Investigation of a methanol processing system comprising of a steam reformer and two preferential oxidation reactors for fuel cells

Methanol steam reforming is able to produce hydrogen-rich syngas onsite for fuel cells and avoids the problems of hydrogen storage. Nevertheless, CO in the reformate needs to be further removed to ppm level before it can be fed into proton exchange membrane fuel cells. In this study, a methanol processing system consisting of a methanol reformer and two-stage preferential oxidation reactors is developed. The hydrogen production performance and scalability of the reformer are experimentally investigated under various operating conditions. The methanol reformer system shows stable methanol conversion rate and linearly increased H₂ flow rate as the number of repeating unit increases. Methanol conversion rate of 96.8% with CO concentration of 1.78% are achieved in the scaled-up system. CO cleanup ability of the two-stage preferential oxidation reactors is experimentally investigated based on the reformate compositions by varying the operating temperature and O₂ to CO ratios. The results demonstrate that the developed CO cleanup train can decrease the CO concentration from 1.6% to below 10 ppm, which meets the requirement of the fuel cell. Finally, stability of the integrated methanol processing system is tested for 180 h operation.     

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.     

Ethanol reforming for hydrogen production in a hybrid electric vehicle: process optimisation

This work is focused at optimizing an ethanol reforming process over a Ni/Cu catalyst to produce a hydrogen rich stream in order to feed a solid polymer fuel cell (SPFC). The effect of the reaction temperature, H₂O/EtOH and O₂/EtOH molar ratios of the feed to the reformer was studied under diluted conditions in order to maximize the hydrogen content and the CO₂/CO_x molar ratio at the outlet of the ethanol reformer. Based on the experimental results, a detailed kinetic scheme of the ethanol reforming was discussed as a function of the temperature, special attention was paid to the role of oxygen in the reaction selectivity and coke formation. Moreover, the coke nature was evaluated by transmission electron microscopy (TEM) and TPO and TPH experiments. The tests carried out at on-board reformer conditions allowed a hydrogen rich mixture (33%) in the outlet reformer flow that can be even increased by water gas sift reactions downstream. The high hydrogen content of the flow to the fuel cell together with the stability of the Ni/Cu catalyst, fully demonstrated by long time runs, can be considered of high interest for SPFC applications.     

Combustion chemistry aspects of alternative fuels reforming for high-temperature fuel cell applications

Solid-oxide fuel cells (SOFC) constitute a particularly attractive technology for sustainable, combined heat and power generation, both at domestic and district levels. The elevated operating temperature of SOFC systems, allows the utilization of a wide spectrum of conventional and alternative fuels, through suitable reforming processes. The high temperatures and fuel rich conditions prevailing in SOFC reformers, enhance syngas yield and reforming efficiency but may give rise to unwanted effects, such as ignition, soot and coke formation and deposition. The above phenomena cannot be described via thermodynamic considerations and can only be effectively tackled through a detailed chemical kinetic approach. The present study provides a comparative assessment of SOFC reformer operation on conventional and alternative hydrocarbon fuels in terms of syngas yield, thermal efficiency and pollutants formation. In particular, the reforming of methane, a typical biogas (comprising of 60% CH₄ and 40% CO₂), methanol and ethanol is numerically assessed by utilizing a recently developed and validated comprehensive detailed kinetic mechanism for C₁–C₆ hydrocarbons, augmented with a PAH model. Chemical aspects of the fuel reforming process are investigated through rate-of-production path and sensitivity analyses. The study supports design guidelines aiming towards identification of optimum operating conditions, for specific applications and fuels. The analysis reveals that the extent of coupling between syngas formation and molecular growth processes is strongly dependent on fuel and operating conditions choice and identifies windows of efficient operation, for each case.     

