A study of steam methanol reforming in a microreactor

Steam reforming of methanol is investigated numerically considering both heat and mass transfer of the species in a packed bed microreactor. The numerical results are shown to be in good agreement with experimental data [M.T. Lee, R. Greif, C.P. Grigoropoulos, H.G. Park, F.K. Hsu, J. Power Sources Transport in, 166 (2007) 194–201] with a BASF F3-01(CuO/ZnO/Al₂O₃) catalyst. A correlation for the conversion efficiency of methanol has been obtained as a function of the operating temperature and a dimensionless time parameter which represents the ratio of the characteristic time of the methanol flow to the time for chemical reaction. The results show that for the constant wall temperature condition the steam reforming process of methanol results in a nearly uniform temperature throughout the microreactor over the range of operating conditions.     

Combined thermal characteristics analysis of steam reforming and combustion for 5 kW domestic PEMFC system

A natural gas-based steam reformer for a domestic polymer electrolyte membrane fuel cell (PEMFC) system is thermodynamically analyzed with a special focus on the heat supply mechanism, which is critical to the endothermic steam reforming process. The interdependence of the reforming and combustion processes is evaluated through a characteristic study of heat transfer from the heat source to the reforming zone. Premixed combustion patterns may be affected by the inclusion of controlling means such as a metal fiber screen or burner placement. In this study, we attempted to enhance reforming performances of a reformer embedded in a 5 kW in-house PEMFC through modification of the combustion pattern by varying the type and placement of the burner and other operating conditions. Reforming input conditions such as steam-carbon ratio (SCR) and fuel distribution ratio (FDR) are also analyzed to quantify the overall performance such as thermal efficiency and fuel conversion rate. In our experiments involving three types of combustors—cylindrical metal fiber burner, flat type metal fiber burner and nozzle-mixing burner—the operating conditions are set so that the SCR and FDR are in the range 3.0–4.0 and 0.4–0.7, respectively. It is found that the cylindrical metal fiber burner at an appropriate location could improve thermal efficiency up to 79% by 10%, compared to other devices. This maximum thermal efficiency output is obtained with 0.63 FDR, which eventually yields 99% hydrogen conversion rate when using a cylindrical metal fiber burner, while the other burners produce 95% conversion. These outputs substantiate that the overall efficiency is strongly affected by an appropriate control for uniform temperature distribution on the catalyst layer.     

Thermodynamic characteristics of reactants and energy conversion in steam reforming of calcium carbide furnace off-gas to produce hydrogen

In this study, to reveal the thermodynamic reaction mechanism and the conversion characteristics of material and energy for the steam reforming of multi-component materials, a chemical equilibrium model was constructed, and the reaction mechanism of the steam reforming of calcium carbide furnace off-gas (CCFG) was also identified. The conversion characteristics of material and energy were ascertained by assessing four independent reactions and their reverse reactions. And the effects of temperature, pressure and steam-to-gas ratio on the conversion ratios of CO and CH₄, the yield of H₂ and the reaction heat were investigated. In addition, a method for determining the process parameters of steam reforming based on the follow-up utilization scheme of CCFG was proposed; the method involves using a four-panel diagram that plots parameters of the steam reforming process. Thus, the range of H₂/CO mole ratio that could be obtained from the equilibrium system of steam reforming of CCFG was determined.     

Thermodynamic analysis of carbon formation boundary and reforming performance for steam reforming of dimethyl ether

Thermodynamic analysis of dimethyl ether steam reforming (DME SR) was investigated for carbon formation boundary, DME conversion, and hydrogen yield for fuel cell application. The equilibrium calculation employing Gibbs free minimization was performed to figure out the required steam-to-carbon ratio (S/C = 0–5) and reforming temperature (25–1000 °C) where coke formation was thermodynamically unfavorable. S/C, reforming temperature and product species strongly contributed to the coke formation and product composition. When chemical species DME, methanol, CO₂, CO, H₂, H₂O and coke were considered, complete conversion of DME and hydrogen yield above 78% without coke formation were achieved at the normal operating temperatures of molten carbonate fuel cell (600 °C) and solid oxide fuel cell (900 °C), when S/C was at or above 2.5. When CH₄ was favorable, production of coke and that of hydrogen were significantly suppressed.     

