Hydrogen production using integrated methanol‐steam reforming reactor with various reformer designs for PEM fuel cells

A 95 mm × 40 mm × 15 mm compact reactor for hydrogen production from methanol‐steam reforming (MSR) is constructed by integrating a vaporizer, reformer, and combustor into a single unit. CuO/ZnO/Al₂O₃ is used as the catalyst for the MSR while the required heat is provided using Platinum (Pt) ‐catalytic methanol combustion. The reactor performance is measured using three reformer designs: patterned micro‐channel; inserted catalyst layer placed in a single plain channel; and catalyst coated directly on the bottom wall of single plain channel. Because of longer reactant residence time and more effective heat transfer, slightly higher methanol conversion can be obtained from the reformer with patterned microchannels. The experimental results show that there is no significant reactor performance difference in methanol conversion, hydrogen (H₂) production rate, and carbon monoxide (CO) composition among these three reformer designs. These results indicated that the flow and heat transfer may not play important roles in compact size reactors. The reformer design with inserted catalyst layer provides convenience in replacing the aged catalyst, which may be attractive in practical applications compared with the conventional packed bed and wall‐coated reformers. Copyright © 2011 John Wiley & Sons, Ltd.     

Experimental evaluation of methanol steam reforming reactor heated by catalyst combustion for kW-class SOFC

The distributed power generation of methanol steam reforming reactor combined with solid oxide fuel cell (SOFC) has the characteristics of outstanding economic advantages. In this paper, a methanol steam reforming reactor was designed which integrates catalyst combustion, vaporization and reforming. By catalyst combustion, it can achieve stable operation to supply fuel for kW-class SOFC in real time without additional heating equipment. The optimal operating condition of the reforming reactor is 523–553 K, and the steam to carbon ratio (S/C) is 1.2. To study the reforming performance, methanol steam reforming (MSR), methanol decomposition (MD), water-gas shift (WGS) were considered. Operating temperature is the greatest factor affecting reforming performance. The higher the reaction temperature, the lower the H₂ and CO₂, the higher the CO and the methanol conversion rate. The methanol conversion rate is up to 95.03%. The higher the liquid space velocity (LHSV), the lower the methanol conversion rate, the lowest is 90.7%. The temperature changes of the reforming reactor caused by the load change of stack takes about 30 min to reach new balance. Local hotspots within the reforming reactor lead to an excessive local temperature to test a small amount of CH₄ in the reforming gas. The methanation reaction cannot be ignored at the operating temperature. The reforming gas contains 70–75% H₂, 3–8% CO, 18–22% CO₂ and 0.0004–0.3% CH₄. Trace amounts of C₂H₆ and C₂H₄ are also found in some experiments. The reforming reactor can stably supply the fuel for up to 1125 W SOFC.     

Recent trends in the development of reactor systems for hydrogen production via methanol steam reforming

Hydrogen is currently receiving significant attention as an alternative energy resource, and among the various methods for producing hydrogen, methanol steam reforming (MSR) has attracted great attention because of its economy and practicality. Because the MSR reaction is inherently activated over catalytic materials, studies have focused on the development of noble metal-based catalysts and the improvement of existing catalysts with respect to performance and stability. However, less attention has been paid to the modification and development of innovative MSR reactors to improve their performance and efficiency. Therefore, in this review paper, we summarize the trends in the development of MSR reactor systems, including microreactors and membrane reactors, as well as the various structured catalyst materials appropriate for application in complex reactors. In addition, other engineering approaches to achieve highly efficient MSR reactors for the production of hydrogen are discussed.     

A study of methanol steam reforming on distributed catalyst bed

Heterogeneous catalytic fixed bed usually suffers from severe limitations of mass and heat transfer. These disadvantages limit reformers to a low efficiency of catalyst utilization. Three catalyst activity distributions have been applied to force the reactor temperature profile to be near isothermal operation for maximization of methanol conversion. A plate-type reactor has been developed to investigate the influence of catalyst activity distribution on methanol steam reforming. Cold spot temperature gradients are observed in the temperature profile along the reactor axis. It has been experimentally verified that reducing cold spot temperature gradients contributes to the improvement of the catalytic hydrogen production. The lowest cold spot temperature gradient of 3 K is obtained on gradient catalyst distribution type A. This is attributed to good characteristics of local thermal effect. Low activity at the reactor inlet with gradual rise along with the reactor flow channel forms the optimal activity distribution. Hydrogen production rate of 161.3 L/h is obtained at the methanol conversion of 93.1% for the gradient distribution type A when the inlet temperature is 543 K.     

