Model-based analysis of reactor geometrical configuration on CO preferential oxidation performance

Modeling studies have been conducted on Preferential Oxidation (PROX) Reaction, covering chemical kinetics and heat/mass transfer phenomena that occur in a shell and tube system, to be used in a beta 5 kWe hydrogen generator for Polymer Electrolyte Fuel Cells (PEFCs). The critical issue in the PROX reactor design is to achieve temperature control along the catalyst bed, because poor selectivities primarily result from excess reactor temperature. Aim of the model is to investigate the effects of the reactor dimensions on process performance, in order to obtain high CO conversion and high selectivity with respect to the undesired H₂ oxidation. The CO removal from simulated reformate was examined, by evaluating the temperature and the gas concentration profiles along the reactor. The sensitivity analysis showed that the overall performance is strongly dependent upon the geometrical configurations examined.     

Pt-Co catalyst-coated channel plate reactor for preferential CO oxidation

To achieve preferential CO oxidation, a Pt-Co catalyst-coated channel plate reactor (CCPR) was produced via conventional mechanical milling and catalyst coating. The proposed reactor performed well under a wide range of operating temperatures and provided satisfactory results at low temperatures (CO concentrations of 1-10 ppm at 413-443 K and 1-50 ppm at 413-453 K). In the proposed CCPR, significant deactivation was not observed during continuous operation for 100 h. In addition, the reactor exhibited excellent tolerance to undesirable conditions, including reaction temperature runaway and feeding stream failure. Characterisation results indicated that the catalytic activity of the proposed CCPR was high due to the formation of Pt₃Co intermetallic compounds and nanoscale metal particles. The capacity per channel of the proposed CCPR was approximately 50-100 times greater than those of conventional microchannel reactors; thus, problems associated with excessive reactors were significantly reduced. In general, the results indicated that CCPR has great potential in the small-scale production of hydrogen for fuel cells.     

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.     

Controller design for polymer electrolyte membrane fuel cell systems for automotive applications

Continuous developments in Proton Exchange Membrane Fuel Cells (PEMFC) make them a promising technology to achieve zero emissions in multiple applications including mobility. Incremental advancements in fuel cells materials and manufacture processes make them now suitable for commercialization. However, the complex operation of fuel cell systems in automotive applications has some open issues yet. This work develops and compares three different controllers for PEMFC systems in automotive applications. All the controllers have a cascade control structure, where a generator of setpoints sends references to the subsystems controllers with the objective to maximize operational efficiency. To develop the setpoints generators, two techniques are evaluated: off-line optimization and Model Predictive Control (MPC). With the first technique, the optimal setpoints are given by a map, obtained off-line, of the optimal steady state conditions and corresponding setpoints. With the second technique, the setpoints time profiles that maximize the efficiency in an incoming time horizon are continuously computed. The proposed MPC architecture divides the fast and slow dynamics in order to reduce the computational cost. Two different MPC solutions have been implemented to deal with this fast/slow dynamics separation. After the integration of the setpoints generators with the subsystems controllers, the different control systems are tested and compared using a dynamic detailed model of the automotive system in the INN-BALANCE project running under the New European Driving Cycle.     

Experimental investigation of coupling phenomena in polymer electrolyte fuel cell stacks

Propagation of performance changes to adjacent cells in polymer electrolyte fuel cell stacks is studied by means of voltage monitoring and local current density measurements in peripheral cells of the stack. A technical fuel cell stack has been modified by implementing two independent reactant and coolant supplies in order to deliberately change the performance of one cell (anomalous cell) and study the coupling phenomena to adjacent cells (coupling cells), while keeping the working conditions of the later cell-group unaltered.Two anomalies are studied: (i) air starvation and (ii) thermal anomaly, in a single anomalous cell in the stack and their coupling to adjacent cells. The results have shown that anomalies inducing considerable changes in the local current density of the anomalous cell (such as air starvation) propagate to adjacent cells affecting their performance. The propagation of local current density changes takes place via the common bipolar plate due to its finite thickness and in-plane conductivity. Consequently, anomalies which do not strongly influence the local current density distribution (such as a thermal anomaly under the studied working conditions) do not propagate to adjacent cells.     

