Comparative study of fuel gas production for SOFC from steam and supercritical-water reforming of bioethanol

Theoretical study of fuel gas (H₂ + CO) production for SOFC from bioethanol was carried out to compare performances between two reforming technologies, including steam reforming (SR) and supercritical-water reforming (SCWR). It demonstrates that the fuel gas productions are comparable among the two reforming systems; however, SCWR requires the operation at much higher temperature and pressure than SR. The maximum hydrogen yield can be obtained at 850 K, atmospheric pressure, ethanol to water molar feed ratio of 1:20 for SR system and at 1300 K, 22.1 MPa, and ethanol to water feed ratio of 1:20 for SCWR. The use of a distillation column to purify the bioethanol feed was proven to improve the fuel conversion efficiency of both systems. The analysis reveals that SCWR is a promising system for fuel production for SOFC when a gas turbine is incorporated to the system for energy recovery. Further, it is not necessary to distil bioethanol to obtain too high ethanol recovery (i.e. >90%) as higher energy consumption at the distillation column could lead to lower overall thermal efficiency.     

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.     

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.     

Comparison and optimization of different fuel processing options for biogas-fed solid-oxide fuel cell plants

The biogas needs to be reformed before electro-chemical conversion in the solid-oxide fuel cell, which can be promoted efficiently with wise thermal management and reforming conditions. To ensure the system safety and catalysts durability, additional mineral-bearing water and carbon deposition should be avoided. This paper conducted a detailed biogas-SOFC CHP system analysis considering four layouts, featuring hot and cold recirculation of the anode off-gas, partial oxidation and complete internal reforming. The process optimization and sensitivity analysis are performed with the design variables including the recirculation ratio, and external reformer temperature. The anode supported SOFC operates at 800 °C and 0.4 A/cm² current density. The results show that pre-reforming with hot recirculation and cold recirculation schemes achieve the highest system efficiency between 56% and 63%. The pre-reforming with hot recirculation scheme has a broader self-sufficient water range eliminating the carbon deposition risk at the recirculation ratio of 42–78% and reforming temperature of 400–650 °C. The no pre-reforming with hot recirculation scheme achieves maximum system efficiency of 58% due to the fuel dilution. Moreover, the partial oxidation with hot recirculation scheme maximum efficiency is limited to 58.9%, given that the partial oxidation reaction is less efficient than steam and dry reforming reactions. The proposed system layout could demonstrate the feasibility of biogas-SOFC with different reforming options especially on small scale with high efficiency and optimal thermal integration opportunities.     

Performance comparison of three solid oxide fuel cell power systems

An energy analysis of three typical solid oxide fuel cell (SOFC) power systems fed by methane is carried out with detailed thermodynamic model. Simple SOFC system, hybrid SOFC‐gas turbine (GT) power system, and SOFC‐GT‐steam turbine (ST) power system are compared. The influences of air ratio and operative pressure on the performance of SOFC power systems are investigated. The net system electric efficiency and cogeneration efficiency of these power systems are given by the calculation model. The results show that internal reforming SOFC power system can achieve an electrical efficiency of more than 49% and a system cogeneration efficiency including waste heat recovery of 77%. For SOFC‐GT system, the electrical efficiency and cogeneration efficiency are 61% and 80%, respectively. Although SOFC‐GT‐ST system is more complicated and has high investment costs, the electrical efficiency of it is close to that of SOFC‐GT system. Copyright © 2013 John Wiley & Sons, Ltd.     

Glycerol oxidation in solid oxide fuel cells based on a Ni-perovskite electrocatalyst

An investigation of the electrochemical oxidation of glycerol as alternative to hydrogen and methane in solid oxide fuel cells (SOFCs) based on a noble metal-free anode catalyst was carried out. The anode electrocatalyst consisted of a Ni-modified La_0.6Sr_0.4Fe_0.8Co_0.2O₃ (LSFCO) perovskite. After thermal activation, air treatment at 1100 °C followed by reduction at 800 °C in H₂, Ni was mainly present as ultrafine La₂NiO₄ particles homogeneously dispersed on the perovskite surface. The thermal activation also caused a modification of perovskite into a lanthanum depleted structure. The thermal reduction at 800 °C determined the occurrence of metallic Ni on the surface. These results were corroborated by X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and X-ray diffraction (XRD). A suitable power density (327 mW cm⁻²) was achieved for the electrolyte supported SOFC fed with chemical-grade glycerol in almost dry condition, i.e. steam to carbon ratio (S/C) of 0.2. The highest electrical efficiency (voltage efficiency) approached 50% at the peak power under mild humidification (S/C = 0.2). Whereas an increase of water to glycerol ratio, caused a progressive decrease of voltage efficiency at the peak power down to 44% for S/C = 2.     

