A hybrid fuel cell system integrated with methanol steam reformer and methanation reactor

In this paper, a hybrid fuel cell system integrated with methanol steam reformer and methanation reactor is demonstrated. Methanol steam reformer employed in this system is to produce hydrogen-rich reformate in connection with a methanation reactor to reduce the carbon monoxide content effectively, and the reformate gas is sent into a low-temperature polymer electrolyte fuel cell for direct electric power generation. The optimum conditions (temperature, water to methanol ratio, and space velocity) for methanol steam reforming (MSR) reaction and methanation (MET) reaction are verified by experiments. A comparison between pure hydrogen, reformate surrogate, and actual reformate is performed. The results show that the power density of this hybrid system achieves 245.2 mW/cm² while it achieves 268.8 mW/cm² when employing pure hydrogen as the fuel. An alternative novel method to solve the problem of hydrogen storage and transportation is provided and the in-situ hydrogen production and utilizing through low-temperature fuel cell system is realized, which is helpful to accelerate the commercialization process of the fuel cell.     

An experimental study on the reaction characteristics of a coupled reactor with a catalytic combustor and a steam reformer for SOFC systems

Steam reforming performance in a coupled reactor that consists of a steam reformer and a catalytic combustor is experimentally investigated in this study. Endothermic steam reforming can occur through the absorption of heat from the catalytic combustion of the anode offgas in a heat-exchanging coupled reactor. The reaction characteristics were observed by varying parameters such as the inlet temperature of the catalytic combustor, the excess air ratio for the catalytic combustion, the fuel utilization rate in the fuel cells, and the steam-to-carbon ratio in the steam reformer. The reactor temperature and reformate composition were measured to analyze the performance of the reactor. The results show the potential applicability and design technologies of the coupled reactor for the fuel processing of high temperature fuel cells using an external reformer.     

Modelling and experimental investigation of compact packed bed design of methanol steam reformer

A comprehensive mathematical model was developed to analyse methanol steam reforming in catalytic packed-bed tubular reactor. All the important aspects of reaction kinetics of main reactions and thermodynamic terms of heat and mass transfer were studied for commercially available CuO/ZnO/Al₂O₃ catalysts from Süd-Chemie. This numerical model was simulated using Engineering Equation Solver (EES). Through the set of organized simulation studies, the basic operational boundary conditions of operating temperature (573 K) with respect to complete conversion of methanol and optimum hydrogen generation, optimum S/C ratio (1.4) of methanol water mixture feed and operating capacity of one tubular reactor array were discovered. At temperatures near 573 K it was found that the reformate gas does not require any purification/filtration to be supplied to a HT-PEMFC as the CO concentration in reformate gas was low (below 30000 ppm). The simulation work for understanding the effect of different operating condition(s) on the reformer performance generated design of experiment for investigation of the efforts carried out to evaluate, build and demonstrate a 0.25 kWe equivalent methanol reformer for HT-PEM fuel cell system.The paper discusses few of the important aspects on the experimental investigation of effect of operating conditions on methanol steam reformer design with packed bed configuration for hydrogen production. The basic investigation included the analysis of effect of design and operating parameters on the methanol conversion and quality of reformate gas generation (amount of CO). The investigation also covers the analysis of heat and mass transfer along with chemical reaction and generation of species to achieve optimum process parameters and system efficiency. These investigations led to finalise, the operating parameters and basic design philosophy of the packed bed tubular methanol steam reformer for 5 kWe HT-PEMFC system application.     

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.     

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.     

Selective CO oxidation over a commercial PROX monolith catalyst for hydrogen fuel cell applications

Preferential oxidation (PROX) of CO over noble-metal-containing monolith catalysts is one of the most promising approaches for removing CO to generate low temperature fuel cell quality H₂. The monolith-supported washcoated catalyst comprising Cu and Fe promoted with Pt is highly effective in reducing the CO in practical reformates to less than 10 ppm over a broad range of feed compositions, inlet temperatures and turn down ratios. It is speculated that Pt dissociates the H₂ which then reduces the CuO to its active state. Pt may also act as a cocatalyst for CO adsorption with metal oxides supplying oxygen for PROX reaction. The catalytic system is operated adiabatically with an inlet temperature between roughly 65–120 °C reaching an exit temperature close to 150 °C with no evidence of reverse water gas shift or methanation. The goal was to find the proper operating conditions to achieve <10 ppm CO. Turn down ratios (varying space velocities) at a factor of 4–5 are routinely achieved up to at least 34,000 h⁻¹ with high steam levels of up to 45%. The wide operating window simplifies the control of the PROX reactor and improves the fuel processor’s performance for fast startup and shutdown and responses to transient loads. The catalyst also retains its performance after multiple start and stops modes of operation in reformate.     