Performance of a polymer electrolyte fuel cell for automotive applications

The objectives of this study were to fabricate a self‐humidifying fuel cell stack of 10 cells with 104 cm² cell areas humidified with water recovered at cathodes, and to measure and simulate the performance of the stack. This involves the simulation of a three‐dimensional model of the heat and mass transfer of the water and the gaseous reactants in the fuel cell components with a water‐cooling system. The results of the stack experiments indicated a maximum power of 250 kW at a current density of 0.5 A/cm². The simulation showed good agreement with the actual performance of the stack. The performance of the self‐humidifying stack with a vapor‐permeating membrane is comparable to a conventional stack with external humidifiers, and it appears very effective in simplifying stack systems. The modeling analysis indicated that for the gas flow directions, at anode and cathode, a parallel flow is superior to a cross flow, and that one cooling cell is necessary for two to three generating cells in order to maintain the fuel cell temperature below 100 °C. © 2002 Wiley Periodicals, Inc. Heat Trans Asian Res, 31(6): 421–429, 2002; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/htj.10041     

An experimental investigation of electro-osmotic drag coefficients in a polymer electrolyte membrane fuel cell

Through the use of a water balance experiment, the electro-osmotic drag coefficients of Nafion 115 were obtained under several conditions (as a function of water content and thermodynamics conditions). For the cases when the anode was fully hydrated (corresponding to water content λ ≈ 14 in the adjacent membrane) and the cathode suffered from drying when dry air was supplied (λ ≈ 2), the electro-osmotic drag coefficients varied from 0.82 (±0.06) to 0.50 (±0.03) H₂O/H⁺ when the current density varied from 0.4 to 1.0 A cm⁻² (95% confidence level). When the current density increased, the electro-osmotic drag coefficient decreased. When the water content at the anode increased from λ ≈ 5 to λ ≈ 14, the cathode was supplied with dry air (λ ≈ 2), and the fuel cell discharged constant current density at 0.6 A cm⁻², the electro-osmotic drag coefficient increased from 0.44 (±0.06) to 0.68 (±0.06) H₂O/H⁺ (95% confidence level). Higher relative humidity gas leads to a higher electro-osmotic drag coefficient at constant current density.     

Effect of reactor heat transfer limitations on CO preferential oxidation

Our recent studies of CO preferential oxidation (PrOx) identified systematic differences between the characteristic curves of CO conversion for a microchannel reactor with thin-film wall catalyst and conventional mini packed-bed lab reactors (m-PBR's). Strong evidence has suggested that the reverse water-gas-shift (r-WGS) side reaction activated by temperature gradients in m-PBR's is the source of these differences. In the present work, a quasi-3D tubular non-isothermal reactor model based on the finite difference method was constructed to quantitatively study the effect of heat transport resistance on PrOx reaction behavior. First, the kinetic expressions for the three principal reactions involved were formed based on the combination of experimental data and literature reports and their parameters were evaluated with a non-linear regression method. Based on the resulting kinetic model and an energy balance derived for PrOx, the finite difference method was then adopted for the quasi-3D model. This model was then used to simulate both the microreactor and m-PBR's and to gain insights into their different conversion behavior.Simulation showed that the temperature gradients in m-PBR's favor the reverse water-gas-shift (r-WGS) reaction, thus causing a much narrower range of permissible operating temperature compared to the microreactor. Accordingly, the extremely efficient heat removal of the microchannel/thin-film catalyst system eliminates temperature gradients and efficiently prevents the onset of the r-WGS reaction.     

