Modelling of hydrogen perm-selective membrane reactors for catalytic methane steam reforming

Methane steam reforming is one of the most important pathways for producing high purity hydrogen. In this context, the use of fixed-bed catalytic reactors equipped with hydrogen perm-selective membranes is an interesting alternative for producing high purity hydrogen in one single step. In this work, this reactor is studied by means of numerical simulations using a 2D model, consisting of mass, energy and momentum balances. The fixed-bed is considered to be formed by Ru/SiO₂ catalyst particles, especially tailored for steam reforming at low temperature and steam-to-carbon ratio, whereas a composite palladium membrane was considered for hydrogen permeation. The model was validated with experimental data, and the adequacy of a simplified 1D model to simulate the membrane reactor was evaluated and discussed in comparison to the 2D model. Then, the model was used to study the influence of the main operating variables (inlet temperature, pressure, space velocity, steam excess and sweep gas rate in the permeate side) on the reactor performance. Finally, the optimum operating conditions, corresponding to a maximum hydrogen permeation rate, were determined, and the behaviour of the optimized reactor is analysed in detail.     

Modeling and simulation of hydrogen production from dimethyl ether steam reforming using exhaust gas

In this paper, hydrogen production from steam reforming of DME (dimethyl ether) has been modeled and simulated using a CFD (computational fluid dynamics) method. The reformation chemistry occurs in a porous catalytic bed where exhaust gas is supplied through the EGR (exhaust gas recycling) valve of the engine to drive the endothermic reaction system. The tightly coupled system of mass, energy, and momentum equations are used to describe the complex physical and chemical process of DME steam reforming. The global reaction kinetics for the reforming is adopted in the CFD model. The mathematical models are introduced into the commercial software Comsol, and then numerical simulations are also performed based on this model. The model predictions are quantitatively validated by experiment data. The simulation results indicate the temperature distribution, mass distribution, DME conversion, and hydrogen production from steam reforming of DME. In addition, the fuel to steam ratio and velocity of exhaust gas are manipulated as operating parameters. These simulation results will provide helpful data to design and operate a bench scale catalytic fluidized bed reactor. Copyright © 2015 John Wiley & Sons, Ltd.     

Numerical studies of sorption-enhanced glycerol steam reforming in a fluidized bed membrane reactor at low temperature

In order to improve the hydrogen production efficiency by glycerol steam reforming, a membrane-assisted fluidized bed reactor with carbon dioxide sorption is developed to enhance the reforming process. Low-temperature operation in a membrane reactor is necessary considering the thermal stability of membrane. In this work, the sorption-enhanced glycerol steam reforming process in a fluidized bed membrane reactor under the condition of low temperature is numerically investigated, where the hydrotalcite is employed as CO₂ sorbents. The impact of operating pressure on the reforming performance is further evaluated. The results demonstrate that the integration of membrane hydrogen separation and CO₂ sorption can effectively enhance the low-temperature glycerol reforming performance. The fuel conversion above 95% can be achieved under an elevated pressure.     

Hydrogen production by reforming of liquid hydrocarbons in a membrane reactor for portable power generation—Experimental studies

One of the most promising technologies for lightweight, compact, portable power generation is proton exchange membrane (PEM) fuel cells. PEM fuel cells, however, require a source of pure hydrogen. Steam reforming of hydrocarbons in an integrated membrane reactor has potential to provide pure hydrogen in a compact system. Continuous separation of product hydrogen from the reforming gas mixture is expected to increase the yield of hydrogen significantly as predicted by model simulations. In the laboratory-scale experimental studies reported here steam reforming of liquid hydrocarbon fuels, butane, methanol and Clearlite^® was conducted to produce pure hydrogen in a single step membrane reformer using commercially available Pd–Ag foil membranes and reforming/WGS catalysts. All of the experimental results demonstrated increase in hydrocarbon conversion due to hydrogen separation when compared with the hydrocarbon conversion without any hydrogen separation. Increase in hydrogen recovery was also shown to result in corresponding increase in hydrocarbon conversion in these studies demonstrating the basic concept. The experiments also provided insight into the effect of individual variables such as pressure, temperature, gas space velocity, and steam to carbon ratio. Steam reforming of butane was found to be limited by reaction kinetics for the experimental conditions used: catalysts used, average gas space velocity, and the reactor characteristics of surface area to volume ratio. Steam reforming of methanol in the presence of only WGS catalyst on the other hand indicated that the membrane reactor performance was limited by membrane permeation, especially at lower temperatures and lower feed pressures due to slower reconstitution of CO and H₂ into methane thus maintaining high hydrogen partial pressures in the reacting gas mixture. The limited amount of data collected with steam reforming of Clearlite^® indicated very good match between theoretical predictions and experimental results indicating that the underlying assumption of the simple model of conversion of hydrocarbons to CO and H₂ followed by equilibrium reconstitution to methane appears to be reasonable one.     