Hydrogen production of two-stage temperature steam reformer integrated with PBI membrane fuel cells to optimize thermal management

An endothermic methanol steam reformer achieves optimal performance at a temperature of about 240 °C. A polybenzimidazole (PBI) membrane fuel cell was operated exothermically at 160 °C–200 °C. To better couple the lower temperature fuel cell to the higher temperature steam reformer, a two-stage temperature steam reformer to integrate into the PBI membrane fuel cell system is proposed. The reformer optimizes thermal management and increases the system efficiency.     

An investigation into the effect of anode purging on the fuel cell performance

The anode purge is a crucial process for the fuel cell long time operation because when the hydrogen is supplied in a circulation mode, any impurities present in hydrogen will gradually accumulate which lead to output voltage loss. A mathematical model is proposed for the purge process based on some operational purge parameters. The governing equations are solved and the effect of purge process on the stack working parameters is analyzed. Purge operational parameters are determined in such a way that the minimum pressure fluctuations in the anode compartment and a compromise between the minimum voltage loss and minimum hydrogen waste are achieved. A semi-stable condition is introduced and indicated that the behavior of voltage loss and hydrogen waste at this condition with respect to purge stop time (duration which the purge valve is closed) is semi-logarithmic.     

Transport phenomena in a steam-methanol reforming microreactor with internal heating

An experimental and theoretical study of steam reforming of methanol is carried out in a packed-bed microreactor with internal heating. Experimental results of the methanol conversion and carbon monoxide concentration in an internally heated reformer are compared with those of an externally heated reformer. Higher methanol conversion and carbon monoxide concentration are obtained for internal heating at the same conditions. The results show the conversion efficiency of methanol and CO concentration increase with increasing internal heating rate over the range of operating conditions. A correlation for the conversion efficiency of methanol has been obtained as a function of the internal heating rate and a dimensionless time parameter which represents the ratio of the characteristic time of the methanol flow to the time for chemical reaction.     

The study of the performance of Ni supported on gadolinium doped ceria SOFC anode on the steam reforming of ethanol

The catalytic performance of Ni/CeGd SOFC anodes prepared by co-precipitation for steam reforming of ethanol at different reaction temperatures was evaluated. The Ni/CeGd SOFC anode calcined at 1073 K exhibited the highest activity and the lowest by-products formation rates during SR at 773 K. The TG and SEM analyses of the used catalysts showed that the deactivation observed for SR at 773 K was associated with the formation of carbon filaments. It was also observed that the increase of reaction temperature from 773 to 1073 K decreased coke formation, which was no longer detected at 1073 K. This result was attributed to the reverse of the Boudouard reaction and the promoting effect of the support on carbon gasification.     

Toward autonomous control of microreactor system for steam reforming of methanol

Since the introduction of microchemical systems (MCS) in the last decade, it has been recognized that one of the most crucial challenges is the implementation of an appropriate control strategy. A novel study in realizing a controllable miniature chemical plant for a small-scale hydrogen source for fuel cells is presented. Catalytic steam reforming (SR) reaction of a methanol–water mixture was the model reaction studied. A microscaled reactor, sensors and actuators, were successfully prepared and integrated by using microelectromechanical systems (MEMS) technology. Microfabricated system components were then interconnected with a comprehensive control algorithm which could form the basis for an eventual autonomous, self-contained system.     