Water balance in a polymer electrolyte fuel cell system

Polymer electrolyte fuel cell (PEFC) systems operating on carbonaceous fuels require water for fuel processing. Such systems can find wider applications if they do not require a supply of water in addition to the supply of fuel, that is, if they can be self-sustaining based on the water produced at the fuel cell stack. This paper considers a generic PEFC system and identifies the parameters that affect, and the extent of their contribution to, the net water balance in the system. These parameters include the steam-to-carbon and the oxygen-to-carbon ratios in the fuel processor, the electrochemical fuel and oxygen utilizations in the fuel cell stack, the ambient pressure and temperature, and the composition of the fuel used. The analysis shows that the amount of water lost from the system as water vapor in the exhaust is very sensitive to the system pressure and ambient temperature, while the amount of water produced in the system is a function of the composition of the fuel. Fuels with a high H/C (hydrogen to carbon atomic ratio) allow the system to be operated as a net water producer under a wider range of operating conditions.     

Hierarchical fault diagnostic method for a polymer electrolyte fuel cell system

This study proposes a hierarchical method for on-line fault detection and diagnosis (FDD) of a stack and balance of plants (BoPs) in a polymer electrolyte fuel cell (PEFC) system. Because the fuel cell system consists of various subsystems with different characteristics, we have developed a multi-stage structure with subsystem-level FDD. In the first stage, faults were diagnosed at the subsystem level. In the next step, component-level faults were identified in the corresponding subsystem. The model-based approach in this study is composed of process estimation, residual generation, and FDD. Supervised machine learning methods were applied to train models for regression and fault classification. Residuals, the difference between analytic redundancies and measured results, were employed as fault indicators, i.e., residuals were used to detect faults and to generate fault patterns. Analytic redundancies were calculated using regression models. Several abrupt and performance degradation faults were considered. Because long-term performance degradations were difficult to introduce in the experimental system, the proposed method was evaluated using test data obtained by artificially decreasing the performance or sensor readings for a short period of time. This study focuses primarily on subsystem-level FDD and demonstrates one scenario of second level FDD. The experimental results verified the accuracy of the model-based approach and demonstrated that the proposed multi-stage hierarchical method effectively diagnosed faults in a PEFC system.     

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.     

A review of accelerated conditioning for a polymer electrolyte membrane fuel cell

A newly fabricated polymer electrolyte membrane (PEM) fuel cell usually needs a so-called break-in/conditioning/incubation period to activate it and reach its best performance. Typically, during this activation period the cell performance increases gradually, and then reaches a plateau without further increase. Depending on the membrane electrode assemblies, this process can take hours and even days to complete, which consumes a considerable amount of hydrogen fuel, leading to a higher operating cost. To provide for accelerated conditioning techniques that can complete the process in a short time period, this paper reviews established conditioning protocols and reported methods to condition PEM single cells and stacks, in an attempt to summarize available information on PEM fuel cell conditioning and the underlying mechanisms. Various techniques are arranged into two categories: on-line conditioning and off-line conditioning. For each technique, the experimental procedure and outcomes are outlined. Finally, weaknesses of the currently used conditioning techniques are indicated and further research efforts are proposed.     

Free vibration analysis of a polymer electrolyte membrane fuel cell

A free vibration analysis of a polymer electrolyte membrane fuel cell (PEMFC) is performed by modelling the PEMFC as a 20 cm × 20 cm composite plate structure. The membrane, gas diffusion electrodes, and bi-polar plates are modelled as composite material plies. Energy equations are derived based on Mindlin's plate theory, and natural frequencies and mode shapes of the PEMFC are calculated using finite element modelling. A parametric study is conducted to investigate how the natural frequency varies as a function of thickness, Young's modulus, and density for each component layer. It is observed that increasing the thickness of the bi-polar plates has the most significant effect on the lowest natural frequency, with a 25% increase in thickness resulting in a 17% increase in the natural frequency. The mode shapes of the PEMFC provide insight into the maximum displacement exhibited as well as the stresses experienced by the single cell under vibration conditions that should be considered for transportation and stationary applications. This work provides insight into how the natural frequencies of the PEMFC should be tuned to avoid high amplitude oscillations by modifying the material and geometric properties of individual components.     