Reforming of methanol to produce hydrogen over the Au/ZnO catalyst

Gold particle with an average size of d_Au ~ 4 nm was dispersed on ZnO by the deposition precipitation method. The fabricated Au/ZnO catalyst was used to produce hydrogen from reforming of methanol. Four reforming reactions, i.e., decomposition of methanol (DM), steam reforming of methanol (SRM), partial oxidation of methanol (POM) and oxidative steam reforming of methanol (OSRM), were evaluated in a fixed bed reactor. A reaction temperature of T_R > 623 K was required for catalyzing reactions of DM and SRM. Interestingly, high methanol conversion (C_MeOH > 90%) was found from reforming reactions of POM and OSRM at an amazing low temperature of T_R < 473 K. Besides, a presentable hydrogen yield (R_H2 ~ 2.4) and a low selectivity of CO (S_CO ~ 1%) were simultaneously attained from the reaction of OSRM. Therefore, the low temperature OSRM reaction over the Au/ZnO catalyst is suggested as a friendly reforming process for on-board production of hydrogen.     

Structural design of self-thermal methanol steam reforming microreactor with porous combustion reaction support for hydrogen production

To replace the traditional electric heating mode and increase methanol steam reforming reaction performance in hydrogen production, methanol catalytic combustion was proposed as heat-supply mode for methanol steam reforming microreactor. In this study, the methanol catalytic combustion microreactor and self-thermal methanol steam reforming microreactor for hydrogen production were developed. Furthermore, the catalytic combustion reaction supports with different structures were designed. It was found that the developed self-thermal methanol steam reforming microreactor had better reaction performance. Compared with A-type, the △T_max of C-type porous reaction support was decreased by 24.4 °C under 1.3 mL/min methanol injection rate. Moreover, methanol conversion and H₂ flow rate of the self-thermal methanol steam reforming microreactor with C-type porous reaction support were increased by 15.2% under 10 mL/h methanol-water mixture injection rate and 340 °C self-thermal temperature. Meanwhile, the CO selectivity was decreased by 4.1%. This work provides a new structural design of the self-thermal methanol steam reforming microreactor for hydrogen production for the fuel cell.     

Experimental study on biomass steam gasification for hydrogen-rich gas in double-bed reactor

Based on Response Surface Methodology, the experiments of biomass catalytic gasification designed by Design-Expert software were carried out in steam atmosphere and double-bed reactor. The response surface was set up with three parameters (gasification temperature, the content of K-based catalyst in gasification bed and the content of Ni-based catalyst in reforming bed) for biomass gasification performance of carbon conversion efficiency and hydrogen yield to make analysis and optimization about the reaction characteristics and gasification conditions. Results showed that gasification temperature and the content of K-based catalyst in gasification bed had significant influence on carbon conversion efficiency and hydrogen yield, whilst the content of Ni-based catalyst in reforming bed affected the gasification reactions to a large extent. Furthermore, appropriate conditions of biomass steam gasification were 800 °C for gasification temperature, 82% for the content of K-based catalyst in gasification bed and 74% for the content of Ni-based catalyst in reforming bed by the optimization model. In these conditions, the steam gasification experiments using wheat straw showed that carbon conversion efficiency was 96.9% while hydrogen yield reached 64.5 mol/kg, which was in good agreement with the model prediction. The role of the reforming bed was also analyzed and evaluated, which provided important insight that the employment of reforming bed made carbon conversion efficiency raised by 4.8%, while hydrogen yield achieved a relative growth of 50.5%.     

H2 production by low pressure methanol steam reforming in a dense Pd–Ag membrane reactor in co-current flow configuration: Experimental and modeling analysis

The aim of this work is to generate a pure or CO_x-free hydrogen stream by using a dense Pd-based packed bed membrane reactor (PBMR) during methanol steam reforming (MSR) reaction and developing a valid model that can provide a tool for deeper analyses of the reaction parameters in the PBMR. Therefore, in this study, a dense Pd–Ag membrane reactor (MR) is used to carry out MSR at different gas hourly space velocity (GHSV), feed molar ratio and sweep gas factor (SF) and for low reaction pressures (1.5–2.5 bar). For a better analysis, a traditional packed bed reactor (PBR) is operated at the same PBMR conditions. In the PBMR setup, a dense Pd–Ag membrane with a thickness of 50 μm is used and also a commercial Cu/ZnO/Al₂O₃ catalyst is packed in both kinds of reactors. Methanol conversion equal to 100% is experimentally achieved in the PBMR at 280 °C, H₂O/CH₃OH = 3/1 and 2.5 bar, while at the same conditions the PBR reaches 91% methanol conversion. Moreover, 46% CO_x-free hydrogen on total hydrogen produced is collected by using sweep gas in the PBMR permeate side. Furthermore, a 1-dimensional and isothermal model is developed for theoretically analyzing MSR performance in both PBMR and PBR, validated by the combined experimental campaign.     