Self-sustained operation and durability testing of a 300 W-class micro-structured LPG fuel processor

A miniaturized fuel processor for LPG has been developed and put into operation as compact hydrogen supply system for low power applications. The fuel processor consists of an integrated micro-structured evaporator and a micro-structured reformer both integrated with micro-structured catalytic burners, heat exchangers, and a micro-structured water-gas shift (WGS) stage. In the current paper, performance data of a coupled LPG steam reformer/catalytic burner are presented, which has been running stably over 1060 h with repeated start-up and shut-down cycles. On top of that, some performance data of complete LPG fuel processors will be shown, which have been operated up to 3500 h in combination with high temperature PEM fuel cell stacks. These fuel processing systems are capable to convert LPG with a nominal hydrogen production rate of 0.263 Nm³ h⁻¹. It could be demonstrated, that the micro-structured devices are not only compact but show also high reliability and durability.     

A combined methanol autothermal steam reforming and PEM fuel cell pilot plant unit: Experimental and simulation studies

An integrated system for hydrogen production via autothermal steam reforming of methanol and consequent power generation in a polymer electrolyte membrane (PEM) fuel cell has been developed and operated at C.P.E.R.I. The pilot plant comprises an autothermal reforming reactor to produce hydrogen, a preferential oxidation reactor (PROX) to reduce CO concentration below 50 ppm and a PEM fuel cell for power generation.The present paper deals with the study of this system, both from an experimental and a theoretical point of view. The experimental work aims to: (a) examine the effect of the reforming temperature on methanol conversion and on the effluent stream concentration, (b) investigate the effect of reaction temperature and O₂/CO ratio on the performance of the PROX reactor, and (c) evaluate the operation of a 10-cell PEM fuel cell, using pure hydrogen and air at three temperature levels. The experimental data are subsequently utilized for the validation of one-dimensional pseudo-homogeneous models that have been developed for the two reactors and also for the identification of the voltage–current characteristic curve of the PEM fuel cell. The validated models are then used to investigate the behavior and explore the interactions, both static and dynamic, among the various process subsystems.     

Syngas production from oxidative methane reforming and CO cleaning with water gas shift reaction

Fuel cell based heat and power cogeneration is considered to be well qualified for a distributed energy system for residential and small business applications. A fuel processing unit including an oxidative steam methane reformer, a high temperature shift reactor and a low temperature shift reactor is under development in South China University of Technology. Performance of the unit is experimentally investigated in a bench-scale experimental setup. Processor performance under typical operating conditions is tested. The influence of reaction temperature, methane space velocity in the oxidative steam methane reformer, and air to carbon molar ratio on unit performances is experimentally studied. It is found that under the typical operating conditions, the total energy efficiency reaches 88.3%. The efficiency can further be improved by utilizing the sensible heat of the reformate gas. The current study has been focused on the chemical performances such as methane conversion of the reformer and CO concentration in the synthesis gas downstream water gas shift reactors. Heat integration of the unit will be further implemented in future to improve energy efficiency.     

Control and experimental characterization of a methanol reformer for a 350 W high temperature polymer electrolyte membrane fuel cell system

This work presents a control strategy for controlling the methanol reformer temperature of a 350 W high temperature polymer electrolyte membrane fuel cell system, by using a cascade control structure for reliable system operation. The primary states affecting the methanol catalyst bed temperature is the water and methanol mixture fuel flow and the burner fuel/air ratio and combined flow. An experimental setup is presented capable of testing the methanol reformer used in the Serenergy H3 350 Mobile Battery Charger; a high temperature polymer electrolyte membrane (HTPEM) fuel cell system. The experimental system consists of a fuel evaporator utilizing the high temperature waste gas from the cathode air cooled 45 cell HTPEM fuel cell stack. The fuel cells used are BASF P1000 MEAs which use phosphoric acid doped polybenzimidazole membranes. The resulting reformate gas output of the reformer system is shown at different reformer temperatures and fuel flows, using the implemented reformer control strategy. The gas quality of the output reformate gas is of HTPEM grade quality, and sufficient for supporting efficient and reliable HTPEM fuel cell operation with CO concentrations of around 1% at the nominal reformer operating temperatures. As expected increasing temperatures also increase the dry gas CO content of the reformate gas and decreases the methanol slip. The hydrogen content of the gas was measured at around 73% with 25% CO₂.     

