Methane steam reforming using a membrane reactor equipped with a Pd-based composite membrane for effective hydrogen production

Herein, a methane steam reforming (MSR) reaction was carried out using a Pd composite membrane reactor packed with a commercial Ru/Al₂O₃ catalyst under mild operating conditions, to produce hydrogen with CO₂ capture. The Pd composite membrane was fabricated on a tubular stainless steel support by the electroless plating (ELP) method. The membrane exhibited a hydrogen permeance of 2.26 × 10^?3 mol m² s^?1 Pa^?0.5, H₂/N₂ selectivity of 145 at 773 K, and pressure difference of 20.3 kPa. The MSR reaction, which was carried out at steam to carbon ratio (S/C) = 3.0, gas hourly space velocity (GHSV) = 1700 h^?1, and 773 K, showed that methane conversion increased with the pressure difference and reached 79.5% at ΔP = 506 kPa. This value was ～1.9 time higher than the equilibrium value at 773 K and 101 kPa. Comparing with the previous studies which introduced sweeping gas for low hydrogen partial pressure in the permeate stream, very high pressure difference (2500–2900 kPa) for increase of hydrogen recovery and very low GHSV (<150) for increase hydraulic retention time (HRT), our result was worthy of notice. The gas composition monitored during the long-term stability test showed that the permeate side was composed of 97.8 vol% H₂, and the retentate side contained 67.8 vol% CO₂ with 22.2 vol% CH₄. When energy was recovered by CH₄ combustion in the retentate streams, pre-combustion carbon capture was accomplished using the Pd-based composite membrane reactor.     

A performance study of methanol steam reforming in an A-type microchannel reactor

The methanol steam reforming (MSR) performance in a microchannel reactor is directly related to the flow pattern design of the microchannel reactor. Hydrogen production improvements can be achieved by optimal design of the flow pattern. In this study, an A-type microchannel reactor with a flow pattern design of one inlet and two outlets was applied to conduct the MSR for hydrogen production. The MSR performance of the A-type microchannel reactor was investigated through numerical analysis by establishing a three-dimensional simulation model and compared with that of the conventional Z-type microchannel reactor. Experiments were also conducted to test the MSR performance and validate the accuracy of the simulation model. The results showed that compared with the conventional Z-type microchannel reactor, the species distributions in the A-type microchannel reactor were more homogeneous. In addition, compared with the Z-type microchannel reactor, the A-type microchannel reactor was shown to effectively increase the methanol conversion rate by up to 8% and decrease the pressure drop by about 20%, regardless of a slightly higher CO mole fraction. It was also noted that with various quantities of microchannels and microchannel cross sections, the A-type microchannel reactor was still more competitive in terms of a higher methanol conversion rate and a lower pressure drop.     

Experiments on hydrogen production from methanol steam reforming in the microchannel reactor

The entire experiments were conducted for microchannel methanol steam reforming, by which, the selection of catalyst, the operating parameters and the configuration of microchannels were discussed thoroughly. It was found that the higher the Cu concentration is, the more the corresponding active surface area of Cu will be, thereby improving the catalytic activity. The Cu-to-Zn ratio in Cu/ZnO/Al₂O₃ catalyst should be set at 1:1. The impacts of reaction temperature, feed flow rate, mixture temperature, and H₂O-to-CH₃OH molar ratio on the methanol conversion rate were also revealed and discussed. Characteristics of micro-reactors with various microchannels, including that 20 mm and 50 mm in length, as well as non-parallel microchannels, were investigated. It was found that the increase of microchannel length can improve the methanol conversion rate significantly. Besides, non-parallel microchannels help to maintain flow and temperature distribution uniformity, which can improve the performance of micro-reactor. In the present experiments, the presence of CO was under the condition that the methanol conversion rate was above 70%.     

