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.     

Methanol decomposition fuel processor for portable power applications

A new fuel processor approach for portable fuel cell power sources significantly improves upon microreformers by overcoming the difficulties with heat deficiencies and contaminants in the product hydrogen. Instead of reforming, the processor uses methanol decomposition to enable the byproduct, carbon monoxide (CO), to be used as the heat source. A hydrogen permselective membrane segregates the CO for combustion in an integrated burner, maximizes the decomposition conversion, and provides pure hydrogen for a fuel cell. Discharging the CO-rich retentate through an ejector to draw combustion air into the burner greatly simplifies the system. High and stable hydrogen yields are attained with optimized catalysts and fuel compositions. The resultant simple, efficient, and self-heating processor produces 85% of the hydrogen content of the fuel. A 20 W autonomous power source based on this novel fuel processor demonstrates a fuel energy density >1.5 Wh g^?1_(electrical), nearly twice as high as microreformer power sources.     

Enhancement of the performance and reliability of CO poisoned PEM fuel cells

CO poisoning is a major issue when reformate is used as a fuel in PEM fuel cells. Normally, it is necessary to reduce the CO to very low levels (∼5 ppm) and to use CO tolerant catalysts, such as Pt–Ru alloys. As an alternative approach, we have studied the use of pulsed oxidation for the regeneration of CO poisoned cells. Results are presented for the regeneration of Pt and Pt–Ru anodes in a PEM fuel cell fed with CO concentrations as high as 10,000 ppm. The results show that periodic removal of CO from the catalyst surface by pulsed oxidation can increase the average cell potential and overall efficiency.Although use of pulsed techniques has been studied before, the careful control of each cell's voltage that this approach requires has limited its use in large fuel cell stacks. When uniform pulsing is done on a stack of fuel cells in series, the variations in voltage across the cells can limit the usefulness of this approach. A novel method that allows each cell in a stack to be separately pulsed under controlled conditions has been developed to overcome this problem. Weak or defective cells in a fuel cell stack can also be supplemented to enhance the power output and reliability of fuel cells. We present the results of experiments and calculations that quantify these benefits, specifically as they relate to PEM fuel cells operating on impure hydrogen produced by reforming fuels.     

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.     

Development of 10-kWe preferential oxidation system for fuel cell vehicles

A preferential oxidation (PROX) reactor for a 10-kWe polymer electrolyte membrane fuel cell (PEMFC) system is developed. Pt-Ru/Al₂O₃ catalyst powder, with a size of 300–600 μm is applied for the PROX reaction. To minimize pressure drop and to avoid hot spots in the catalyst bed, the reactor is designed as a dual-staged, multi-tube system. The performance of the 10-kWe PROX unit is evaluated by feeding simulated gasoline reformate which contains 1.2 wt.% carbon monoxide (CO). The CO concentration of the treated reformate is lower than 20 ppm in the steady-state and is under 30 ppm at 65% load change. Hydrogen loss in the steady-state is about 1.5% and the pressure drop across the reactor is 4 psi. Start-up characteristics of the 10-kWe PROX system are also investigated. It takes 3 min to reduce the CO concentration to below 20 ppm. Several controllable factors are found to shorten the start-up time.     

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.     

Fuel processors for fuel cell APU applications

The conversion of liquid hydrocarbons to a hydrogen rich product gas is a central process step in fuel processors for auxiliary power units (APUs) for vehicles of all kinds. The selection of the reforming process depends on the fuel and the type of the fuel cell.For vehicle power trains, liquid hydrocarbons like gasoline, kerosene, and diesel are utilized and, therefore, they will also be the fuel for the respective APU systems.The fuel cells commonly envisioned for mobile APU applications are molten carbonate fuel cells (MCFC), solid oxide fuel cells (SOFC), and proton exchange membrane fuel cells (PEMFC). Since high-temperature fuel cells, e.g. MCFCs or SOFCs, can be supplied with a feed gas that contains carbon monoxide (CO) their fuel processor does not require reactors for CO reduction and removal. For PEMFCs on the other hand, CO concentrations in the feed gas must not exceed 50 ppm, better 20 ppm, which requires additional reactors downstream of the reforming reactor.This paper gives an overview of the current state of the fuel processor development for APU applications and APU system developments. Furthermore, it will present the latest developments at Fraunhofer ISE regarding fuel processors for high-temperature fuel cell APU systems on board of ships and aircrafts.     