Conversion of jet fuel and butanol to syngas by filtration combustion

Replacing batteries with fuel cells is a promising approach for powering portable devices; however, hydrogen fuel generation and storage are challenges to the acceptance of this technology. A potential solution to this problem is on-site fuel reforming, in which a rich fuel/air mixture is converted to a hydrogen-rich syngas. In this paper, we present experimental results of the conversion of jet fuel (Jet-A) and butanol to syngas by non-catalytic filtration combustion in a porous media reactor operating over a wide range of equivalence ratios and inlet velocities. Since the focus of this study is the production of syngas, our primary results are the hydrogen yield, the carbon monoxide yield, and the energy conversion efficiency. In addition, the production of soot that occurred during testing is discussed for both fuels. Finally, an analysis of the potential for these fuels and others to be converted to syngas based on the present experiments and data available in the literature is presented. This study is intended to increase the understanding of filtration combustion for syngas production and to illuminate the potential of these fuels for conversion to syngas by non-catalytic methods.     

Fuel flexibility study of an integrated 25 kW SOFC reformer system

The operation of solid oxide fuel cells on various fuels, such as natural gas, biogas and gases derived from biomass or coal gasification and distillate fuel reforming has been an active area of SOFC research in recent years. In this study, we develop a theoretical understanding and thermodynamic simulation capability for investigation of an integrated SOFC reformer system operating on various fuels. The theoretical understanding and simulation results suggest that significant thermal management challenges may result from the use of different types of fuels in the same integrated fuel cell reformer system. Syngas derived from coal is simulated according to specifications from high-temperature entrained bed coal gasifiers. Diesel syngas is approximated from data obtained in a previous NFCRC study of JP-8 and diesel operation of the integrated 25 kW SOFC reformer system. The syngas streams consist of mixtures of hydrogen, carbon monoxide, carbon dioxide, methane and nitrogen. Although the SOFC can tolerate a wide variety in fuel composition, the current analyses suggest that performance of integrated SOFC reformer systems may require significant operating condition changes and/or system design changes in order to operate well on this variety of fuels.     

Concept design of a novel reformer producing hydrogen for internal combustion engines using fuel decomposition method: Performance evaluation of coated monolith suitable for on-board applications

Hydrogen addition effectively reduces the fuel consumption of spark ignition engines. We propose a new on-board reformer that produces hydrogen at high concentrations and enables multi-mode operations. For the proposed reformer, we employ a catalytic fuel decomposition reaction via a commercial NiO–CaAl₂O₄ catalyst. We explore the physical and chemical aspects of the reforming process using a fixed bed micro-reactor operating at temperatures of 550–700 °C. During reduction, methane is decomposed to form hydrogen and carbon. Carbon formation is critical to hydrogen production, and free space for carbon growth is essential at low temperatures (≤600 °C). We define a new accumulated conversion ratio that quantitatively measures highly transient catalytic decomposition. The free space of the coated monolith clearly aided low-temperature decomposition with negligible pressure drop. The coated substrate is therefore suitable for on-board applications considering that our reformer concept also utilizes the catalytic fuel decomposition reaction.     

Optimization of Jet-A fuel reforming for aerospace applications

This paper focuses on the optimization of Jet-A fuel reforming for use with solid-oxide fuel cells in aerospace applications. Because of the specialized operating conditions and reforming requirements, a broad range of reforming inlet conditions need to be considered. Both equilibrium calculations for reforming of a Jet-A surrogate and zero-dimensional modeling with detailed chemistry for reforming of a kerosene surrogate are performed over a wide range of conditions with varying inlet temperature, operating pressure, steam-to-carbon ratio, and oxygen-to-carbon ratio. While equilibrium calculations provide some insight into the efficiency of the final reformer, the kinetics modeling can account for the finite residence time of the gas within the reformer. Calculations using finite-rate gas-phase chemistry indicate that the most efficient mode of reforming is achieved using a short-contact partial oxidation reactor operating with minimal water addition. Certain factors to consider for the development of a future catalytic reformer, such as local hot-spots and coke deposition on the catalyst, are also discussed.     

