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.     

Differential evolution (DE) strategy for optimization of methane steam reforming and hydrogenation of nitrobenzene in a hydrogen perm‐selective membrane thermally coupled reactor

In this work, a thermally coupled membrane reactor is proposed for methane steam reforming and hydrogenation of nitrobenzene. The steam reforming process is carried out in the assisted membrane surface of the endothermic side, while the hydrogenation reaction of nitrobenzene to aniline is carried out on the other membrane surface of the exothermic side. The differential evolution (DE) strategy is applied to optimize this reactor considering nitrobenzene and methane conversion as the main objectives. The co‐current mode is investigated in this study, and the achieved optimization results are compared with those of conventional steam reformer reactor operated under the same feed conditions. The optimum values of feed temperature of exothermic side, feed molar flow rate of nitrobenzene, the steam‐to‐nitrobenzene molar ratio and the hydrogen‐to‐nitrobenzene molar ratio are determined during the optimization process. The simulation results show that the methane conversion and consequently hydrogen recovery yield are increased by 39.3% and 1.57, respectively, which contribute to aniline production with 27.3% saving in hydrogen supply from external and a reduction in environmental problems due to 100% nitrobenzene conversion. The optimization results justify the feasibility of coupling these reactions. Experimental proof‐of‐concept is needed to establish the validity and safe operation of the novel reactor. Copyright © 2012 John Wiley & Sons, Ltd.     

Simultaneous production of two types of synthesis gas by steam and tri‐reforming of methane using an integrated thermally coupled reactor: mathematical modeling

In this work, tri‐reforming and steam reforming processes have been coupled thermally together in a reactor for production of two types of synthesis gases. A multitubular reactor with 184 two‐concentric‐tubes has been proposed for coupling reactions of tri‐reforming and steam reforming of methane. Tri‐reforming reactions occur in outer tube side of the two‐concentric‐tube reactor and generate the needed energy for inner tube side, where steam reforming process is taking place. The cocurrent mode is investigated, and the simulation results of steam reforming side of the reactor are compared with corresponding predictions for thermally coupled steam reformer and also conventional fixed‐bed steam reformer reactor operated at the same feed conditions. This reactor produces two types of syngas with different H₂/CO ratios. Results revealed that H₂/CO ratio at the output of steam and tri‐reforming sides reached to 1.1 and 9.2, respectively. In this configuration, steam reforming reaction is proceeded by excess generated heat from tri‐reforming reaction instead of huge fired‐furnace in conventional steam reformer. Elimination of a low performance fired‐furnace and replacing it with a high performance reactor causes a reduction in full consumption with production of a new type of synthesis gas. The reactor performance is analyzed on the basis of methane conversion and hydrogen yield in both sides and is investigated numerically for various inlet temperature and molar flow rate of tri‐reforming side. A mathematical heterogeneous model is used to simulate both sides of the reactor. The optimum operating parameters for tri‐reforming side in thermally coupled tri‐reformer and steam reformer reactor are methane feed rate and temperature equal to 9264.4 kmol h^?1 and 1100 K, respectively. By increasing the feed flow rate of tri‐reforming side from 28,120 to 140,600 kmol h^?1, methane conversion and H₂ yield at the output of steam reforming side enhanced about 63.4% and 55.2%, respectively. Also by increasing the inlet temperature of tri‐reforming side from 900 to 1300 K, CH₄ conversion and H₂ yield at the output of steam reforming side enhanced about 82.5% and 71.5%, respectively. The results showed that methane conversion at the output of steam and tri‐reforming sides reached to 26.5% and 94%, respectively with the feed temperature of 1100 K of tri‐reforming side. Copyright © 2013 John Wiley & Sons, Ltd.     