Operation of PEM fuel cells at 120–150 °C to improve CO tolerance

Sulfonic acid modified perfluorocarbon polymer proton exchange membrane (PEM) fuel cells operated at elevated temperatures (120–150 °C) can greatly alleviate CO poisoning on anode catalysts. However, fuel cells with these PEMs operated at elevated temperature and atmospheric pressure typically experience low relative humidity (RH) and thus have increased membrane and electrode resistance. To operate PEM fuel cells at elevated temperature and high RH, work is needed to pressurize the anode and cathode reactant gases, thereby decreasing the efficiency of the PEM fuel cell system. A liquid-fed hydrocarbon-fuel processor can produce reformed gas at high pressure and high relative humidity without gas compression. If the anode is fed with this high-pressure, high-relative humidity stream, the water in the anode compartment will transport through the membrane and into the ambient pressure cathode structure, decreasing the cell resistance. This work studied the effect of anode pressurization on the cell resistance and performance using an ambient pressure cathode. The results show that high RH from anode pressurization at both 120 and 150 °C can decrease the membrane resistance and therefore increase the cell voltage. A cell running at 150 °C obtains a cell voltage of 0.43 V at 400 mA cm⁻² even with 1% CO in H₂. The results presented here provide a concept for the application of a coupled steam reformer and PEM fuel cell system that can operate at 150 °C with reformate and an atmospheric air cathode.     

Critical flow rate of anode fuel exhaust in a PEM fuel cell system

A manual purge line was added into the exterior fuel exhaust stream of a Ballard PEM stack in a Nexa™ power module. With the addition of manual exhaust purge, high levels of inert gases were intentionally added to the anode feed without changing normal operational procedures. A new method of determining the critical minimum flow rate in the anode exhaust stream was given by an anode mass balance. This type of operation makes dual use of membranes in the MEAs as both gas purifiers and as solid electrolytes. The PEM stack was successfully operated with up to ca. 7% nitrogen or carbon dioxide in the absence of a palladium-based hydrogen separator at ca. 200 W power level. Nitrogen in the anode stream was concentrated from 7.5% to 91.6%. The system maintained a fuel efficiency of 99% at a manual purge rate of 2.22 ml s⁻¹ and no auto purge. The fuel cell stack efficiency was 64% and the stack output efficiency was 75%. The overall system efficiency was 39%. After troublesome CO and H₂S poisons were removed, a hydrocarbon reformate containing high levels of CO₂ and H₂O was further used in the Nexa™ stack. The size and complexity of the fuel processing system may be reduced at a specified power level by using this operational method.     

Techno-economic analysis of fuel cell auxiliary power units as alternative to idling

This paper presents a techno-economic analysis of fuel-cell-based auxiliary power units (APUs), with emphasis on applications in the trucking industry and the military. The APU system is intended to reduce the need for discretionary idling of diesel engines or gas turbines. The analysis considers the options for on-board fuel processing of diesel and compares the two leading fuel cell contenders for automotive APU applications: proton exchange membrane fuel cell and solid oxide fuel cell. As options for on-board diesel reforming, partial oxidation and auto-thermal reforming are considered. Finally, using estimated and projected efficiency data, fuel consumption patterns, capital investment, and operating costs of fuel-cell APUs, an economic evaluation of diesel-based APUs is presented, with emphasis on break-even periods as a function of fuel cost, investment cost, idling time, and idling efficiency. The analysis shows that within the range of parameters studied, there are many conditions where deployment of an SOFC-based APU is economically viable. Our analysis indicates that at an APU system cost of $ 100 kW⁻¹, the economic break-even period is within 1 year for almost the entire range of conditions. At $ 500 kW⁻¹ investment cost, a 2-year break-even period is possible except for the lowest end of the fuel consumption range considered. However, if the APU investment cost is $ 3000 kW⁻¹, break-even would only be possible at the highest fuel consumption scenarios. For Abram tanks, even at typical land delivered fuel costs, a 2-year break-even period is possible for APU investment costs as high as $ 1100 kW⁻¹.     