Methane steam reforming: Kinetics and modeling over coating catalyst in micro-channel reactor

Kinetics of methane steam reforming for hydrogen production has been studied through experiment in a micro-channel reactor over coating catalyst. The catalyst coating prepared by cold spray on stainless steel substrate is based on a mixture of Ni–Al oxides which is normally employed in industry for methane primary steam reforming. Two kinetic laws namely parallel as well as inverse models have been derived at atmospheric pressure, and power law type kinetics have been established using non-linear least squares optimization. With the above kinetics, simulation study has been carried out to find out temperature distribution in the micro-channel over coating catalyst at two different types of boundary conditions. The results show a quite different “cold spot” character and reactants, products distribution character in the reaction channel due to its own distinct heat and mass transfer features. The kinetics and simulation study results can be applied in aid of micro-channel reactor design, and suggestion has been proposed for catalytic coating preparation and optimization.     

Oxidative steam reforming of methane to synthesis gas in microchannel reactors

Oxidative steam reforming of methane to synthesis gas (syngas) over an alumina supported bimetallic Pt–Rh catalyst was comparatively investigated in coated and packed microchannel reactors. In the first configuration, thin layers of catalysts are coated on opposite walls of a single microchannel, while the second one is described by particulate catalysts packed into an empty microchannel of dimensions identical with the first one. Both geometries are compared on the basis of methane conversion and CO selectivity measured at different values of parameters, namely reaction temperature (773–923 K), molar steam-to-carbon (S/C = 0–3.0) and oxygen-to-carbon (O₂/C = 0.47–0.63) ratios in the feed, and contact time (0.36–0.71 mg min cm⁻³). Although methane conversions are found to be comparable, the coated catalyst gave significantly higher CO selectivities than the packed counterpart in the whole parameter range. Increase in all of the parameter values led to improvement in methane conversion, while CO selectivity increased only with temperature and contact time. Molar H₂/CO ratios obtained in the coated microchannel reactor are found to vary between 1.0 and 3.0 which are at least three times smaller than those produced in the packed microchannel reactor. Catalyst deactivation is not detected in both configurations. Stable operation up to 72 h over coated microchannel verified mechanical and chemical stability of the Pt–Rh coating that produced syngas with H₂/CO ratio of 2.12 at temperatures lower than employed in industrial reformers. Different flow distribution properties of coated and packed microchannels seem to play roles in affecting the product distribution.     

Methanol steam reforming in a microchannel reactor by Zn-, Ce- and Zr- modified mesoporous Cu/SBA-15 nanocatalyst

Hydrogen production by steam reforming of methanol was studied over several Cu/SAB-15-based nanocatalysts in a parallel-type microchannel reactor. The catalysts were prepared through impregnation method and XRD, BET, FT-IR, FE-SEM, TEM, H₂-TPR and TGA techniques were used to characterize surface and structural properties of the synthesized catalysts. The effects of reaction temperature, WHSV and S/C molar ratio on the methanol conversion and selectivities of the gaseous products were studied. Then, effects of the metallic promoters were investigated to improve performance of the catalysts. It was revealed that ZnO and CeO₂ promoters have positive effects on decreasing CO selectivity and ZrO₂ promotes methanol conversion. Furthermore, ZrO₂ and CeO₂ were declared to improve stability of the catalyst. Among the evaluated catalysts, Cu/ZnO/CeO₂/ZrO₂/SBA-15 can provide optimal methanol conversion with low CO concentration in the gaseous products. For this catalyst, the methanol conversion and hydrogen selectivity reached 95.2% and 94.6%, respectively.     

Modeling and simulation of methane steam reforming in a thermally coupled membrane reactor

A distributed mathematical model for thermally coupled membrane reactor that is composed of three channels is developed for methane steam reforming. Methane combustion takes place in the first channel on a Pt/δ–Al₂O₃$\text{Pt}/\delta \text{–}{\text{Al}}_2{\text{O}}_3$ catalyst layer that supplies the necessary heat for the endothermic steam reforming reaction. In the second channel, catalytic steam reforming reactions take place in the presence of Ni/MgO–Al₂O₃ catalyst. The combustion catalyst forms a thin layer next to the reactor wall to minimize the heat transfer resistance. Selective permeation of hydrogen through the palladium membrane is achieved either by co-current or counter-current flow of sweep gas through the third channel. The burner is modeled as a monolith reactor and the reformer is assumed to behave as a pseudo-homogenous reactor. The mass and energy balance equations for the thermally coupled membrane reactor form a set of 22 coupled ordinary differential equations. With the application of appropriate boundary conditions, the distributed reactor model for steady-state operation is solved as a boundary value problem. The model equations are discretized using spline collocation on finite elements. The discretized nonlinear modeling equations, along with the boundary conditions, form a system of algebraic equations that are solved using the trust region dogleg method. The performance of the reactor is numerically investigated for various key operating variables such as inlet fuel concentration, inlet steam/methane ratio, inlet reformer gas temperature and inlet reformer gas velocity. Simulations for both the co-current and the countercurrent flow modes are also performed using different sweep gas flow rates. For each case, the reactor performance is analyzed based on methane conversion and hydrogen recovery yield.     

