Comparisons between methane and methanol steam reforming in thermally integrated microchannel reactors for hydrogen production: A computational fluid dynamics study

This paper addresses the issues related to the design and operation of steam reforming combined with catalytic combustion in thermally integrated microchannel reactors for hydrogen production. Comparisons were made between methanol and methane steam reforming, representing a low and a high temperature process respectively, under the same operating conditions to determine whether methanol-based thermally integrated systems can be more energy-efficient than methane-based ones. Computational fluid dynamics simulations were performed to gain insight into the reactor performance and thermal behavior. The effect of various design parameters was investigated to identify suitable ranges of operating conditions, and an analysis of heat and mass transfer was performed to design a highly efficient system. It was shown that steam reforming of both fuels is feasible in millisecond reactors under a variety of conditions, but very careful design is necessary. Methanol reforming can be more efficient, offering a better solution not only to simplify design but also to improve power and efficiency. The wall thermal conductivity is essential to the design and optimization of these systems, as it can significantly affect the overall energy balance. There is no significant difference in reactor performance between different channel heights at the same flow rate. The ratio of the flow rates on opposite sides of the reactor is an important design parameter and must be carefully adjusted to improve efficiency and eliminate hot spots. Finally, a simple operating strategy was proposed to achieve variable power output, and design recommendations were made.     

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

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

Metal oxides as combustion catalysts for a stratified,dual bed partial oxidation catalyst

Bimetallic, dual bed catalysts made up of metal oxides were investigated in the millisecond catalytic partial oxidation of methane to synthesis gas. A metal oxide combustion catalyst containing manganese, chromium, or copper was coupled with a nickel reforming catalyst to carry out the partial oxidation of methane. These catalysts produce hydrogen yields that compare to a platinum/nickel dual bed catalyst at a fraction of the cost. The high space velocity of the millisecond reactor improves performance by giving high rates of heat convection from the exothermic, upstream combustion catalyst to the downstream, endothermic reforming catalyst. Additionally, over a 10 h experiment, the catalyst activity did not decrease.     

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.     

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.     

Direct reforming of Methane–Ammonia mixed fuel on Ni–YSZ anode of solid oxide fuel cells

To control the temperature distribution in the Ni–YSZ (yttria-stabilized zirconia) anode of solid oxide fuel cells (SOFCs) by efficiently utilizing the heat generated by electrochemical reactions, the supply of methane–ammonia mixed fuel is proposed. The reaction characteristics of reforming/decomposition of the mixed fuel on a Ni–YSZ catalyst are experimentally investigated. A mixture gas of methane, steam, ammonia, and balance argon is supplied to a packed bed catalyst placed in a quartz tube in an electric furnace. The crushed Ni–YSZ anode of SOFCs is used as the catalyst. The exhaust gas composition is analyzed by gas chromatography and the streamwise temperature distribution of the catalyst bed is measured by an infrared camera. It is found that ammonia decomposition preferentially proceeds and steam methane reforming becomes active after sufficient ammonia has been consumed. A low-temperature region is formed by steam methane reforming owing to its strongly endothermic nature. Its position moves downstream while its magnitude decreases as the ammonia concentration in the fuel increases. This shows that the local temperature distribution can be controlled by tuning the ratio of methane to ammonia in the mixed fuel. It is also found that, at a certain mixture ratio, the mixed fuel realizes a hydrogen production rate higher than that for only methane or ammonia.     

Research and development of on-site small skid-mounted natural gas to hydrogen generator in China

Using skid-mounted natural gas to hydrogen generator in hydrogen refueling station can significantly reduce the cost of hydrogen. In 2021, China successfully built the first 250 Nm³/h on-site skid-mounted natural gas to hydrogen generator, which was successfully debug-ed in Foshan, providing hydrogen products with purity ≥99.999% for FCVs. This paper summarized the technological process and development, analyzed the risk and the safety design of skid-mounted natural gas to hydrogen generator. Several key factors affecting compactness are analyzed, including process and technical route, reforming reformer and catalyst, heat exchange network, heat exchanger and steam generation system, PSA unit and overall integrated design, etc. In addition, innovative strategies to optimize the compactness of the device are given from the aspects of process flow, reforming reformer and steam generation system.The suggestions are put forward for the development and application of on-site skid-mounted natural gas to hydrogen generator.     

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.     

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.     