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

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

A novel integrated thermally coupled configuration for methane-steam reforming and hydrogenation of nitrobenzene to aniline

In this work, a novel thermally coupled reactor containing the steam reforming process in the endothermic side and the hydrogenation of nitrobenzene to aniline in the exothermic side has been investigated. In this novel configuration, the conventional steam reforming process has been substituted by the recuperative coupled reactors which contain the steam reforming reactions in the tube side, and the hydrogenation reaction in the shell side. The co-current mode is investigated and the simulation results are compared with corresponding predictions for an industrial fixed-bed steam reformer reactor operated at the same feed conditions. The results show that although synthesis gas productivity is the same as conventional steam reformer reactor, but aniline is also produced as an additional valuable product. Also it does not need to burn at the furnace of steam reformer. The performance of the reactor is numerically investigated for different inlet temperature and molar flow rate of exothermic side. The reactor performance is analyzed based on methane conversion, hydrogen yield and nitrobenzene conversion. The results show that exothermic feed temperature of 1270 K can produce synthesis gas with 26% methane conversion (the same as conventional) and nitrobenzene conversion in the outlet of the reactor is improved to 100%. This new configuration eliminates huge fired furnace with high energy consumption in steam reforming process.     

CFD simulation of methane steam reforming in a membrane reactor: Performance characteristics over range of operating window

Methane steam reforming is the most widely used pathway for hydrogen production. In this context, the use of a fixed bed catalytic reactor with a hydrogen-selective membrane is one of the most promising technologies to produce high purity hydrogen gas. In this work, the membrane reactor three-dimensional computational fluid dynamic (CFD) model was developed to investigate the performance. In this model, methane steam reforming global kinetic model has been coupled with the CFD model using User-Defined Function (UDF). Whereas, hydrogen permeation across the membrane is implemented by introducing source and sink formulation. The CFD simulation results were compared to the experimental data, where the developed model successfully captured the experimentally observed trends. We studied the influence of the various operating parameters, as temperature, steam to carbon ratio, sweep gas flow configuration and space velocity on the overall performance. The main observation and attained optimal operation windows from the study was discussed to provide insight into the factors affecting the overall performance.     

Transient numerical modeling and model predictive control of an industrial-scale steam methane reforming reactor

A steam methane reforming reactor is a key equipment in hydrogen production, and numerical analysis and process control can provide a critical insight into its reforming mechanisms and flexible operation in real engineering applications. The present paper firstly studies the transport phenomena in an industrial-scale steam methane reforming reactor by transient numerical simulations. Wall effect and local non thermal equilibrium is considered in the simulations. A temperature profile of the tube outer wall is given by user defined functions integrated into the ANSYS FLUENT software. Dynamic simulations show that the species distribution is closely related to the temperature distribution which makes the temperature of the reactor tube wall an important factor for the hydrogen production of the reformer and the thermal conductivity of the catalyst network is crucial in the heat transfer in the reactor. Besides, there exists a delay of the reformer's hydrogen production when the temperature profile of the tube wall changes. Among inlet temperature, inlet mass flow rate and inlet steam-to-carbon (S/C) ratio, the mass flow rate is the most influencing factor for the hydrogen production. The dynamic matrix control (DMC) scheme is subsequently designed to manipulate the mole fraction of hydrogen of the outlet to the target value by setting the temperature profile trajectory of the reforming tube with time. The proportional-integral control strategy is also studied for comparison. The closed-loop simulation results show that the proposed DMC control strategy can reduce the overshoot and have a small change of the input variable. In addition, the disturbances of feed disturbance can also be well rejected to assure the tracking performance, indicating the superiority of the DMC controller. All the results give insight to the theoretical analysis and controller design of a steam methane reformer and demonstrate the potential of the CFD modeling in study the transport mechanism and the idea of combining CFD modeling with controller design for the real application.     

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.     

Modeling of fluidized bed membrane reactors for hydrogen production from steam methane reforming with Aspen Plus

Hydrogen production via steam methane reforming with in situ hydrogen separation in fluidized bed membrane reactors was simulated with Aspen Plus. The fluidized bed membrane reactor was divided into several successive steam methane sub-reformers and membrane sub-separators. The Gibbs minimum free energy sub-model in Aspen Plus was employed to simulate the steam methane reforming process in the sub-reformers. A FORTRAN sub-routine was integrated into Aspen Plus to simulate hydrogen permeation through membranes in the sub-separator based on Sieverts' law. Model predictions show satisfactory agreement with experimental data in the literature. The influences of reactor pressure, temperature, steam-to-carbon ratio, and permeate side hydrogen partial pressure on reactor performances were investigated with the model. Extracting hydrogen in situ is shown to shift the equilibrium of steam methane reactions forward, removing the thermodynamic bottleneck, and improving hydrogen yield while neutralizing, or even reversing, the adverse effect of pressure.     

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.     