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 internal steam reforming in solid oxide fuel cells at intermediate temperatures

The internal steam reforming of methane (CH₄) on conventional solid oxide fuel cell (SOFC) anode (nickel-yttria stabilized zirconia or Ni-YSZ) offers significant advantages compared to the external reforming process. However, the technology is currently facing some major issues such as coking and oxidation of anode during operation. Here we report a low-temperature sinterable catalyst, Ce_0·77Ni_0·2Mn_0·03O_2-δ (CNMnO), applied on top of Ni-YSZ to perform the steam reforming reaction. A single cell with CNMnO/Ni-YSZ/YSZ/GDC/LSC configuration produces a peak power density of 492 mW cm^?2 in wet hydrogen and 371 mW cm^?2 in wet methane, at 600 °C. The cell also shows exceptional durability against Ni oxidation when tested in wet methane under 0.2 A cm^?2 for 100 h. The improved performance and durability of the catalyst layer has been attributed to the nanosized precipitated Ni and Mn particles distributed on the surface of individual CNMnO particles.     

The effects of fuel variability on the electrical performance and durability of a solid oxide fuel cell operating on biohythane

Biohythane is typically composed of 60/30/10 vol% CH₄/CO₂/H₂ and can be produced via two-stage anaerobic digestion of renewable and low carbon biomass with much greater efficiency compared with CH₄/CO₂ biogas. This work investigates the effects of fuel variability on the electrical performance and fuel processing of a commercially available anode supported solid oxide fuel cell (SOFC) operating on biohythane mixtures at 750 °C. Cell electrical performance was characterised using current-voltage curves and electrochemical impedance spectroscopy. Fuel processing was characterised using quadrupole mass spectroscopy. It is shown that when H₂/CO₂ is blended with CH₄ to make biohythane, the SOFC efficiency is significantly increased, high SOFC durability is achieved, and there are considerable savings in CH₄ consumption. Enhanced electrical performance was due to the additional presence of H₂ and promotion of CH₄ dry reforming, the reverse Boudouard and reverse water-gas shift reactions. These processes alleviated carbon deposition and promoted electrochemical oxidation of H₂ as the primary power production pathway. Substituting 50 vol% CH₄ with 25/75 vol% H₂/CO₂ was shown to increase cell power output by 81.6% at 0.8 V compared with pure CH₄. This corresponded to a 3.4-fold increase in the overall energy conversion efficiency and a 72% decrease in CH₄ consumption. A 260 h durability test demonstrated very high cell durability when operating on a typical 60/30/10 vol% CH₄/CO₂/H₂ biohythane mixture under high fuel utilisation due to inhibition of carbon deposition. Overall, this work suggests that decarbonising gas grids by substituting natural gas with renewably produced H₂/CO₂ mixtures (rather than pure H₂ derived from fossil fuels), and utilising in SOFC technology, gives considerable gains in energy conversion efficiency and carbon emissions savings.     

Thermally integrated fuel processor design for fuel cell applications

Effective thermal integration could enable the use of compact fuel processors with PEM fuel cell-based power systems. These systems have potential for deployment in distributed, stationary electricity generation using natural gas. This paper describes a concept wherein the latent heat of vaporization of H₂O is used to control the axial temperature gradient of a fuel processor consisting of an autothermal reformer (ATR) with water gas shift (WGS) and preferential oxidation (PROX) reactors to manage the CO exhaust concentration. A prototype was experimentally evaluated using methane fuel over a range of external heat addition and thermal inputs. The experiments confirmed that the axial temperature profile of the fuel processor can be controlled by managing only the vapor fraction of the premixed reactant stream. The optimal temperature profile is shown to result in high thermal efficiency and a CO concentration less than 40 ppm at the exit of the PROX reactor.     

High performance of direct methane-fuelled solid oxide fuel cell with samarium modified nickel-based anode

Natural gas is one of the most attractive fuels for solid oxide fuel cell (SOFC), while the anode activity for methane fuel has a great influence on the performance and stability of SOFC. Samarium is a good catalyst promoter for methane reforming. In this work, samarium is used to modify nickel catalyst, which results in small nickel oxide particles. The SmNi-YSZ (yttria-stabilized zirconia) anode has smaller particles and better interfacial contact between nickel and YSZ compared with conventional Ni-YSZ anode. The fine structure of SmNi-YSZ anode results in high activity for electrochemical oxidation of hydrogen and low polarization resistance of the cell. The performance of SmNi-YSZ anode cell with humidified methane as fuel is greatly improved, which is similar to that with hydrogen as fuel. The maximum power densities of SmNi-YSZ anode cell are 1.56 W cm⁻² for humidified hydrogen fuel and 1.54 W cm⁻² for humidified methane fuel at 800 °C. The maximum power density is increased by 221% when samarium is used to modify Ni-YSZ anode for humidified methane fuel at 650 °C. High cell performance results in good stability of SmNi-YSZ anode cell and the cell runs stably for more than 600 min for humidified methane fuel.     