Comparison of steam and autothermal reforming of methanol using a packed-bed low-cost copper catalyst

Small-scale reformers for hydrogen production via steam and autothermal reforming of hydrocarbon feedstocks can be a solution to the lack of hydrogen distribution infrastructure. A packed-bed reactor is one possible design for such purpose. However, the two reforming processes of steam and autothermal methods have different characteristics, thus they have different and often opposite design requirements. In implementing control strategy for small-scale reformers, understanding the overall chemical reactions and the reactor physical properties becomes essential. This paper presents some inherent features of a packed-bed reactor that can both improve and/or degrade the performance of a packed-bed reactor with both reforming modes.The high thermal resistance of the packed bed is disadvantageous to steam reforming (SR), but it is beneficial to the autothermal reforming (ATR) mode with appropriate reactor geometry. The low catalyst utilization in steam reforming can help to prevent the unconverted fuel leaving the reactor during transient by allowing briefly for higher reactant fuel flow rates. In this study, experiments were performed using three reactor geometries to illustrate these properties and a discussion is presented on how to take advantages of these properties in reactor design.     

Thermodynamic performance analysis of the influence of multi-factor coupling on the methanol steam reforming reaction

This work presents the H₂ production from methanol steam reforming (MSR) process by thermodynamic equilibrium analysis using the Gibbs free energy minimization method and multi-factor coupling method. To determine desirable procedure parameters with maximum methanol conversion and H₂ content and minimum CO content, the impacts of the temperature: 100–400 °C, steam-to-methanol (S/C) molar ratio: 1.0–3.0, and pressure: 0.5–3.0 atm were investigated. The dominant factor under the action of multiple factors and the specific influence of each factor on the MSR process were verified, simultaneously. For proton exchange membrane fuel cell (PEMFC), to keep the CO content of the reformate within a desired range, and under the premise of complete methanol conversion, the MSR process can be operated at lower temperature, higher S/C ratio and atmospheric pressure. Combined with practice process, the optimum values of the temperature, S/C ratio and pressure to produce reformate were identified to be 200–300 °C,1.6–2.0 and 1.0 atm, respectively.     

High-entropy alloy anode for direct internal steam reforming of methane in SOFC

High-entropy alloy (HEA) anode and reforming catalyst, supported on gadolinium-doped ceria (GDC), have been synthesized and evaluated for the steam reforming of methane under SOFC operating conditions using a conventional fixed-bed catalytic reactor. As-synthesized HEA catalysts were subjected to various characterization techniques including N₂ adsorption/desorption analysis, SEM, XRD, TPR, TPO and TPD. The catalytic performance was evaluated in a quartz tube reactor over a temperature range of 700–800 °C, pressure of 1 atm, gas hourly space velocity (GHSV) of 45,000 h^?1 and steam-to-carbon (S/C) ratio of 2. The conversion and H₂ yield were calculated and compared. HEA/GDC exhibited a lower conversion rate than those of Ni/YSZ and Ni/GDC at 700 °C, but showed superior stability without any sign of carbon deposition unlike Ni base catalyst. HEA/GDC was further evaluated as an anode in a SOFC test, which showed high electrochemical stability with a comparable current density obtained on Ni electrode. The SOFC reported low and stable electrode polarization. Post-test analysis of the cell showed the absence of carbon at and within the electrode. It is suggested that HEA/GDC exhibits inherent robustness, good carbon tolerance and stable catalytic activity,` which makes it a potential anode candidate for direct utilization of hydrocarbon fuels in SOFC applications.     

Nano Ni layered anode for enhanced MCFC performance at reduced operating temperature

Nanoparticles of Ni and Ni–Al₂O₃ were coated on a molten carbonate fuel cell (MCFC) anode by spray method to enlarge the electrochemical reaction sites at triple phase boundaries (TPBs). Both nano Ni coated anode and nano Ni–Al₂O₃ anode exhibited significant reduction of anode polarization, thanks to smaller charge transfer resistance. The maximum power density of nano Ni coated anode was 159 mW cm⁻² at current density of 300 mA cm⁻² operating at 600 °C. This is about 7% increase from the standard cell performance tested and compared in the study. Although low performance of nano coated Ni–Al₂O₃ cell is observed due to electrolyte consumption, the stability of cell performance during operation time is more favorable in MCFCs operation.     