Compartment model for steam reforming of methane in a membrane-assisted bubbling fluidized-bed reactor

A compartment model was developed to describe the flow pattern of gas within the dense zone of a membrane-assisted fluidized-bed reactor (MAFBR), in the bubbling mode of operation for steam reforming of methane both with (adiabatic) and without (isothermal) entering oxygen. Considering such a flow pattern and using the experimental data reported elsewhere [Roy S, Pruden BB, Adris AM, Grace JR, Lim CJ. Fluidized-bed steam methane reforming with oxygen input. Chem Eng Sci 1999; 54:2095–2102.], the parameters of the developed model (i.e., number of compartments for the bubble and emulsion phases) were determined and fair agreements were obtained between model predictions and experimental data. The developed model was utilized to describe the behavior of an industrial scale adiabatic and isothermal MAFBR. Moreover, the influences of various operating and design parameters such as steam-to-methane ratio (SMR), oxygen-to-methane ratio (OMR), operating temperature and pressure, and the number of hydrogen membrane tubes on the performance capability of the MAFBR were investigated. Furthermore, the performance capability of the MAFBR was optimized subject to the various operating and design constraints, including 1 ≤ SMR ≤ 4 and 500 ≤ T ≤ 1250 K, in the bubbling regime.     

The effect of non-uniform temperature on the sorption-enhanced steam methane reforming in a tubular fixed-bed reactor

The effect of non-uniform temperature on the sorption-enhanced steam methane reforming (SE-SMR) in a tubular fixed-bed reactor with a constant wall temperature of 600 °C is investigated numerically by an experimentally verified unsteady two-dimensional model. The reactor uses Ni/Al₂O₃ as the reforming catalyst and CaO as the sorbent. The reaction of SMR is enhanced by removing the CO₂ through the reaction of CaO + CO₂ → CaCO₃ based on the Le Chatelier's principle. A non-uniform temperature distribution instead of a uniform temperature in the reactor appears due to the rapid endothermic reaction of SMR followed by an exothermic reaction of CO₂ sorption. For a small weight hourly space velocity (WHSV) of 0.67 h^?1 before the CO₂ breakthrough, both a low and a high temperature regions exist simultaneously in the catalyst/sorbent bed, and their sizes are enlarged and the temperature distribution is more non-uniform for a larger tube diameter (D). Both the CH₄ conversion and the H₂ molar fraction are slightly increased with the increase of D. Based on the parameters adopted in this work, the CH₄ conversion, the H₂ and CO molar fractions at D = 60 mm are 84.6%, 94.4%, and 0.63%, respectively. After CO₂ breakthrough, the reaction of SMR dominates, and the reactor performance is remarkably reduced due to low reactor temperature.For a higher value of WHSV (4.03 h^?1) before CO₂ breakthrough, both the reaction times for SMR and CO₂ sorption become much shorter. The size of low temperature region becomes larger, and the high temperature region inside the catalyst/sorbent bed doesn't exist for D ≥ 30 mm. The maximum temperature difference inside the catalyst/sorbent bed is greater than 67 °C. Both the CH₄ conversion and H₂ molar fraction are slightly decreased with the increase of D. However, this phenomenon is qualitatively opposite to that for small WHSV of 0.67 h^?1. The CH₄ conversion and H₂ molar fraction at D = 60 mm are 52.6% and 78.7%, respectively, which are much lower than those for WHSV = 0.67 h^?1.     

