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.     

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.     

Experimental and theoretical analysis of a natural gas fuel processor

In this study, a natural gas fuel processor was experimentally and theoretically investigated. The constructed 2.0 kWth fuel processor is suitable for a residential-scale high temperature proton exchange membrane fuel cell. The system consists of an autothermal reformer; gas clean-up units, namely high and low-temperature water-gas shift reactors; and utilities including feeding unit, burner, evaporator and heat exchangers. Commercial monolith catalysts were used in the reactors. The simulation was carried out by using ASPEN HYSYS program. A validated kinetic model and adiabatic equilibrium model were both presented and compared with experimental data. The nominal operating conditions which were determined by the kinetic model were the steam-to-carbon ratio of 3.0, the oxygen-to-carbon ratio of 0.5 and the inlet temperatures of 450 °C for autothermal reformer, 400 °C for high-temperature water-gas shift reactor and 310 °C for low-temperature water-gas shift reactor. Experimental results at the nominal condition showed that the performance criteria of the hydrogen yield, the fuel conversion and the efficiency were 2.53, 93.5% and 82.3% (higher heating value-HHV), respectively. The validated kinetic model was further used for the determination of 2–10kWthermal fuel processor efficiency which was increasing linearly up-to 86.3% (HHV).     

A techno-economic evaluation of the hydrogen production for energy generation using an ethanol fuel processor

The techno-economic analysis of a process to convert ethanol into H₂ to be used as a fuel for PEM fuel cells of H₂-powered cars was done. A plant for H₂ production was simulated using experimental results obtained on monolith reactors for ethanol steam reforming and WGS steps. The steam reforming (Rh/CeSiO₂) and WGS (Pt/ZrO₂) monolith catalysts remained quite stable during long-term startup/shut down cycles, with no carbon deposition. The H₂ production cost was significantly affected by the ethanol price. The monolith catalyst costs contribution was lower than that of conventional reactors. The H₂ production cost obtained using the expensive Brazilian ethanol price (0.81 US$/L ethanol) was US$ 8.87/kg H₂, which is lower than the current market prices (US$ 13.44/kg H₂) practiced at H₂ refueling stations in California. This result showed that this process is economically feasible to provide H₂ as a fuel for H₂-powered cars at competitive costs in refueling stations.     

A diesel fuel processor for stable operation of solid oxide fuel cells system: II. Integrated diesel fuel processor for the operation of solid oxide fuel cells

Post-reforming experimental results for the complete removal of light hydrocarbons from diesel reformate are introduced in part I. In part II of the paper, an integrated diesel fuel processor is investigated for the stable operation of SOFCs. Several post-reforming processors have been operated to suppress both sulfur poisoning and carbon deposition on the anode catalyst. The integrated diesel fuel processor is composed of an autothermal reformer, a desulfurizer, and a post-reformer. The autothermal reforming section in the integrated diesel fuel processor effectively decomposes aromatics, and converts fuel into H₂-rich syngas. The subsequent desulfurizer removes sulfur-containing compounds present in the diesel reformate. Finally, the post-reformer completely removes the light hydrocarbons, which are carbon precursors, in the diesel reformate. We successfully operate the diesel reformer, desulfurizer, and post-reformer as microreactors for about 2500 h in an integrated mode. The degradation rate of the overall reforming performance is negligible for the 2000 h, and light hydrocarbons and sulfur-containing compounds are completely removed from the diesel reformate.     

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.     

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.     

Static and dynamic modeling of a diesel fed fuel cell power supply

Fuel cell supplied auxiliary power units could ease the development of fuel cell systems in transportation application if they are fed by conventional hydrocarbons like diesel. Then a fuel processor has to be used to convert the hydrocarbon in a hydrogen rich gas mixture with a low rate of contaminant. The temperatures of the fuel processor modules and the mass flows have to be controlled. The energetic macroscopic representation (EMR) is a causal, graphic modeling tool for complex multi-domain systems that can be used for the design of the control structure through the inversion of model. In this work EMR is used to model a diesel supplied low temperature fuel cell unit including the fuel processor, the fuel cell stack (HTPEM) as well as the supply system of the mass flows. The presented fuel processor and HTPEM models are validated against experimental results. The structure of the temperature and mass flow controls in the fuel processor and supply system are derived. Both the model and the control are implemented in Matlab/Simulink™ and validated.     

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.     

Methanol fuel processor and PEM fuel cell modeling for mobile application

The use of hydrocarbon fed fuel cell systems including a fuel processor can be an entry market for this emerging technology avoiding the problem of hydrogen infrastructure. This article presents a 1 kW low temperature PEM fuel cell system with fuel processor, the system is fueled by a mixture of methanol and water that is converted into hydrogen rich gas using a steam reformer. A complete system model including a fluidic fuel processor model containing evaporation, steam reformer, hydrogen filter, combustion, as well as a multi-domain fuel cell model is introduced. Experiments are performed with an IDATECH FCS1200™ fuel cell system. The results of modeling and experimentation show good results, namely with regard to fuel cell current and voltage as well as hydrogen production and pressure. The system is auto sufficient and shows an efficiency of 25.12%. The presented work is a step towards a complete system model, needed to develop a well adapted system control assuring optimized system efficiency.     

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.     

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.     

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.     

