Bio-fuel reformation for solid oxide fuel cell applications. Part 3: Biodiesel–diesel blends

The auto-thermal reforming (ATR) performance of diesel blended with biodiesel (e.g., B5, B10, B20, B40, and B80) was investigated and compared to pure diesel and biodiesel ATR in a single-tube reformer with ceramic monolith wash-coated rhodium/ceria–zirconia catalyst. The initial operating condition of the ATR of all studied fuels was set as total moles of oxygen from air, water, and fuel per mole of carbon (O/C) = 1.47, moles of water to carbon (H₂O/C) = 0.6, and gas hourly space velocity = 33,950 h⁻¹ at 1223 K reformer temperature, to achieve the same syngas (H₂ + CO) production rate. A direct photo-acoustic micro-soot meter was applied to quantify the dynamic evolution of carbon formation and a mass spectrometer was used to measure the gas composition of reformer effluents. The blends with more biodiesel content were found to have a lower syngas production rate and reforming efficiency, and require more air and higher reformer temperature to avoid carbon formation. Strong correlations between ethylene and solid carbon concentration were observed in the reformation of all the fuels and blends, with more biodiesel content tending to have higher ethylene production. This study is one component of a three-part investigation of bio-fuel reforming, also including fuel vaporization and reactant mixing (Part 1) and biodiesel (Part 2).     

Autothermal reforming of n-dodecane and desulfurized Jet-A fuel for producing hydrogen-rich syngas

Catalytic reforming is a technology to produce hydrogen and syngas from heavy hydrocarbon fuels in order to supply hydrogen to fuel cells. A lab-scale 2.5 kW_t autothermal reforming (ATR) system with a specially designed reformer and combined analysis of balance-of-plant was studied and tested in the present study. NiO–Rh based bimetallic catalysts with promoters of Ce, K, and La were used in the reformer. The performance of the reformer was studied by checking the hydrogen selectivity, CO_x selectivity, and energy conversion efficiency at various operating temperatures, steam to carbon ratios, oxygen to carbon ratios, and reactants' inlet temperatures. The experimental work firstly tested n-dodecane as the surrogate of Jet-A fuel to optimize operating conditions. After that, desulfurized commercial Jet-A fuel was tested at the optimized operating conditions. The design of the reformer and the catalyst are recommended for high performance Jet-A fuel reforming and hydrogen-rich syngas production.     

Development of integrated reformer systems for syngas production

Precision Combustion, Inc. (PCI) has developed autothermal reformer (ATR) units based on its patented Microlith^® technology and demonstrated stable, coke-free operation using JP-8 consisting of up to 70 ppm_w sulfur for 1100 h with complete fuel conversion and reforming efficiency of ∼85%. The feasibility of operating ATR reformers with distillate fuels containing higher sulfur (up to 400 ppm_w) has also been demonstrated for 55 h, while producing syngas (i.e., H₂ and CO) at >80% reforming efficiency and at complete fuel conversion. Reformer test results, demonstrating water neutral operation, catalyst sulfur tolerance, removal of sulfur to <1 ppm_v, and maintenance of higher hydrocarbons to levels acceptable for fuel cell stacks, provide a measure of the ATR performance that can be expected under realistic conditions with readily available fuels. The results also give valuable insights to the system design and operation strategy for integrated power generation systems.     

Evaluating the impact of enhanced anode CO tolerance on performance of proton-exchange-membrane fuel cell systems fueled by liquid hydrocarbons