Hydrogen production from steam reforming using an indirect heating method

In this work, a methanol steam reforming (MSR) reactor was operated using an indirect heating method. A thermal circuit was constructed between the MSR reactor and the electrical heater to supply the heat required for the endothermic reaction, and deionized water was used as the heat transfer medium (HTM). The MSR reactors featured a shell-and-tube type design to operate at high pressures. A Cu/Zn catalyst was installed on the tube side, and HTM was supplied to the shell side. To improve the heat transfer performance, the heat transfer area between the shell and tube was increased from 598 to 1117 cm². Because the MSR reactor had a sufficient heat exchange area corresponding to the catalytic reaction rate, the heat exchange area had little effect on methanol conversion. However, the heat exchange area had a greater effect on the performance because the operating temperature of reactor was lower. Under the same operating temperature conditions, the MSR reactor operated under the indirect heating method showed relatively higher methanol conversion than the MSR reactor operated in an electric furnace because of the effective heat transfer by the latent heat of saturated steam. The MSR reactor based on the indirect heating method was continuously operated at 250 °C for 72 h to verify characteristic start-up and operation. The results showed that the MSR reactor could be operated at a constant temperature; however, low methanol conversion at low operating temperatures led to slow catalyst degradation. In addition, the MSR reactor required more than 2 h for initial start-up and for restart after emergency shutdown because the HTM needed to be evaporated and pressurized to the target pressure.     

Mathematical modeling of hydrogen production using methanol steam reforming in the coupled membrane reactor when the output materials of the reformer section is used as feed for the combustion section

Hydrogen is one of the most abundant elements on Earth's surface. It is not in nature in its pure form, but it can produce by various methods such as methanol steam reforming, partial oxidation, electrolysis, etc. In the present study, using the mass and energy conservation law, hydrogen production in coupled membrane reactors has been modeled using the methanol steam reforming process using two different methods in the coupled membrane reactor. A separate (fresh) methanol is used as feed for the combustion section in the first method. While in the second method, the reformer reactor's output material is used as feed for the combustion section. After simplifying using the required assumptions, the governing equations solved using the ode45 (shooting method) numerical method using MATLAB software. The results of this study show that the conversion of methanol in the coupled membrane reactor when separate methanol is used as feed in the combustion reactor, while in the same reactor, the output material of the reformer section used as feed in the combustion section, is 92% and 88.5% respectively. In this study, the effect of different parameters on the methanol conversion rate is investigated. Finally, it found that with increasing temperature and pressure and decreasing membrane thickness in coupled membrane reactors, methanol conversion rate increases. The percentage of hydrogen recovery in the two coupled membrane reactors is almost equal to 92%.     

Production of hydrogen from methanol steam reforming using CuPd/ZrO2 catalysts – Influence of the catalytic surface on methanol conversion and CO selectivity

Electricity generation for mobile applications by proton exchange membrane fuel cells (PEMFCs) is typically hindered by the low volumetric energy density of hydrogen. Nevertheless, nearly pure hydrogen can be generated in-situ from methanol steam reforming (MSR), with Cu-based catalysts being the most common MSR catalysts. Cu-based catalysts display high catalytic performance, even at low temperatures (ca. 250 °C), but are easily deactivated. On the other hand, Pd-based catalysts are very stable but show poor MSR selectivity, producing high concentrations of CO as by-product. This work studies bimetallic catalysts where Cu was added as a promoter to increase MSR selectivity of Pd. Specifically, the surface composition was tuned by different sequences of Cu and Pd impregnation on a monoclinic ZrO₂ support. Both methanol conversion and MSR selectivity were higher for the catalyst with a CuPd-rich surface compared to the catalyst with a Pd-rich surface. Characterization analysis indicate that the higher MSR selectivity results from a strong interaction between the two metals when Pd is impregnated first (likely an alloy). This sequence also resulted in better metallic dispersion on the support, leading to higher methanol conversion. A H₂ production rate of 86.3 mmol h^?1 g^?1 was achieved at low temperature (220 °C) for the best performing catalyst.     