Methane steam reforming for producing hydrogen in an atmospheric-pressure microwave plasma reactor

A methane steam reforming process for producing mainly hydrogen in an atmospheric-pressure microwave plasma reactor is demonstrated. Nano carbon powders, CO_x, C₂H₂, C₂H₄, and HCN were also formed. Intermediates such as OH, NH, CH, and active N₂ were identified using optical emission spectroscopy. The selectivity of H₂ was greater than 92.7% at inlet H₂O/CH₄ molar ratio (R) ≧ 0.5, and was higher than that obtained using methane plasmalysis because steam inhibited the formation of C₂H₂. The highest methane conversion was obtained at R = 1, reaching 91.6%, with the lowest specific energy consumption of H₂ formation at [CH₄]_in = 5%, 1.0 kW, and 12 slpm. The plasma-assisted catalysis process, which packed Ni/Al₂O₃ catalysts in the discharge zone and supplied heat using hot effluents, was used to elevate the methane conversion and hydrogen selectivity. However, large amounts of 40–70 nm carbon powder, which is electrically conductive, were produced, resulting in rapid catalyst deactivation due to carbon being deposited on the surface and in the pores of catalysts.     

Methane steam reforming in a Pd-Ag membrane reformer: An experimental study on reaction pressure influence at middle temperature

In this experimental work, methane steam reforming (MSR) reaction is performed in a dense Pd-Ag membrane reactor and the influence of pressure on methane conversion, CO_x-free hydrogen recovery and CO_x-free hydrogen production is investigated. The reaction is conducted at 450 °C by supplying nitrogen as a sweep gas in co-current flow configuration with respect to the reactants. Three experimental campaigns are realized in the MR packed with Ni-ZrO catalyst, which showed better performances than Ni-Al₂O₃ used in a previous paper dealing with the same MR system. The first one is directed to keep constant the total pressure in both retentate and permeate sides of the membrane reactor. In the second case study, the total retentate pressure is kept constant at 9.0 bar, while the total permeate pressure is varied between 5.0 and 9.0 bar. As the best result of this work, at 450 °C and 4.0 bar of total pressure difference between retentate and permeate sides, around 65% methane conversion and 1.2 l/h of CO_x-free hydrogen are reached, further recovering 80% CO_x-free hydrogen over the total hydrogen produced during the reaction. Moreover, a study on the influence of hydrogen-rich gas mixtures on the hydrogen permeation through the Pd-Ag membrane is also performed and discussed.     

Design of an annular microchannel reactor (AMR) for hydrogen and/or syngas production via methane steam reforming

A bench-scale annular microchannel reactor (AMR) prototype with microchannel width of 0.3 mm and total catalyst length of 9.53 × 10⁻² m active for the endothermic steam reforming of methane is presented. Experimental results at a steam to methane feed molar ratio of 3.3:1, reactor temperature of 1023 K, and pressure of 11 bar confirm catalyst power densities upwards of 1380 W per cm³ of catalyst at hydrogen yields >98% of thermodynamic equilibrium. A two-dimensional steady-state computational fluid dynamic model of the AMR prototype was validated using experimental data and subsequently employed to identify suitable operating conditions for an envisioned mass-production AMR design with 0.3 mm annular channel width and a single catalyst length of 254 mm. Thermal efficiencies, defined based upon methane and product hydrogen higher heating values (HHVs), of 72.7–57.7% were obtained from simulations for methane capacities of 0.5–2S LPM (space velocities of 195,000–782,000 h⁻¹) at hydrogen yields corresponding to 99%–75% of equilibrium values. Under these conditions, analysis of local composition, temperature and pressure indicated that catalyst deactivation via coke formation or Nickel oxidation is not thermodynamically favorable. Lastly, initial analysis of an envisioned 10 kW autothermal reformer combining 19 parallel AMRs within a single methane-air combustion chamber, based upon existing manufacturing capabilities within Power & Energy, Inc., is presented.     

Ethanol steam reforming reaction in a porous stainless steel supported palladium membrane reactor

In this experimental work, the ethanol steam reforming reaction is performed in a porous stainless steel supported palladium membrane reactor with the aim of investigating the influence of the membrane characteristics as well as of the reaction pressure. The membrane is prepared by electroless plating technique with the palladium layer around 25 μm deposited onto a stainless steel tubular macroporous support. The experimental campaign is directed both towards permeation and reaction tests. Firstly, pure He and H₂ are supplied separately between 350 and 400 °C in the MR in permeator modality for calculating the ideal selectivity αH₂/He. Thus, the MR is packed with 3 g of a commercial Co/Al₂O₃ catalyst and reaction tests are performed at 400 °C, by varying the reaction pressure from 3.0 to 8.0 bar. Experimental results in terms of ethanol conversions as well as recovery and purity of hydrogen are given and compared with some results in the same research field from the open literature.As best result of this work, 100% ethanol conversion is reached at 400 °C and 8 bar, recovering a hydrogen-rich stream consisting of more than 50% over the total hydrogen produced from reaction, having a purity around 65%.     

