Integrated fuel cell APU based on a compact steam reformer for diesel and a PEMFC

This paper presents experimental results of a diesel steam reforming fuel processor operated in conjunction with a gas cleanup module and coupled operation with a PEM fuel cell. The fuel processor was operated with two different precious-metal based reformer catalysts, using diesel surrogate with a sulfur content of less than 2 ppmw as fuel. The first reformer catalyst entails an increasing residual hydrocarbon concentration for increasing reformer fuel feed. The second reformer catalyst exhibits a significantly lower residual hydrocarbon concentration in the reformate gas.     

Coupled operation of a diesel steam reformer and an LT- and HT-PEFC

Polymer electrolyte fuel cells (PEFC) combined with diesel fuel processors offer a great potential for auxiliary power units (APU) in mobile applications. In a joint research project with partners from industry, Oel-Waerme-Institut GmbH is developing an integrated modular fuel cell system for mobile power generation in caravans and yachts. The system includes a steam reforming fuel processor that allows the operation of low-temperature (LT-) as well as high-temperature (HT-) PEFC.     

Experimental and computational investigations of a compact steam reformer for fuel oil and diesel fuel

The present work describes the optimisation of a compact steam reformer for light fuel oil and diesel fuel. The reformer is based upon a catalytically coated micro heat exchanger that thermally couples the reforming reaction with a catalytic combustion. Since the reforming process is sensitive to reaction temperatures and internal flow patterns, the reformer was modelled using a commercial CFD code in order to optimise its geometry. Fluid flow, heat transfer and chemical reactions were considered on both sides of the heat exchanger. The model was successfully validated with experimental data from reformer tests with 4 kW, 6 kW and 10 kW thermal inputs of light fuel oil. In further simulations the model was applied to investigate parallel flow, counter flow and cross flow conditions along with inlet geometry variations for the reformer. The experimental results show that the reformer design allows inlet temperatures below 773 K because of its internal superheating capability. The simulation results indicate that two parallel flow configurations provide fast superheating and high fuel conversion rates. The temperature increase inside the reactor is influenced by the inlet geometry on the combustion side.     

Fast start-up of a diesel fuel processor for PEM fuel cells

Fuel cell systems based on liquid fuels are particularly suitable for auxiliary power generation due to the high energy density of the fuel and its easy storage. Together with industrial partners, Oel-Waerme-Institut is developing a 3 kW_el PEM fuel cell system based on diesel steam reforming to be applied as an APU for caravans and yachts. The start-up time of a fuel cell APU is of crucial importance since a buffer battery has to supply electric power until the system is ready to take over. Therefore, the start-up time directly affects the battery capacity and consequently the system size, weight, and cost.     

Diesel steam reforming with a nickel-alumina spinel catalyst for solid oxide fuel cell application

Liquid hydrocarbons (LC) are considered as fuel cells feed and, more particularly, as solid oxide fuel cell feed. Cost-effective LC-reforming catalysts are critically needed for the successful commercialization of such technologies. An alternative to noble metal catalysts, proposed by the authors in a previous publication, has been proven efficient for diesel steam reforming (SR). Nickel, less expensive and more readily available than noble metals, was used in a form that prevents deactivation. The catalyst formulation is a Ni-alumina spinel (NiAl₂O₄) supported on alumina (Al₂O₃) and yttria-stabilized zirconia (YSZ).SR of commercial diesel was undertaken for more than 15 h at high gas hourly space velocities and steam-to-carbon ratios lower than 2. Constant diesel conversion and high hydrogen concentrations were obtained. Ni catalyst characterization revealed no detectable amounts of carbon on the spinel catalyst surface Ni. The effect of catalyst composition (Ni concentration and YSZ presence) was studied to understand and optimize the developed catalyst. Two phenomena were found to be influenced by relative catalyst composition: water-gas-shift vs reforming reaction extent, and concentration of light hydrocarbons in products.     

Performance improvement of diesel autothermal reformer by applying ultrasonic injector for effective fuel delivery

Technology for the reforming of heavy hydrocarbons, such as diesel, to supply hydrogen for fuel cell applications is very attractive and challenging due to its delicate control requirements. The slow reforming kinetics of aromatics contained in diesel, sulfur poisoning, and severe carbon deposition make it difficult to obtain long-term performance with high reforming efficiency. In addition, diesel has a critical mixing problem due to its high boiling point, which results in a fluctuation of reforming efficiency. An ultrasonic injector (UI) have been devised for effective diesel delivery. The UI can atomize diesel into droplets (∼40 μm) by using a piezoelectric transducer and consumes much less power than a heating-type vapourizer. In addition, reforming efficiencies increase by as much as 20% compared with a non-UI reformer under the same operation conditions. Therefore, it appears that effective fuel delivery is linked to the reforming kinetics on the catalyst surface. A 100-W_e, self-sustaining, diesel autothermal reformer using the UI is designed. In addition, the deactivation process of the catalyst, by carbon deposition, is investigated in detail.     