Enhancement of membrane hydrogen separation on glycerol steam reforming in a fluidized bed reactor

Membrane hydrogen separation can effectively promote fuel conversion and hydrogen yield by means of altering chemical equilibrium of reforming reactions. In this work, the enhancing process of glycerol steam reforming via a fluidized bed membrane reactor is numerically investigated. Under the framework of the Euler-Euler method, chemical kinetic model is implemented and the reforming performance with and without membrane separation is compared. The effect of densified zones caused by membrane separation is examined. Meanwhile, the impacts of operating parameters including hydrogen partial pressure on the permeate side and fuel gas velocity on densified zones and hydrogen yield are evaluated. The results demonstrate that the excessive reduction of hydrogen partial pressure on the permeate side and the increase of feed gas velocity are detrimental to fuel conversion and hydrogen yield.     

Numerical modeling of an automotive derivative polymer electrolyte membrane fuel cell cogeneration system with selective membranes

Cogeneration power plants based on fuel cells are a promising technology to produce electric and thermal energy with reduced costs and environmental impact. The most mature fuel cell technology for this kind of applications are polymer electrolyte membrane fuel cells, which require high-purity hydrogen.The most common and least expensive way to produce hydrogen within today's energy infrastructure is steam reforming of natural gas. Such a process produces a syngas rich in hydrogen that has to be purified to be properly used in low temperature fuel cells. However, the hydrogen production and purification processes strongly affect the performance, the cost, and the complexity of the energy system.Purification is usually performed through pressure swing adsorption, which is a semi-batch process that increases the plant complexity and incorporates a substantial efficiency penalty. A promising alternative option for hydrogen purification is the use of selective metal membranes that can be integrated in the reactors of the fuel processing plant. Such a membrane separation may improve the thermo-chemical performance of the energy system, while reducing the power plant complexity, and potentially its cost. Herein, we perform a technical analysis, through thermo-chemical models, to evaluate the integration of Pd-based H₂-selective membranes in different sections of the fuel processing plant: (i) steam reforming reactor, (ii) water gas shift reactor, (iii) at the outlet of the fuel processor as a separator device. The results show that a drastic fuel processing plant simplification is achievable by integrating the Pd-membranes in the water gas shift and reforming reactors. Moreover, the natural gas reforming membrane reactor yields significant efficiency improvements.     

Steam reforming of propane in a fluidized bed membrane reactor for hydrogen production

Steam reforming of propane was carried out in a fluidized bed membrane reactor to investigate a feedstock other than natural gas for production of pure hydrogen. Close to equilibrium conditions were achieved inside the reactor with fluidized catalyst due to the very fast steam reforming reactions. Use of hydrogen permselective Pd₇₇Ag₂₃ membrane panels to extract pure hydrogen shifted the reaction towards complete conversion of the hydrocarbons, including methane, the key intermediate product. Irreversible propane steam reforming is limited by the reversibility of the steam reforming of this methane. To assess the performance improvement due to pure hydrogen withdrawal, experiments were conducted with one and six membrane panels installed along the height of the reactor. The results indicate that a compact reformer can be achieved for pure hydrogen production for a light hydrocarbon feedstock like propane, at moderate operating temperatures of 475–550 °C, with increased hydrogen yield.     

Performance analysis of a membrane‐based reformer‐combustor reactor for hydrogen generation