A compact integrated fuel-processing system for proton exchange membrane fuel cells

A compact integrated fuel-processing system consisting of a plate-fin reformer (PFR) and a multi-stage preferential oxidation reactor is designed in this paper. The PFR, which was based on a plate-fin heat exchanger, is very compact, and reactant vaporization, methanol steam reforming and combustion are all integrated in it. Both internal plate-fins and external catalytic combustion were used to enhance heat transfer of the reformer, which offers both high methanol conversion ratio and low CO concentration, so that the water–gas shift reactor, which provides primary CO cleanup, is not necessary in this fuel-processing system. This will result in simplification of the fuel-processing system design and capital cost reduction. The performance of the main components in the fuel-processing system has been investigated. The axial temperatures of the different chambers in PFR were uniform, and the temperatures at the inlet and outlet of the PROX reactors were controlled strictly by plate-fin exchangers so that it could minimize parasitic hydrogen oxidation. In addition, the results indicated that this fuel-processing system can provide a high concentration of hydrogen and the system efficiency is always maintained above 75%. It is further demonstrated that the fuel-processing system could be operated autothermally and exhibited good test stability.     

Hydrogen production with integrated microchannel fuel processor for portable fuel cell systems

An integrated microchannel methanol processor was developed by assembling unit reactors, which were fabricated by stacking and bonding microchannel patterned stainless steel plates, including fuel vaporizer, heat exchanger, catalytic combustor and steam reformer. Commercially available Cu/ZnO/Al₂O₃ catalyst was coated inside the microchannel of the unit reactor for steam reforming. Pt/Al₂O₃ pellets prepared by ‘incipient wetness’ were filled in the cavity reactor for catalytic combustion. Those unit reactors were integrated to develop the fuel processor and operated at different reaction conditions to optimize the reactor performance, including methanol steam reformer and methanol catalytic combustor. The optimized fuel processor has the dimensions of 60 mm × 40 mm × 30 mm, and produced 450sccm reformed gas containing 73.3% H₂, 24.5% CO₂ and 2.2% CO at 230–260 °C which can produce power output of 59 Wt.     

Effects of fuel cell anode recycle on catalytic fuel reforming

The presence of steam in the reactant gas of a catalytic fuel reformer decreases the formation of carbon, minimizing catalyst deactivation. However, the operation of the reformer without supplemental water reduces the size, weight, cost, and overall complexity of the system. The work presented here examines experimentally two options for adding steam to the reformer inlet: (I) recycle of a simulated fuel cell anode exit gas (comprised of mainly CO₂, H₂O, and N₂ and some H₂ and CO) and (II) recycle of the reformate from the reformer exit back to the reformer inlet (mainly comprised of H₂, CO, and N₂ and some H₂O and CO₂). As expected, anode gas recycle reduced the carbon formation and increased the hydrogen concentration in the reformate. However, reformer recycle was not as effective due principally to the lower water content in the reformate compared to the anode gas. In fact, reformate recycle showed slightly increased carbon formation compared to no recycle. In an attempt to understand the effects of individual gases in these recycle streams (H₂, CO, CO₂, N₂, and H₂O), individual gas species were independently introduced to the reformer feed.     

Microfibrous structured catalytic packings for miniature methanol fuel processor: Methanol steam reforming and CO preferential oxidation

The microfibrous structured catalytic packings for miniature fuel processor consisting of a methanol steam reformer and a subsequent CO cleanup train has been investigated experimentally. A highly void and tailorable sinter-locked microfibrous carrier consisting of 3.5 vol% 8 μm diameter Ni-fibers is used to entrap 35 vol% 150-250 μm catalyst particulates for both methanol steam reforming (MSR) and CO preferential oxidation (PROX). We demonstrate a microfibrous entrapped Pd-ZnO/Al₂O₃ catalyst packings for high efficiency hydrogen production by the MSR reaction. The use of microfibrous entrapment technology significantly enhances the catalyst utilization efficiency by a 4-fold improvement of the weight hourly space velocity (WHSV), compared to the single Pd-ZnO/Al₂O₃ particulates as keeping the methanol conversion at >98%. The microfibrous entrapped Pt-Co/Al₂O₃ catalyst packings can drive the CO from 2% down to <50 ppm at 150 °C with O₂/CO ratio of 1 using a gas hourly space velocity (GHSV) of 32,000 h⁻¹. Finally, a prototype fuel processor system integrating MSR reformer and CO PROX train is demonstrated as three reactors in series. Such test rig is capable of producing roughly 1700 standard cubic centimeter per minute (sccm) PEMFC-grade H₂ (equivalent to ∼163 W of electric power) in a longer-term test, in which the MSR reactor is operated at 300 °C using a methanol/water (1/1.1, mole) mixture WHSV of 9 h⁻¹ and CO PROX reactors at 150 °C using an O₂/CO molar ratio of 1.3, respectively. In the test of this prototype system, MSR reactor delivers >97% methanol conversion throughout the entire 1200-h test; the CO cleanup train placed in line after 800-h MSR illustrates the capability to decrease the CO concentration from ∼3.5% to ∼1% at PROX-1 and then to less than 20 ppm at PROX-2 until to the end of test.     