Recent advances in anode electrocatalysts for low-temperature PEM fuel cells are increasing tolerance for CO in the H₂-rich anode stream. This study explores the impact of potential improvements in CO-tolerant electrocatalysts on the system efficiency of low-temperature Nafion-based PEM fuel cell systems operating in conjunction with a hydrocarbon autothermal reformer and a preferential CO oxidation (PROx) reactor for CO clean-up. The incomplete H₂ clean-up by PROx reactors with partial CO removal can present conditions where CO-tolerant anode electrocatalysts significantly improve overall system efficiency. Empirical fuel cell performance models were based upon voltage-current characteristics from single-cell MEA tests at varying CO concentrations with new Pt-Mo alloy reformate-tolerant electrocatalysts tested in conjunction with this study. A system-level model for a liquid-fueled PEM fuel cell system with a 5 kW full power output is used to study the trade-offs between the improved performance with decreased CO concentration and the increased penalties from the air supply to the PROx reactor and associated reduction in H₂ partial pressures to the anode. As CO tolerance is increased over current state-of-the-art Pt alloy catalysts, system efficiencies improve due primarily to higher fuel cell voltages and to a lesser extent to reductions in parasitic loads. Furthermore, increasing CO tolerance of anode electrocatalysts allows for the potential for reduced system costs with minimal efficiency penalty by reducing PROx reactor size through reduced CO conversion requirements.     

Investigation of a methanol processing system comprising of a steam reformer and two preferential oxidation reactors for fuel cells

Methanol steam reforming is able to produce hydrogen-rich syngas onsite for fuel cells and avoids the problems of hydrogen storage. Nevertheless, CO in the reformate needs to be further removed to ppm level before it can be fed into proton exchange membrane fuel cells. In this study, a methanol processing system consisting of a methanol reformer and two-stage preferential oxidation reactors is developed. The hydrogen production performance and scalability of the reformer are experimentally investigated under various operating conditions. The methanol reformer system shows stable methanol conversion rate and linearly increased H₂ flow rate as the number of repeating unit increases. Methanol conversion rate of 96.8% with CO concentration of 1.78% are achieved in the scaled-up system. CO cleanup ability of the two-stage preferential oxidation reactors is experimentally investigated based on the reformate compositions by varying the operating temperature and O₂ to CO ratios. The results demonstrate that the developed CO cleanup train can decrease the CO concentration from 1.6% to below 10 ppm, which meets the requirement of the fuel cell. Finally, stability of the integrated methanol processing system is tested for 180 h operation.     

Fuel flexibility study of an integrated 25 kW SOFC reformer system

The operation of solid oxide fuel cells on various fuels, such as natural gas, biogas and gases derived from biomass or coal gasification and distillate fuel reforming has been an active area of SOFC research in recent years. In this study, we develop a theoretical understanding and thermodynamic simulation capability for investigation of an integrated SOFC reformer system operating on various fuels. The theoretical understanding and simulation results suggest that significant thermal management challenges may result from the use of different types of fuels in the same integrated fuel cell reformer system. Syngas derived from coal is simulated according to specifications from high-temperature entrained bed coal gasifiers. Diesel syngas is approximated from data obtained in a previous NFCRC study of JP-8 and diesel operation of the integrated 25 kW SOFC reformer system. The syngas streams consist of mixtures of hydrogen, carbon monoxide, carbon dioxide, methane and nitrogen. Although the SOFC can tolerate a wide variety in fuel composition, the current analyses suggest that performance of integrated SOFC reformer systems may require significant operating condition changes and/or system design changes in order to operate well on this variety of fuels.     

Dealing with fuel contaminants in biogas-fed solid oxide fuel cell (SOFC) and molten carbonate fuel cell (MCFC) plants: Degradation of catalytic and electro-catalytic active surfaces and related gas purification methods

