Optimization of a counter-flow microchannel reactor using hydrogen assisted catalytic combustion for steam reforming of methane

The objective of this study is to optimize a microchannel reactor using hydrogen assisted catalytic combustion for steam reforming of methane. Hydrogen assisted catalytic combustion does not require preheating because the catalytic combustion of hydrogen occurs at room temperature. After start-up by hydrogen catalytic combustion, fuels of hydrogen and methane were changed to methane. The geometric configuration of the counter-flow reactor was optimized by the simulation model under steady state condition. The hydrogen flow rate in the counter-flow reactor was also optimized by transient simulations using the response surface methodology. As a result, the counter-flow reactor showed extremely short start-up time because of the optimized configuration and the optimized hydrogen flow rate. Hot spots were avoided because of the hydrogen shut-off after start-up. The operating characteristics of the counter-flow reactor were compared with those of the co-flow reactor.     

Steam reforming of methane over Ni catalyst in micro-channel reactor

A comprehensive study on the catalytic performance of Ni catalyst to implement millisecond steam reforming of methane (SRM) reaction in micro-channel reactors was conducted in this work. A new method to manufacture the metal-ceramics complex substrate as catalyst support was presented, that is, a layer of nano-particles, α-Al₂O₃, was thermally sprayed on a metallic substrate, usually FeCrAlloy. Ni or Rh catalyst was then impregnated on the substrate, forming firm and active catalyst coatings. The fall-off rate of the catalyst can be neglected after the plates experienced the high-temperature SRM reaction, showing the reliability in long-term use and the excellent catalytic performance for SRM reaction in micro-channel reactors. In comparison with the expensive Rh catalyst, Ni also showed wonderful performance to catalyze the SRM reaction in micro-reactors within milliseconds. Using the appropriate reactor design, CH₄ conversion reached above 90% when the residence time was as short as 32 ms for catalyst loading of 6.8 g/m². When the residence time was longer than 100 ms, CH₄ conversion was above 98%. Besides, catalyst deactivation was not detected for 500 h on stream with S/C ratio of 3.0, and for 12 h with S/C of 1.0 as well. Extensive characterizations on these Ni catalyst plates using XRD, SEM, TEM and XPS demonstrated that Ni catalysts prepared in this work did not show any sign of deactivation after being used in the micro-channel system under high-temperature operation.     

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

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

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

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

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

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

Glycerol steam reforming in a bench scale continuous flow heat recovery reactor

In the present study glycerol was successfully gasified using a diesel engine waste heat recovery system obtaining hydrogen and methane rich gaseous products. The reforming reactor was equipped with a vaporization pre-chamber to ensure uniform reactants distribution and a fixed reaction bed, being mounted in countercurrent flow configuration with the engine combustion gases stream. Accordingly, the reactions were conducted at gradually increased temperature conditions; starting at around 300 °C in the top section of the reaction bed and finishing in a controlled outlet bed temperature of 600–800 °C. When compared to homogeneous temperature reactors, the configuration used here produced a syngas of higher methane and ethylene contents. With regards to the reactor performance, syngas lower heat values of more than 22 MJ/kg were achieved with glycerol feed concentrations within 50–70% and outlet bed temperatures above 700 °C, corresponding to cold gas efficiencies of around 85%. The present results indicate that glycerin can be utilized as a syngas feedstock for steam reforming processes based on waste heat recovery.     

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.     

A heterogeneous dynamic model for the simulation and optimisation of the steam methane reforming reactor

In the current paper the dynamic behaviour of an industrial heterogeneous catalytic packed-bed reactor for the steam reforming of methane is examined. The model consists of a set of partial differential equations describing the physico-chemical processes that take place both in solid and gas phases accounting for diffusional limitations within the catalyst particles. The model was validated against literature data, while the heat provided to the reactor wall was optimised in terms of the optimal H₂ yield using a quadratic wall temperature profile. The values of the physico-chemical properties were adjusted to the severe operating conditions (high pressures and temperatures) of the reactor accounting for multicomponent gas mixture properties. It is shown that the 2-phase reactor concept along with the optimised wall temperature profile capture very well the dynamic conversion, the temperature and the partial pressure profiles both at bed and at particle level.     

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.     

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

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

Further development of a microchannel steam reformer for diesel fuel

This paper presents results from the ongoing optimisation of a microchannel steam reformer for diesel fuel which is developed in the framework of the development of a PEM fuel cell system for vehicular applications. Four downscaled reformers with different catalytic coatings of precious metal were operated in order to identify the most favourable catalyst formulation. Diesel surrogate was processed at varying temperatures and steam to carbon ratios (S/C). The reformer performance was investigated considering hydrogen yield, reformate composition, fuel conversion, and deactivation from carbon formation. Complete fuel conversion is obtained with several catalysts. One catalyst in particular is less susceptible to carbon formation and shows a high selectivity.     

