Performance of yttria-stabilized zirconia fuel cell using H2–CO2 gas system and CO–O2 gas system

This paper reports the performance of an yttria-stabilized zirconia fuel cell (YSZ) using five kinds of gas systems. The final target of this research is to establish the combined fuel cell systems which can produce a H₂ fuel and circulate CO₂ gas in the production process of electric power. A large electric power was measured in the H₂–O₂ gas system and the CO–O₂ gas system at 1073 K. The formation process of O²⁻ ions in the endothermic cathodic reaction (1/2O₂+2e⁻→O²⁻) controlled the cell performance in both the gas systems. The electric power of the H₂–CO₂ gas system, which allowed to change CO₂ gas into a CO fuel (H₂+CO₂→H₂O+CO) in the cathode, was 1/31–1/11 of the maximum electric power for the H₂–O₂ gas system. This result is related to the larger endothermic energy for the formation of O²⁻ ions from CO₂ molecules at the cathode (CO₂+2e⁻→CO+O²⁻) than from O₂ molecules. The CO–H₂O gas system and the H₂–H₂O gas system was expected to produce a H₂ fuel in the cathode (CO+H₂O→H₂+CO₂, H₂+H₂O→H₂+H₂O). Although relatively high OCV values (open circuit voltage) were measured in these gas systems, no electric power was measured. At this moment, it was difficult to apply H₂O vapor as an oxidant to the cathodic reaction in a YSZ fuel cell.     

Overpotential Behavior of Carbon Monoxide Fuel in a Molten Carbonate Fuel Cell

The overpotential of carbon monoxide (CO) fuel was analyzed with a 100‐cm² class molten carbonate fuel cell. The overpotential at the anode was measured using the steady state polarization, inert gas step addition, and reactant gas addition methods. Then, the overpotential was compared between normal hydrogen fuel (H₂:CO₂:H₂O = 0.69:0.17:0.14 atm, inlet composition) and CO fuels (CO:CO₂:H₂O = 0.5:0.5:0 atm and 0.43:0.43:0.14 atm, inlet compositions). The CO fuel without H₂O showed a much greater overpotential at 150 mA cm^–2 than the CO fuel with H₂O. This implies that the water‐gas‐shift reaction prevails at the anode and humidification of CO fuel is an efficient way to reduce anodic overpotential. The anodic overpotential with CO:CO₂:H₂O = 0.43:0.43:0.14 atm was about 73% of that of the H₂ fuel at 150 mA cm^–2. The anode showed gas‐phase mass‐transfer limitations with CO fuels.     

Gas hydrate formation from hydrogen/carbon dioxide and nitrogen/carbon dioxide gas mixtures

Gas hydrates from CO₂/N₂ and CO₂/H₂ gas mixtures were formed in a semi-batch stirred vessel at constant pressure and temperature of 273.7 K. These mixtures are of interest to CO₂ separation and recovery from flue gas and fuel gas, respectively. During hydrate formation the gas uptake was determined and the composition changes in the gas phase were obtained by gas chromatography. The rate of hydrate growth from CO₂/H₂ mixtures was found to be the fastest. In both mixtures CO₂ was found to be preferentially incorporated into the hydrate phase. The observed fractionation effect is desirable and provides the basis for CO₂ capture from flue gas or fuel gas mixtures. The separation from fuel gas is also a source of H₂. The impact of tetrahydrofuran (THF) on hydrate formation from the CO₂/N₂ mixture was also observed. THF is known to substantially reduce the equilibrium formation conditions enabling hydrate formation at much lower pressures. THF was found to reduce the induction time and the rate of hydrate growth.     

Modular Stack‐Internal Air Humidification Concept‐Verification in a 1 kW Stack

The analysis of the complete H₂/air polymer electrolyte fuel cell system shows that process air humidification is one of the biggest obstacles for a high performance portable system in the kW range. Therefore, a new concept, with passive process air humidification integrated into the stack, has been developed. Humidification in each cell makes the process independent from the number of cells and the operation mode, thus making the concept fully scalable. Without external humidification the system is simpler, smaller, and cheaper. The humidification of the process air is achieved by transfer of product water from the exhaust air, through part of the membrane, to the dry intake air. Tests have shown that cells using the concept of internal humidification and operated with dry air at 70 ° have almost the same performance as when operated with external humidification. A 42‐cell stack with this internal humidification concept was built and integrated into a portable 1 kW power generator system.     