Biodiesel fuel processor for APU applications

Tail pipe emission reduction, increased use of renewable fuels and efficient supply of auxiliary power for road vehicles using fuel cells have been the main drivers of the European project BIOFEAT (biodiesel fuel processor for a fuel cell auxiliary power unit for a vehicle). Within the project a biodiesel fuelled heat integrated fuel processor for 10 kW_e capacity has been designed and constructed. Demonstration tests showed a high quality reformate with less than 10 ppm of CO and a gross efficiency of 87%.     

Modeling and dynamics of an autothermal JP5 fuel reformer for marine fuel cell applications

In this work, a dynamic model of an integrated autothermal reformer (ATR) and proton exchange membrane fuel cell (PEM FC) system and model-based evaluation of its dynamic characteristics are presented. The ATR reforms JP5 fuel into a hydrogen rich flow. The hydrogen is extracted from the reformate flow by a separator membrane (SEP), then supplied to the PEM FC for power generation. A catalytic burner (CB) and a turbine are also incorporated to recuperate energy from the remaining SEP flow that would otherwise be wasted. A dynamic model of this system, based on the ideal gas law and energy balance principles, is developed and used to explore the effects of the operating setpoint selection of the SEP on the overall system efficiency. The analysis reveals that a trade-off exists between the SEP efficiency and the overall system efficiency. Finally the open loop system simulation results are presented and conclusions are drawn on the SEP operation.     

Analysis of the energy efficiency of innovative ATR-based PEM fuel cell system with hydrogen membrane separation

In this work we report a simulative energy efficiency analysis performed on innovative fuel processor – PEM fuel cell systems in which hydrogen is produced via methane autothermal reforming, separated with a membrane unit coupled with a water gas shift reactor and then converted into electric energy by means of the PEM fuel cell.     

Energy efficiency of membrane-based fuel processors – PEM fuel cell systems

This work presents a simulative energy efficiency analysis performed on fuel processor – PEMFC systems, considering methane as fuel and steam reforming or autothermal reforming as processes to produce hydrogen. Computation of energy efficiency takes into account the power required by the auxiliary units, coupling of the fuel processor with the fuel cell as well as heat recovery and integration.     

Self-sustained operation of a kWe-class kerosene-reforming processor for solid oxide fuel cells

In this paper, fuel-processing technologies are developed for application in residential power generation (RPG) in solid oxide fuel cells (SOFCs). Kerosene is selected as the fuel because of its high hydrogen density and because of the established infrastructure that already exists in South Korea. A kerosene fuel processor with two different reaction stages, autothermal reforming (ATR) and adsorptive desulfurization reactions, is developed for SOFC operations. ATR is suited to the reforming of liquid hydrocarbon fuels because oxygen-aided reactions can break the aromatics in the fuel and steam can suppress carbon deposition during the reforming reaction. ATR can also be implemented as a self-sustaining reactor due to the exothermicity of the reaction. The kW_e self-sustained kerosene fuel processor, including the desulfurizer, operates for about 250 h in this study. This fuel processor does not require a heat exchanger between the ATR reactor and the desulfurizer or electric equipment for heat supply and fuel or water vaporization because a suitable temperature of the ATR reformate is reached for H₂S adsorption on the ZnO catalyst beds in desulfurizer. Although the CH₄ concentration in the reformate gas of the fuel processor is higher due to the lower temperature of ATR tail gas, SOFCs can directly use CH₄ as a fuel with the addition of sufficient steam feeds (H₂O/CH₄ ≥ 1.5), in contrast to low-temperature fuel cells. The reforming efficiency of the fuel processor is about 60%, and the desulfurizer removed H₂S to a sufficient level to allow for the operation of SOFCs.     

In-depth characterization through dimensional analysis of the performance of a membrane-integrated fuel processor for high purity hydrogen generation

Efficient production of high purity hydrogen from reforming of natural or synthetic hydrocarbons is an enabling technology for the competitiveness of hydrogen-based systems. Specifically, fuel processors based on membrane-integrated reformers are one of the most promising technologies being potentially more efficient than state-of-the-art fuel processors. The effects of the operating parameters on the performance of the complete membrane-integrated fuel processor are relevant and have not been properly investigated, especially in terms of mutual interactions. Therefore, we analyze the effects of the pressure and temperature of the steam reforming reactor as well as of the steam to fuel and air to fuel ratios, on the system efficiency. To this aim, we use a steady state model developed in Aspen Plus® that implements a hybrid lumped-distributed parameter approach. To generalize our results to diverse system sizes and fuel compositions we conduct a dimensional analysis to express all the parameters in non-dimensional form.The results show that the fuel processor efficiency based on lower heating value varies between 75% and 84% as a function of the operating parameters. Notably, it always exceeds 75% that is the reference value for a state-of-the-art fuel processor based on pressure swing adsorption purification. We also note that the retentate composition has a relevant impact on the fuel processor operation. Specifically, when the retentate is rich in fuel content the fuel processor can turn in exothermic regime or can suffer oxygen starvation in the catalytic oxidation reaction. However, when the fuel processor operates in regular conditions the only relevant mutual interaction is between the steam to fuel and air to fuel ratios. Also, the fuel processor efficiency is mostly sensitive to the operating temperature and to the steam to fuel ratio. The 770 °C optimal temperature implies that only dense ceramic membranes can be used to build a fuel processor that operates at the maximum possible efficiency. Finally, leveraging on such results we evaluate the preliminary design of an innovative tubular plug flow reactor with layer catalysts.