A 75-kW methanol reforming fuel cell system

A 75-kW methanol reforming fuel cell system, which consists of a fuel cell system and a methanol auto-thermal reforming fuel processor has been developed at Dalian Institute of Chemical Physics, Chinese Academy of Sciences (CAS). The core of the fuel cell system is a group of CO tolerant PEMFC stacks with a double layer composite structured anode. The fuel cell stacks show good CO tolerance even though 140 ppm CO was present in the reformate stream during transients. The auto-thermal reforming (ATR) fuel cell processor could adiabatically produce a suitable reformate without external energy consumption. The output of hydrogen-rich reformate was approximately 120 N m³ h⁻¹ with a H₂ content near 53% and the CO concentrations generally were under 30 ppm. The fuel cell system was integrated with the methanol reforming fuel processor and the peak power output of the fuel cell system exceeded 75 kW in testing. The hydrogen utilization approached 70% in the fuel cell system.     

Design and development of a diesel and JP-8 logistic fuel processor

The paper describes the design and performance of a breadboard prototype for a 5 kW fuel-processor for powering a solid oxide fuel cell (SOFC) stack. The system was based on a small, modular catalytic Microlith auto-thermal (ATR) reactor with the versatility of operating on diesel, Jet-A or JP-8 fuels. The reforming reactor utilized Microlith substrates and catalyst technology (patented and trademarked). These reactors have demonstrated the capability of efficiently reforming liquid and gaseous hydrocarbon fuels at exceptionally high power densities. The performance characteristics of the auto-thermal reactor (ATR) have been presented along with durability data. The fuel processor integrates fuel preparation, steam generation, sulfur removal, pumps, blowers and controls. The system design was developed via ASPEN^® Engineering Suite process simulation software and was analyzed with reference to system balance requirements. Since the fuel processor has not been integrated with a fuel cell, aspects of thermal integration with the stack have not been specifically addressed.     

Diesel fuel processor for PEM fuel cells: Two possible alternatives (ATR versus SR)

There are large efforts in exploring the on-board reforming technologies, which would avoid the actual lack of hydrogen infrastructure and related safety issues. From this view point, the present work deals with the comparison between two different 10 kW_e fuel processors (FP) systems for the production of hydrogen-rich fuel gas starting from diesel oil, based respectively on autothermal (ATR) and steam-reforming (SR) process and related CO clean-up technologies; the obtained hydrogen rich gas is fed to the PEMFC stack of an auxiliary power unit (APU). Based on a series of simulations with Matlab/Simulink, the two systems were compared in terms of FP and APU efficiency, hydrogen concentration fed to the FC, water balance and process scheme complexity. Notwithstanding a slightly higher process scheme complexity and a slightly more difficult water recovery, the FP based on the SR scheme, as compared to the ATR one, shows higher efficiency and larger hydrogen concentration for the stream fed to the PEMFC anode, which represent key issues for auxiliary power generation based on FCs as compared, e.g. to alternators.     

Chemical looping reforming of ethanol for syngas generation: A theoretical investigation

Chemical looping reforming (CLR) is a novel technology that can be used for reforming of cheaply available abundant biofuel like ethanol for the production of hydrogen/syngas for fuel cells. A systematic thermodynamic study for the CLR process using selected oxygen carriers was done to analyze the products and energy requirements of the CLR process in the temperature range of 500–1200 °C at 1 bar pressure for ethanol. The results showed favorable conditions for syngas manufacture from this process. Fe₂O₃ was found to be the best performing oxygen carrier followed by calcium and sodium sulfates, while Mn oxides were the least preferred oxygen carriers for CLR of ethanol process. The optimum process temperature was found to be 1000 °C. The actual CLR‐ethanol process shows exothermicity against the theoretical endothermic partial oxidation of ethanol. The results obtained in this theoretical study can pave the way for experimental programs for syngas generation for SOFC‐type fuel cells. Similar studies can be undertaken for other fuels for fuel processor development by CLR process. Copyright © 2012 John Wiley & Sons, Ltd.     