Technical and economic study of integrated system of solid oxide fuel cell,palladium membrane reactor,and CO2 sorption enhancement unit

This paper deals with the integrated system of solid oxide fuel cell (SOFC), palladium membrane reactor (PMR), and CO₂ sorption enhancement (SE) unit. Three configurations of the SOFC systems fed by biogas are considered, i.e., PMR–SOFC, SE–PMR–SOFC, and SE–PMR–SOFC with a retentate gas recycling (SER–PMR–SOFC). The SOFC system equipped with a conventional reformer (CON–SOFC) is considered as a base case. The simulation results show that the capture of CO₂ in biogas before being fed to PMR (SE–PMR–SOFC) can improve H₂ recovery. The performance of SE–PMR–SOFC can be further enhanced by recycling retentate gas from PMR to CO₂ sorption enhancement unit (SER–PMR–SOFC). Compared to CON–SOFC, both SE–PMR–SOFC and SER–PMR–SOFC give higher power density and thus require smaller stack size (the stack size reduction of 1.55% and 8.27% are observed for SE–PMR–SOFC and SER–PMR–SOFC, respectively). The economic analysis is performed to identify the potential benefits of each SOFC configuration. The results indicate that SE–PMR–SOFC and SER–PMR–SOFC are not cost-effective systems compared with CON–SOFC; however, the capture of CO₂ in these SOFC systems offers an environmental benefit. High %total CO₂ capture and low cost of CO₂ capture are achieved under these SOFC systems.     

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.     

Removing H2S from Biogas Using Sorbents for Solid Oxide Fuel Cell Applications

Desulfurization of biogas is essential for its application in solid oxide fuel cells. The influence of CH₄, CO₂, H₂, and O₂ as well as the effect of moisture onto desulfurization performance of an activated carbon, an adsorbent based on a CuO‐MnO mixture, and a zeolite adsorbent were analyzed. The use of moisturized gas had no negative influence on the H₂S adsorption performance of activated carbon. The CuO‐MnO sorbent showed the best performance, but the presence of moisture had a negative influence. The performance of zeolite dropped for three gas mixtures, while for two other mixtures moisture had little to no influence on H₂S adsorption performance.     

Gasification characteristics of combustible wastes in a 5 ton/day fixed bed gasifier

The gasification characteristics of combustible wastes were determined in a 5 ton/day fixed bed gasifier (1.2 m I.D. and 2.8m high). The fixed bed gasifier consisted of air compressor, oxygen tank, MFC, fixed bed gasifier, cyclone, heat exchanger, solid/gas separator, water fluidized bed reactor and blower. To capture soot or unburned carbon from the gasification reaction, solid/gas separator and water fluidized bed were used. The experiments with 10–50 hours of operation were carried out to determine the effects of bed temperature, solid/oxygen ratio and oxidant on the gas composition, calorific value and carbon conversion. The calorific values of the produced gas decreased with an increase of bed temperature because combustion reaction happened more actively. The gas composition of partial oxidation of woodchip is CO: 34.4%, H₂: 10.7%, CH₄: 6.0%, CO₂: 48.9% and that of RPF is CO: 33.9%, H₂: 26.1%, CH₄: 10.7%, CO₂: 29.2%. The average calorific values of produced gas were about 1,933 kcal/Nm³, 2,863 kcal/Nm³, respectively. The maximum calorific values were 3,100 kcal/Nm³ at RPF/oxygen ratio: 7     

ALTERNATIVE GENERATION OF H2, CO AND H2, CO2 MIXTURES FROM STEAM-CARBON DIOXIDE REFORMING OF METHANE AND THE WATER GAS SHIFT WITH PERMEABLE (MEMBRANE) REACTORS

A new process is proposed which converts CO₂ and CH₄ containing gas streams to synthesis gas, a mixture of CO and H₂ via the catalytic reaction scheme of steam-carbon dioxide reforming of methane or the respective one of only carbon dioxide reforming of methane, in permeable (membrane) reactors. The membrane reformer (permreactor) can be made by reactive or inert materials such as metal alloys, microporous ceramics, glasses and composites which all are hydrogen permselective. The rejected CO reacts with steam and converted catalytically to CO₂ and H₂ via the water gas shift in a consecutive permreactor made by similar to the reformer materials and alternatively by high glass transition temperature polymers. Both permreactors can recover H₂ in permeate by using metal membranes, and H₂ rich mixtures by using ceramic, glass and composite type permselective membranes. H₂ and CO₂ can be recovered simultaneously in water gas shift step after steam condensation by using organic polymer membranes. Product yields are increased through permreactor equilibrium shift and reaction separation process integration.