Analysis of phase change heat transfer with annulus 1 kW class methanol steam reforming reaction under high-pressure operation

A fuel cell air independent propulsion (AIP) system of underwater vehicle requires a hydrogen storage system. The methanol steam reforming system is a candidate of hydrogen storage which can produce hydrogen from chemical reaction. Different from reforming system for station fuel cell system, the methanol steam reformer (MSR) for underwater vehicle requires high-pressure operation.Since the longitudinal temperature uniformity is a core parameter of conversion efficiency of steam reforming system, this study is focused on computational analysis of phase change heat transfer through the annulus for methanol steam reforming reaction. The annulus MSR using phase change material was developed to improve the temperature uniformity. The simulation model is verified with safety and performance analysis code (SPACE). The performance parameters of MSR were flow arrangement, steam to carbon ratio (SCR), and gas hourly space velocity (GHSV). The results were analyzed in terms of the hydrogen yield, heat flux, liquid mass flow rate, and methanol conversion rate. The flow arrangement varied the methanol conversion rate to a minor extent of approximately 0.1% because wall temperature was maintained uniformly. In the case of SCR, the hydrogen yield at SCR 2.5 was 0.637 (dry basis), which was the highest yield rate. Also, if GHSV was increased, hydrogen yield decreased from 0.690 (dry basis) to 0.527 (dry basis). The heat transfer pattern was also analyzed and it was found that steam is interactively condensed along with the progress of the reforming reaction.     

Modeling and optimization of an industrial hydrogen unit in a crude oil refinery

The main goal of this research is the modeling and optimization of an industrial hydrogen unit in a domestic oil refinery at steady state condition. The considered process consists of steam methane reforming furnace, low and high temperature shift converters, CO₂ absorption column and methanation reactor. In the first step, the reactors are heterogeneously modeled based on the mass and energy balance equations considering heat and mass transfer resistances in the gas and catalyst phases. The CO₂ absorption column is simulated based on the equilibrium non-ideal approach. In the second step, a single objective optimization problem is formulated to maximize hydrogen production in the plant considering operating and economic constraints. The feed temperature, firebox temperature, and steam flow rate in the reformer, feed temperature in shift converters, lean amine flow rate in the absorption column, and feed temperature in the methanator are selected as decision variables. The calculated effectiveness factors and mass transfer coefficients prove that the methane reforming is inertia-particle mass transfer control, while shift and methanation reactions are surface reaction control. The simulation results show that applying the optimal condition on the system increases hydrogen production capacity from 85.93 to 105.5 mol s⁻¹.     

Simulation of methane steam reforming in a catalytic micro-reactor using a combined analytical approach and response surface methodology

In this study, a steady-state analytical model for heat and mass transfer in a 2D micro-reactor coated with a Nickel-based catalyst is developed to investigate microscale hydrogen production. Appropriate correlations for each species’ net rate of production or consumption, mass diffusivity, and the heat of reactions are developed using a detailed reaction mechanism of methane steam reforming. The energy and species conservation equations are then solved for the reactive mixture coupled with the wall energy equation. Finally, the response surface methodology (RSM) is employed to study the effects of channel height, inlet velocity and temperature, wall thickness and conductivity, and external heat flux on CH4 conversion. It is found that the inlet gas temperature, among different parameters, has the most influence on the overall performance of the microchannel hydrogen production. Also, the maximum necessary heat of reforming reaction increases by 84% and 26% if the CH₄ conversion changes from 50% to 60% and 60% to 70%, respectively. The developed analytical simulation can be a useful tool for designing experiments in micro-scale hydrogen production.     

An internal reformer for a pressurised SOFC system

A novel reformer design has been demonstrated that converts the methane required for a multi kilowatt SOFC stack. Results show the influence of temperature and the benefits of operating at elevated pressure on the reforming-catalyst fundamental reaction kinetics. Due to the high heat demand of the steam reforming reaction, efficient heat transfer between the SOFC stack and the reforming catalyst is essential. Parameters such as the volume/surface area ratio, choice of catalyst, and catalyst metal loading are key to the design, and these have been determined through a combination of computer modelling and experimental measurements. The thermal properties of the unit have been evaluated over a range of temperatures and fuel compositions that simulate system operating-conditions in the final product.     