On-board reforming of biodiesel and bioethanol for high temperature PEM fuel cells: Comparison of autothermal reforming and steam reforming

In the 21st century biofuels will play an important role as alternative fuels in the transportation sector. In this paper different reforming options (steam reforming (SR) and autothermal reforming (ATR)) for the on-board conversion of bioethanol and biodiesel into a hydrogen-rich gas suitable for high temperature PEM (HTPEM) fuel cells are investigated using the simulation tool Aspen Plus. Special emphasis is placed on thermal heat integration. Methyl-oleate (C₁₉H₃₆O₂) is chosen as reference substance for biodiesel. Bioethanol is represented by ethanol (C₂H₅OH). For the steam reforming concept with heat integration a maximum fuel processing efficiency of 75.6% (76.3%) is obtained for biodiesel (bioethanol) at S/C = 3. For the autothermal reforming concept with heat integration a maximum fuel processing efficiency of 74.1% (75.1%) is obtained for biodiesel (bioethanol) at S/C = 2 and λ = 0.36 (0.35). Taking into account the better dynamic behaviour and lower system complexity of the reforming concept based on ATR, autothermal reforming in combination with a water gas shift reactor is considered as the preferred option for on-board reforming of biodiesel and bioethanol. Based on the simulation results optimum operating conditions for a novel 5 kW biofuel processor are derived.     

Technical design and economic evaluation of a PEM fuel cell system

The main objectives of this study are to develop the economic models and their characterization trends for the common unit processes and utilities in the fuel cell system. In this study, a proton electrolyte membrane fuel cell (PEMFC) system is taken as a case study. The overall system consists of five major units, namely auto-thermal reformer (ATR), water gas shift reactor (WGS), membrane, pressure swing adsorber (PSA) and fuel cell stack. Besides that, the process utilities like compressor, heat exchanger, water adsorber are also included in the system. From the result, it is determined that the specific cost of a PEM fuel cell stack is about US$ 500 per kW, while the specific manufacturing and capital investment costs are in the range of US$ 1200 per kW and US$ 2900 per kW, respectively. Besides that the electricity cost is calculated as US$ 0.04 kWh. The results also prove that the cost of PEM fuel cell system is comparable with other conventional internal engine.     

Hydrogen-rich syngas production and carbon dioxide formation using aqueous urea solution in biogas steam reforming by thermodynamic analysis

Biogas is a renewable biofuel that contains a lot of CH₄ and CO₂. Biogas can be used to produce heat and electric power while reducing CH₄, one of greenhouse gas emissions. As a result, it has been getting increasing academic attention. There are some application ways of biogas; biogas can produce hydrogen to feed a fuel cell by reforming process. Urea is also a hydrogen carrier and could produce hydrogen by steam reforming. This study then employes steam reforming of biogas and compares hydrogen-rich syngas production and carbon dioxide with various methane concentrations using steam and aqueous urea solution (AUS) by Thermodynamic analysis. The results show that the utilization of AUS as a replacement for steam enriches the production of H₂ and CO and has a slight CO₂ rise compared with pure biogas steam reforming at a temperature higher than 800 °C. However, CO₂ formation is less than the initial CO₂ in biogas. At the reaction temperature of 700 °C, carbon formation does not occur in the reforming process for steam/biogas ratios higher than 2. These conditions led to the highest H₂, CO production, and reforming efficiency (about 125%). The results can be used as operation data for systems that combine biogas reforming and applied to solid oxide fuel cell (SOFC), which usually operates between 700 °C to 900 °C to generate electric power in the future.     

Techno-economic assessment of a chemical looping reforming combined cycle plant with iron and tungsten based oxygen carriers

Chemical looping reforming (CLR) is an efficient technology that transforms hydrocarbons into hydrogen (H₂) and carbon dioxide (CO₂) with the use of an oxygen carrier. The three-reactor CLR (TRCLR) uses natural gas as fuel similar to a conventional steam-methane reforming (SMR) process. In the current study, two of the most suitable oxygen carriers with base metals iron (Fe) and tungsten (W) are investigated. The model of the CLR unit integrated with a combined cycle power plant is developed using Aspen Plus. The results show that the W-based TRCLR plants are 4 %-points more efficient in terms of H₂ production efficiency. In terms of electrical efficiency, the Fe-based TRCLR plant produces excess power at an efficiency of 1.6% whereas the W-based plant requires 3% of extra power from the grid. As a result, the Fe-based plant is 2.6 %-points more efficient than the W-based plant in terms of global efficiency. The costs of H₂ production for the Fe and W-based plants are estimated to be $1.66/kg and $16.92/kg, respectively. Compared to the SMR process, the cost of H₂ production from the Fe-based TRCLR plant is about 31% lower.     