Renewable syngas & hydrogen synthesis via steam reforming of glycerol over ceria-mediated exsolved metal nano catalysts

Currently, catalyst design and development has drawn much attention as results of its strategic importance in the area of energy applications particular those involving biomass conversion. This work tailored exsolution of metal catalysts through the use of ceria for enhanced structural and catalytic behaviour in steam reforming of glycerol. Aside the understanding that defects due to A-site deficiency facilitates formation of vacant sites and exsolution of metal catalysts on the B-site of perovskite systems, this work has exemplified that metals such as ceria significantly influences the exsolution and general morphological surface architecture and catalytic behaviour. The exsolved nickel catalysts anchored and socketed on a titanate support and the ceria's basic surface properties and oxygen storage-release behaviour has modified the perovskite surface chemistry and enhanced catalytic behaviour particularly deactivation due to carbon deposition and reusability. Other exsolvable dopant metal species such as Fe and Co forms alloys with nickel on the surface and the synergy between the dopant metals in the alloy yielded better results. Furthermore, in one of the catalyst systems, the most commonly observed tolerable A-site deficiency and doping limit of 2% known for SrTiO₃ perovskite was overstretched by 0.5% (2.5%) thereby increasing the defect chemistry. The catalyst system with such formulation has shown a dramatic exsolution phenomenon and catalytic behaviour and robust suppression of coke deposition. CO selectivity >60% and H₂ selectivity >40% was recorded with all the catalyst systems. The catalysts used in this work are useful for applications in energy and production of value added chemicals.     

Simulation of steam reforming of biogas in an industrial reformer for hydrogen production

The paper aims to investigate the steam reforming of biogas in an industrial-scale reformer for hydrogen production. A non-isothermal one dimensional reactor model has been constituted by using mass, momentum and energy balances. The model equations have been solved using MATLAB software. The developed model has been validated with the available modeling studies on industrial steam reforming of methane as well as with the those on lab-scale steam reforming of biogas. It demonstrates excellent agreement with them. Effect of change in biogas compositions on the performance of industrial steam reformer has been investigated in terms of methane conversion, yields of hydrogen and carbon monoxide, product gas compositions, reactor temperature and total pressure. For this, compositions of biogas (CH₄/CO₂ = 40/60 to 80/20), S/C ratio, reformer feed temperature and heat flux have been varied. Preferable feed conditions to the reformer are total molar feed rate of 21 kmol/h, steam to methane ratio of 4.0, temperature of 973 K and pressure of 25 bar. Under these conditions, industrial reformer fed with biogas, provides methane conversion (93.08–85.65%) and hydrogen yield (1.02–2.28), that are close to thermodynamic equilibrium condition.     

In situ detection of anode flooding of a PEM fuel cell

This paper proposes an early detection scheme of anode flooding in a PEM fuel cell. Through experimental testing of an eight-cell hydrogen-fueled polymer electrolyte stack it is shown that anode flooding can be detected prior to a rapid voltage decline. The proposed detection scheme requires no additional costly instrumentation and uses the existing voltage scan cards.     

