Methane Steam Reforming Reaction Research Articles

Ultracompact methane steam reforming reactor based on microwaves susceptible structured catalysts for distributed hydrogen production

Hydrogen is a potential green energy vector. Since the heating of the reforming processes commonly used for its production is obtained by burning hydrocarbons, it has a substantial CO2 footprint. One of the most critical aspects in the methane steam reforming (MSR) reaction is the heat transfer to the catalytic volume, due to the high heat fluxes required to obtain high methane conversions. Consequently, the reactor has complex geometries, along with the heating medium being characterized by temperatures higher than 1000 °C; expensive construction materials and high reaction volumes are therefore needed, resulting in slow thermal transients. These aspects increase the costs (both operative and fixed) as well as cause a decrease in the whole process efficiency. The heat transfer limitations due to the endothermicity of methane steam reforming reaction could be effectively overcome by microwave (MW) heating. This heating technique, that depends only on the dielectric properties of the materials, can result in an efficient and faster method for transferring heat directly to the catalyst, thus generating the heat directly inside the catalytic volume. In this work, Ni-based catalysts, differing from each other by the Ni loading (7 and 15 wt% with respect to the washcoat) were prepared. The catalysts were characterized by means of several techniques and tested in the MW-assisted methane steam reforming reaction. Furthermore, the energy balance of the entire process was performed to calculate the energy efficiency, making a preliminary evaluation of its feasibility in distributed hydrogen production also possible. The results of the preliminary tests showed that the prepared structured catalysts are very susceptible to the MW radiation, and that in the presence of the MSR reaction, it is possible to make the system reach a temperature of 900 °C. In the same tests, the CH4 conversion showed a good approach to the thermodynamic equilibrium values starting at temperatures of about 800 °C at a value of gas hourly space velocity (GHSV) of about 5000 h−1. The energy efficiency of the lab-scale system, calculated as the ratio among the energy absorbed by the system and the energy supplied by the microwaves, was about 50%. Future studies will deal with the microwave reactor optimization, aiming at the increase of the energy efficiency of the system, as well as to obtain a higher CH4 conversion at lower temperatures and increase the H2 yield and selectivity.

Effect of Mg Contents on Catalytic Activity and Coke Formation of Mesoporous Ni/Mg-Aluminate Spinel Catalyst for Steam Methane Reforming

Ni catalysts are most suitable for a steam methane reforming (SMR) reaction considering the activity and the cost, although coke formation remains the main problem. Here, Ni-based spinel catalysts with various Mg contents were developed through the synthesis of mesoporous Mg-aluminate supports by evaporation-induced self-assembly followed by Ni loading via incipient wetness impregnation. The mesoporous Ni/Mg-aluminate spinel catalysts showed high coke resistance under accelerated reaction conditions (0.0014 gcoke/gcat·h for Ni/Mg30, 0.0050 gcoke/gcat·h for a commercial catalyst). The coke resistance of the developed catalyst showed a clear trend: the higher the Mg content, the lower the coke deposition. The Ni catalysts with the lower Mg content showed a higher surface area and smaller Ni particle size, which originated from the difference of the sintering resistance and the exsolution of Ni particles. Despite these advantageous attributes of Ni catalysts, the coke resistance was higher for the catalysts with the higher Mg content while the catalytic activity was dependent on the reaction conditions. This reveals that the enhanced basicity of the catalyst could be the major parameter for the reduction of coke deposition in the SMR reaction.

Effects of exit-stream mixtures of the steam reforming on the intermediate-temperature solid oxide fuel cells with nickel-based anodes

Hydrocarbon fuel attracts attention due to its abundant source and low cost. However, carbon deposition damages solid oxide fuel cells (SOFC), especially intermediate-temperature solid oxide fuel cells (IT-SOFCs). We applied the external SOFC system, in which a steam methane-reforming reactor was connected before SOFCs. This work shows a simplified process in the steam methane reformer, where the methane and steam ratio was under control. The steam methane reformer was simulated by Aspen Plus to optimize the gas mixture for SOFCs. Detailed analyses show that carbon formation is related to different fuel compositions and operating conditions. Proper steam injection in feed effectively improves carbon formation—observed in the temperature-programmed oxidation method. Carbon morphology analyses provide a better understanding of carbon growth paths. The completed IT-SOFC assessment shows avoidance of carbon damage and indicates a potential integration in the development of SOFCs.