Fuel effects on start-up energy and efficiency for automotive PEM fuel cell systems

This paper investigates the effects of various fuels on hydrogen production for automotive PEM fuel cell systems. Gasoline, methanol, ethanol, dimethyl ether and methane are compared for their effects on fuel processor size, start-up energy and overall efficiencies for 50 kW_e fuel processors. The start-up energy is the energy required to raise the temperature of the fuel processor from ambient temperature (20 °C) to that of the steady-state operating temperatures. The fuel processor modeled consisted of an equilibrium-ATR (autothermal), high-temperature water gas shift (HTS), low-temperature water gas shift (LTS) and preferential oxidation (PrOx) reactors. The individual reactor volumes with methane, dimethyl ether, methanol and ethanol were scaled relative to a gasoline-fueled fuel processor meeting the 2010 DOE technical targets. The modeled fuel processor volumes were, 25.9 L for methane, 30.8 L for dimethyl ether, 42.5 L for gasoline, 43.7 L for ethanol and 45.8 L for methane. The calculated fuel processor start-up energies for the modeled fuels were, 2712 kJ for methanol, 3423 kJ for dimethyl ether, 6632 kJ for ethanol, 7068 kJ for gasoline and 7592 kJ for methane. The modeled overall efficiencies, correcting for the fuel processor start-up energy using a drive cycle of 33 miles driven per day, were, 38.5% for dimethyl ether, 38.3% for methanol, 37% for gasoline, 34.5% for ethanol and 33.2% for methane assuming a steady-state efficiency of 44% for each fuel.     

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.     

Onboard fuel processor for PEM fuel cell vehicles

To lower vehicle greenhouse gas emissions, many automotive companies are exploring fuel cell technologies, which combine hydrogen and oxygen to produce electricity and water. While hydrogen storage and infrastructure remain issues, Renault and Nuvera Fuel Cells are developing an onboard fuel processor, which can convert a variety of fuels into hydrogen to power these fuel cell vehicles.The fuel processor is now small enough and powerful enough for use on a vehicle. The catalysts and heat exchangers occupy 80 l and can be packaged with balance of plant controls components in a 150-l volume designed to fit under the vehicle. Recent systems can operate on gasoline, ethanol, and methanol with fuel inputs up to 200 kWth and hydrogen efficiencies above 77%. The startup time is now less than 4 min to lower the CO in the hydrogen stream to the target value for the fuel cell.     

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.     

Development of a small DMFC bipolar plate stack for portable applications

The direct methanol fuel cell (DMFC) is regarded as a promising candidate in portable electronic power applications. Bipolar plate stacks were systematically studied by controlling the operating conditions, and by adjusting the stack structure design parameters, to develop more commercial DMFCs. The findings indicate that the peak power of the stack is influenced more strongly by the flow rate of air than by that of the methanol solution. Notably, the stack performance remains constant even as the channel depth is decreased from 1.0 to 0.6 mm, without loss of the performance in each cell. Furthermore, the specific power density of the stack was increased greatly from ∼60 to ∼100 W l⁻¹ for stacks of 10 and 18 cells, respectively. The current status of the work indicates that the power output of an 18-cell short stack reaches 33 W in air at 70 °C. The outer dimensions of this 18-cell short stack are only 80 mm × 80 mm × 51 mm, which are suitable for practical applications in 10–20 W DMFC portable systems.     

International Lead Award

The University of Duisburg-Essen and the Center for Fuel Cell Technology (ZBT Duisburg GmbH) have developed a compact multi-fuel steam reformer suitable for natural gas, propane and butane. Fuel processor prototypes based on this concept were built up in the power range from 2.5 to 12.5 kW thermal hydrogen power for different applications and different industrial partners. The fuel processor concept contains all the necessary elements, a prereformer step, a primary reformer, water gas shift reactors, a steam generator, internal heat exchangers, in order to achieve an optimised heat integration and an external burner for heat supply as well as a preferential oxidation step (PrOx) as CO purification. One of the built fuel processors is designed to deliver a thermal hydrogen power output of 2.5 kW according to a PEM fuel cell stack providing about 1 kW electrical power and achieves a thermal efficiency of about 75% (LHV basis after PrOx), while the CO content of the product gas is below 20 ppm. This steam reformer has been combined with a 1 kW PEM fuel cell. Recirculating the anodic offgas results in a significant efficiency increase for the fuel processor. The gross efficiency of the combined system was already clearly above 30% during the first tests. Further improvements are currently investigated and developed at the ZBT.     