Fuel cell and hydrogen technologies are re-gaining momentum in a number of sectors including industrial, tertiary and residential ones. Integrated biogas fuel cell plants in wastewater treatment plants and other bioenergy recovery plants are nowadays on the verge of becoming a clear opportunity for the market entry of high-temperature fuel cells in distributed generation (power production from a few kW to the MW scale).High-temperature fuel cell technologies like molten carbonate fuel cells (MCFCs) and solid oxide fuel cells (SOFCs) are especially fit to operate with carbon fuels due to their (direct or indirect) internal reforming capability. Especially, systems based on SOFC technology show the highest conversion efficiency of gaseous carbon fuels (e.g., natural gas, digester gas, and biomass-derived syngas) into electricity when compared to engines or gas turbines. Also, lower CO₂ emissions and ultra-low emissions of atmospheric contaminants (SO_X, CO, VOC, especially NO_X) are generated per unit of electricity output. Nonetheless, stringent requirements apply regarding fuel purity. The presence of contaminants within the anode fuel stream, even at trace levels (sometimes ppb levels) can reduce the lifetime of key components like the fuel cell stack and reformer. In this work, we review the complex matrix (typology and amount) of different contaminants that is found in different biogas types (anaerobic digestion gas and landfill gas). We analyze the impact of contaminants on the fuel reformer and the SOFC stack to identify the threshold limits of the fuel cell system towards specific contaminants. Finally, technological solutions and related adsorbent materials to remove contaminants in a dedicated clean-up unit upstream of the fuel cell plant are also reviewed.     

Development and design of experiments optimization of a high temperature proton exchange membrane fuel cell auxiliary power unit with onboard fuel processor

In this work, the concept development, system layout, component simulation and the overall DOE system optimization of a HT-PEM fuel cell APU with a net electric power output of 4.5 kW and an onboard methane fuel processor are presented.A highly integrated system layout has been developed that enables fast startup within 7.5 min, a closed system water balance and high fuel processor efficiencies of up to 85% due to the recuperation of the anode offgas burner heat. The integration of the system battery into the load management enhances the transient electric performance and the maximum electric power output of the APU system.Simulation models of the carbon monoxide influence on HT-PEM cell voltage, the concentration and temperature profiles within the autothermal reformer (ATR) and the CO conversion rates within the watergas shift stages (WGSs) have been developed. They enable the optimization of the CO concentration in the anode gas of the fuel cell in order to achieve maximum system efficiencies and an optimized dimensioning of the ATR and WGS reactors.Furthermore a DOE optimization of the global system parameters cathode stoichiometry, anode stoichiometry, air/fuel ratio and steam/carbon ratio of the fuel processing system has been performed in order to achieve maximum system efficiencies for all system operating points under given boundary conditions.     

Conceptual design and selection of a biodiesel fuel processor for a vehicle fuel cell auxiliary power unit

Within the European project BIOFEAT (biodiesel fuel processor for a fuel cell auxiliary power unit for a vehicle), a complete modular 10 kW_e biodiesel fuel processor capable of feeding a PEMFC will be developed, built and tested to generate electricity for a vehicle auxiliary power unit (APU). Tail pipe emissions reduction, increased use of renewable fuels, increase of hydrogen-fuel economy and efficient supply of present and future APU for road vehicles are the main project goals. Biodiesel is the chosen feedstock because it is a completely natural and thus renewable fuel.Three fuel processing options were taken into account at a conceptual design level and compared for hydrogen production: (i) autothermal reformer (ATR) with high and low temperature shift (HTS/LTS) reactors; (ii) autothermal reformer (ATR) with a single medium temperature shift (MTS) reactor; (iii) thermal cracker (TC) with high and low temperature shift (HTS/LTS) reactors. Based on a number of simulations (with the AspenPlus^® software), the best operating conditions were determined (steam-to-carbon and O₂/C ratios, operating temperatures and pressures) for each process alternative. The selection of the preferential fuel processing option was consequently carried out, based on a number of criteria (efficiency, complexity, compactness, safety, controllability, emissions, etc.); the ATR with both HTS and LTS reactors shows the most promising results, with a net electrical efficiency of 29% (LHV).     

Fast starting fuel processor for automotive fuel cell systems

A fuel processor was constructed which incorporated two burners with direct steam generation by water injection into the burner exhaust. These burners with direct water vaporization enabled rapid fuel processor start-up for automotive fuel cell systems. The fuel processor consisted of a conventional chain of reactors: auto-thermal reformer (ATR), water gas shift (WGS) reactor and preferential oxidation (PrOx) reactor. The criticality of steam to the fuel reforming process was illustrated. By utilizing direct vaporization of water, and hydrogen for catalyst light-off, excellent start performance was obtained with a start time of 20 s to 30% power and 140 s to full power.     