Rapid start-up strategy of 1 kWe diesel reformer by solid oxide fuel cell integration

A rapid start-up strategy of a diesel reformer for on-board fuel cell applications was developed by fuel cell integration. With the integration with metal-supported solid oxide fuel cell which has high thermal shock resistance, a simpler and faster start-up protocol of the diesel reformer was obtained compared to that of the independent reformer setup without considering fuel cell integration. A reformer without fuel cell integration showed unstable reactor temperatures during the start-up process, which affects the reforming catalyst durability. By utilizing waste heat from the fuel cell stack, steam required at the diesel autothermal reforming could be stably provided during the start-up process. The developed diesel reformer was thermally sustainable after the initial heat-up process. As a result, the overall start-up time of the reformer after the diesel supply was reduced to 9 min from the diesel supply compared to 22 min without fuel cell integration.     

Genetic algorithm-based strategy for the steam reformer optimization

The steam reforming reaction is widely used for obtaining hydrogen. The reforming reaction has a strong endothermic character, which means it requires a considerable and continuous heat supply to proceed. Due to the process character, a highly non-uniform temperature field develops inside the reactor. It has a consequence in large temperature gradients, leading to the catalyst degradation and a reduced lifetime of the reforming unit. The aim of the presented research is to unify the temperature field developing in the reactor, for easier control of the process and extension of the reformer's life expectancy. A conventional plug-flow reactor consists of a cylindrical pipe body filled with catalyst. The presented methodology included optimizing the catalyst distribution in the reactor to acquire the most uniform temperature field possible. A genetic algorithm is selected as an optimization technique for finding the most advantageous alignment of the catalyst. It is an example of evolutionary algorithms, basing on rules similar to natural selection. The algorithm generates a random, initial population of reactors and the reforming simulation is executed for each of them. The computation results are then evaluated and ranked using predefined fitness functions. The ranked reactors parameters' are further recombined with selection probability based on the fitness values, until a whole new population is created and the algorithm's loop restarts. The higher the fitness value of a specific reactor, the higher are the chances of passing its segments composition to the proceeding generation. The fitness computation leaves a vast space for improvements, as it may be computed based on many different process' parameters. This work focuses on distinguishing differences in the algorithm performance, depending on the formula for fitness calculation. The algorithm's converging speed, overall fitness values of specimens and optimization results were investigated and compared. The results show that the algorithm with an updated fitness calculation procedure performs considerably better. Only about 50% of computational time was required, to acquire results of the same quality for the presented numerical cases, when comparing with the previously prepared procedure.     

Long-term stability at fuel processing of diesel and kerosene

The long-term stability at autothermal reforming of diesel fuel and kerosene was studied using Juelich's autothermal reformer ATR 9.2, which is equipped with a commercial proprietary RhPt/Al₂O₃–CeO₂ catalyst. The experiment was run for 10,000 h of time on stream at constant reaction conditions with an O₂/C molar ratio of 0.47, a H₂O/C molar ratio of 1.9, and a gas hourly space velocity of 30,000 h⁻¹. Kerosene produced via the gas-to-liquid process and diesel fuel synthesized via the bio-to-liquid route were used. Both fuels were almost free of mass fractions of sulfur and aromatics. The trends for the desired main products of autothermal reforming H₂, CO, CO₂, and CH₄ were almost stable when kerosene was used. When the fuel mass flow was switched to diesel fuel however, different modes of catalyst deactivation occurred (active sites blocked by carbonaceous deposits, sintering processes), leading to a decrease in the concentrations of H₂ and CO₂ with a simultaneous increase in the CO content. This paper defines carbon conversion as the decisive criterion for evaluating the long-term stability during autothermal reforming of kerosene and diesel fuel. Carbon conversion was diminished via three different pathways during the long-term experiment. Undesired byproducts found in the gas phase leaving the reactor had the strongest impact on carbon conversion. These byproducts included ethene, propene, and benzene. Furthermore, a liquid oily residue was detected floating on the condensed unconverted mass flow of water. This happened once during the whole experiment. Finally, undesired organic byproducts were dissolved in the mass flow of unconverted water. These were found to be straight-chain and branched paraffins, esters, alcohols, acids, aldehydes, ketones, etc. Nevertheless, at the end of the long-term experiment, carbon conversion still amounted to more than 98.2%.     