Temperature and hydrogen flow rate controls of diesel autothermal reformer for 3.6 kW PEM fuel cell system with autoignition delay time analysis

In this paper catalyst temperature and hydrogen flow rate controls are an area of interest for autothermal reforming (ATR) of diesel fuel to provide continuous and necessary hydrogen flow to the on-board fuel cell vehicle system. ATR control system design is important to ensure proper and stable performance of fuel processor and fuel cell stack. Fast system response is required for varying load changes in the on-board fuel cell system. To cope with control objectives, a combination of PI and PID controllers are proposed to keep the controlled variables on their setpoints. ATR catalyst temperature is controlled with feedback PID controller through variable OCR (oxygen to carbon ratio) manipulation and kept to the setpoint value of 900 °C. Additionally diesel auto-ignition delay time is implemented through fuel flow rate delay to avoid complete oxidation of fuel. Hydrogen flow rate to the fuel cell stack is kept to setpoint of required hydrogen flow rate according to fuel cell load current using PI controller. An integrated dynamic model of fuel processor and fuel cell stack is also developed to check the fuel cell voltage. Product gas composition of 35, 18 and 4% is achieved for hydrogen, nitrogen, and carbon dioxide, respectively. The results show fast response capabilities of fuel processor following the fuel cell load change and successfully fulfills the control objectives.     

Development of a robust and efficient biogas processor for hydrogen production. Part 1: Modelling and simulation

The present work deals with the modelling and simulation of a biogas Demo-processor for green hydrogen production via Autothermal reforming (ATR) process aimed at covering a wide span of potential applications, from fuel cells feed up to the production of pure hydrogen. The biogas ATR unit is composed of a structured catalyst support close coupled to a wall-flow filter that retain soot particles that can be formed during the ATR reaction. Modelling and simulation (CFD and FEM) were carried out to select the innovative catalyst support with promising results for the fuel processor. 3D digital sample reconstruction was performed for the selection of the appropriate porous structures commercially available for the soot filtration and furthermore, 2D CFD analysis was also used to examine flow uniformity issues due to soot trap integration downstream to the ATR. Moreover, the inherent flexibility of the model performed allowed its application in the assessment of the Demonstration plant operating in real conditions. Besides, Aspen simulation has demonstrated that the ATR process is the most promising process to hydrogen production compared to other types of reforming process.     

Final step for CO syngas clean-up: Comparison between CO-PROX and CO-SMET processes

The performance of the CO preferential oxidation (PROX) process was compared with the CO selective methanation (SMET) one, both applied as the last clean-up process step of a fuel processor unit (FPU) to remove CO from syngas. The FPU was completed with the reformer (autothermal reformer ATR or steam reformer SR) and a non-isothermal water gas shift (NI-WGS) reactor. Furthermore, the reforming of different hydrocarbon fuels, among those most commonly found in service stations (gasoline, light diesel oil and compressed natural gas) was examined. The comparison, in terms of different FPU configurations and fuels, was carried out by a series of steady-state system simulations in Aspen Plus^®. From the obtained data, the performance of CO-PROX was not very different from that of CO-SMET, making it complex to give a definitive answer on the best FPU scheme. The most promising fuel processor with respect to performance is a chain of ATR, NI-WGS and CO-SMET. However, maintaining the same chain of clean-up reactors, the FPU with SR instead of ATR could also be a satisfactory choice. Even if there are lower efficiencies and H₂ specific production compared to the ATR-based FPU, the SR-based one does not produce a syngas with the high N₂ concentration typical of the ATR-based FPU. The syngas dilution by nitrogen is somehow detrimental for the stack efficiency, when syngas feeds PEM-FCs, since it lowers the polarization curve.     

