Biogas as hydrogen source for fuel cell applications

In the last decade, production of biogas from biomass degradation has attracted the attention of several research groups. The interest on this hydrogen source is focused on the potential use of this gas as raw material to supply high temperature fuel cells (HTFC). This paper reports a wide research investigation carried out at CNR-ITAE on biogas reforming processes (steam reforming, autothermal reforming and partial oxidation). A mathematical model was developed, in Aspen Plus, and an experimental validation was made in order to confirm model results. Simulations were performed to determine the reformed gas composition and the system energy balance as a function of process temperature and pressure. The value of Gas Hour Space Velocity (GHSV) was selected for calculating compositions at full equilibrium, as it is expected in operative large scale plant. To obtain a realistic evaluation of the reforming processes efficiency, the energy balance for each examined process was developed as available energy of outlet syngas on inlet required energy ratio. The comparison between values of efficiency process gives useful indication about their reliability to be integrate with fuel cell systems.     

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.     

Autothermal reforming of gasoline for fuel cell applications: Controller design and analysis

In this work, we address the control system options available to an autothermal reforming (ATR) reactor. The targeted application is within an on-board fuel processor for a hydrogen-fed low-temperature fuel cell. The feedback controller employs air feed rate as the manipulated variable and a measurement of catalyst temperature as the control variable. Disturbances include significant fluctuations in the measured temperature as well as large throughput changes, owning to the on-board application. Our investigation includes an analysis of a simple feedback configuration as well as feed-forward control structure. It is concluded that the feedback only method is insufficient for the unique challenges associated with on-board operation, which include fast start-up and quick load changes. While the feed-forward configuration improves performance, we found a fair amount of sensitivity with respect to model mismatch. The general conclusion is that some form of advanced control will be needed to meet the stringent performance requirements of the on-board fuel processor application.     

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.     

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.     

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.     

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.     

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).     

Exergy analysis of an integrated fuel processor and fuel cell (FP–FC) system

Fuel cells have great application potential as stationary power plants, as power sources in transportation, and as portable power generators for electronic devices. Most fuel cells currently being developed for use in vehicles and as portable power generators require hydrogen as a fuel. Chemical storage of hydrogen in liquid fuels is considered to be one of the most advantageous options for supplying hydrogen to the cell. In this case a fuel processor is needed to convert the liquid fuel into a hydrogen-rich stream. This paper presents a second-law analysis of an integrated fuel processor and fuel cell system. The following primary fuels are considered: methanol, ethanol, octane, ammonia, and methane. The maximum amount of electrical work and corresponding heat effects produced from these fuels are evaluated. An exergy analysis is performed for a methanol processor integrated with a proton exchange membrane fuel cell, for use as a portable power generator. The integrated FP–FC system, which can produce 100 W of electricity, is simulated with a computer model using the flow-sheeting program Aspen Plus. The influence of various operating conditions on the system efficiency is investigated, such as the methanol concentration in the feed, the temperature in the reformer and in the fuel cell, as well as the fuel cell efficiency. Finally, it is shown that the calculated overall exergetic efficiency of the FP–FC system is higher than that of typical combustion engines and rechargeable batteries.     

Power generation using a mesoscale fuel cell integrated with a microscale fuel processor

An integrated fuel reformer and fuel cell system for microscale (10–500 mW) power generation is being developed and demonstrated as an alternative to conventional batteries. In this system, thermal energy is transformed to electricity by stripping the hydrogen from the hydrocarbon fuel (reforming) and converting the hydrogen to electricity in a proton exchange membrane (PEM) fuel cell. The fabrication and operation of a mesoscale fuel cell based on phosphoric acid doped polybenzimidazole (PBI) technology is discussed, along with tests integrating the methanol processor with the fuel cell. The PBI membrane had high ionic conductivity at high temperatures (>150 °C), and sustained the high conductivity at low relative humidity at these temperatures. This high-temperature stability and high ionic conductivity enabled the membrane to tolerate extremely high levels of carbon monoxide up to 10% without significant degradation in performance. The combined fuel cell/reformer system was successfully operated to enable the production of 23 mW of electrical power.     