Thermodynamic analysis of hydrogen production via sorption-enhanced steam methane reforming in a new class of variable volume batch-membrane reactor

Combined reaction–separation processes are a widely explored method to produce hydrogen from endothermic steam reforming of hydrocarbon feedstock at a reduced reaction temperature and with fewer unit operation steps, both of which are key requirements for energy efficient, distributed hydrogen production. This work introduces a new class of variable volume batch reactors for production of hydrogen from catalytic steam reforming of methane that operates in a cycle similar to that of an internal combustion engine. It incorporates a CO₂ adsorbent and a selectively permeable hydrogen membrane for in situ removal of the two major products of the reversible steam methane reforming reaction. Thermodynamic analysis is employed to define an envelope of ideal reactor performance and to explore the tradeoff between thermal efficiency and hydrogen yield density with respect to critical operating parameters, including sorbent mass, steam to methane ratio and fraction of product gas recycled. Particular attention is paid to contrasting the variable volume batch-membrane reactor approach to a conventional fixed bed reaction–separation approach. The results indicates that the proposed reactor is a viable option for low temperature distributed production of hydrogen from methane, the primary component of natural gas feedstock, motivating a detailed study of reaction/adsorption kinetics and heat/mass transfer effects.     

Numerical analysis of methanol steam reforming reactor heated by catalytic combustion for hydrogen production

Thermal coupling of endothermic and exothermic reactions is an important pathway for integrated thermal management within a methanol steam reforming reactor heated by methanol catalytic combustion. In this study, a numerical model is developed for heat and mass transfer calculations, methanol steam reforming and catalytic combustion reactions, which is used to explore the effects of design parameters on compact parallel channel reactor performance. Efficiency of the integrated reactor is optimized by the coupling of endothermic and exothermic reactions using conventional wall material. Temperature uniformity is improved by the adjustment of the flow arrangement and the catalyst distribution. This work provides an effective energy management strategy and tool which can be adopted in the design of portable hydrogen generation systems.     

Effect of in-situ and ex-situ injection of steam on staged-gasification for hydrogen production

K modified Ni-based catalysts are used to investigate the effect of in-situ and ex-situ injection of steam (ISI and ESI) on biomass pyrolysis and in-line catalytic steam reforming in a two-stage fixed bed reactor. The results show that 0.5 wt% K is appropriate to modify the Ni-based catalysts for steam reforming of biomass pyrolysis vapor. Compared to the catalytic cracking without steam addition, both ISI and ESI increase the gas yield and the carbon conversion efficiency (X_c) of the pyrolysis vapors. And the ESI is more beneficial to the conversion of pyrolysis vapors to small molecular gases. The maximum hydrogen concentration, hydrogen yield and carbon conversion efficiency (X_c) of staged-gasification can reach 53.8%, 31 mmol/g-bio, and 94.6%, respectively, when both stages are at 700 °C with ex-situ steam injection (S/C = 1.2) and 3 g catalyst loaded in the second stage. Also, the steam is beneficial to removing the depositions of graphitized coke and small molecular polycyclic aromatic hydrocarbon on the catalysts. However, it is yet difficult for steam to react with the highly ordered carbonaceous.     

Enhancement of pure hydrogen production through the use of a membrane reactor

Pure hydrogen production is of great interest as it is an energy carrier which can be used in PEM fuel cells for power production. Methane Steam Reforming (MSR) is commonly used for hydrogen production although the produced hydrogen is not free of other components. Membrane Reactors (MR) enable a pure hydrogen product stream and allows the reaction to take place at significantly lower temperatures (lower than 550 °C) than in conventional reactors (greater than 800 °C) with comparable methane conversion. This is achieved by hydrogen removal through a permselective Pd–Ag based membrane that cause a favorable shift in chemical equilibrium towards hydrogen production. In the present study, a two-dimensional, nonlinear, and pseudo-homogeneous mathematical model of a catalytic fixed-bed membrane reactor for methane steam reforming over a nickel-based foam supported catalyst is presented. Simulated results referring to the distribution of species, methane conversion, temperature and hydrogen flowrate along the reactor for different radial positions are obtained and analyzed. The performance of structured catalyst and catalyst supported on foam configurations under the same operating conditions is also studied. Experimental results for the membrane facilitate the identification of suitable operating conditions.     

Micro methanol reformer combined with a catalytic combustor for a PEM fuel cell

This paper presents the development of a micro methanol reformer for portable fuel cell applications. The micro reformer consists of a methanol steam reforming reactor, catalytic combustor, and heat exchanger in-between. Cu/ZnO was selected as a catalyst for a methanol steam reforming and Pt for a catalytic combustion of hydrogen with air. Porous ceramic material was used as a catalyst support due to the large surface area and thermal stability. Photosensitive glass wafer was selected as a structural material because of its thermal and chemical stabilities. Performance of the reformer was measured at various test conditions and the results showed a good agreement with the three-dimensional analysis of the reacting flow. Considering the energy balance of the reformer/combustor model, the off-gas of fuel cell can be recycled as a feed of the combustor. The catalytic combustor generated the sufficient amount of heat to sustain the steam reforming of methanol. The conversion of methanol was 95.7% and the hydrogen flow of 53.7 ml/min was produced including 1.24% carbon monoxide. The generated hydrogen was the sufficient amount to operate 4.5 W polymer electrolyte membrane fuel cells.     