A complete miniaturized microstructured methanol fuel processor/fuel cell system for low power applications

A complete miniaturized methanol fuel processor/fuel cell system was developed and put into operation as compact hydrogen supplier for low power application. The whole system consisting of a micro-structured evaporator, a micro-structured reformer and two stages of preferential oxidation of CO (PROX) reactor, micro-structured catalytic burner, and fuel cell was operated to evaluate the performance of the whole production line from methanol to electricity. The performance of micro methanol steam reformer and PROX reactor was systematically investigated. The effect of reaction temperature, steam to carbon ratio, and contact time on the methanol steam reformer performance is presented in terms of catalytic activity, selectivity, and reformate yield. The performance of PROX reactor fed with the reformate produced by the reformer reactor was evaluated by the variation of reaction temperature and oxygen to CO ratio. The results demonstrate that micro-structured device may be an attractive power source candidate for low power application.     

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.     

Modeling study on a two-stage hydrogen purification process of pressure swing adsorption and carbon monoxide selective methanation for proton exchange membrane fuel cells

A two-stage hydrogen purification process based on pressure swing adsorption (PSA) and CO selective methanation (CO-SMET) is proposed to meet the stringent requirements of H₂-rich fuel for kW-scale skid-mounted or distributed proton exchange membrane fuel cell systems. The reforming gas is purified using dynamic adsorption model of PSA with activated carbon for initial purification and then kinetic model of CO-SMET with 50 wt% Ni/Al₂O₃ for CO deep removal. Sensitive analyses of the gas hourly space velocity, adsorption time and adsorption pressure etc. are studied. The results show that excellent H₂ purity and CO concentration below 1000 ppm for the initial target using the three-bed and four-bed PSA system at shorter adsorption time and higher pressure, and then CO concentration below 10 ppm with H₂ purity over 99.94% on CO-SMET. This work provides a small-scale and hydrogen-saving process for hydrogen purification can be achieved by the two-stage process.     

Fuel cell feed system based on H2 production by a compact multi-fuel catalytic ATR reactor

Hydrogen fuel cells seem the most viable solution to the pollution reduction and the energy growing demand. Very compact and small size production plant for distribute H₂ production may reduce hydrogen transport and storage difficulties. Due to the high reactor compactness and thermal self-sustainability, the auto-thermal reforming (ATR) reaction of gaseous and liquid hydrocarbons can be the optimal solution. Fossil hydrocarbons like methane, gasoline and diesel still remain the favourite feed for catalytic auto-thermal reformer, due to the widespread existing delivery pipelines and the high energy density. Unfortunately, due to the different characteristics of liquid and gaseous fuels, it's very difficult to realize a multi-fuel processor characterized by high performances in terms of thermal efficiency and hydrogen yield, and, up to now, very low number of papers dealing with multi-fuel reformers is present in the literature.     

Performance of a PEMFC system integrated with a biogas chemical looping reforming processor: A theoretical analysis and comparison with other fuel processors (steam reforming,partial oxidation and auto-thermal reforming)