Bio-fuel reformation for solid oxide fuel cell applications. Part 3: Biodiesel–diesel blends

The auto-thermal reforming (ATR) performance of diesel blended with biodiesel (e.g., B5, B10, B20, B40, and B80) was investigated and compared to pure diesel and biodiesel ATR in a single-tube reformer with ceramic monolith wash-coated rhodium/ceria–zirconia catalyst. The initial operating condition of the ATR of all studied fuels was set as total moles of oxygen from air, water, and fuel per mole of carbon (O/C) = 1.47, moles of water to carbon (H₂O/C) = 0.6, and gas hourly space velocity = 33,950 h⁻¹ at 1223 K reformer temperature, to achieve the same syngas (H₂ + CO) production rate. A direct photo-acoustic micro-soot meter was applied to quantify the dynamic evolution of carbon formation and a mass spectrometer was used to measure the gas composition of reformer effluents. The blends with more biodiesel content were found to have a lower syngas production rate and reforming efficiency, and require more air and higher reformer temperature to avoid carbon formation. Strong correlations between ethylene and solid carbon concentration were observed in the reformation of all the fuels and blends, with more biodiesel content tending to have higher ethylene production. This study is one component of a three-part investigation of bio-fuel reforming, also including fuel vaporization and reactant mixing (Part 1) and biodiesel (Part 2).     

Hydrogen production from steam reforming of coke oven gas and its utility for indirect reduction of iron oxides in blast furnace

Hydrogen and synthesis gas (syngas) can be produced from steam reforming (SR) of coke oven gas (COG). When the reforming gas is used for indirect reduction (IR) of iron oxides in blast furnaces (BFs), carbon dioxide emissions can be lessened. Motivated from utilizing hydrogen and mitigating greenhouse gas emissions in ironmaking, the reaction phenomena of SR of COG are investigated thermodynamically. Low-temperature and high-temperature IR of iron oxides using reforming gas as a feedstock is also analyzed. With appropriate operating conditions, the maximum H₂ and syngas yields are 3.5 and 4.2 mol (mol fuel)⁻¹, respectively. Two different reforming gases are employed to reduce iron oxides. When the reforming gas/hematite (R/H) molar ratio is no less than 1, Fe₂O₃ conversion is always higher than 98.5%, whether low-temperature or high-temperature IR is carried out. This reveals that COG possesses the potential as a reducing agent in BFs. The reactions of IR from the two reforming gases are almost identical, implying that the operation of SR from COG for producing hydrogen or syngas and reducing iron oxides in BFs is flexible.     

Steam reforming of n-heptane for production of hydrogen and syngas

Simultaneous production of hydrogen and syngas from the catalytic reforming of n-heptane in circulating fast fluidized bed reactors (CFFBR) and circulating fast fluidized bed membrane reactors (CFFBMR) is investigated. This paper presents modeling and simulation approach for the analysis of these reformers. Complete conversion of heptane (100%) is attained at high steam to carbon feed ratios and shorter reactor lengths by both configurations. However, the CFFBMR is very efficient in hydrogen production and can produce exit hydrogen yield up to 473.14% higher than the CFFBR. It was found that operating the CFFBMR at the optimal conditions results in a minimum value of hydrogen to carbon monoxide ratio (H₂/CO) within the recommended practical range for the syngas used as a feedstock for the gas to liquid processes (GTL). The results of the sensitivity analysis conducted for the CFFBMR has shown that the reaction side pressure and the feed temperature have significant effects on increasing the heptane conversion (up to 100%) and the temperature effect is stronger than the reaction side pressure effect. Considerable improvement in the hydrogen to carbon monoxide ratio (H₂/CO) has been achieved by increasing the reaction side pressure, while the high feed temperature has negative effect on this ratio. It seems that the practical range of H₂/CO ratio can be achieved by controlling the reformer length and the right combinations of the operating conditions.     