A new direct methanol fuel cell with a zigzag-folded membrane electrode assembly

We propose a new direct methanol fuel cell with a zigzag-folded membrane electrode assembly. This fuel cell is formed by a membrane, which is made up of anode and cathode electrodes on a zigzag-folded sheet, separated by insulation film and current collectors. Individual anodes, cathodes and membranes form a unit cell, which is connected to the adjacent unit cell. The fuel cell can achieve high output voltage through easy in-series connection. Since it is not necessary to connect electrodes, as in the manner of conventional bipolar plates, there is no increase in fabrication cost and no degradation in reliability. The fuel feeds for the anode and cathode are achieved through methanol and air feeds on each electrode, which do not require electricity to run a pump or blower. The experimental cells were formed with an active area of 16 cm × 2 cm on membrane-folded cells. Filter papers with slits were inserted between anodes to improve their methanol supply. A power density of 3 mW cm⁻² was obtained at a methanol concentration of 2 M at ambient temperature. The cell power was affected by the slit area on cathode.     

Methanol conditioning for improved performance of formic acid fuel cells

This paper considers the effect of methanol pretreatment on the performance of a direct formic acid fuel cell (DFAFC). We find that conditioning of the cell in methanol results in a substantial increase in current. The current at 60 °C increases from 95 to 320 mA/cm² at 0.3 V. The maximum power density increases from 33 to 119 mW/cm². The cell resistance decreases from 0.37 to 0.32 Ω cm². CO stripping experiments show that the catalyst is not being greatly affected by these changes. Our interpretation of the data is that the anode layer of membrane electrolyte assembly (MEA) undergoes some change during the methanol conditioning. The change improves the performance.     

Dynamic behaviour of SOFC short stacks

Electrical output behaviour obtained on solid oxide fuel cell stacks, based on planar anode supported cells (50 or 100 cm² active area) and metallic interconnects, is reported. Stacks (1–12 cells) have been operated with cathode air and anode hydrogen flows between 750 and 800 °C operating temperature. At first polarisation, an activation phase (increase in power density) is typically observed, ascribed to the cathode but not clarified. Activation may extend over days or weeks. The materials are fairly resistant to thermal cycling. A 1-cell stack cycled five times in 4 days at heating/cooling rates of 100–300 K h⁻¹, showed no accelerated degradation. In a 5-cell stack, open circuit voltage (OCV) of all cells remained constant after three full cycles (800–25 °C). Power output is little affected by air flow but markedly influenced by small fuel flow variation. Fuel utilisation reached 88% in one 5-cell stack test. Performance homogeneity between cells lay at ±4–8% for three different 5- or 6-cell stacks, but was poor for a 12-cell stack with respect to the border cells. Degradation of a 1-cell stack operated for 5500 h showed clear dependence on operating conditions (cell voltage, fuel conversion), believed to be related to anode reoxidation (Ni). A 6-cell stack (50 cm² cells) delivering 100 W_el at 790 °C (1 kW_el L⁻¹ or 0.34 W cm⁻²) went through a fuel supply interruption and a thermal cycle, with one out of the six cells slightly underperforming after these events. This cell was eventually responsible (hot spot) for stack failure.     

A 28-W portable direct borohydride–hydrogen peroxide fuel-cell stack

A 28-W direct borohydride–hydrogen peroxide fuel-cell stack operating at 25 °C is reported for contemporary portable applications. The fuel cell operates with the peak power-density of ca. 50 mW cm⁻² at 1 V. This performance is superior to the anticipated power-density of 9 mW cm⁻² for a methanol–hydrogen peroxide fuel cell. Taking the fuel efficiency of the sodium borohydride–hydrogen peroxide fuel cell as 24.5%, its specific energy is ca. 2 kWh kg⁻¹. High power-densities can be achieved in the sodium borohydride system because of its ability to provide a high concentration of reactants to the fuel cell.