Multidimensional Modeling of Steam-Methane-Reforming-Based Fuel Processor for Hydrogen Production

We present a three-dimensional (3-D) steam-methane-reforming (SMR) model consisting of a steam-reforming (SR) reactor, water gas shift reactor, preferential oxidation reactor, catalytic burner, heat exchangers, and balance of plant components. The mass and energy balance equations are derived considering the kinetic expressions of various SMR reactions and implemented in the commercial computational fluid dynamics software program Fluent by employing user-defined functions. The 3-D SMR model is then applied to a 10-kW SR reformer geometry and simulated for comparison with in-house experimental data. The simulation results and the experimental data show good agreement, and the model accurately captures the experimental exhaust gas compositions and the reactor outlet temperatures. The proposed 3-D simulation tool for predicting various transport and chemical processes is highly desirable from the viewpoint of design and optimization of full-scale SMR-based fuel processors.

Egg-shell-type Ni supported on MgAl2O4 pellets as catalyst for steam methane reforming: Enhanced coke-resistance and pellet stability

The steam methane reforming (SMR) reaction generally occurs on the surface of pellet catalysts due to the high reaction rate. We herein prepared egg-shell-type pellet catalysts using tube-shaped MgAl2O4 pellets as a support for effective utilization of the catalytically active component (nickel) by selectively localizing the metallic nickel particles in the outer region of the pellets. Formation of the egg-shell-type catalysts was confirmed by cross-sectional imaging and scanning electron microscopy-energy dispersive X-ray spectroscopy. As a comparison, the homo-type catalysts, in which nickel was uniformly distributed throughout the pellet, were also prepared. In the SMR reaction with a steam to carbon ratio (S/C) of 3, the catalytic activity of the egg-shell-type catalyst with Ni loading of 3.5 wt.% matched or exceeded that of the homo-type catalyst with Ni loading of 5 wt.% despite the lower Ni loading of the former, over the entire weight hourly space velocity range (6,000–24,000 mL·gcat–1 h–1). To rapidly evaluate coke formation with the given pellet catalysts, experiments were performed with an S/C of 0.5. Under this condition, the methane conversion of the given catalysts was similar. However, the egg-shell-type catalysts showed better coke resistance and pellet stability than the homo-type catalyst. Overall, the egg-shell-type catalysts exhibit excellent properties in terms of long-term stability and carbon resistance. Thus, the egg-shell-type catalysts are more suitable for SMR reactions than the conventional homo-type catalyst.

Thermodynamic equilibrium analysis of steam methane reforming based on a conjugate solution of material balance and law action mass equations with the detailed energy balance

Thermodynamic equilibrium analysis of the steam methane reforming (SMR) process to synthesis gas was studied. For this purpose, the system equations of the material balance and the equations of law mass action were solved by dichotomy method. The investigation was performed for a wide range of operational conditions such as a temperature, pressure, and inlet steam-to-methane ratio. The results obtained, with the help of developed algorithms, were compared with the results obtained via different commercial and open-source programs. All results are in excellent agreement. The operational conditions for the probable formation of carbon were determined. It was established that for the temperature range above 1100 K, the probability of carbon formation is absent for steam-to-methane ratio above units. In order to determine the amount of heat supplied per 1 mol to the reformer, the heat balance equation was obtained to achieve a targeted degree of methane conversion. With the help of the heat balance equation, it was established that the resulting transformation of substances in the steam methane reformer can be presented as a sequential heating of feed streams of methane and steam from the inlet temperature T1 to the outlet temperature T2, heat for SMR reaction at the temperature T2, and heat for transformation of the part of the produced carbon monoxide (CO) via the water-gas shift (WGS) reaction at the temperature T2. The presented algorithm of thermodynamic analysis gives an appearance of the dependence of the product composition and the amount of required heat from operating conditions such as the temperature, pressure, and steam-to-methane ratio.