Characterization of kilowatt-scale autothermal reformer for production of hydrogen from heavy hydrocarbons

Catalytic autothermal reforming is considered one of the most effective methods of producing hydrogen from heavy hydrocarbon fuels, such as diesel fuel, for fuel cell or emissions reduction applications. This article describes an investigation of the reactor characteristics and catalytic efficiency of a kilowatt-scale catalytic autothermal reformer currently being developed at Argonne National Laboratory. Dodecane and hexadecane were used individually as surrogates for diesel fuels to simply the reaction study and the interpretation of the test results. The reforming of these hydrocarbon fuels was examined at a variety of oxygen-to-carbon and steam-to-carbon ratios at gas hourly space velocities ranging from 10,000 to 100,000 h⁻¹. At steady state, the product composition correlated well with that calculated from thermodynamic equilibrium at a representative equivalent temperature. The oxygen-to-carbon ratio was determined to be the most significant operating parameter that influenced the reforming efficiency; the reforming efficiency (and the selectivity to CO_x) increased with increasing oxygen-to-carbon ratio up to about 0.42, at which value the maximum efficiency was attained.     

Hydrogen rich gas production by the autothermal reforming of biodiesel (FAME) for utilization in the solid-oxide fuel cells: A thermodynamic analysis

The thermodynamics of the autothermal reforming (ATR) of biodiesel (FAME) for production of hydrogen is simulated and evaluated using Gibbs free minimization method. Simulations are performed with water-biodiesel molar feed ratios (WBFR) between 3 and 12, and oxygen-biodiesel molar feed ratio (O_XBFR) from 0 to 4.8 at reaction temperature between 300 and 800 °C at 1 atm. Yields of H₂ and CO are calculated as functions of WBFR, O_XBFR and temperature at 1 atm. Hydrogen rich gas can be produced by the ATR of biodiesel for utilization in solid-oxide fuel cells (SOFCs). The best operating conditions for the ATR reformer are WBFR≥9 and O_XBFR = 4.8 at 800 °C by optimization of the operating parameters. Yields of hydrogen and carbon monoxide are 68.80% and 91.66% with 54.14% and 39.2% selectivities respectively at the above conditions. The hydrogen yield from biodiesel is higher than from unmodified oils i.e., transesterification increases hydrogen yield. Increase in saturation of the esters, results in increase in methane selectivity, while an increase in unsaturation results in a decrease in methane selectivity. Increase in degree of both saturation and unsaturation of esters, increases coke selectivity. Similarly an increase in the linoleic content of esters, increases coke selectivity.     

Numerical prediction of operating characteristics of micro-gas turbine combustor with on-board reformed EGR system using co-simulation model and 1D reduced model

In this study, an on-board reforming gas turbine system was proposed to expend the combustion stability and operating points of as gas turbine combustor aiming for fuel lean condition. On-board reforming does not store the syngas unlike the existing conventional reforming device, but formed syngas as the operating load changes and participates in combustion. In previous research conducted for this study, a concept single nozzle combustor was designed that satisfies the thermal output of 150 kW and the turbine inlet temperature of 1200 K. In addition, by designing a non-catalytic partial oxidation-based concept reformer, syngas formation was confirmed in various operation points. In previous research, closed-loop analysis was performed to analyze the independent effects of combustor and reformer. However, in this study, open-loop analysis that simulates the combustor and reformer simultaneously was performed to analyze the effect of the combined system at various operating points. As a result, improved combustion was confirmed by the generation of OH radicals when the oxidizing agent was diluted with increasing hydrogen content. This is similar to the lean OH radical distribution in a low-oxidizing environment, which is the basic characteristics of moderate or intense low-oxygen dilution combustion. The reformer analyzed the reaction by changing the reformate fuel inlet velocity. Through this, it was confirmed that the mixedness inside the reformer improved as the reformate fuel inlet velocity. Finally, to calculate the efficiency of the hydrogen addition operating points under various conditions, suitable operating points were derived by comparison with conventional partial oxidation reforming. The operating range of moderate or intense low oxygen dilution combustion in an on-board reforming gas turbine system was numerically predicted. This is expected to greatly contribute to the study to improve the stability of moderate or intensive low oxygen dilution combustion in the future.     