Fast starting fuel processor for automotive fuel cell systems

A fuel processor was constructed which incorporated two burners with direct steam generation by water injection into the burner exhaust. These burners with direct water vaporization enabled rapid fuel processor start-up for automotive fuel cell systems. The fuel processor consisted of a conventional chain of reactors: auto-thermal reformer (ATR), water gas shift (WGS) reactor and preferential oxidation (PrOx) reactor. The criticality of steam to the fuel reforming process was illustrated. By utilizing direct vaporization of water, and hydrogen for catalyst light-off, excellent start performance was obtained with a start time of 20 s to 30% power and 140 s to full power.     

Development of a robust and efficient biogas processor for hydrogen production. Part 2: Experimental campaign

In this study, a robust and efficient decentralized fuel processor based on the direct autothermal reforming (ATR) of biogas with a nominal production rate of 50 Nm³/h of hydrogen and a plant efficiency of about 65% was developed and tested. The ATR unit is composed of a structured catalyst support for the biogas reforming close coupled to a catalytic wall-flow filter to retain eventual soot particles.The performance of the conventional random foam and homogeneous lattice supports structures for the production of hydrogen from the ATR reaction was investigated. 15–0.05 wt%-Ni-Rh/MgAl₂O₄-SiSiC structured catalyst and LiFeO₂-SiC monolith were selected for the conversion of biogas to hydrogen and for the syngas post-treatment process, respectively. For all the experiments, a model synthetic biogas was used and the catalytic activities were evaluated in three different experimental facilities: lab bench, pilot test rig and demonstration plant. High methane conversions (>95%) and hydrogen yields (>1.8) reached in the lab bench were also achieved in the pilot and demonstration plant operating at different GHSV.Results of duration test using a foam coupled to the filter has demonstrated that the pre-commercial processor is reliable while offering a satisfactory reproducibility and negligible pressure drop. A thermodynamic equilibrium and a cold gas efficiency of 90% were reached for an inlet temperature of 500 °C, O/C: 1.1 and S/C: 2.0, as predicted with the Aspen simulation.     

Selection of appropriate primary fuel for hydrogen production for different fuel cell types: Comparison between decomposition and steam reforming

In order to select a proper hydrogen production system being compatible with fuel cell, a variety of interesting primary fuels such as light hydrocarbons and alcohols were tested in the decomposition (D) and the steam reforming (SR) processes by thermodynamic approach. The reaction performances of the systems particularly under thermally self-sustained condition were focused on. To obtain self-sustained condition, two approaches, splitting feed and splitting gas product streams to the burner for heat supply to endothermic hydrogen processor, are investigated. Our results revealed that splitting gas product gave higher carbon capture than splitting feed but lower in hydrogen yield. As expected, steam reforming provides higher hydrogen production, however, lower in hydrogen purity and carbon capture comparing to decomposition process. By considering primary fuels, D-alcohols could be applied to MCFC and SOFC, among these, D-C₂H₅OH was preferable because it gives the highest ratio of H₂/CO. For D-light hydrocarbon systems, which is operated at 1100 K providing 97% hydrogen purity, is suitable to be connected to MCFC, SOFC and also PEMFC.     

LCA evaluation for the hydrogen production from biogas through the innovative BioRobur project concept

BioRobur is a project aimed to produce hydrogen from biogas through an auto-thermal reforming (ATR) process, in which innovative catalytic systems are used to promote the ATR reactions involved in the process for the conversion of biogas into syngas. A detailed LCA study of hydrogen production from biogas ATR using the BioRobur technology has been performed. LCA analysis has been also conducted for other two conventional processes for the production of hydrogen from biogas: the steam reforming and water hydrolysis (a biogas-fueled Internal Combustion engine (ICE) followed by an Electrolyser). A comparison between these technologies has been made from both the environmental and the energetic viewpoints. The LCA has demonstrated that BioRobur is the most environmentally friendly of considered processes. Moreover, the ICE plus Electrolyser has resulted to be the because of the very large amount of biogas needed for the least efficient process, due to the low conversion yield of biogas into energy of the ICE.     