Intrinsic methane steam reforming kinetics on nickel-ceria solid oxide fuel cell anodes

Direct internal reforming in solid oxide fuel cells (SOFCs) is advantageous as it enables to heat and steam from the exothermic hydrogen oxidation reaction in the endothermic steam reforming reaction. However, it may increase potentially deteriorating temperature gradients as well. The temperature and concentration profiles can be accurately simulated with adequate SOFC models and intrinsic methane steam reforming (MSR) kinetics. Therefore, this study aims to derive intrinsic MSR kinetics suitable for control-oriented dynamic SOFC models. The individual influences of the methane, steam and hydrogen partial pressures on the MSR reaction are experimentally studied on functional electrolyte supported cells with nickel-gadolinium doped cerium anodes. A non-proportional dependence of the MSR rate on the methane partial pressure and a slight negative dependence on the steam partial pressure are observed, but the effect of the hydrogen partial pressure seems insignificant. Various kinetic rate equations are parameterised with the experimental data and an ideal plug flow reactor model. An intrinsic Langmuir-Hinshelwood mechanism for a rate determining step between associatively adsorbed methane and dissociatively adsorbed steam on the catalyst surface shows good agreement with the experimental data, and is thermodynamically and physically consistent.

Maximum Hydrogen Production Rate Optimization for Tubular Steam Methane Reforming Reactor

Abstract The performance of a steam methane reforming (SMR) reactor is optimized by using the theory of finite time thermodynamics in this paper. The maximum hydrogen production rate (HPR) and the corresponding optimal exterior wall temperature (EWT) and the optimal pressure of the reaction mixture (PRM) profiles in the SMR reactor are obtained by using nonlinear programming method. In the optimization process, the fixed inlet mole flow rate of components, the thresholds of the state variables and the conservation equations are taken as the constraints. The performance of the optimal reactor is compared with that of the reference reactor with a linear EWT profile. The results show that the HPR of the optimal reactor increases by about 11.8 %. The optimal EWT profile is alike with the linear EWT profile. The HPR increases with the increase of the inlet temperature of reaction mixture and the decrease of the inlet PRM. The influence of the TRM on the HPR is smaller than that of the PRM. The results obtained herein are helpful to the optimal design of practical tubular reactors.

The coupling performance during reactive sorption enhanced reforming (ReSER) process: Simulation and experimental studies

The coupling performance of nano-CaO carbonation with the steam methane reforming (SMR) during reactive sorption enhanced reforming process (ReSER) for hydrogen production was studied by simulation and experimental evaluation. A two-dimensional axial symmetric pseudo-homogeneous mathematic model was established based on nano-CaO carbonation kinetics with the Boltzmann equation style and SMR reaction kinetics. The coupling performance was studied by varying carbonation rate constant (kcarb) and the maximum carbonation conversion (Xmax) in the model. The mathematic model was numerically solved by the COMSOL Multiphysics software and experimentally evaluated using commercial nano-CaO as the CO2 adsorbent. An average relative deviation of 3.86% of CH4 conversion was obtained between the simulated and experimental results. The simulation results indicated the conversion of the CH4 was improved from 88% to 95.3% by increasing kcarb from 1.6 s−1 to 5.74 s−1 and the period of pre-breakthrough time could be extended from 2 min to 20 min by increasing Xmax from 0.3 to 0.9. CH4 conversion of maximum 94.1% when reaction was under 650 °C and 1 bar, the highest molar fraction of H2 of 99.7% when reaction at 600 °C and 1 bar, and the maximum enhancement factor of 45.4% was obtained at 576.3 °C, 2.8 bar.