GC-MS determination of low hydrocarbon species (C1–C6) from a diesel partial oxidation reformer

The partial oxidation (POx) reforming of Ultra Low Sulphur-Diesel (ULSD), rapeseed methyl ester (RME) - biodiesel and Fischer–Tropsch synthetic diesel fuels (SD) were studied by using a fixed-bed reactor. The ease of reforming the three fuels was first examined at different O/C feed ratios at constant gas hourly space velocity (GHSV) of 35 k h⁻¹ over a prototype monolith catalyst (1%Rh/CeO₂–ZrO₂). The hydrocarbon species (C₁–C₆) produced in the reformer were analyzed using direct gas injection gas chromatography mass spectrometry (GC-MS). Under the same O/C ratios for 35 k h⁻¹ the fuels conversion and process efficiency was dependent on the fuel type, and followed the general trend: SD > biodiesel > ULSD. The GC-MS analysis shows that both, biodiesel and ULSD diesel produced significantly higher amounts of alkenes compared to SD fuel. Fuel with relatively high aromatics content such diesel can be efficiently reformed to syngas over the catalyst used in this study but the reformer operating range (e.g. O/C ratio and space velocity) is limited compared to paraffinic fuels such as FT-SD. At increased GHSV of 45 k h⁻¹ and O/C = 1.75, the diesel fuel conversion efficiency to syngas (H₂ and CO) was improved significantly and the formation of intermediate species such as methane, ethylene, and propylene was reduced considerably as a result of the increased peak reaction temperatures. The reduced HC species and increased H₂ concentration in the reactor product gas from the reforming of FT-SD fuel can provide significant advantages to the IC engine applications.     

Design of a methanol reformer for on-board production of hydrogen as fuel for a 3 kW High-Temperature Proton Exchange Membrane Fuel Cell power system

The method of Computational Fluid Dynamics is used to predict the process parameters and select the optimum operating regime of a methanol reformer for on-board production of hydrogen as fuel for a 3 kW High-Temperature Proton Exchange Membrane Fuel Cell power system. The analysis uses a three reactions kinetics model for methanol steam reforming, water gas shift and methanol decomposition reactions on Cu/ZnO/Al₂O₃ catalyst. Numerical simulations are performed at single channel level for a range of reformer operating temperatures and values of the molar flow rate of methanol per weight of catalyst at the reformer inlet. Two operating regimes of the fuel processor are selected which offer high methanol conversion rate and high hydrogen production while simultaneously result in a small reformer size and a reformate gas composition that can be tolerated by phosphoric acid-doped high temperature membrane electrode assemblies for proton exchange membrane fuel cells. Based on the results of the numerical simulations, the reactor is sized, and its design is optimized.     

The assessment of reformation in a porous medium-catalyst hybrid reformer under excess enthalpy condition

A porous medium-catalyst hybrid reformer for hydrogen-rich syngas production by dry autothermal reforming (DATR) was investigated in this study. In the reforming process, the reaction under excess enthalpy was explored by visualization in packed-bed catalyst reactor. The hybrid design was arranged with a porous medium (PM) in the upstream of the catalyst packed-bed. In the arrangement, the reactants were preheated by internal heat recirculation and the selectivity of H₂-rich syngas was enhanced by the catalyst surface reaction. Controlled parameters included CO₂/CH₄ and O₂/CH₄ ratios, gas hourly space velocity (GHSV) with or without porous medium. The experimental results demonstrated that the reforming reaction with the hybrid reformer could achieve excess enthalpy under the tested parameters. The excess enthalpy ratio was between 0.15 and 0.55. The temperature measurement along the axial position and image observation of the catalyst packed-bed indicated that the flame was stably held at the interface of the PM and the catalyst bed, and this enhanced fuel conversion and reforming efficiencies, especially in the low methane conversion condition. In the dry autothermal reforming process, part of the chemical energy released from the reaction supplies the energy required for a self-sustaining reaction. Therefore, the selection of the parameters was determined to achieve high reforming efficiency and low energy loss percentage. The results showed that the energy loss percentage was between 12.7 and 24.6% and reforming efficiency was between 64.4 and 79.5% with the best reforming parameter settings (O₂/CH₄ = 0.7–0.9 and CO₂/CH₄ = 0.0–2.0).     