Combined methane reforming by carbon dioxide and steam in proton conducting solid oxide fuel cells for syngas/power co-generation

Methane and carbon dioxide mixture can be used as the fuel in a proton conducting solid oxide fuel cell (SOFC) for power/syngas co-generation and greenhouse gas reduction. However, carbon deposition and low conversion ratio are potential problems for this technology. Apart from using functional catalytic layer in the SOFC to enhance CH₄ dry reforming, adding H₂O into the fuel stream could facilitate the CH₄ conversion and enhance the co-generation performance of the SOFC. In this work, the effects of adding H₂O to the CO₂CH₄ fuel on the performance of a tubular proton conducting SOFC are studied numerically. Results show that the CH₄ conversion is improved from 0.830 to 0.898 after adding 20% H₂O to the anode. Meanwhile, the current density is increased from 2832 A m⁻² to 3064 A m⁻² at 0.7 V. Sensitivity studies indicate that the H₂:CO ratio can be effectively controlled by the amount of H₂O addition and the H₂ starvation can be alleviated, especially at high current density conditions.     

Comparison of efficiencies of low, mean and high temperature fuel cell Systems

Fuel cell systems are always said to show high electrical efficiency. The results achieved up to now, however, differ considerably, especially between the various fuel cell types all using natural gas as fuel. With the presented study the reasons for the different results and general potentials for fuel cell systems are highlighted. For that purpose several system lay-out concepts were elaborated for PEFC, PAFC and SOFC.The performed energy balance calculations for eight different plant concepts (three PEFC, two PAFC and three SOFC) for steady state operation with methane revealed that because of external reforming PEFC and PAFC systems are limited to about 67% and 70%, respectively, for the fuel utilisation. High temperature fuel cells can achieve at least 80% because of the possibility of internal reforming, or even over 90% in case of anode off-gas recycling. In combination with a cell voltage which is about 100 mV lower than that of MCFC and planar SOFC, PEFC can only achieve 38% of electrical net efficiency, PAFC 42% and tubular SOFC 54%. The latter is similar to MCFC, which is operated at higher cell voltage but lower fuel utilisation. The highest efficiency with up to 63% can be achieved with planar SOFC systems, because this concept allows high fuel utilisation together with high cell voltages.     

Fine interface contact and high activity of nickel-based anode modified by gadolinium for hydrogen and methane fuel

In this work, gadolinium is used to modify nickel catalyst, which can improve the properties of nickel oxide particle and inhibit its sintering and grain growth. Interface contact between nickel catalyst and YSZ is significantly improved and fine anode microstructure can be obtained when gadolinium is used to modify Ni-YSZ anode. Fine interface contact of GdNi-YSZ anode can accelerate charge transfer process and steam formation process, which leads to high activity for electrochemical oxidation of hydrogen and low impedance resistance. The remarkable characteristic of GdNi-YSZ anode cell is that the cell performance for humidified methane fuel is greatly improved due to the high anode activity for methane reforming and electrochemical oxidation of hydrogen. The maximum power density of GdNi-YSZ anode cell with humidified methane as fuel can reach 1.59 W/cm² at 800 °C and 0.46 W/cm² at 650 °C. High performance of GdNi-YSZ anode cell with humidified methane as fuel leads to much H₂O produced during the electrochemical oxidation process, which can depress carbon deposition and improve the cell stability for humidified methane fuel.     

Combustion chemistry aspects of alternative fuels reforming for high-temperature fuel cell applications

Solid-oxide fuel cells (SOFC) constitute a particularly attractive technology for sustainable, combined heat and power generation, both at domestic and district levels. The elevated operating temperature of SOFC systems, allows the utilization of a wide spectrum of conventional and alternative fuels, through suitable reforming processes. The high temperatures and fuel rich conditions prevailing in SOFC reformers, enhance syngas yield and reforming efficiency but may give rise to unwanted effects, such as ignition, soot and coke formation and deposition. The above phenomena cannot be described via thermodynamic considerations and can only be effectively tackled through a detailed chemical kinetic approach. The present study provides a comparative assessment of SOFC reformer operation on conventional and alternative hydrocarbon fuels in terms of syngas yield, thermal efficiency and pollutants formation. In particular, the reforming of methane, a typical biogas (comprising of 60% CH₄ and 40% CO₂), methanol and ethanol is numerically assessed by utilizing a recently developed and validated comprehensive detailed kinetic mechanism for C₁–C₆ hydrocarbons, augmented with a PAH model. Chemical aspects of the fuel reforming process are investigated through rate-of-production path and sensitivity analyses. The study supports design guidelines aiming towards identification of optimum operating conditions, for specific applications and fuels. The analysis reveals that the extent of coupling between syngas formation and molecular growth processes is strongly dependent on fuel and operating conditions choice and identifies windows of efficient operation, for each case.     