Modeling and simulation of circulating fast fluidized bed reactors and circulating fast fluidized bed membrane reactors for production of hydrogen by oxidative reforming of methane

Modeling and simulation of circulating fast fluidized bed reactors (CFFBR) and circulating fast fluidized bed membrane reactors (CFFBMR) for hydrogen production by oxidative reforming of methane are presented in this paper. The results show that the CFFBR suffers from serious problems of hot spot temperatures. The combined effect of the oxygen distribution and the hydrogen membrane in the CFFBMR eliminates the hot spot temperatures and the danger of the reactor thermal runaway and mitigates nicely the temperature along the length of the CFFBMR. The investigation shows that the oxidative reforming of methane in the CFFBMR with oxygen distribution is cost-effective and inexpensive alternative route to the conventional steam reforming of methane processes due to the in situ heat integration of exothermic and endothermic reactions. The key role of the design parameters on the performance of the reactors are recognized through sensitivity analysis. The simulation results indicate that almost complete conversion of methane (99.99%), high exit hydrogen yield of 3.00 and low exit temperature of 569.8 °C are obtained by proper selection of design parameters of the CFFBMR with oxygen distribution. This achievement occurs at low feed temperature of 350.0 °C, which does not have destructive effects on the catalyst, reactor and membrane.     

Autothermal hydrogen generation from methanol in a ceramic microchannel network

In this paper, the authors present the first demonstration of a new class of integrated ceramic microchannel reactors for all-in-one reforming of hydrocarbon fuels. The reactor concept employs precision-machined metal distributors capable of realizing complex flow distribution patterns with extruded ceramic microchannel networks for cost-effective thermal integration of multiple chemical processes. The presently reported reactor is comprised of five methanol steam reforming channels packed with CuO/γ-Al₂O₃, interspersed with four methanol combustion channels washcoated with Pt/γ-Al₂O₃, for autothermal hydrogen production (i.e., without external heating). Results demonstrate the capability of this new device for integrating combustion and steam reforming of methanol for autothermal production of hydrogen, owing to the axially self-insulating nature of distributor-packaged ceramic microchannels. In the absence of any external insulation, stable reforming of methanol to hydrogen at conversions >90% and hydrogen yields >70% was achieved at a maximum reactor temperature of 400 °C, while simultaneously maintaining a packaging temperature <50 °C.     

Hydrogen production with integrated microchannel fuel processor for portable fuel cell systems

An integrated microchannel methanol processor was developed by assembling unit reactors, which were fabricated by stacking and bonding microchannel patterned stainless steel plates, including fuel vaporizer, heat exchanger, catalytic combustor and steam reformer. Commercially available Cu/ZnO/Al₂O₃ catalyst was coated inside the microchannel of the unit reactor for steam reforming. Pt/Al₂O₃ pellets prepared by ‘incipient wetness’ were filled in the cavity reactor for catalytic combustion. Those unit reactors were integrated to develop the fuel processor and operated at different reaction conditions to optimize the reactor performance, including methanol steam reformer and methanol catalytic combustor. The optimized fuel processor has the dimensions of 60 mm × 40 mm × 30 mm, and produced 450sccm reformed gas containing 73.3% H₂, 24.5% CO₂ and 2.2% CO at 230–260 °C which can produce power output of 59 Wt.     

Fast start-up of microchannel fuel processor integrated with an igniter for hydrogen combustion

A Pt–Zr catalyst coated FeCrAlY mesh is introduced into the combustion outlet conduit of a newly designed microchannel reactor (MCR) as an igniter of hydrogen combustion to decrease the start-up time. The catalyst is coated using a wash-coating method. After installing the Pt–Zr/FeCrAlY mesh, the reactor is heated to its running temperature within 1 min with hydrogen combustion. Two plate-type heat-exchangers are introduced at the combustion outlet and reforming outlet conduits of the microchannel reactor in order to recover the heat of the combustion gas and reformed gas, respectively. Using these heat-exchangers, methane steam reforming is carried out with hydrogen combustion and the reforming capacity and energy efficiency are enhanced by up to 3.4 and 1.7 times, respectively. A compact fuel processor and fuel-cell system using this reactor concept is expected to show considerable advancement.