Nickel Exsolution‐Driven Phase Transformation from an n=2 to an n=1 Ruddlesden‐Popper Manganite for Methane Steam Reforming Reaction in SOFC Conditions

AbstractAn original way to perform the exsolution of Ni nanoparticles on a ceramic support was explored for the development of methane steam reforming catalyst in SOFC anode conditions. The n=2 Ruddlesden‐Popper (RP) phase La1.5Sr1.5Mn1.5Ni0.5O7±δ has been synthesized by the Pechini method and subsequently reduced with an H2‐N2 mixture at different temperatures and reducing times to induce the formation of two phases: LaSrMnO4 (n=1 RP) decorated with metallic Ni nanoparticles. Preliminary measurements of catalytic behavior for the steam reforming have been carried out in a reduction‐reaction process with a mixture of 82 mol %CH4, 18 mol %N2 and low steam to carbon ratio (S/C=0.15). The catalyst exhibits a selectivity for CO production (0.97), 14.60 mol % CH4 conversion and around 24.19 mol % H2 production. Such catalytic behavior was maintained for more than 4 h, with a constant rate of hydrogen production and CH4 conversion rate.

Bench-Scale Steam Reforming of Methane for Hydrogen Production

The effects of reaction parameters, including reaction temperature and space velocity, on hydrogen production via steam reforming of methane (SRM) were investigated using lab- and bench-scale reactors to identify critical factors for the design of large-scale processes. Based on thermodynamic and kinetic data obtained using the lab-scale reactor, a series of SRM reactions were performed using a pelletized catalyst in the bench-scale reactor with a hydrogen production capacity of 10 L/min. Various temperature profiles were tested for the bench-scale reactor, which was surrounded by three successive cylindrical furnaces to simulate the actual SRM conditions. The temperature at the reactor bottom was crucial for determining the methane conversion and hydrogen production rates when a sufficiently high reaction temperature was maintained (>800 °C) to reach thermodynamic equilibrium at the gas-hourly space velocity of 2.0 L CH4/(h·gcat). However, if the temperature of one or more of the furnaces decreased below 700 °C, the reaction was not equilibrated at the given space velocity. The effectiveness factor (0.143) of the pelletized catalyst was calculated based on the deviation of methane conversion between the lab- and bench-scale reactions at various space velocities. Finally, an idling procedure was proposed so that catalytic activity was not affected by discontinuous operation.

The role of Pt loading on La2O3-Al2O3 support for methane conversion reactions via partial oxidation and steam reforming

The effects of Pt loadings on the catalytic performance of the La2O3-Al2O3-supported Pt nanoparticles are investigated during the partial oxidation (POM) and steam reforming of methane (SRM). From analyses of XRD, UV–Vis, TPR, CO-DRIFTS, XPS, Raman spectroscopy, cyclohexane dehydrogenation reaction, Pt surface species and their dispersions were dully observed. The good degrees of interaction between Pt nanoparticles and lanthana species in the support gave robust catalysts in POM, evidenced by XPS and TEM for low Pt loadings. Arrhenius plots for SRM showed an apparent activation energy of 70 kJ mol−1 for all Pt(x wt%)/Al2O3-La2O3 catalysts. An enrichment of the Pt species at loadings superior to 0.5 wt% resulted in Pt nanoparticles weakly interacting with the La2O3-Al2O3 support and the consequent sintering of the particles in SRM and POM reactions. On the contrary, best catalytic results and a more stable performance during POM in 24 h on stream was observed, when dispersing a 0.5 wt% of Pt on the support. A strong interaction between the PtOx species and the support was crucial for La2O3 preserve the high dispersion of the Pt entities. This favored the reactivity of surface oxygen species coming from LaPtOx[Pto]n. Indeed, this chemical entity was located on the surface of the solid, at the periphery of Pto particles, being further converted into La2PtOx[Pto]n−1. The decomposition of CH4 to CO and H2 as well as the coke gasification on the accessible Pt sites gave better conversions for Pt(0.5 wt%)/Al2O3-La2O3 compared with the other solids with higher Pt loadings.

Computational fluid dynamics and experimental validation of a compact steam methane reformer for hydrogen production from natural gas

A three-dimensional (3D) computational fluid dynamics (CFD) model of an annulus steam methane reforming (SMR) reactor was developed for producing 2.5 Nm3/h of H2 from natural gas. The feed and combustion gases played a role in a counter-current heat exchange owing to a narrow sleeve equipped between the combustor and catalytic reactor. The momentum, energy, and mass conservation equations were integrated with a realizable k–ε turbulence model, discrete ordinates radiation model, and reversible SMR reaction kinetics. The CFD results such as axial temperature profiles and producer gas compositions were validated against the experimental data measured in this study. The thermal efficiency of the compact SMR reactor was 60%, and the heat flux through the reactor wall was 39 kW/m2. The overall heat transfer coefficient from the sleeve to the catalytic reactor was 158 W/m2/K. The sleeve-type SMR reactor flattened the temperature profile along the reactor length.