Hydrogen is mostly produced in conventional steam methane reforming plants. In this work, we proposed a membrane‐based reformer‐combustor reactor (MRCR) for hydrogen generation in order to improve heat recovery and overall thermal efficiency. The proposed configuration will also reduce the complexity in existing steam methane reforming (SMR) plants. The proposed MRCR comprises combustion zone, hydrogen permeate zone, and SMR zone. A computational fluid dynamics model was developed using ANSYS‐Fluent software to simulate and analyze the performance of the proposed MRCR. Results show that high hydrogen yields were observed at high reformer pressures (RPs) and low gas hourly space velocities (GHSVs). Furthermore, by increasing the steam to methane ratio and addition of excess air in the combustion side, the hydrogen yield from the MRCR decreases. This is attributed to the reduction in the effective temperature of the hydrogen membrane. High RP, low GHSV, and low steam to methane ratio that increased the hydrogen yield also decreased carbon monoxide (CO) emissions. For an increased RP from 1 to 10 bar, the CO emission decreased by about 99%. The reduction in CO emission at high RP would be attributed to the effect of water gas shift reaction in the MRCR. Results of the extensive parametric study presented in this work can be used to determine the operating conditions based on tradeoffs between hydrogen yield (mole H₂/mole CH₄), hydrogen production rate (kg of H₂/h), allowable CO emissions, and exhaust gas temperature for other applications such as gas turbine.     

Modeling and analysis of a 5 kWe HT-PEMFC system for residential heat and power generation

We present a high-temperature proton exchange membrane fuel cell (HT-PEMFC) system model that accounts for fuel reforming, HT-PEMFC stack, and heat-recovery modules along with heat exchangers and balance of plant (BOP) components. In the model developed for analysis, the reaction kinetics for the fuel reforming processes are considered to accurately capture exhaust gas compositions and reactor temperatures under various operating conditions. The HT-PEMFC stack model is simplified from the three-dimensional HT-PEMFC CFD models developed in our previous studies. In addition, the parasitic power consumption and waste heat release from the various BOP components are calculated based on their heat-capacity curves. An experimental fuel reforming reactor for a 5.0 kW_e HT-PEMFC system was tested to experimentally validate the fuel reforming sub model. The model predictions were found to be in good agreement with the experimental data in terms of exhaust gas compositions and bed temperatures. Additionally, the simulation revealed the impacts of the burner air-fuel ratio (AFR) and the steam reforming reactor steam-carbon ratio on the system performance and efficiency. In particular, the combined heat and power efficiency of the system increased up to 78% when the burner AFR was properly adjusted. This study clearly illustrates that an HT-PEMFC system requires a high degree of thermal integration and optimization of the system configuration and operating conditions.     

Performance evaluation of PdAg membrane reactor in glycerol steam reforming process: Development of the CFD model

In the present paper, a CFD modeling of palladium membrane reactor, in which hydrogen produced through glycerol steam reforming, is presented. A comprehensive and precise kinetic and permeation model was used. On the basis of the equations and assumptions, an excellent agreement between model prediction and experimental data was achieved. Pressure, velocity and concentration distribution of various component within the Membrane Reactor (MR) were predicted. Moreover, the performance of both a Traditional Reactor (TR) and a MR was compared in various condition. The effects of some operating conditions such as temperature, pressure, feed flow rate and flow pattern on the glycerol conversion, hydrogen recovery and CO selectivity were evaluated. The most effective parameter was pressure: increasing it from 1 to 10 bar in co-current MR, the glycerol conversion, H2 recovery and CO selectivity were shifted from 46%, 17% and 6.6%–81%, 56% and 0.8%, respectively. The CFD model indicates that the performance of glycerol steam reforming improves when MR is used instead of TR. At various operating conditions the glycerol convertion enhanced 10–64% and CO selectivity reduced 7.5–99.0% in the MR when compared with the TR.     

Demonstration of a scaled-down autothermal membrane methane reformer for hydrogen generation

A novel concept for hydrogen generation by methane steam reforming in a thermally coupled catalytic fixed bed membrane reformer is experimentally demonstrated. The reactor, built from three concentric compartments, indirectly couples the endothermic methane steam reforming with the exothermic methane oxidation, while hydrogen is separated by a permselective Pd membrane. The study focuses on the determination of the key operation parameters and understanding their influence on the reactor performance. It has been shown that the reactor performance is mainly defined by the dimensionless ratio of the methane steam reforming feed flow rate to the hydrogen maximal membrane flow rate and by the ratio of the oxidation and steam reforming methane feed flow rates.     