Minimization of hot spot in a microchannel reactor for steam reforming of methane with the stripe combustion catalyst layer

Hot spot formation is inevitable in a heat exchanger microchannel reactor used for steam reforming of methane because of the local imbalance between the generated and absorbed heat. A stripe configuration of the combustion catalyst layer was suggested to make the catalytic combustion rate uniform in order to minimize the hot spot near the inlet. The stripe configuration was optimized by response surface methodology with computational fluid dynamics. With the optimal catalyst layer, the hot spot was not observed near the inlet and the maximum temperature decreased by 130 K from that of the uniform catalyst layer without any conversion loss. The maximum relative particle diameters of the uniform and the optimal stripe catalyst layer were about 3.68 and 2.51, respectively, and the surface-averaged particle diameter of the optimal stripe catalyst layer was 7.64% less than that of the uniform stripe catalyst layer.     

A study of steam methanol reforming in a microreactor

Steam reforming of methanol is investigated numerically considering both heat and mass transfer of the species in a packed bed microreactor. The numerical results are shown to be in good agreement with experimental data [M.T. Lee, R. Greif, C.P. Grigoropoulos, H.G. Park, F.K. Hsu, J. Power Sources Transport in, 166 (2007) 194–201] with a BASF F3-01(CuO/ZnO/Al₂O₃) catalyst. A correlation for the conversion efficiency of methanol has been obtained as a function of the operating temperature and a dimensionless time parameter which represents the ratio of the characteristic time of the methanol flow to the time for chemical reaction. The results show that for the constant wall temperature condition the steam reforming process of methanol results in a nearly uniform temperature throughout the microreactor over the range of operating conditions.     

Thermal integration of a cylindrically symmetric methanol fuel processor for portable fuel cell power

The realization of a proven approach combining small hydrogen fuel cells with reformed methanol has continued to be elusive. This is so because of the overwhelming challenge of thermally integrating a chemical process involving many steps, each at a unique temperature, within a confined volume. In addition, heat loss to the environment becomes correspondingly higher as overall size shrinks due to increasing surface-to-volume ratio, requiring an inordinate use of system volume on thermal insulation. To address these challenges, we present a study based on extrapolation of experiment which incorporates novel cylindrical symmetry of the methanol fuel processor based on microchemical system technology. Models for two different fuel processor-proton exchange fuel cell systems of 4-W and 20-W scale are presented. ASPEN process simulation was used to establish basic system operating parameters. Finite difference modeling of the axisymmetric configuration was used to establish the heat flows in the systems. The results indicate strong potential for the cylindrical arrangement to provide viable self-contained small form factor battery replacements.     

Experiments on hydrogen production from methanol steam reforming in the microchannel reactor

The entire experiments were conducted for microchannel methanol steam reforming, by which, the selection of catalyst, the operating parameters and the configuration of microchannels were discussed thoroughly. It was found that the higher the Cu concentration is, the more the corresponding active surface area of Cu will be, thereby improving the catalytic activity. The Cu-to-Zn ratio in Cu/ZnO/Al₂O₃ catalyst should be set at 1:1. The impacts of reaction temperature, feed flow rate, mixture temperature, and H₂O-to-CH₃OH molar ratio on the methanol conversion rate were also revealed and discussed. Characteristics of micro-reactors with various microchannels, including that 20 mm and 50 mm in length, as well as non-parallel microchannels, were investigated. It was found that the increase of microchannel length can improve the methanol conversion rate significantly. Besides, non-parallel microchannels help to maintain flow and temperature distribution uniformity, which can improve the performance of micro-reactor. In the present experiments, the presence of CO was under the condition that the methanol conversion rate was above 70%.     

Efficient bimetallic catalysts for hydrogen generation from diesel fuel

Fuel cell requires hydrogen as its fuel source for generating power. Hydrogen for use in auxiliary power units is produced in a fuel processor by the catalytic reforming of hydrocarbons. Diesel, jet fuel, gasoline, as well as natural gas, are potential fuels that all have existing infrastructure of manufacture and distribution, for hydrogen production for fuel cell applications. It is well known that essentially all hydrocarbon feeds contain sulfur at different concentrations. In addition to coking, sulfur poisoning is the main force for deactivation of pre-reforming and reforming catalysts. The objective of this paper is to develop, test and characterize efficient catalysts for hydrogen generation from diesel autothermal reforming. Bimetallic catalysts exhibited superior performance compared to the commercial catalyst and the monometallic counterparts. BET, TPD, TPR, and XPS were utilized for surface analysis of these formulations, which showed that the enhanced stability is due to a strong metal–metal and metal–support interaction in the catalyst.     