Numerical research on carbon activity, fuel utilization, chemical reaction, and temperature distribution for IT single planar SOFC

ABSTRACTA steady-state and three-dimensional (3-D) model has been established for an intermediate temperature planar anode-supported solid oxide fuel cell. The model couples charge transfer, mass transfer, momentum transfer, and energy transfer equations. Chemical reactions (methane cracking reaction (MCR), Boudouard reaction, methane steam reforming reaction (MSR), and water gas shift reaction (WGSR)) and electrochemical oxidation of H2 and CO are considered. The variations of carbon activity, fuel utilization, and temperature distribution have been discussed with polarization and concentration separately. The thermal stress distribution in the positive electrode-electrolyte-negative electrode (P-E-N) structure is also discussed. The simulation results agree well with the literature.

Preparation of Ni-based egg-shell-type catalyst on cylinder-shaped alumina pellets and its application for hydrogen production via steam methane reforming

Nickel-based ‘egg-shell-type’ catalysts were prepared using cylinder-shaped alumina pellets as supports. In the egg-shell-type catalysts, nickel was selectively located in the outer region of the alumina pellets. Ethylene glycol or 1-octanol were used as hydrophobic solvents to retard internal penetration of the alumina pellets by the nickel nitrate solution. Without hydrophobic solvent, a ‘homo-type’ catalyst with even nickel distribution inside the alumina pellets was achieved. Cross-sectional images and SEM-EDS analysis of the cylinder-shaped alumina pellets showed that nickel concentration in the egg-shell-type catalyst was higher in the outer region and decreased towards the inner region of the alumina pellets. The egg-shell-type nickel distribution was maintained after subsequent magnesium impregnation and calcination processes. X-ray diffraction patterns and temperature programmed reduction profiles showed that the only difference between homo-type and egg-shell type catalysts, when their nickel loading was the same, was the nickel distribution inside pellets; and this was shown to cause significant difference in their catalytic activity in the steam methane reforming (SMR) reaction. For the homo-type catalyst, nickel loading of 3.5 wt% was insufficient for the SMR reaction, as metallic nickel particles were evenly distributed through the entire alumina pellet. However, nickel loading of 3.5 wt% was sufficient for the egg-shell-type catalyst, because active sites with metallic nickel particles were concentrated in the outer region of the pellets. These experimental results confirmed that the egg-shell-type nickel distribution is a favorable design for an SMR reaction catalyst.

Hydrogen production of nickel–scandia-stabilized zirconia and copper/nickel–scandia-stabilized zirconia catalysts through steam methane reforming for solid oxide fuel cell operation

In this study, the catalytic activities of the steam methane reforming (SMR) reactions with two catalysts, including nickel–scandia-stabilized zirconia (Ni–SSZ) and copper/nickel–scandia-stabilized zirconia (Cu/Ni–SSZ), were examined and compared. The microstructure and crystallinity of the as-prepared catalysts were characterized by scanning electron microscopy, Raman spectroscopy, and X-ray diffraction. Mass spectrometer was applied in the outlet streams, in order to simultaneously monitor the time-dependent kinetics in the reactor for an activity test and conversion examination. Finally, thermogravimetric analysis (TGA) and Raman spectrometer were implemented for further verification of carbon residuals on the catalysts. It was found that the incorporation of Cu on Ni–SSZ imposed significant constraints on the growth of nickel crystallites from NiO during the annealing process in reducing atmospheres. The methane conversion of Ni–SSZ and Cu/Ni–SSZ catalysts (annealed at 300 °C for 2 h) was 36.2 and 26.0%, respectively. However, the amount of carbon residuals on Cu/Ni–SSZ catalyst (300 °C for 2 h) was 18.6%, which is lower than that of the Ni–SSZ catalysts (33.2%) from TGA results. Further Raman experiments revealed that more graphite-like carbon residuals and less defects or amorphous carbons (IG/ID = 2.0) were found in the case of Cu/Ni–SSZ catalysts (300 °C for 2 h). Among the catalysts in this study, the Cu/Ni–SSZ catalyst (300 °C for 2 h) is considered as a promising catalyst for SMR reaction, since it has a fair methane conversion, and characterized higher CO2 selectivity and lower CO selectivity without compromising the hydrogen purity. More importantly, the least amount of carbon residuals was found in Cu/Ni–SSZ catalyst (300 °C for 2 h), which assured a better lifetime.