Enhancement effect of heat recovery on hydrogen production from catalytic partial oxidation of methane

The effect of heat recovery on hydrogen production from catalytic partial oxidation of methane (CPOM) and its reaction characteristics in a reactor are investigated using numerical simulations. The reactor is featured by a Swiss-roll structure in which a rhodium (Rh) catalyst bed is embedded at the center of the reactor. By recovering the waste heat from the product gas to preheat the reactants, it is found that the combustion, steam reforming and dry reforming of methane in the catalyst bed are enhanced to a great extent. As a result, the methane conversion and hydrogen yield are improved more than 10%. Considering the operation conditions, a high performance of hydrogen production from CPOM can be achieved if the number of turns in the reactor is increased or the gas hourly space velocity (GHSV) of the reactants in the catalyst bed is lower. However, with the condition of heat recovery, the flow direction of the reactants in the reactor almost plays no part in affecting the performance of CPOM. In summary, the predictions reveal that the reactor with a Swiss-roll structure can be applied for implementing CPOM with high yield of hydrogen.     

Tri-reformer with O2 side-stream distribution for syngas production

Methane tri-reforming combines steam reforming, dry reforming and partial oxidation of methane in a single reactor. The heat generated by the exothermic partial oxidation of methane can be used to supply the energy for the other two endothermic reactions (dry and steam reforming of methane). The thermoneutral condition allows the use of a tri-reformer with a simpler reactor structure since no external heat supply is necessary. Thermodynamic analysis of the thermoneutral reactor was performed using Gibbs free energy minimization approach. Conventional tri-reformers have heat and mass management problems. We developed a novel tri-reformer concept that utilizes proper distribution of O₂ gas to the reactor to address the problems. The optimization of the proposed reactor was performed with the objective function of minimizing total annual cost. Maintaining the peak temperatures by adjusting the O₂ flow rate at the distribution point along the reactor was shown to provide good load flexibility for the change in methane flow rate.     

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.     

Design and operational considerations of packed-bed membrane reactor for distributed hydrogen production by methane steam reforming

Methane steam reforming will still account for most of hydrogen production in the coming decades. Membrane reactor can play a key role in both energy saving and process/equipment compactness, particularly for its decentralized applications. Here we design a particles-based packed-bed membrane reactor and explore the operational window and design challenges by conducting systematic study experimentally and computationally, particularly emphasizing geometrical scale of membrane reactor and catalyst activity. The results show that membrane reactor presents maximum hydrogen flux by consuming unit methane under the optimized operation conditions of GHSV (i.e., 1134 hr^?1) and steam-to-carbon ratio (i.e., 2), and computational study shows that optimal operation window is around 30 atm and 773.15 K. Moreover, the design criteria of “Catalyst activity – Membrane performance – Radial depth” is revealed quantitatively and catalyst activity is identified as the key limiting factor for further process intensification. Briefly, these results shed some lights on operation, optimal design, and further improvement of membrane reactor in methane steam reforming.     

Mini CHP based on the electrochemical generator and impeded fluidized bed reactor for methane steam reforming

The paper presents a configuration of mini CHP with the methane reformer and planar solid oxide fuel cell (SOFC) stacks. This mini CHP may produce electricity and superheated steam as well as preheat air and methane for the reformer along with cathode air used in the SOFC stack as an oxidant. Moreover, the mathematical model for this power plant has been created. The thermochemical reactor with impeded fluidized bed for autothermal steam reforming of methane (reformer) considered as the basis for the synthesis gas (syngas) production to fuel SOFC stacks has been studied experimentally as well. A fraction of conversion products has been oxidized by the air fed to the upper region of the impeded fluidized bed in order to carry out the endothermic methane steam reforming in a 1:3 ratio as well as to preheat products of these reactions. Studies have shown that syngas containing 55% of hydrogen could be produced by this reactor. Basic dimensions of the reactor as well as flow rates of air, water and methane for the conversion of methane have been adjusted through mathematical modelling.The paper provides heat balances for the reformer, SOFC stack and waste heat boiler (WHB) intended for generating superheated water steam along with preheating air and methane for the reformer as well as the preheated cathode air. The balances have formed the basis for calculating the following values: the useful product fraction in the reformer; fraction of hydrogen oxidized at SOFC anode; gross electric efficiency; anode temperature; exothermic effect of syngas hydrogen oxidation by air oxygen; excess entropy along with the Gibbs free energy change at standard conditions; electromotive force (EMF) of the fuel cell; specific flow rate of the equivalent fuel for producing electric and heat energy. Calculations have shown that the temperature of hydrogen oxidation products at SOFC anode is 850 °C; gross electric efficiency is 61.0%; EMF of one fuel cell is 0.985 V; fraction of hydrogen oxidized at SOFC anode is 64.6%; specific flow rate of the equivalent fuel for producing electric energy is 0.16 kg of eq.f./(kW·h) while that for heat generation amounts to 44.7 kg of eq.f./(GJ). All specific parameters are in agreement with the results of other studies.     