Simulation of exhaust gas reforming of propane in a heat exchange integrated microchannel reactor

Exhaust gas reforming of propane to a hydrogen-rich mixture in a single, heat-exchange integrated, adiabatic, catalytic microchannel is modeled and simulated at different exhaust gas compositions from conventional gasoline and diesel fueled engines. Propane is considered as the model hydrocarbon for the complex fuels such as gasoline and diesel. The single microchannel is considered to be the characteristic unit of the catalytic exhaust gas reformer involving identical channels located parallel to each other. Steady-state simulations, carried out by the finite volume method, involve parametric variations of the total feed flow rate, and the amounts of propane and steam injected externally into the exhaust gas (reformer feed) stream. The results show that effective heat transfer and uniform temperature distribution, which are critical for the successful operation of the exhaust gas reformer, can be obtained in the microchannel configuration even at low gas hourly space velocities (GHSVs) at which the conventional packed-bed reformers usually lead to remarkable hot-spot formation. Production of H₂ and CO is favored by the addition of higher amounts of propane and steam into the reformer feed. Increasing the total feed flow rate, hence the GHSV is found to improve heat distribution along the microchannel at the expense of reduced product yields due to insufficient contact time.     

Hydrogen production by steam methane reforming in a membrane reactor equipped with a Pd composite membrane deposited on a porous stainless steel

With the aim of producing hydrogen at low cost and with a high conversion efficiency, steam methane reforming (SMR) was carried out under moderate operating conditions in a Pd-based composite membrane reactor packed with a commercial Ru/Al₂O₃ catalyst. A Pd-based composite membrane with a thickness of 4–5 μm was prepared on a tubular stainless steel support (diameter of 12.7 mm, length of 450 mm) using electroless plating (ELP). The Pd-based composite membrane had a hydrogen permeance of 2.4 × 10^?3 mol m^?1 s^?1 Pa^?0.5 and an H₂/N₂ selectivity of 618 at a temperature of 823 K and a pressure difference of 10.1 kPa. The SMR test was conducted at 823 K with a steam-to-carbon ratio of 3.0 and gas hourly space velocity of 1000 h^?1; increasing the pressure difference resulted in enhanced methane conversion, which reached 82% at a pressure difference of 912 kPa. To propose a guideline for membrane design, a process simulation was conducted for conversion enhancement as a function of pressure difference using Aspen HYSYS^®. A stability test for SMR was conducted for ～120 h; the methane conversion, hydrogen production rate, and gas composition were monitored. During the SMR test, the carbon monoxide concentration in the total reformed stream was <1%, indicating that a series of water gas shift reactors was not needed in our membrane reactor system.     

Evaluation of the economic impact of hydrogen production by methane decomposition with steam reforming of methane process

There has been considerable interest in the development of more efficient processes to generate hydrogen. Currently, steam methane reforming (SMR) is the most widely applied route for producing hydrogen from natural gas. Researchers worldwide have been working to invent more efficient routes to produce hydrogen. One of the routes is thermocatalytic decomposition of methane (TCDM) - a process that decomposes methane thermally to produce hydrogen from natural gas. TCDM has not yet been commercialized. However, the aim of this work was to conduct an economic and environmental analysis to determine whether the TCDM process is competitive with the more popular SMR process. The results indicate that the TCDM process has a lower carbon footprint. Further research on TCDM catalysts could make this process economically competitive with steam methane reforming.     

Production of enriched methane by a molten-salt concentrated solar power plant coupled with a steam reforming process: An LCA study

Enriched Methane is a gas mixture consisting of methane and a certain amount of hydrogen (10–30%vol) that finds out several applications such as fuel of Internal Combustion Engines (ICEs). To produce EM, a steam reforming reactor whose heat duty is supplied by a molten-salt stream heated up by a concentrating solar power (CSP) plant can be used, in order to generate the hydrogen steam by solar energy. In fact, molten salts at temperatures up to 550 °C can allow to reach the necessary thermal level inside the reactor to promote steam reforming reaction.     

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.     

An experimental study on the reaction characteristics of a coupled reactor with a catalytic combustor and a steam reformer for SOFC systems

Steam reforming performance in a coupled reactor that consists of a steam reformer and a catalytic combustor is experimentally investigated in this study. Endothermic steam reforming can occur through the absorption of heat from the catalytic combustion of the anode offgas in a heat-exchanging coupled reactor. The reaction characteristics were observed by varying parameters such as the inlet temperature of the catalytic combustor, the excess air ratio for the catalytic combustion, the fuel utilization rate in the fuel cells, and the steam-to-carbon ratio in the steam reformer. The reactor temperature and reformate composition were measured to analyze the performance of the reactor. The results show the potential applicability and design technologies of the coupled reactor for the fuel processing of high temperature fuel cells using an external reformer.     

Modelling of one-dimensional heterogeneous catalytic steam methane reforming over various catalysts in an adiabatic packed bed reactor

Kinetic data relevant to steam methane reforming (SMR) are often applied to catalysts and conditions for which they have not been derived. In this work, kinetic rates for the two SMR and water gas shift reactions were derived for 12 commonly used reforming catalysts based on conversion data obtained from the literature. Subsequently, these rates were tested in dynamic operation, steady-state, and equilibrium using a 1-D reactor model developed in-house with gPROMS model builder. Modelling outputs were further validated independently at equilibrium using the software chemical equilibrium with applications (CEA), and the literature. The effect of variables such as temperature, pressure, steam to carbon ratio (S/C), and gas mass flux (G_s) on the performance of the SMR process was then studied in terms of fuel and steam conversion (%), H₂ purity (%), H₂ yield (wt. % of CH₄) and selectivity of the carbon-based products. A comparative study was then performed for the 12 catalysts. Some catalysts showed better activity owing to their fast kinetics when they are tested in mild industrial conditions, while others performed better in more severe industrial conditions, substantiating that the choice of a catalyst ought to depend on the operating conditions.