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.     

Start-up strategies of an experimental fuel processor

In this work, cold start-up of a methane fuel processor is explored. The experimental fuel processor is intended to provide hydrogen for a proton exchange membrane (PEM) fuel cell for the power generation (3 kWe). A dynamic model describing a series of reactors, the reformer, three water–gas shift reactors, and preferential reactor is constructed. Two important factors for rapid start-up are identified: speed of temperature front propagation and acceptable CO concentration. Steady-state analyses reveal that the fuel feed flow rate with fixed steam-to-carbon and air-to-carbon ratios is an ideal manipulated variable. Considering both large initial heat flux and gradual transition back to nominal operation, the shape of feed manipulation is determined. With the feed scenario available, the fuel processor start-up can be formulated as a constrained optimization problem and can be solved numerically. From optimization result, a heuristic is generated for rapid start-up of a fuel processor. This leads to a 25% improvement in the start-up time. Finally, issues of design modification are explored for further reduction in the start-up time.     

Operating line analysis of fuel processors for PEM fuel cell systems

At least three different definitions of fuel processor efficiency are in widespread use in the fuel cell industry. In some instances the different definitions are qualitatively the same and differ only in their quantitative values. However, in certain limiting cases, the different efficiency definitions exhibit qualitatively different trends as system parameters are varied. In one limiting case that will be presented, the use of the wrong efficiency definition can lead a process engineer to believe that a theoretical maximum in fuel processor efficiency exists at a particular operating condition, when in fact no such efficiency optimum exists. For these reasons, the objectives of this paper are to: (1) quantitatively compare and contrast these different definitions, (2) highlight the advantages and disadvantages of each definition and (3) recommend the correct definition of fuel processor efficiency.     

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.     

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.     

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.     

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.     

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.     

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.     

A 5 kWt catalytic burner for PEM fuel cells: Effect of fuel type,fuel content and fuel loads on the capacity of the catalytic burner

For proton exchange membrane fuel cell systems (PEMFC) integrated with fuel processors, the calorific value of reformate gases produced during the start-up phase must be recovered. An appropriate exhaust after treatment system has crucial importance for PEMFC systems. Catalytic combustion is a promising alternative regarding its total oxidation capability of low calorific value gases at low temperatures, thereby reducing environmentally hazardous emissions. The aim of the study is to develop an after treatment system using a catalytic burner with a nominal capacity of 5 kW_t, which is also adaptive to partial loads of PEM fuel cell capacity. Fuel type, fuel composition and fuel loads are important parameters determining the operating window of the catalytic burner. Precious metal based catalysts, as proved to be the most active catalysts for the oxidation of hydrocarbons, can withstand temperatures of about 1073 K without exhibiting a rapid deactivation. This is the main barrier dictating the operating window and thereby determining the capacity of the burner. In this work, 1.5% natural gas (NG) alone was found to be the upper limit to control the catalyst bed temperature below 1073 K. In the case of catalytic combustion of hydrogen–NG mixture, 7% of hydrogen with NG up to 0.6% could be totally oxidized below 1073 K. Within the experimented ranges of fuel loads, between 2.5 kW_t and 5.5 kW_t, the temperature of the catalyst bed was seen to increase with increasing the fuel load at constant fuel percentages. It has been observed that fuel type was another parameter affecting the exhaust gas temperature.     

Experimental investigation on a methane fuel processor for polymer electrolyte fuel cells

This study presents experimental study on a novel methane fuel processing system for hydrogen (H₂) production. The unit includes into a single package the autothermal reformer, the CO shift converter, the preferential oxidation reactor and the internal heat exchangers. Effects of operative conditions, related to the H₂ productivity, on the performances, were investigated experimentally, in order to evaluate the integration of the fuel processor with a Polymer Electrolyte Fuel Cell (PEFC) system for residential applications. The sensitivity analysis showed that the overall performance is strongly dependent upon the operative conditions considered.     

Energy efficiency analysis of an integrated glycerin processor for PEM fuel cells: Comparison with an ethanol-based system

The aim of this work is to analyze energetically the use of glycerin as the primary hydrogen source to operate a proton exchange membrane fuel cell. A glycerin processor system based on its steam reforming is described departing from a previous process model developed for ethanol processing. Since about 10% w/w of glycerin is produced as a byproduct when vegetable oils are converted into biodiesel, and due to the later is increasing its production abruptly, a large glycerin excess is expected to oversaturate the market. The reformed stream contains mainly H₂ but also CO, CO₂, H₂O and CH₄. As CO is a poison for PEM fuel cell type, a stream purification step is previously required. The purification subsystem consists of two water gas shift reactors and a CO preferential oxidation reactor to reduce the CO levels below 10 ppm. The reforming process is governed by endothermic reactions, requiring thus energy to proceed. Depending on the system operation point, the energy requirements can be fulfilled by burning an extra glycerin amount (to be determined), which is the minimal that meets the energy requirements. In addition a self-sufficient operation region can be distinguished. In this context, the water/glycerin molar ratio, the glycerin steam reformer temperature, the system pressure, and the extra glycerin amount to be burned (if necessary) are the main decision variables subject to analysis. Process variables are calculated simultaneously, updating the composite curves at each iteration to obtain the best possible energy integration of the process. The highest net system efficiency value computed is 38.56% based on the lower heating value, and 34.71% based on the higher heating value. These efficiency values correspond to a pressure of 2 atm, a water/glycerin molar ratio of 5, a glycerin steam reformer temperature of 953 K, and an extra glycerin amount burned of 0.27 mol h⁻¹. Based on the main process variables, suitable system operation zones are identified. As in practice, most PEM fuel cells operate at 3 atm, optimal variable values obtained at this condition are also reported. Finally, some results and aspects on the system performance of both glycerin and ethanol processors operated at 3 atm are compared and discussed.     