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.     

Effects of gas recycle on performance of solid oxide fuel cell power systems

An energy analysis of solid oxide fuel cell (SOFC) power systems with gas recycles fed by natural gas is carried out. Simple SOFC system, SOFC power systems with anode and cathode gas recycle respectively and SOFC power system with both anode and cathode gas recycle are compared. Influences of reforming rate, air ratio and recycle ratio of electrode exhaust gas on performance of SOFC power systems are investigated. Net system electric efficiency and cogeneration efficiency of these power systems are given by a calculation model. Results show that internal reforming SOFC power system can achieve an electrical efficiency of more than 44% and a system cogeneration efficiency including waste heat recovery of 68%. For SOFC power system with anode gas recycle, an electrical efficiency is above 46% and a cogeneration efficiency of 88% is obtained. In the case of cathode gas recycle, an electrical efficiency and a cogeneration efficiency is more than 51% and 78% respectively. Although SOFC system with both anode and cathode gas is more complicated, the electrical efficiency of it is close to 52%.     

Modeling electrochemical partial oxidation of methane for cogeneration of electricity and syngas in solid-oxide fuel cells

This paper uses computational models to evaluate strategies for scaling electrochemical partial oxidation (EPOX) processes from the laboratory scale to practical application. In addition to producing electrical energy alone, solid-oxide fuel cells (SOFC) can be operated with hydrocarbon fuel streams to produce synthesis gas (H₂ and CO) as well. SOFC systems are usually operated to consume most of the fuel and produce electricity. However, by operating with a hydrocarbon fuel at relatively high flow rates, the exhaust-gas composition can be predominantly syngas. In this case the steam (and CO₂), produced from electrochemical and thermal reactions, reacts to reform the hydrocarbon fuel within the catalytic anode support structure. A practical limitation of electrochemical partial oxidation operation is the fact that carbon tends to deposit on Ni-based anode catalysts. The present paper explores the use of barrier layers to prevent carbon deposits. The results show that a tubular cell can be designed to deliver syngas and electricity using methane as the primary fuel.     

Design of an integrated fuel processor for residential PEMFCs applications

KIER has been developing a novel fuel processing system to provide hydrogen rich gas to residential PEMFCs system. For the effective design of a compact hydrogen production system, each unit process for steam reforming and water gas shift, has a steam generator and internal heat exchangers which are thermally and physically integrated into a single packaged hardware system. The newly designed fuel processor (prototype II) showed a thermal efficiency of 78% as a HHV basis with methane conversion of 89%. The preferential oxidation unit with two staged cascade reactors, reduces, the CO concentration to below 10 ppm without complicated temperature control hardware, which is the prerequisite CO limit for the PEMFC stack. After we achieve the initial performance of the fuel processor, partial load operation was carried out to test the performance and reliability of the fuel processor at various loads. The stability of the fuel processor was also demonstrated for three successive days with a stable composition of product gas and thermal efficiency. The CO concentration remained below 10 ppm during the test period and confirmed the stable performance of the two-stage PrOx reactors.     

A new phenomenon of a fuel-free current during intermittent fuel flow over Ni-YSZ anode in direct methane SOFCs

A solid oxide fuel cell (SOFC) test unit was constructed with YSZ electrolyte as the support, and with Ni-YSZ anode (Ni:YSZ = 3:5 in weight) and Pt cathode. Direct methane SOFC operation at 800 °C with 10% CH₄ in argon was carried out. A new phenomenon of the generation of the electrical current without the fuel was observed and termed the fuel-free current. An operation of intermittent methane supply was designed to take advantage of three driving forces, i.e. methane in the gas phase, the deposited carbon at the anode surface, and a deficiency of the bulk lattice-oxygen concentration on the anode side, for the generation of the electrical current. A continuous generation of the electrical current is obtained with a methane pulse of only one-fifth of the total operation time. The operation of intermittent methane flow can reduce or even avoid SOFC deactivation by the carbon deposition; at the same time, the deposited carbon can be fully utilized for the power generation. It was also found that hydrogen from methane has been mostly evolved to the outlet gaseous product and the amount of CO formation is much higher than that of CO₂; the operation of intermittent methane flow can further increase the amount of CO over that of CO₂; these are beneficial for the co-generation of synthesis gas.