Electrochemical reforming of methane using SrZr0.5Ce0.4Y0.1O3-δ proton-conductor cell combined with paper-structured catalyst

Reforming of hydrocarbon which is an important hydrogen production method proceeds in two steps, i.e. steam reforming and shift reaction. Due to different thermodynamics, the two reactions are conventionally conducted at different temperatures. This study examines one step methane reforming by use of proton-conducting electrochemical cell in combination with a reforming catalyst. Promotion of the reforming reaction was intended by extracting hydrogen via electrochemical hydrogen pumping with a proton conductor cell. In order to compensate for the slow kinetics of the steam reforming, a paper catalyst loaded with Ni was placed in front of the electrochemical cell. Electrolyte support cells were used to verify this concept, and the effect of the electrochemical hydrogen pump was investigated from the composition of the outlet gas. Electrode support cells using a thin film electrolyte was used to reduce overvoltage. It is demonstrated that the steam reforming reaction and the shift reaction take place in one electrochemical cell. Effective catalyst placement and energy efficiency is discussed.     

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.     

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.     

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

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

Solar enriched methane production by steam reforming process: Reactor design

A novel hybrid plant for a mixture of methane and hydrogen (enriched methane) production from a steam reforming reactor whose heat duty is supplied by a molten salt stream heated up by a concentrating solar power (CSP) plant developed by ENEA is here presented. By this way, a hydrogen stream, mixed with natural gas, is produced from solar energy by a consolidated production method as the steam reforming process and by a pre-commercial technology as molten salts parabolic mirrors solar plant. After the hydrogen production plant, the residual heat stored in molten salt stream is used to produce electricity and the plant is co-generative (hydrogen + electricity).The heat-exchanger-shaped reactor is dimensioned by a design tool developed in MatLab environment. A reactor 3.5 m long and with a diameter of 2″ is the most efficient in terms of methane conversion (14.8%) and catalyst efficiency (4.7 Nm³/h of hydrogen produced per kg_cat).     

Thermochemical waste‐heat recuperation by steam methane reforming with flue gas addition

The process flow schematic of fuel‐consuming equipment with thermochemical waste‐heat recuperation by steam methane reforming with an addition of flue gas to the reaction mixture is suggested. The advantages of such a thermochemical recuperation (TCR) system compared with the TCR system by steam methane reforming are shown and justified. Based on the first law energy analysis, the heat inputs and outputs of the TCR system were determined. To determine the exhaust gases heat transformed into chemical energy of a new synthetic fuel, the thermodynamic analysis by minimizing Gibbs energy via Aspen HYSYS was performed. It was found that with an increase in the mole fraction of combustion products in the reaction mixture, the enthalpy of the methane reforming reaction increases, especially noticeable at the temperature range above 1000 K. Based on the heat, balance of the TCR system was established that the addition of combustion products to the reaction mixture has the following effects: reducing the heat input for steam production in a steam generator; reduction of the steam generator size because of the need to produce a smaller amount of steam in comparison with TCR by pure steam methane reforming; and reducing the amount of heat transferred through the wall of the reformer and, as a consequence, reduction in size of the reformer.     

Autothermal reforming of methane for producing high-purity hydrogen in a Pd/Ag membrane reactor

Autothermal reforming of methane includes steam reforming and partial oxidizing methane. Theoretically, the required endothermic heat of steam reforming of methane could be provided by adding oxygen to partially oxidize the methane. Therefore, combining the steam reforming of methane with partial oxidation may help in achieving a heat balance that can obtain better heat efficacy. Membrane reactors offer the possibility of overcoming the equilibrium conversion through selectively removing one of the products from the reaction zone. For instance, only can hydrogen products permeate through a palladium membrane, which shifts the equilibrium toward conversions that are higher than the thermodynamic equilibrium. In this study, autothermal reforming of methane was carried out in a traditional reactor and a Pd/Ag membrane reactor, which were packed with an appropriate amount of commercial Ni/MgO/Al₂O₃ catalyst. A power analyzer was employed to measure the power consumption and to check the autothermicity. The average dense Pd/Ag membrane thickness is 24.3 μm, which was coated on a porous stainless steel tube via the electroless palladium/silver plating procedure. The experimental operating conditions had temperatures that were between 350 °C and 470 °C, pressures that were between 3 atm and 7 atm, and O₂/CH₄ = 0–0.5. The effects of the operating conditions on methane conversion, permeance of hydrogen, H₂/CO, selectivities of CO_x, amount of power supply, and the carbon deposition of the catalyst after the reaction is thoroughly discussed in this paper. The experimental results indicate that an optimum methane conversion of 95%, with a hydrogen production rate of 0.093 mol/m². S, can be obtained from the autothermal reforming of methane at H₂O/CH₄ = 1.3 and O₂/CH₄ near 0.4, at which the reaction does not consume power, and the catalysts are not subject to any carbon deposition.