Oxidative steam reforming of ethanol over Rh based catalysts in a micro-channel reactor

Oxidative steam reforming of ethanol (OSRE) was studied over Rh/CeO₂/Al₂O₃ catalysts in a micro-channel reactor. First, the catalyst support, Al₂O₃, was deposited on to the metallic substrate by washcoating and then the CeO₂ and active metal were sequentially impregnated. The effect of support composition as well as active metal composition on oxidative steam reforming of ethanol in a micro-channel reactor was studied at atmospheric pressure, with water to ethanol molar ratio of 6 and oxygen to ethanol molar ratio ranging from 0.5 to 1.5, over a temperature range of 350-550 °C. Ceria added to 1%Rh/Al₂O₃ showed higher activity and selectivity than 1%Rh/Al₂O₃ alone. Out of the various catalysts tested, 2%Rh/20%CeO₂/Al₂O₃ performed well in terms of activity, selectivity and stability. The OSRE performance was compared with that of SRE over 2%Rh/20%CeO₂/Al₂O₃ catalyst at identical operating conditions. Compared to SRE, the activity in OSRE was higher; however the selectivity to desired products was slightly lower. The H₂ yield obtained in OSRE was ∼112 m³ kg⁻¹ h⁻¹, as compared to ∼128 m³ kg⁻¹ h⁻¹ in SRE. The stability test performed on 2%Rh/20%CeO₂/Al₂O₃ at 500 °C for OSRE showed that the catalyst was stable for ∼40 h and then started to deactivate slowly. The comparison between packed bed reactor and micro-channel reactor showed that the micro-channel reactor can be used for OSRE to produce hydrogen without any diffusional effects in the catalyst layer.     

An analytical and experimental investigation of high-pressure catalytic steam reforming of ethanol in a hydrogen selective membrane reactor

The objective of this work was to explore the benefits of high-pressure steam reforming of ethanol for the production of hydrogen needed to refuel the high-pressure tanks of fuel cell (polymer electrolyte) vehicles. This paper reports on the potential efficiency benefits and challenges of pressurized reforming and options for dealing with the challenges; it reports the results from experiments in a micro-reactor, followed by a modeling study of the reactor to project the dependence of the hydrogen yields on process parameters. The experiments were conducted in the range of approximately 7–70 atm, 600–750 °C, steam-to-carbon molar ratios of 3–12, and gas hourly space velocities of 8500–83,000 per hour. By placing a hydrogen-transporting palladium-alloy membrane within the catalyst zone, this study quantified the beneficial effect of hydrogen extraction from the reforming zone. The model was used to explore the parameter space to define the reactor and conditions that would be needed to approach the efficiency targets for distributed hydrogen production plants. The results indicate that the tested catalyst was sufficiently active, and the hydrogen yield achieved with the experimental membrane reactor was limited by the low hydrogen flux of the tested membrane. The reactor model predicts that a membrane with at least 20 times higher flux than currently evaluated would be sufficient to generate hydrogen yields to match efficiency targets of 72%.     

Mathematical simulation of hydrogen production via methanol steam reforming using double-jacketed membrane reactor

The hydrogen production and purification via methanol reforming reaction was studied in a double-jacketed Pd membrane reactor using a 1-D, non-isothermal mathematical model. Both mass and heat transfer behavior were evaluated simultaneously in three parts of the reactor, annular side, permeation tube and the oxidation side. The simulation results exhibited that increasing the volumetric flow rate of hydrogen in permeation side could enhance hydrogen permeation rate across the membrane. The optimum velocity ratio between permeation and annular sides is 10. However, hydrogen removal could lower the temperature in the reformer. The hydrogen production rate increases as temperature increases at a given Damköhler number, but the methanol conversion and hydrogen recovery yield decrease. In addition, the optimum molar ratio of air and methanol was 1.3 with three air inlet temperatures. The performance of a double-jacketed membrane reactor was compared with an autothermal reactor by judging against methanol conversion, hydrogen recovery yield and production rate. Under the same reaction conditions, the double-jacketed reactor can convert more methanol at a given reactor volume than that of an autothermal reactor.     