Availability of steam impacts coke properties in steam reforming of acetic acid

Steam to carbon ratio (S/C) determines the availability of oxygen-containing species during steam reforming, which not only affect the amount of coke formed, but also might impact physicochemical properties of the coke generated. In this study, the effect of S/C on the coke formation in steam reforming of acetic acid was assessed. The results indicated that dissociative absorption of acetic acid generated the intermediates containing both CO and CC groups even at 100 °C. At low S/C, the insufficient 1OH reacted with carbonaceous intermediates such as CH_x to form more carbonyl species, leading to significant coking and lower gas yields. Sufficient 1OH at high S/C facilitated transformation of the carbonyl-containing species into gases, minimizing coking. The varied amount of coke showed significant effect on the diffraction of metallic nickel phase, the particle size of Ni and the absorption for the Si–O–Si functional groups on spent catalysts. The coke formed at low S/C was more aromatic with high thermal stabilities, while the coke formed at high S/C was more aliphatic with low thermal stabilities. The involvement 1OH species in coking process determined not only properties but also morphologies of the coke. The coke formed at low S/C showed bamboo-like, dendritic or twisted rope-like structure. While the higher S/C favored the generation of the carbon nanotubes with smooth outer surface.     

Paper-structured catalyst for the steam reforming of biodiesel fuel

Architectonics of the paper-structured catalyst for the application to the biofuel reformer or direct internal reforming SOFC (DIRSOFC) was studied. Inorganic fiber network, “paper”, composed of yttria-stabilized zirconia (YSZ) fiber (Zf), alumina fiber (Af) and inorganic binder (Al₂O₃ sol (As) or ZrO₂ sol (Zs) or CeO₂ sol (Cs)) was prepared by a simple paper-making process. Then, the catalytic activities of the Ni and Ni–MgO loaded papers called “paper-structured catalysts (PSCs)” for the steam reforming of biodiesel fuels (BDFs) were evaluated. Ni–MgO loaded PSC using Cs as an inorganic binder, Ni–MgO/ZfAfCs, exhibited excellent performance over Ru/γAl₂O₃ catalyst beads. Formation of light hydrocarbons, especially C₂H₄, was eliminated and water–gas shift reaction was more promoted compared to the catalyst beads.     

Investigation of anode flow field for direct dimethyl ether fuel cell

In this work, we presented the novel anode flow field for direct dimethyl ether fuel cell (DDFC). The anode flow field of the DDFC consisted of hydrophilic, hydrophobic, and diffusion region (with a ratio of region areas of 3:6:1). The maximum power density of the DDFC with novel anode flow field was 67 mW cm⁻², which was higher than that of the cell fed with conventional flow field (60 mW cm⁻²). The electrochemical impedance spectra analyses revealed that the mass transfer resistance of novel anode flow field was lower than that of conventional flow field. The constant current operation curves showed that the performance decay ratio of the novel anode flow field was lower than that of conventional one. It indicated that the novel flow field benefited the long-term operation of DDFC.     

Effect of pollutants on biogas steam reforming

This study reports the influence of biogas poisoning on a Ni based catalyst working under steam reforming conditions (atmospheric pressure, T = 1073 K and H₂O/CH₄ = 2 mol/mol). A biogas stream composed by CH₄ and CO₂ with a ratio 55/45 vol.%, added with different chemical species (H₂S, hydrocarbons mixture and D5) as contaminants, was used as inlet gas stream.First, effect of poisoning on Ni catalyst were separately evaluated and the boundary concentrations for each contaminants were revealed (0.4 ppm, 200 ppm and 0.5 ppm for H₂S, hydrocarbons and D5 respectively) to assure Ni stable performances on time on stream (100 h at 50,000 h^?1 of GHSV). Successively, a comparison between Ni catalytic behaviors in presence of two combined poisoning in the biogas (H₂S + Hydrocarbons and Hydrocarbons + D5) was carried out.It was found that the effect of combined poisoning, even though it considered in moderate concentration, is harmful for Ni catalyst activity. Methane conversion on time on stream was reduced from 86% to 40% after 50 h, when the couple of poisoning Hydrocarbons + D5 was added to the inlet gas stream, while a lower deactivation pattern (about 73%) was leaded by couple H₂S + Hydrocarbons. Both poisoning mixtures promoted coke deposition on Ni catalyst surface (about ≥0.5 mgC/g_cat·h) independently by poisoning chemical characteristics probably due to adsorption/deposition of contaminants on catalytic sites.