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.     

Catalytic reforming of natural gas for hydrogen production in a pilot fluidized-bed membrane reactor: Mapping of operating and feed conditions

A fluidized-bed membrane reformer was operated in two independent laboratories to map various operating conditions, to investigate the effects of changing the composition of the natural gas feed stream and to verify earlier experimental trials. Two feed natural gases were tested, containing either 95.5 or 90.1 mol% of methane (3.6 or 9.9 mol% of other gaseous higher hydrocarbons). Experimental tests investigated the influence of total membrane area, reactor pressure, permeate pressure and natural gas feed rates. A permeate-H₂-to reactor natural gas feed molar ratio >2.3 was achieved with six two-sided membrane panels under steam reforming conditions and a pressure differential across the membranes of 785 kPa. The total cumulative reforming time reached 395 h, while hydrogen purity exceeded 99.99% during all tests.     

Oxidative steam reforming of ethanol over a Pt/Al2O3 catalyst in a Pd-based membrane reactor

In this study, the ability of a Pd-Ag membrane reactor of producing ultrapure hydrogen via oxidative steam reforming of ethanol has been evaluated. A self supported Pd-Ag tube of wall thickness 60 μm has been filled with a commercial Pt-based catalyst and assembled into a membrane module in a finger-like configuration. In order to evaluate the hydrogen yield behavior under different operating conditions, experimental tests have been performed at temperatures of 400 and 450 °C and pressures of 150 and 200 kPa. The oxidative steam reforming of ethanol has been carried out by feeding the membrane reactor with a gas stream containing a dilute water-ethanol mixture and air. Different water/ethanol feed flow rates (5, 10, 15 g h⁻¹), several water/ethanol (4, 10, 13) and oxygen/ethanol (0.3, 0.5, 0.7) feed molar ratios have been tested. The results pointed out that the highest hydrogen yield (moles of permeated hydrogen per mole of ethanol fed) corresponding to almost 4.1 has been attained at 450 °C and 200 kPa of lumen pressure by using a water/ethanol/oxygen feed molar ratio of 10/1/0.5.The results of these tests have been compared with those reported for the ethanol steam reforming in a Pd-Ag membrane reactor filled with the same Pt-based catalyst. This comparison has shown a positive effect on the hydrogen yield of small oxygen addition in the feed stream.     

Plasma reforming for hydrogen production: Pathways,reactors and storage

Hydrogen is an energy carrier with a very high energy density (>119 MJ/kg). Pure hydrogen is barely available; thus, it requires extraction from its compounds. Steam reforming and water electrolysis are commercially viable technologies for hydrogen production from water, alcohols, methane, and other hydrocarbons; however, both processes are energy-intensive. Current study aims at understanding the methane and ethanol-water mixture pathway to generate hydrogen molecules. The various intermediate species (like CH_X, CH₂O, CH₃CHO) are generated before decomposing methane/ethanol into hydrogen radicals, which later combine to form hydrogen molecules. The study further discusses the various operating parameters involved in plasma reforming reactors. All the reactors work on the same principle, generating plasma to excite electrons for collision. The dielectric barrier discharge reactor can be operated with or without a catalyst; however, feed flow rate and discharge power are the most influencing parameters. In a pulsed plasma reactor, feed flow rate, electrode velocity, and gap are the main factors that can raise methane conversion (40–60%). While the gliding arc plasma reactor can generate up to 50% hydrogen yield at optimized values of oxygen/carbon ratio and residence time, the hydrogen yield in the microwave plasma reactor is affected by flow rate and feed concentration. Therefore, all the reactors have the potential to generate hydrogen at lower energy demand.     

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%.