In this work, the performance of a PEMFC (proton exchange membrane fuel cell) system integrated with a biogas chemical looping reforming processor is analyzed. The global efficiency is investigated by means of a thermodynamic study and the application of a generalized steady-state electrochemical model. The theoretical analysis is carried out for the commercial fuel cell BCS 500W stack. From literature, chemical looping reforming (CLR) is described as an attractive process only if the system operates at high pressure. However, the present research shows that advantages of the CLR process can be obtained at atmospheric pressure if this technology is integrated with a PEMFC system. The performance of a complete fuel cell system employing a fuel processor based on CLR technology is compared with those achieved when conventional fuel processors (steam reforming (SR), partial oxidation (PO) and auto-thermal reforming (ATR)) are used. In the first part of this paper, the Gibbs energy minimization method is applied to the unit comprising the fuel- and air-reactors in CLR or to the reformer (SR, PO, ATR). The goal is to investigate the characteristics of these different types of reforming process to generate hydrogen from clean model biogas and identify the optimized operating conditions for each process. Then, in the second part of this research, material and energy balances are solved for the complete fuel cell system processing biogas, taking into account the optimized conditions found in the first part. The overall efficiency of the PEMFC stack integrated with the fuel processor is found to be dependent on the required power demand. At low loads, efficiency is around 45%, whereas, at higher power demands, efficiencies around 25% are calculated for all the fuel processors. Simulation results show that, to generate the same molar flow-rate of H₂ to operate the PEMFC stack at a given current, the global process involving SR reactor is by far much more energy demanding than the other technologies. In this case, biogas is burnt in a catalytic combustor to supply the energy required, and there is a concern with respect to CO₂ emissions. The use of fuel processors based on CLR, PO or ATR results in an auto-thermal global process. If CLR based fuel processor is employed, CO₂ can be easily recovered, since air is not mixed with the reformate. In addition, the highest values of voltage and power are achieved when the PEMFC stack is fed on the stream coming from SR and CLR fuel processors. When a H₂ mixture is produced by reforming biogas through PO and ATR technologies, the relative anode overpotential of a single cell is about 55 mV, whereas, with the use of CLR and SR processes, this value is reduced to ∼37 and 24 mV, respectively. In this way, CLR can be seen as an advantageous reforming technology, since it allows that the global process can be operated under auto-thermal conditions and, at the same time, it allows the PEMFC stack to achieve values of voltage and power closer to those obtained when SR fuel processors are used. Thus, efforts on the development of fuel processors based on CLR technology operating at atmospheric pressure can be considered by future researchers. In the case of biogas, the CO₂ captured can produce additional economical benefits in a ‘carbon market’.     

Metal membrane-type 25-kW methanol fuel processor for fuel-cell hybrid vehicle

A 25-kW on-board methanol fuel processor has been developed. It consists of a methanol steam reformer, which converts methanol to hydrogen-rich gas mixture, and two metal membrane modules, which clean-up the gas mixture to high-purity hydrogen. It produces hydrogen at rates up to 25 N m³/h and the purity of the product hydrogen is over 99.9995% with a CO content of less than 1 ppm. In this fuel processor, the operating condition of the reformer and the metal membrane modules is nearly the same, so that operation is simple and the overall system construction is compact by eliminating the extensive temperature control of the intermediate gas streams. The recovery of hydrogen in the metal membrane units is maintained at 70–75% by the control of the pressure in the system, and the remaining 25–30% hydrogen is recycled to a catalytic combustion zone to supply heat for the methanol steam-reforming reaction. The thermal efficiency of the fuel processor is about 75% and the inlet air pressure is as low as 4 psi. The fuel processor is currently being integrated with 25-kW polymer electrolyte membrane fuel-cell (PEMFC) stack developed by the Hyundai Motor Company. The stack exhibits the same performance as those with pure hydrogen, which proves that the maximum power output as well as the minimum stack degradation is possible with this fuel processor. This fuel-cell ‘engine’ is to be installed in a hybrid passenger vehicle for road testing.     