CO and H₂ can be combined in first step to be used for chemical synthesis or as fuel in power generation cycles. Mixtures of CO₂ and H₂ in second step can be used for synthesis as well (e.g., alternative methanol synthesis) and as direct feed in molten carbonate fuel cells. Pure H₂ from the above processes can be used also for synthesis or as fuel in power systems and fuel cells. The overall process can be considered environmentally benign because it offers an in-situ abatement of the greenhouse CO₂ and CH₄ gases and related hydrocarbon-CO₂ feedstocks (e.g., coal, landfill, natural, flue gases), through chemical reactions, to the upgraded calorific value synthesis gas and H₂, H₂ mixture products.     

H2 rich product gas by steam gasification of biomass with in situ CO2 absorption in a dual fluidized bed system of 8 MW fuel input

The steam gasification of solid biomass by means of the absorption enhanced reforming process (AER process) yields a high quality product gas with increased hydrogen content. The product gas can be used for a wide range of applications which covers the conventional combined heat and power production as well as the operation of fuel cells, the conversion into liquid fuels or the generation of synthetic natural gas and hydrogen. On the basis of a dual fluidized bed system, steam gasification of biomass is coupled with in situ CO₂ absorption to enhance the formation of hydrogen. The reactive bed material (limestone) used in the dual fluidized bed system realizes the continuous CO₂ removal by cyclic carbonation of CaO and calcination of CaCO₃. Biomass gasification with in situ CO₂ absorption has been substantially proven in pilot plant scale of 100 kW fuel input. The present paper outlines the basic principles of steam gasification combined with the AER process the investigations in reactive bed materials, and concentrates further on the first time application of the AER process on industrial scale. The first time application has been carried out within an experimental campaign at a combined heat and power plant of 8 MW fuel input. The results are outlined with regard to the process conditions and achieved product gas composition. Furthermore, the results are compared with standard steam gasification of biomass as well as with application of absorption enhanced reforming process at pilot plant scale.     

Effect of H2/O2 addition in increasing the thermal efficiency of a diesel engine

Using hydrogen as an additive to enhance the conventional diesel engine performance has been investigated by several researchers and the outcomes are very promising. However, the problems associated with the production and storage of pure hydrogen currently limits the application of pure hydrogen in diesel engine operation. On-board hydrogen-oxygen generator, which produces H₂/O₂ mixture through electrolysis of water, has significant potential to overcome these problems. This paper focuses on evaluating the performance enhancement of a conventional diesel engine through the addition of H₂/O₂ mixture, generated through water electrolysis. The experimental works were carried out under constant speed with varying load and amount of H₂/O₂ mixture. Results show that by using 4.84%, 6.06%, and 6.12% total diesel equivalent of H₂/O₂ mixture the brake thermal efficiency increased from 32.0% to 34.6%, 32.9% to 35.8% and 34.7% to 36.3% at 19 kW, 22 kW and 28 kW, respectively. These resulted in 15.07%, 15.16% and 14.96% fuel savings. The emissions of HC, CO₂ and CO decreased, whereas the NO_x emission increased.     

New Stack Design of Micro‐tubular SOFCs for Portable Power Sources

Micro‐tubular solid oxide fuel cells (SOFCs) have high thermal stability and higher volumetric power density, which are considered to be ideal features for portable power sources and auxiliary power units for automobile. Here, we report a new stack design using anode supported micro‐tubular SOFCs with 2 mm diameter using Gd doped CeO₂ (GDC) electrolyte, NiO‐GDC anode and (La, Sr)(Co, Fe)O₃ (LSCF)‐GDC cathode. The new stack consists of three bundles with five tubular cells, sealing layers and interconnects and fuel manifolds. The performance of the stack whose volume is 1 cm³ was shown to be 2.8 V OCV and maximum power output of 1.5 W at 500 °C, applying air only by natural convection. The results also showed strong dependence of the fuel flow rates on the stack performance, which was correlated to the gas diffusion limitation.     