CFD study of heat and mass transfer in ethanol steam reforming in a catalytic membrane reactor

This work shows the analysis of ethanol steam reforming process within a catalytic membrane reactor. A 2-D non-isothermal CFD model was developed using Comsol Multiphysics, based on previous experimentally validated isothermal model. A comprehensive heat and mass transfer study was carried out utilizing the model. Operating conditions such as liquid hourly space velocity (LHSV) (3.77–37.7 h^?1), temperature (673–823 K), reaction side pressure (4–10 bar) and permeate side sweep gas flow pattern were discussed. A temperature gradient along the reactor was observed from the model and a “cold spot” was seen at the reactor entrance area, which is unfavorable for the highly endothermic ethanol steam reforming process. By changing the sweep gas pattern to counter-current, the “cold spot” appears to be smaller with a reduced temperature drop. By studying the individual reaction rates, reverse methane steam reforming (methanation) was observed, caused by the low temperature in the “cold spot”. Optimal operating conditions were found to be under LHSV = 37.7 h^?1 and counter-current sweep gas conditions.     

Autothermal reforming of n‐hexadecane over Rh catalyst to produce syngas in microchannel reactor using finite element method

Numerical study on the autothermal reforming of n‐hexadecane, which can be used in proton exchange membrane fuel cell for automotive applications, in microchannels is necessary. A 2D computational fluid dynamics (CFD) model, with combustion and reforming channels thermally coupled and separated by a metal medium wall, is developed and studied in terms of hydrogen production and catalyst activity. Rh supported on CeO₂ is used as a catalyst and applied to the inner surface of the channels, where the catalytic endothermic and exothermic reactions occur. CFD analysis shows considerable results in terms of reactor performance. Along the reactor channel length, the mole percentage of hydrogen is 86% after over 2 hours of catalyst activity. The corresponding fuel conversion in respective channels is 85% on the catalytic surface of the reactor. The predicted hydrogen production from the CFD model is 59% higher than that as equilibrium conditions. Heat conduction through the medium solid wall depends on the thermal conductivity of a material. In this model, a metal solid wall with thermal conductivity of 40 W/m K, which transfers heat from the combustion channel within milliseconds, is used. The calculated model operating temperature in the reforming channel ranges from 660 to 850 K.     

Multi-objective optimization of aniline and hydrogen production in a directly coupled membrane reactor

A numerical study of aniline production by hydrogenation of nitrobenzene (NBH) and hydrogen production by steam methane reforming (SMR) in a directly coupled membrane reactor is developed. This membrane reactor was proposed aiming to decarbonize heating in SMR and to favor the recovery of all products. Aniline recovery is improved in this reactor as water, a byproduct in NBH, is consumed in SMR. The simulation is performed using a heterogeneous-one dimensional model (Dusty gas model) and results are compared against the homogeneous model. The operating conditions of the reactor were selected using a multi-objective optimization method, genetic algorithms. The aims of the optimization were: methane conversion maximization, minimum membrane area, minimum reactor size, hydrogen yield maximization, nitrobenzene conversion maximization and the maximization of hydrogen recovery. This process was able to achieve complete conversion of methane and nitrobenzene. The hydrogen yield achieved can be as high as the maximum (～4). 35% of this hydrogen was used as a reactant for aniline production. 99% of the unreacted hydrogen was recovered and purified. As the steam flow was minimized, aniline was obtained with a molar composition (70%), 2.1 times higher than that obtained in a conventional process for aniline production (33%). CO₂ was obtained with a purity of 97%, hence, CO₂ carbon capture and storage techniques were also favored. In addition, the energy requirements of heating of feedstock, reaction and recovery system of this novel process was 2.7 times lower than that of conventional processes carried out independently.     

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.     

Simulation of a porous ceramic membrane reactor for hydrogen production

A systematic simulation study was performed to investigate the performance of a porous ceramic membrane reactor for hydrogen production by means of methane steam reforming. The results show that the methane conversions much higher than the corresponding equilibrium values can be achieved in the membrane reactor due to the selective removal of products from the reaction zone. The comparison of isothermal and non-isothermal model predictions was made. It was found that the isothermal assumption overestimates the reactor performance and the deviation of calculation results between the two models is subject to the operating conditions. The effects of various process parameters such as the reaction temperature, the reaction side pressure, the feed flow rate and the steam to methane molar feed ratio as well as the sweep gas flow rate and the operation modes, on the behavior of membrane reactor were analyzed and discussed.     