Design and demonstration of an ethanol fuel processor for HT-PEM fuel cell applications

This work describes the development of a compact ethanol fuel processor for small scale high temperature polymer electrolyte membrane fuel cell (HT-PEMFC) systems with 200–500 W electrical power output. Promising markets for reformer fuel cell systems based on ethanol are mobile or portable leisure and security power supply applications as well as small scale stationary off grid power supply and backup power. Main components of the fuel processor to be developed were the reformer reactor, the shift converter, a catalytic burner and heat exchangers. Development focused in particular on the homogeneous evaporation of the liquid reactants ethanol and water for the reformer and burner and on the development of an efficient and autarkic start-up method, respectively. Theoretical as well as experimental work has been carried out for all main components separately including for example catalyst screening and evaporator performance tests in a first project period. Afterwards all components have been assembled to a complete fuel processor which has been qualified with various operation parameter set-ups. A theoretically defined basic operation point could practically be confirmed. The overall start-up time to receive reformate gas with appropriate quality to feed an HT-PEMFC (x_CO < 2%) takes around 30 min. At steady state operation the hydrogen power output is around 900 W with H₂ and CO fractions of 41.2% and 1.5%, respectively.     

Ru–Ni/GA-MMO composites as highly active catalysts for CO selective methanation in H2-rich gases

CO selective methanation (CO-SMET) is as an ideal H₂-rich gases purification measurement for proton exchange membrane fuel cell system. Herein, the graphene aerogel-mixed metal oxide (GA-MMO) supported Ru–Ni bimetallic catalysts are exploited for CO-SMET in H₂-rich gases. The results reveal that a three-dimensional network structure GA-MMO aerogel with higher specific surface area, better thermal stability and more defects or structural disorders is formed when MMO:GO mass ratio is in the range of 1–4. After loading of Ru, more NiO are reduced to metallic Ni by hydrogen spillover effect, and thus obviously enhances the reactivity. The GA-MMO supported Ru–Ni catalyst exhibits more excellent metal dispersion, reducibility, stronger CO adsorption and activation than the MMO supported Ru–Ni catalyst, thereby resulting in better catalytic performance and stability. This work offers new insights into the construction of highly active catalyst for the efficient generation of high-quality H₂ from H₂-rich gases.     

Investigations on the behaviour of 2 kW natural gas fuel processor

In this paper, the first experimental investigations on a pre-commercial natural gas steam reformer have been presented. The fuel processor unit contains the elements as follows: desulfurizer, steam reformer reactor, CO shift converter, CO preferential oxidation (PROX) reactor, steam generator, burner and heat exchangers.The fuel processor produces 45 Nl/min of syngas in which the hydrogen concentration is about 75 vol.% and the other chemical species are nitrogen, carbon dioxide and methane. The CO concentration is below 1 ppmv, so that this reforming system is suitable for the integration with a PEM fuel cell stack.The experimental activity has been conducted in a test station, properly designed to measure the behaviour of the fuel processor. The laboratory test facility is equipped by a National Instruments Compact DAQ real-time data acquisition and control system running Labview™ software. Several measurement instruments and controlling devices have been installed. Furthermore, a gas chromatograph is used to measure the product gas composition during the tests.The aim of this work has been to analyze the behaviour of this pre-commercial steam reforming unit during its operation cycle in different operating conditions (full and partial loads) in order to study its integration with a PEM fuel cell for developing a high efficiency microcogeneration system for residential applications.     

Optimal design of an experimental methanol fuel reformer

We report on the steady state modeling of an experimental methanol fuel reformer for fuel cell applications. The fuel reformer consists of an AutoThermal Reformer (ATR) followed by an Oxygen Removal (OR) reactor, Steam Reformer (SR) and Water Gas Shift (WGS) reactor. The effluent from the WGS is fed to a series of three Preferential Oxidation (PROX) reactors that reduce the CO concentration to less than 40 ppm. A mathematical model of the reformer is developed and selected parameters of the model are fit to experimental data collected from a fuel reformer that was designed, built and operated by the Material and Chemical Research Laboratories (MCL) of the Industrial Technology Research Institute (ITRI) in Hsinchu, Taiwan. In order to develop a compact and high-performance fuel reformer system, the mathematical model is used to design a reformer that has the minimum possible combined volume of the steam reformer and water gas shift reactor. The result is that the volume of the optimized reactor units can be reduced by 17.2% without a significant change in the overall efficiency.