Sorption-enhanced dimethyl ether synthesis—Multiscale reactor modeling

As an opportunity for the attenuation of atmospheric CO₂ emissions, conversion of carbon dioxide into valuable oxygenates as fuel additives or fuel surrogates was explored conceptually in terms of a potentially feasible dimethyl ether (DME) conversion process. Incentives for application of conventional CO₂–DME conversion process are insufficient due to low CO₂ conversion, and DME yield and selectivity. In-situ H₂O removal by adsorption (sorption-enhanced reaction process) can lead to the displacement of the water gas shift equilibrium and therefore, the enhancement of CO₂ conversion into methanol and the improvement of DME productivity. A two-scale, isothermal, unsteady-state model has been developed to evaluate the performance of a sorption-enhanced DME synthesis reactor. Modeling results show that under H₂O removal conditions, methanol and DME yields and DME selectivity are favoured and the methanol selectivity decreases. The increase of methanol and DME yields and DME selectivity becomes more important at higher CO₂ feed concentration because a relatively large amount of water is produced followed by a large quantity of water removed from the system. Also, the drop in the fraction of unconverted methanol becomes more important when CO₂ feed concentration is higher and the dehydration reaction is favoured. Therefore, application of the sorption-enhanced reaction concept allows the use of CO₂ as a constituent of the synthesis gas as the in-situ H₂O removal accelerates the reverse water gas shift reaction.     

A novel dual circulating fluidized bed system for chemical looping processes

A fluidized bed system combining two circulating fluidized bed reactors is proposed and investigated for chemical looping combustion. Direct hydraulic communication of the two circulating fluidized bed reactors via a fluidized loop seal allows for high rates of global solids circulation and results in a stable solids distribution in the system. A 120 kW fuel power bench scale unit was designed, built, and operated. Experimental results are presented for natural gas as fuel using a nickel‐based oxygen carrier. No carbon was lost to the air reactor under any conditions operated. It is shown from fuel power variations that a turbulent/fast fluidized bed regime in the fuel reactor is advantageous. Despite the relatively low riser heights (air reactor: 4.1 m, fuel reactor: 3.0 m), high CH₄ conversion and CO₂ yield of up to 98% and 94%, respectively, can be reported for the material tested. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

An investigation of fuel composition and flow‐rate effects in a H2S fuelled sofc: Experiments and thermodynamic analysis

Hydrogen sulphide (H₂S)‐fuelled solid oxide fuel cells (SOFCs) can potentially generate useful electrical energy while disposing of H₂S, a toxic by‐product of the fossil fuel industry, on site. Experimental results from H₂S fuelled SOFCs exhibit characteristics, for example, an unusual dependence of cell performance on fuel composition and flow‐rate, which are poorly explained in the literature. In this work we: (a) present results for experiments where the composition and flow‐rates were varied for both the fuel and oxidant streams to analyse their effect on fuel cell performance, and (b) develop and use a thermodynamic analysis to help understand these experimental results. Through this work, we shed further light on two basic questions unanswered so far, (1) Why does the flow‐rate of the fuel affect the open circuit potential of the fuel cell? (2) Which of the chemical species present in the fuel is oxidised on the anode? Our experiments and analysis suggest that H₂S, and not H₂ produced from H₂S dissociation, is preferentially electro‐oxidised on the anode in our experiments. © 2011 Canadian Society for Chemical Engineering     

Minimizing fuel and environmental costs for a variable-load power plant (co-)firing fuel oil and natural gas: Part 1. Modeling of gaseous emissions from boiler units

This work was aimed at modeling of major gaseous emissions (NO_x, SO₃, SO₂, CO₂) from boiler units of a power plant firing (or co-firing) fuel oil and natural gas for variable operating conditions (load and load-related variables: excess air, flue gas recirculation, etc.). The emission rate of the pollutants for the co-firing was estimated for a particular boiler using these characteristics for the burning of each fuel in the boiler on its own and taking into account energy fractions (contributions) of fuel oil and natural gas to the boiler heat input. The gaseous emissions (in terms of emission concentrations, emission rates and specific emissions) from a 200-MW boiler unit firing low-S fuel oil and from a 310-MW boiler unit firing (or co-firing) medium-S fuel oil and natural gas were estimated and compared for 50–100% unit loads based on actual fuel properties and load-related operating variables of these units. Upper limit for the energy fraction of medium-S fuel oil was determined for the 310-MW boiler unit co-firing the two fuels with the aim to meet the national emission standard for SO₂.     