Detailed analysis of the operational characteristics of the steam reformer and water–gas shift reactors for 5 kW HT-PEMFCs

The reactors designed for 5-kW high-temperature polymer electrolyte fuel cells are able to evaluate the performance of the steam reformer and each water–gas shift reactor independently. The goal of the experiments is to obtain the best overall performance for steam reforming while minimizing the CO concentration and maximizing the hydrogen yield. For this purpose, the performance of the steam reforming reactor unit with two types of flow paths was evaluated while evaluating the performance of various series of component combinations of the high-, middle-, and low-temperature shifts. Via experiment, thermal control followed by the appropriate heating and cooling mechanism is key to successful reaction performance. In addition to an individual unit-based experiment, numerical analyses were executed to understand the local chemical performance inside a reactor unit. These numerical analyses show good agreement with the experimental data measured at the outlet and provide a comprehensive detailed internal reaction mechanism such as the thermal conditions and CO concentration effect. Both experiments and numerical analyses can fundamentally improve the reaction performance by finding the optimal values of many control parameters.     

Thermodynamic analysis of a membrane-assisted chemical looping reforming reactor concept for combined H2 production and CO2 capture

There is great consensus that hydrogen will become an important energy carrier in the future. Currently, hydrogen is mainly produced by steam reforming of natural gas/methane on large industrial scale or by electrolysis of water when high-purity hydrogen is needed for small-scale hydrogen plants. Although the conventional steam reforming process is currently the most economical process for hydrogen production, the global energy and carbon efficiency of this process is still relatively low and an improvement of the process is key for further implementation of hydrogen as a fuel source. Different approaches for more efficient hydrogen production with integrated CO₂ capture have been discussed in literature: Chemical Looping Combustion (CLC) or Chemical Looping Reforming (CLR) and membrane reactors have been proposed as more efficient alternative reactor concepts relative to the conventional steam reforming process. However, these systems still present some drawbacks. In the present work a novel hybrid reactor concept that combines the CLR technology with a membrane reactor system is presented, discussed and compared with several other novel technologies. Thermodynamic studies for the new reactor concept, referred to as Membrane-Assisted Chemical Looping Reforming (MA-CLR), have been carried out to determine the hydrogen recovery, methane conversion as well as global efficiency under different operating conditions, which is shown to compare quite favorably to other novel technologies for H₂ production with CO₂ capture.     

Hydrogen production from glycerol steam reforming for low- and high-temperature PEMFCs

This paper presents a thermodynamic study of a glycerol steam reforming process, with the aim of determining the optimal hydrogen production conditions for low- and high-temperature proton exchange membrane fuel cells (LT-PEMFCs and HT-PEMFCs). The results show that for LT-PEMFCs, the optimal temperature and steam to glycerol molar ratio of the glycerol reforming process (consisting of a steam reformer and a water gas shift reactor) are 1000 K and 6, respectively; under these conditions, the maximum hydrogen yield was obtained. Increasing the steam to glycerol ratio over its optimal value insignificantly enhanced the performance of the fuel processor. For HT-PEMFCs, to keep the CO content of the reformate gas within a desired range, the steam reformer can be operated at lower temperatures; however, a high steam to glycerol ratio is required. This requirement results in an increase in the energy consumption for steam generation. To determine the optimal conditions of glycerol steam reforming for HT-PEMFC, both the hydrogen yield and energy requirements were taken into consideration. The operational boundary of the glycerol steam reformer was also explored as a basic tool to design the reforming process for HT-PEMFC.     

A two-dimensional mathematical model for the catalytic steam reforming of methane in both conventional fixed-bed and fixed-bed membrane reactors for the Production of hydrogen

A modelling and simulation study of catalytic steam reforming of methane is presented in this paper. A two-dimensional pseudo-heterogeneous model is developed to simulate a conventional fixed-bed reactor (FBR) as well as a fixed-bed membrane reactor (FBMR) with sweep gas added in both co-current modes for the two reactor configurations. The developed model is based on mass and energy balance equations for the catalyst phase and the gas phase in both FBR and FBMR reactors. Firstly, a study is done for describing that the temperature profiles of gaseous and solid phases reach to stable state as well as the component distributions in the two FBR and FBMR reactors. The model covers the aspect of the partial pressure of hydrogen in the membrane reactor with the permeation of hydrogen across a Pd-based membrane. The conversion of methane is significantly enhanced by the partial removal of hydrogen as from the shell side as a result of diffusion through the Pd-based membrane. Simulation results demonstrated that methane conversion of 97.21% can be achieved in FBR at operating temperature of 1250 K relative to methane conversion of 99.79% to 923 K in FBMR. The yield of hydrogen achieved to level from 2.154 in FBR at operating temperature of 1250 K while the yield of hydrogen reached to level from 3.731 with a thickness from 1.7 μm in FBMR reactor.