A natural-gas fuel processor for a residential fuel cell system

A system model was used to develop an autothermal reforming fuel processor to meet the targets of 80% efficiency (higher heating value) and start-up energy consumption of less than 500 kJ when operated as part of a 1-kWe natural-gas fueled fuel cell system for cogeneration of heat and power. The key catalytic reactors of the fuel processor – namely the autothermal reformer, a two-stage water gas shift reactor and a preferential oxidation reactor – were configured and tested in a breadboard apparatus. Experimental results demonstrated a reformate containing ∼48% hydrogen (on a dry basis and with pure methane as fuel) and less than 5 ppm CO. The effects of steam-to-carbon and part load operations were explored.     

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.     

Design of a methanol reformer for on-board production of hydrogen as fuel for a 3 kW High-Temperature Proton Exchange Membrane Fuel Cell power system

The method of Computational Fluid Dynamics is used to predict the process parameters and select the optimum operating regime of a methanol reformer for on-board production of hydrogen as fuel for a 3 kW High-Temperature Proton Exchange Membrane Fuel Cell power system. The analysis uses a three reactions kinetics model for methanol steam reforming, water gas shift and methanol decomposition reactions on Cu/ZnO/Al₂O₃ catalyst. Numerical simulations are performed at single channel level for a range of reformer operating temperatures and values of the molar flow rate of methanol per weight of catalyst at the reformer inlet. Two operating regimes of the fuel processor are selected which offer high methanol conversion rate and high hydrogen production while simultaneously result in a small reformer size and a reformate gas composition that can be tolerated by phosphoric acid-doped high temperature membrane electrode assemblies for proton exchange membrane fuel cells. Based on the results of the numerical simulations, the reactor is sized, and its design is optimized.     

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.     

Exergy analysis of an ethanol fuelled proton exchange membrane (PEM) fuel cell system for automobile applications

An integrated ethanol fuelled proton exchange membrane fuel cell (PEMFC) power system was investigated following a second law exergy analysis. The system was assumed to have the typical design for automobile applications and was comprised of a vaporizer/mixer, a steam reformer, a CO-shift reactor, a CO-remover (PROX) reactor, a PEMFC and a burner. The exergy analysis was applied for different PEMFC power and voltage outputs assuming the ethanol steam reforming at about 600 K and the CO-shift reaction at about 400 K. A detailed parametric analysis of the plant is presented and operation guidelines are suggested for effective performance. In every case, the exergy analysis method is proved to allow an accurate allocation of the deficiencies of the subsystems of the plant and serves as a unique tool for essential technical improvements.     

Micro methanol reformer combined with a catalytic combustor for a PEM fuel cell

This paper presents the development of a micro methanol reformer for portable fuel cell applications. The micro reformer consists of a methanol steam reforming reactor, catalytic combustor, and heat exchanger in-between. Cu/ZnO was selected as a catalyst for a methanol steam reforming and Pt for a catalytic combustion of hydrogen with air. Porous ceramic material was used as a catalyst support due to the large surface area and thermal stability. Photosensitive glass wafer was selected as a structural material because of its thermal and chemical stabilities. Performance of the reformer was measured at various test conditions and the results showed a good agreement with the three-dimensional analysis of the reacting flow. Considering the energy balance of the reformer/combustor model, the off-gas of fuel cell can be recycled as a feed of the combustor. The catalytic combustor generated the sufficient amount of heat to sustain the steam reforming of methanol. The conversion of methanol was 95.7% and the hydrogen flow of 53.7 ml/min was produced including 1.24% carbon monoxide. The generated hydrogen was the sufficient amount to operate 4.5 W polymer electrolyte membrane fuel cells.