Further development of a microchannel steam reformer for diesel fuel

This paper presents results from the ongoing optimisation of a microchannel steam reformer for diesel fuel which is developed in the framework of the development of a PEM fuel cell system for vehicular applications. Four downscaled reformers with different catalytic coatings of precious metal were operated in order to identify the most favourable catalyst formulation. Diesel surrogate was processed at varying temperatures and steam to carbon ratios (S/C). The reformer performance was investigated considering hydrogen yield, reformate composition, fuel conversion, and deactivation from carbon formation. Complete fuel conversion is obtained with several catalysts. One catalyst in particular is less susceptible to carbon formation and shows a high selectivity.     

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.     

Effect of sub-freezing temperatures on a PEM fuel cell performance, startup and fuel cell components

The cold-start behavior and the effect of sub-zero temperatures on fuel cell performance were studied using a 25-cm² proton exchange membrane fuel cell (PEMFC). The fuel cell system was housed in an environmental chamber that allowed the system to be subjected to temperatures ranging from sub-freezing to those encountered during normal operation. Fuel cell cold-start was investigated under a wide range of operating conditions. The cold-start measurements showed that the cell was capable of starting operation at −5 °C without irreversible performance loss when the cell was initially dry. The fuel cell was also able to operate at low environmental temperatures, down to −15 °C. However, irreversible performance losses were found if the cell cathode temperature fell below −5 °C during operation. Freezing of the water generated by fuel cell operation damaged fuel cell internal components. Several low temperature failure cases were investigated in PEM fuel cells that underwent sub-zero start and operation from −20 °C. Cell components were removed from the fuel cells and analyzed with scanning electron microscopy (SEM). Significant damage to the membrane electrode assembly (MEA) and backing layer was observed in these components after operation below −5 °C. Catalyst layer delamination from both the membrane and the gas diffusion layer (GDL) was observed, as were cracks in the membrane, leading to hydrogen crossover. The membrane surface became rough and cracked and pinhole formation was observed in the membrane after operation at sub-zero temperatures. Some minor damage was observed to the backing layer coating Teflon and binder structure due to ice formation during operation.     

Heat-up and start-up modeling of direct internal reforming solid oxide fuel cells

In this paper, a transient heat transfer model to simulate the heat-up and start-up periods of co- and counter-flow direct internal reforming solid oxide fuel cells is developed and presented. In this comprehensive model, all the heat transfer mechanisms, i.e. conduction, convection, and radiation, and all the polarization nodes, i.e. ohmic, activation, and concentration, are considered. The heat transfer model is validated using the results of a benchmark test and two numerical studies obtained from the literature. After validating the model, the heat-up, start-up, and steady-state behaviors of the cell are investigated. In addition, the first principal thermal stresses are calculated to find the probability of failure of the cell during its operation. The results of the present model are in good agreement with the literature data. It is also shown for the given input data that counter-flow case yields a higher average current density and power density, but a lower electrical efficiency of the cell. For the temperature controlled heat-up and start-up strategy, the maximum probability of failure during the operation of the cell is found to be 0.068% and 0.078% for co- and counter-flow configurations, respectively.     

Static and dynamic modeling of a diesel fuel processing unit for polymer electrolyte fuel cell supply

This article introduces the energetic macroscopic representation (EMR) as approach for the dynamic modeling of a diesel fuel processing unit. The EMR is the first step toward model-based control structure development. The autothermal fuel processing system containing: heat exchanger, reformer, desulfurization, water gas shift, preferential oxidation and condensation is divided into a multitude simple subblocks. Each subblock describes an elementary step of the fuel conversion, several of these blocks may occur in a single module. Calculations are carried out using two basic principles: mass and energy balances. For model-based control development, it is imperative that the model represents dynamic behavior, therefore temperature and pressure dynamics are taken into account in the model. It is shown that the model is capable to predict the stationary behavior of the entire fuel processing unit correctly by comparison with given data. Predictions regarding reformer heat up, temperature and pressure dynamics are also provided.     

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.     

Optimization of hydrogen feeding procedure in PEM fuel cell systems for transportation

The hydrogen feeding sub-system is one of balance of plant (BOP) components necessary for the correct operation of a fuel cell system (FCS). In this paper the performance of a 6 kW PEM (Proton Exchange Membrane) FCS, able to work with two fuel feeding procedures (dead-end or flow-through), was experimentally evaluated with the aim to highlight the effect of the anode operation mode on stack efficiency and durability. The FCS operated at low reactant pressure (<50 kPa) and temperature (<330 K), without external humidification. The experiments were performed in both steady state and dynamic conditions. The performance of some cells in dead-end mode worsened during transient phases, while a more stable working was observed with fuel recirculation. This behavior evidenced the positive role of the flow-through procedure in controlling flooding phenomena, with the additional advantage to simplify the management issues related to hydrogen purge and air stoichiometric ratio. The flow-through modality resulted a useful way to optimize the stack efficiency and to reduce the risks of fast degradation due to reactant starvation during transient operative phases.     

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).