFC is by adding H₂O to CH₄ to initiate methane steam reforming (MSR) and water gas shift reaction (WGSR). As the methane carbon dioxide reforming (MCDR: CH₄ + CO₂ ↔ 2CO + 2H₂) is feasible in the SOFC anode, it is unknown whether H₂O is needed or not for landfill gas fueled SOFC. In this study, a numerical model is developed to investigate the characteristics of SOFC running on landfill gas. Parametric simulations show that H₂O addition may decrease the performance of short SOFC at typical operating conditions as H₂O dilute the fuel concentration. However, it is interesting to find that H₂O addition is needed at reduced operating temperature, lower operating potential, or in SOFC with longer gas channel, mainly due to less temperature reduction in the downstream and easier oxidation of H₂ than CO. This preliminary study could help identify strategies for converting landfill gas into electrical power in Hong Kong.     

Effect of operating conditions and gas flow patterns on the system performances of IIR-SOFC fueled by methanol

Mathematical models of an indirect internal reforming solid oxide fuel cells (IIR-SOFC) fueled by methanol were developed to analyze the thermal coupling of the internal endothermic steam reforming with exothermic electrochemical reactions and predict the system performance. The simulations indicated that IIR-SOFC fueled by methanol can be well performed as autothermal operation, although slight temperature gradient occurred at the entrance of the reformer chamber. Sensitivity analysis of five important parameters (i.e. operating voltage, reforming catalyst reactivity, inlet steam to carbon ratio, operating pressure and flow direction) was then performed. The increase of operating voltage lowered the average temperature along the reformer chamber and improved the electrical efficiency, but it oppositely reduced the average current density. Greater temperature profile along the system can be obtained by applying the catalyst with lower reforming reactivity; nevertheless, the current density and electrical efficiency slightly decreased. By using high inlet steam to carbon ratio, the cooling spot at the entrance of the reformer can be reduced but both current density and electrical efficiency were decreased. Lastly, with increasing operating pressure, the system efficiency increased and the temperature dropping at the reformer chamber was minimized.