Improved configuration of supported nickel catalysts in a steam reformer for effective hydrogen production from methane

The heat and mass transfer characteristics in a steam reformer are investigated via experimental and numerical approaches and a new configuration of packed catalysts is proposed for effective hydrogen production. Prior to the numerical investigation, parametric studies are carried for the furnace temperature, steam-to-carbon (S:C) ratio, and gas flow rate. After validation of the developed code, numerical work is undertaken to determine the relationship of the operating parameters. Based on the experimental and numerical results, and with the goal of obtaining optimum heat transfer characteristics and an efficient catalyst array, a new configuration for the packed bed is proposed and numerically investigated taking into account the endothermicity of the steam reforming reaction. A bed packed repeatedly with inert and active catalysts is found to be an efficient means to obtain the same, or better, hydrogen production with small amounts of the active catalysts compared with a typical steam reformer.     

Recent advances in diesel autothermal reformer design

The autothermal reforming of diesel fuel is a catalytic process that runs at temperatures of 700 °C–900 °C. Long-chain hydrocarbon molecules react with steam and O₂, yielding a product gas that mainly consists of CO, CO₂, CH₄ and H₂. H₂ is essential for the operation of fuel cell systems. The Forschungszentrum Jülich has been engaged in the cooperative development of technical apparatus for this reaction to be applied in fuel cell systems over the past 15 years, together with many other research groups worldwide, and this paper deals with reactor ATR 14, which is considered the preliminary end-product of Jülich's research and development in this field. This paper briefly summarizes Jülich's earlier reactor generations and then describes the most recent improvements embodied in the ATR 14. Additionally, the experimental evaluation of the ATR 14 is presented, which demonstrates that it can be operated over a broad load range and with almost complete carbon conversion.     

Impact of gas-phase reactions in the mixing region upstream of a diesel fuel autothermal reformer

The use of diesel fuel to power a solid oxide fuel cell (SOFC) presents several challenges. A major issue is deposit formation in either the external reformer, the anode channel, or within the SOFC anode itself. One potential cause of deposit formation under autothermal reforming conditions is the onset of gas-phase reactions upsteam of the catalyst to form ethylene, a deposit precursor. Another potential problem is improper mixing of the fuel, air, and steam streams. Incomplete mixing leads to fuel rich gas pockets in which gas phase pyrolysis chemistry might be accelerated to produce even more ethylene. We performed a combined experiment/modeling analysis to identify combinations of temperature and reaction time that might lead to deposit formation. Two alkanes, n-hexane and n-dodecane, were selected as surrogates for diesel fuel since a detailed mechanism is available for these species. This mechanism was first validated against n-hexane pyrolysis data. It was then used to predict fuel conversion and ethylene production under a variety of reforming conditions, ranging from steam reforming to catalytic partial oxidation. Assuming that the reactants are perfectly mixed at 800 K, the predictions suggest that a mixture must reach the catalyst in less than 0.1 s to avoid formation of potentially troublesome quantities of ethylene. Additional calculations using a simple model to account for improper mixing demonstrate the need for the components to be transported to the catalyst on a much shorter time scale, since both the relatively lean and relatively rich regions react faster and rapidly form ethylene.     

In situ regeneration of the Ni-based catalytic reformer of a 5 kW PEMFC system

The paper reports the results of on-site regeneration catalytic bed of the natural gas reformer in a 5 kW PEM fuel cell system. The Ni catalyst previously poisoned by sulphur from the available natural gas, could be re-activated by injection of pure water steam, following the method developed for industrial reformers using the same metal catalyst: this method was shown to be perfectly efficient, provided no natural gas was fed during the operation. Results of the tests conducted are presented and discussed in relation to published data on S-sorption on Ni surfaces.     

Biogas steam reformer for hydrogen production: Evaluation of the reformer prototype and catalysts

This work aims to investigate a biogas steam reforming prototype performance for hydrogen production by mass spectrometry and gas chromatography analyses of catalysts and products of the reform. It was found that 7.4% Ni/NiAl₂O₄/γ-Al₂O₃ with aluminate layer and 3.1% Ru/γ-Al₂O₃ were effective as catalysts, given that they showed high CH₄ conversion, CO and H₂ selectivity, resistance to carbon deposition, and low activity loss. The effect of CH₄:CO₂ ratio revealed that both catalysts have the same behavior. An increase in CO₂ concentration resulted in a decrease in H₂/CO ratio from 2.9 to 2.4 for the Ni catalyst at 850 °C, and from 3 to 2.4 for the Ru catalyst at 700 °C. In conclusion, optimal performance has been achieved in a CH₄:CO₂ ratio of 1.5:1. H₂ yield was 60% for both catalysts at their respective operating temperature. Prototype dimensions and catalysts preparation and characterization are also presented.