Numerical modeling of a non-flooding hybrid polymer electrolyte fuel cell

Experimental results were recently reported regarding a novel “non-flooding” hybrid fuel cell consisting of proton exchange membrane (PEM) and anion exchange membrane (AEM) half-cells on opposite sides of a water-filled, porous intermediate layer. Product water formed in the porous layer, where it could permeate to the exterior of the cell, rather than at the electrodes. Although electrode flooding was mitigated, the reported power output was low. To investigate the potential for increased power output, a physicochemical charge transport model of the porous electrolyte layer is reported here. Traditional electrochemical modeling was generalized in a novel way to consider both ion transport and reaction in the aqueous phase and electronic conduction in the graphitic scaffold using a unified Poisson–Nernst–Planck framework. Though the model used no arbitrary or fitting parameters, the ionic resistance calculated for the porous layer agreed well with the highly non-Ohmic experimental values previously reported for the entire fuel cell. Interestingly, electronic charge carriers in the scaffold were found to obviate the need for counterion presence in this unique electrolyte structure. Still, the thickness- and temperature-dependent model results offer limited prospects for improving the power output.     

Analysis and control of a hybrid fuel delivery system for a polymer electrolyte membrane fuel cell

A polymer electrolyte membrane fuel cell (PEM FC) system as a power source used in mobile applications should be able to produce electric power continuously and dynamically to meet the demand of the driver by consuming the fuel, hydrogen. The hydrogen stored in the tank is supplied to the anode of the stack by a fuel delivery system (FDS) that is comprised of supply and recirculation lines controlled by different actuators. Design of such a system and its operation should take into account several aspects, particularly efficient fuel usage and safe operation of the stack.     

Model-based fault diagnosis in PEM fuel cell systems

In this work, a model-based fault diagnosis methodology for PEM fuel cell systems is presented. The methodology is based on computing residuals, indicators that are obtained comparing measured inputs and outputs with analytical relationships, which are obtained by system modelling. The innovation of this methodology is based on the characterization of the relative residual fault sensitivity. To illustrate the results, a non-linear fuel cell simulator proposed in the literature is used, with modifications, to include a set of fault scenarios proposed in this work. Finally, it is presented the diagnosis results corresponding to these fault scenarios. It is remarkable that with this methodology it is possible to diagnose and isolate all the faults in the proposed set in contrast with other well known methodologies which use the binary signature matrix of analytical residuals and faults.     

Development of polymer electrolyte membrane fuel cell stack

The proton exchange membrane fuel cell (PEMFC) is one of the strongest contenders as a power source for space, electric vehicle and domestic applications. Since 1988 intensive research is being carried out at our centre to develop PEMFCs. The main RandD activities are: (i) to develop a method for the electrode preparation (ii) to enhance platinum utilisation using low platinum loading and (iii) to design multicell stacks. The results of RandD development of the above activities are discussed in this paper.     

Development of small polymer electrolyte fuel cell stacks

The results on the research and development of small polymer electrolyte fuel cell stacks, including the assembly of single cell. 6-cell and 21-cell modules, are described. The important characteristics of the systems are: (i) membrane and electrode assemblies were made with Nafion^® 115 and 117 membranes and particularly low catalyst loading electrodes presenting a geometric area of 20 cm² and a catalyst loading of 0.4 mg Pt/cm²: (ii) bipolar plates were fabricated using a nonporous graphite material in which a series/parallel flow field was machined out: (iii) external distribution of gases to the cells was done using parallel manifolding; (iv) cooling systems were tested employing water/air cooling plates distributed every three cells throughout the stack; (v) the reactant gases were externally humidified using temperature controlled humidification bottles. Testing of the stacks was conducted in a specially designed test station employing nonpressurized H₂/O₂ reactants and measuring the individual and the overall cell voltage vs. current under several conditions for the overall system operation.