Experiments on hydrogen production from methanol steam reforming in fluidized bed reactor

A novel approach for the hydrogen production which integrated methanol steam reforming and fluidized bed reactor (FBR) was proposed. The reaction was carried out over Cu/ZnO/Al₂O₃ catalysts. The critical fluidized velocities under different catalyst particle sizes and masses were obtained. The influences of the operating parameters, including that of H₂O-to-CH₃OH molar ratio, feed flow rate, reaction temperature, and catalyst mass on the performance of methanol steam reforming were investigated in FBR to obtain the optimum experimental conditions. More uniform temperature distribution, larger surface volume ratio and longer contacting time can be achieved in FBR than that in fixed bed reactor. The results indicate that the methanol conversion rate in FBR can be as high as 91.95% while the reaction temperatures is 330 °C, steam-to-carbon molar ratio is 1.3, and feed flow rate is 540 ml/h under the present experiments, which is much higher than that in the fixed bed.     

Pure hydrogen production in a Pd-Ag multi-membranes module by methane steam reforming

An experimental test campaign has been carried out in order to investigate the performances in terms of pure hydrogen production of a multi-membrane module coupled with a methane reforming fixed bed reactor. The effect of operating parameters such as the temperature, the pressure, the water/methane feed flow rates and the feed molar ratio has been studied. The hydrogen produced into the traditional reformer has been recovered in the shell side of the membrane module by vacuum pumping. The membrane module consists of 19 Pd/Ag permeator tubes of wall thickness 150 μm, diameter 10 mm and length 250 mm: these dense permeators permitted to separate ultra-pure hydrogen.The experiments have been carried out with the reaction pressure of 100-490 kPa, the temperature of the reformer of 570-720 °C and the temperature of the Pd/Ag membranes module of 300-400 °C. A water/methane stream of molar ratio of 4/1 and 5/1 has been fed into the methane reformer at GSHV of 1547.6 and 1796.1 L_(STP) kg⁻¹ h⁻¹. Hydrogen yield value of about 3 has been measured at reaction pressure of 350 kPa, temperature reformer of 720 °C and methane feed flow rate of 6.445 × 10⁻⁴ mol s⁻¹.     

A transient study of double-jacketed membrane reactor via methanol steam reforming

A non-isothermal unsteady-state model was established to simulate methanol steam reforming using a double-jacketed Pd membrane reactor. At steady state, a self-sustained membrane reactor was achieved by the oxidation of residual methanol and hydrogen from reformer for endothermic steam reforming. The molar fractions of species and reformer temperature were analyzed under co-current operation between oxidation and reformer sides. The start-up of reformer was simulated under two conditions: (1) The catalyst temperature was lower than the influent temperature and (2) The catalyst temperature was higher than influent temperature. Condition 1 yielded higher methanol conversion and reformer temperature than condition 2 at steady state. Moreover, the instability of species can be minimized on condition 1 during start-up. The fluctuation of membrane reactor at steady state was also studied. Two strategies were compared to analyze the reformer response when temporary extra hydrogen was required. The results showed that increasing inlet methanol outperformed increasing reformer temperature.     

Hydrogen production from ethanol steam reforming in a micro-channel reactor

Ethanol steam reforming was studied over a supported Ir/CeO₂ catalyst in a micro-channel structured reactor. The catalyst coating was deposited on the channel walls and showed a remarkably high homogeneity and an excellent adherence to the stainless steel substrate, leading to stable performance during long-term runs. Hydrogen yields exceeding 40 L_H2 g_cat⁻¹ h⁻¹ were achieved during testing with partial ethanol conversion of 65% and a residence time in the order of a few milliseconds. This hydrogen productivity was found significantly higher than in a comparable conventional fixed-bed reactor hence being extremely promising for hydrogen production in micro fuel cell applications.