Measurement and analysis of carbon formation during diesel reforming for solid oxide fuel cells

Experiments and equilibrium analysis were conducted to study carbon formation during diesel reforming for a solid oxide fuel cell-based auxiliary power unit (APU) application. A photo-acoustic instrument provided direct measurements of solid carbon concentration in the reformer effluent stream, which could be correlated to reformate gas composition (as determined via mass spectrometer) and reformer temperature. These measurements were complimented by equilibrium calculations based upon minimization of total Gibbs free energy. It was determined that oxygen-to-carbon ratio (O/C), fuel utilization fraction and anode recycle fraction all influence the degree of carbon formation, and that once significant carbon concentration is measured, the reformer performance begins to show marked degradation. At a fixed operating point, lowering the reformer temperature produced by far the largest change in effluent carbon concentration. Systematic variation in O/C, fuel utilization and anode recycle revealed the interdependence among reformer temperature, effluent gas composition and carbon concentration, with a strong correlation between carbon and ethylene concentrations observed for [C₂H₄] > 0.8%. After each experiment, baseline reformer performance could be recovered by operation under methane partial oxidation (POx) conditions, indicating that reformer degradation results at least in part from carbon deposition on the reformer catalyst.     

Thermodynamic analysis and heat integration for hydrogen production from bio-butanol for SOFC application: Steam reforming vs. autothermal reforming

Thermodynamic analysis of hydrogen production by steam reforming and autothermal reforming of bio-butanol was investigated for solid oxide fuel cell applications. The effects of reformer operating conditions, e.g., reformer temperature, steam to carbon molar ratio, and oxygen to carbon molar ratio, were investigated with the objective to maximize hydrogen production and to reduce utility requirements of the process and based on which favorable conditions of reformer were proposed. Process flow diagram for steam reforming and autothermal reforming integrated with solid oxide fuel cell was developed. Heat integration with pinch analysis method was carried out for both the processes at favorable reformer conditions. Power generation, electrical efficiency, useful energy for co-generation application, and utility requirements for both the processes were compared.     

Experimental study of hydrogen production and soot particulate matter emissions from methane rich-combustion in inert porous media

A detailed experimental study of stationary Thermal Partial Oxidation (TPOX) within inert porous media has been conducted. The reaction zone of the tested TPOX reformer is designed so as to enable stationary conversion of fuel/air mixtures for a wide range of operational conditions. Operating characteristics of the process have been examined for two different porous matrices, with different thermal and transport properties, namely SiSiC open foam structure and a packed bed of pure Al₂O₃ packing material in the form of cylindrical rings. The influence of reactants preheating was also examined since the reformer is meant for integration within high temperature fuel cell systems. The operating regime was scanned for reactants' inlet temperature of 400 °C and 550 °C, varying the thermal load in a range from 350 kW/m² up to 2600 kW/m² and the equivalence ratio from 1.9 up to 2.9. Temperature profiles within the reaction region of the reformer were recorded for all tested conditions while gas samples were on-line analyzed for the major species H₂, CO, CO₂, and minor species CH₄, C₂H₂. At reactants' inlet temperatures of 400 °C and 600 °C, for a fixed thermal load of 1540 kW/m² and for selected equivalence ratios around the sooting limit of the process (φ = 2.2–2.6), soot particle size distributions were measured in the exhaust gas with a Scanning Mobility Particle Sizer (SMPS). The results show that the better thermal properties and the higher porosity in the case of the SiSiC matrix enables longer residence times for slow reforming reactions to evolve towards equilibrium and yields syngas with significantly less soot in terms of particle numbers and mass concentration.