Catalytic performance of a high-cell-density Ni honeycomb catalyst for methane steam reforming

The catalysis of methane steam reforming (MSR) by pure Ni honeycombs with high cell density of 2300 cells per square inch (cpsi) was investigated to develop efficient and inexpensive catalysts for hydrogen production. The Ni honeycomb catalyst was assembled using 30-μm-thick Ni foils, and showed much higher activity than that of a Ni honeycomb catalyst with cell density of 700 cpsi at a steam-to-carbon ratio of 1.36 and a gas hourly space velocity of 6400 h−1 in a temperature range of 873–1173 K. Notably, the activity increased approximately proportional to the increasing geometric specific surface area of the honeycombs. The turnover rate of the Ni honeycomb catalyst was higher than that of supported Ni catalysts. The changes in chemical state of the Ni catalyst during hydrogen reduction and MSR reaction were analyzed by in situ X-ray absorption fine structure spectroscopy, which revealed that deactivation was mainly due to oxidation of the surface Ni atoms. These results demonstrated that the high-cell-density Ni honeycomb catalyst exhibits good performance for MSR reaction, and easy regeneration of the deactivated Ni honeycomb catalyst is possible only via hydrogen reduction.

Exploring novel hydrogen production processes by integration of steam methane reforming with chemical-looping combustion (CLC-SMR) and oxygen carrier aided combustion (OCAC-SMR)

This article discusses the concept of combining steam methane reforming (SMR) with fluidized beds of oxygen carrier particles and presents results from process simulations in Aspen Plus of new process outlines with and without carbon capture. Conventionally, heat to steam reforming tubes is provided by gas-fired burners, which transfer heat to the tube’s surface mainly by radiation. An alternative approach to provide heat to the endothermic SMR reaction is to use fluidized bed technology, utilizing oxygen carrier particles as bed material. Two novel configurations of the steam reforming process are proposed. The first concept incorporates SMR with a single bubbling fluidized bed reactor of oxygen carrier particles, or Oxygen Carrier Aided Combustion (OCAC). The second combines Chemical Looping Combustion (CLC) with an external fluidized bed heat exchanger (FBHE) used for SMR. Here, biomass is used as supplementary fuel in the furnace. The results for the OCAC-based system show that the cold gas efficiency can be increased compared to a reference case describing a conventional process, and at the same time decrease CO2 emissions by 4%. The biomass-fuelled CLC configuration displays surprisingly large negative CO2 emissions, corresponding to a CO2 emission reduction by 151% compared to the reference case.

High specific surface area supports for highly active Rh catalysts: Syngas production from methane at high space velocity

A series of high specific surface area mesoporous supports (CeO2, CeO2-Al2O3, and Al2O3) were synthesized by the surfactant-assisted precipitation method using cetyltrimethylammonium bromide (CTAB) as template. Highly dispersed Rh-based catalysts were prepared by the wetness impregnation technique. The physico-chemical properties of the as-prepared supports and catalysts were investigated by N2-physisorption, CO-chemisorption, XRD, and H2-TPR measurements. Catalytic performance was evaluated towards the methane steam reforming (MSR) reaction up to 300 h of time-on-stream varying temperature (700–800 °C), steam-to-carbon (S/C = 2–3), and space velocity (88–200 SL·gcat−1·h−1); turnover frequencies were calculated at each reaction condition. All catalysts exhibited high activity strictly connected with high specific surface area (105–325 m2 g−1) and metal dispersion (34.3–84.0%). Significant enhanced stability was observed for Al2O3-containing catalysts towards the MSR reaction at high space velocity.

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.