Development of biogas reforming Ni-La-Al catalysts for fuel cells

In this work, the results obtained for Ni-La-Al catalysts developed in our laboratory for biogas reforming are presented. The catalyst 5% Ni/5% La₂O₃-γ-Al₂O₃ has operated under kinetic control conditions for more than 40 h at 700 °C and feeding CH₄/CO₂ ratio 1/1, similar to the composition presented in biogas streams, being observed a stable behaviour.     

Critical issues in heat transfer for fuel cell systems

The current state of the art in fuel cell system development will be reviewed with an emphasis of the critical issues on heat transfer.

The heat transfer issues for both PEM based systems and SOFC based fuel cell systems will be addressed.

For systems that are based on hydrocarbon fuels a reforming step is needed and critical heat transfer issues are also present in this fuel processing part of the system where the primary feedstock is converted to reformate. Also, in both the PEM and SOFC fuel cell itself, heat transfer is a critical issue. It will be shown what are the implications of the fuel cell heat transfer to the total system architecture for the various fuel cell applications (stationary power, transport).

The heat transfer issues in fuel cell system development will be clarified with several examples.     

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%.     

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.     

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.     

Effects of methane processing strategy on fuel composition,electrical and thermal efficiency of solid oxide fuel cell

Natural gas is a cheap and abundant fuel for solid oxide fuel cell (SOFC), generally integrating the SOFC system with methane pre-treating system for improving the stability of SOFC. In this paper, the accurate effects of methane processing strategy on fuel composition, electrical efficiency and thermal efficiency of SOFC are investigated based on the thermodynamic equilibrium. Steam reforming of methane is an endothermic process and can produce 3 mol of H₂ and 1 mol of CO from 1 mol of methane, and thus the electrical efficiency of SOFC is high at the same O/C ratio and equivalent fuel utilization, whereas the thermal efficiency is low. On the contrary, partial oxidation of methane is an exothermal process and only produces 2 mol of H₂ and 1 mol of CO from 1 mol of methane, and thus the electrical efficiency of SOFC is low at the same O/C ratio and equivalent fuel utilization, whereas the thermal efficiency is high. When the O/C ratio is 1.5, the electrical efficiency of SOFC is 55.3% for steam reforming of methane, while 32.7% for partial oxidation of methane. High electrical efficiency of SOFC can be achieved and carbon deposition can be depressed by selecting suitable O/C ratio from methane pretreatment according to the accurate calculation and analysis of effects of different methane processing strategies on the electrical efficiency and thermal efficiency of SOFC.     

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.     

Hydrogen production by natural gas in a compact ATR-based kW-scale fuel processor

In the present work, the design and testing of a very compact reaction system thermally integrated for the distributed hydrogen production by natural gas reforming is reported. The system is based on hydrocarbon Auto-Thermal Reforming, followed by a Water-Gas Shift module. A compact heat exchanger was placed between the two catalytic stages, in order to assure an appropriate thermal integration, thus avoiding any other external heat duties. Experimental results demonstrated that the integrated configuration assured a good management of thermal fluxes in the system, in which an effective heat recovery from ATR exhaust gas to reactants was realized. Preliminary tests showed very impressive performances of the system, both by processing methane and natural gas. Despite a quite inefficient WGS stage, the processor was able to produce up to 10 Nm³/h of hydrogen, assuring a thermal efficiency higher than traditional systems.     

Preliminary design of a small-scale system for the conversion of biogas to electricity by HT-PEM fuel cell

In this work a novel concept for the decentralized conversion of biogas to electricity is introduced. It consists of five segments: gas supply, gas treatment, gas reforming, gas usage and post-combustion. The system was designed in a regional project called GREEN-FC. The project is dealing with a design study for the conversion of 1 m³ h⁻¹ biogas to electricity, based on equilibrium calculations for steam reforming and water–gas shift reaction in combination with CFD simulations. The simulation results revealed that the system converts methane fully and delivers a maximum yield of hydrogen with a low concentration of carbon monoxide, thus making it suitable for a high-temperature polymer–electrolyte membrane (HT-PEM) fuel cell. The calculated electrical efficiency of the novel process is approximately 40%. Another important result of this work is the modular prototype design, because the individual components of the prototype can be replaced. For example alternative reactors that convert biogas into hydrogen and other technologies that use hydrogen can be included.     

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.