Co-gasification of coal and wood in a dual fluidized bed gasifier

In the last decade the reduction of CO₂ emissions from fossil fuels became a worldwide topic. Co-gasification of coal and wood provides an opportunity to combine the advantages of the well-researched usage of fossil fuels such as coal with CO₂-neutral biomass. Gasification itself is a technology with many advantages. The producer gas can be used in many ways; for electric power generation in a gas engine or gas turbine, for Fischer-Tropsch synthesis of liquid fuels and also for production of gaseous products such as synthetic natural gas (bio SNG). Moreover, the use of the producer gas in fuel cells is under investigation. The mixture of coal and wood leads to the opportunity to choose the gas composition as best befits the desired process. Within this study the focus of investigation was of gasification of coal and wood in various ratios and the resulting changes in producer gas composition. Co-gasification of coal and wood leads to linear producer gas composition changes with linear changing load ratios (coal/wood). Hydrogen concentrations rise with increasing coal ratio, while CO concentrations decrease. Due to the lower sulfur and nitrogen content of wood, levels of the impurities NH₃ and H₂S in the producer gas fall with decreasing coal ratio. It is also shown that the majority of sulfur is released in the gasification zone and, therefore, no further cleaning of the flue gas is necessary. All mixture ratios, from 100 energy% to 0 energy% coal, performed well in the 100 kW dual fluidized bed gasifier. Although the gasifier was originally designed for wood, an addition of coal as fuel in industrial sized plants based on the same technology should pose no problems.     

Monitoring the degradation of a solid oxide fuel cell stack during 10,000 h via electrochemical impedance spectroscopy

A 5-cell solid oxide fuel cell stack was tested during 10,000 h of continuous operation with simulated reformate gas as fuel (71 vol.% H₂, 20.7 vol.% CO₂ and 8.3 vol.% steam) under high fuel utilization (73%) and constant current load (0.5 A cm^?2 or 25 A) at 750 °C. In situ electrochemical impedance spectroscopy was used to monitor the evolution of ohmic and polarisation resistances of individual cells in the stack without interrupting the current load. Impedance spectra were recorded on each cell periodically (every 1000 h) or after uncontrolled incidents happened with the test setup. It has been found that the stack degradation is mainly attributed to the increased ohmic resistance, pointing to possible causes such as interconnect corrosion and reduced effective contact areas between cells and interconnects. The degradation rate during the first 5000 h was about 1% kh^?1, but increased afterwards up to 1.5% kh^?1 due to the impact of incidents. Both types of incidents (fuel supply fluctuations and overloading failure of the electronic load) were complicated by inhomogeneous fuel distribution among cells, leading to most probably partial re-oxidation of the anode, accelerating the stack degradation.     

PEM – Fuel Cell System for Residential Applications

Viessmann is developing a PEM fuel cell system for residential applications. The uncharged PEM fuel cell system has a 2 kW electrical and 3 kW thermal power output. The Viessmann Fuel Processor is characterized by a steam‐reformer/burner combination in which the burner supplies the required heat to the steam reformer unit and the burner exhaust gas is used to heat water. Natural gas is used as fuel, which is fed into the reforming reactor after passing an integrated desulphurisation unit. The low temperature (600 °C) fuel processor is designed on the basis of steam reforming technology. For carbon monoxide removal, a single shift reactor and selective methanisation is used with noble metal catalysts on monoliths. In the shift reactor, carbon monoxide is converted into hydrogen by the water gas shift reaction. The low level of carbon monoxide at the outlet of the shift reactor is further reduced, to approximately 20 ppm, downstream in the methanisation reactor, to meet PEM fuel cell requirements. Since both catalysts work at the same temperature (240 °C), there is no requirement for an additional heat exchanger in the fuel processor. Start up time is less than 30 min. In addition, Viessmann has developed a 2 kW class PEFC stack, without humidification. Reformate and dry air are fed straight to the stack. Due to the dry operation, water produced by the cell reaction rapidly diffuses through the electrolyte membrane. This was achieved by optimising the MEA, the gas flow pattern and the operating conditions. The cathode is operated by an air blower.     

煤气化费托合成/电联产系统建模及热力学分析

建立包括分布参数F-T合成反应器模型、考虑燃料气热值的燃气轮机模型及其他能够体现内部关键参数耦合关系的系统级单元子模型,并用于研究集成联产系统的整体热力学性能.首先,对合成气H2/CO、表观气速对F-T合成反应器合成气转化率和F-T合成尾气组成影响分析,结果表明F-T合成尾气存在CO/H2提高、CO2增浓的特点.综合考...