Key issues in the microchemical systems-based methanol fuel processor: Energy density,thermal integration,and heat loss mechanisms

Microreactor technology is a promising approach in harnessing the high energy density of hydrocarbons and is being used to produce hydrogen-rich gases by reforming of methanol and other liquid hydrocarbons. However, on-demand H₂ generation for miniature proton exchange membrane fuel cell (PEMFC) systems has been a bottleneck problem, which has limited the development and demonstration of the PEMFC for high-performance portable power. A number of crucial challenges exist for the realization of practical portable fuel processors. Among these, the management of heat in a compact format is perhaps the most crucial challenge for portable fuel processors. In this study, a silicon microreactor-based catalytic methanol steam reforming reactor was designed, fabricated, and demonstrated in the context of complete thermal integration to understand this critical issue and develop a knowledge base required to rationally design and integrate the microchemical components of a fuel processor. Detailed thermal and reaction experiments were carried out to demonstrate the potential of microreactor-based on-demand H₂ generation. Based on thermal characterization experiments, the heat loss mechanisms and effective convective heat coefficients from the planar microreactor structure were determined and suggestions were made for scale up and implementation of packaging schemes to reduce different modes of heat losses.     

Fuel cell feed system based on H2 production by a compact multi-fuel catalytic ATR reactor

Hydrogen fuel cells seem the most viable solution to the pollution reduction and the energy growing demand. Very compact and small size production plant for distribute H₂ production may reduce hydrogen transport and storage difficulties. Due to the high reactor compactness and thermal self-sustainability, the auto-thermal reforming (ATR) reaction of gaseous and liquid hydrocarbons can be the optimal solution. Fossil hydrocarbons like methane, gasoline and diesel still remain the favourite feed for catalytic auto-thermal reformer, due to the widespread existing delivery pipelines and the high energy density. Unfortunately, due to the different characteristics of liquid and gaseous fuels, it's very difficult to realize a multi-fuel processor characterized by high performances in terms of thermal efficiency and hydrogen yield, and, up to now, very low number of papers dealing with multi-fuel reformers is present in the literature.     

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.     

Overview of hydrogen production from biogas reforming: Technological advancement

In this article, possibilities of biogas reforming techniques for hydrogen production are discussed. The consideration of biogas reforming to produce H₂ and fuel cell application from membrane technology is presented. In steam reforming process, methane requires a high temperature for reaction, but a suitable catalyst can manage a higher temperature. The ratio of H₂/CO is close to 3, which means higher H₂ yield (above 70%). The ratio of H₂/CO to nearly 2 and H₂ yield almost 67% and also reduces the soot formation for partial oxidation process. In Auto thermal reforming, higher yield of H₂ is around 74% with the ratio of H₂/CO close to 2.8. The dry reforming process leads to a molar ratio H₂/CO of nearly one and H₂ yield of approximately 50%. The ratio of H₂/CO correspondingly improves and generates H₂ yield of approximately 60% for dry oxidation reforming process. For sustainable decentralized power generation in remote and rural areas, large-scale development of H₂ energy technology is required. Biogas reforming is an auspicious process for the production of green hydrogen gas as well as for reducing overburden on natural gas. The main benefit of using biogas for H₂ production as a renewable energy source is reducing excessive burden on natural gas and greenhouse gas emissions. Nowadays, the importance of renewable H₂ production has increased due to many reasons such as depletion of fossil fuel reserves, global environmental issues, energy issues, and demand for pure H₂.     

A review of biomass-derived fuel processors for fuel cell systems

Fuel cell coupled with biomass-derived fuel processor can convert renewable energy into a useful form in an environmental-friendly and CO₂-neutral manner. It is considered as one of the most promising energy supply systems in the future. Biomass-derived fuels, such as ethanol, methanol, biodiesel, glycerol, and biogas, can be fed to a fuel processor as a raw fuel for reforming by autothermal reforming, steam reforming, partial oxidation, or other reforming methods. Catalysts play an important role in the fuel processor to convert biomass fuels with high hydrogen selectivity. The processor configuration is another crucial factor determining the application and the performance of a biomass fuel processing system. The newly developed monolithic reactor, micro-reactor, and internal reforming technologies have demonstrated that they are robust in converting a wide range of biomass fuels with high efficiency. This paper provides a review of the biomass-derived fuel processing technologies from various perspectives including the feedstock, reforming mechanisms, catalysts, and processor configurations. The research challenges and future development of biomass fuel processor are also discussed.