Hydrogen production using integrated methanol‐steam reforming reactor with various reformer designs for PEM fuel cells

A 95 mm × 40 mm × 15 mm compact reactor for hydrogen production from methanol‐steam reforming (MSR) is constructed by integrating a vaporizer, reformer, and combustor into a single unit. CuO/ZnO/Al₂O₃ is used as the catalyst for the MSR while the required heat is provided using Platinum (Pt) ‐catalytic methanol combustion. The reactor performance is measured using three reformer designs: patterned micro‐channel; inserted catalyst layer placed in a single plain channel; and catalyst coated directly on the bottom wall of single plain channel. Because of longer reactant residence time and more effective heat transfer, slightly higher methanol conversion can be obtained from the reformer with patterned microchannels. The experimental results show that there is no significant reactor performance difference in methanol conversion, hydrogen (H₂) production rate, and carbon monoxide (CO) composition among these three reformer designs. These results indicated that the flow and heat transfer may not play important roles in compact size reactors. The reformer design with inserted catalyst layer provides convenience in replacing the aged catalyst, which may be attractive in practical applications compared with the conventional packed bed and wall‐coated reformers. Copyright © 2011 John Wiley & Sons, Ltd.     

Optimization of tri-reformer reactor to produce synthesis gas for methanol production using differential evolution (DE) method

This paper presents a study on optimization of a fixed bed tri-reformer reactor (TR). This reactor has been used instead of conventional steam reformer (CSR) and auto thermal reformer (CAR). A theoretical investigation has been performed in order to evaluate the optimal operating conditions and enhancement of methane conversion, hydrogen production and desired H₂/CO ratio as a synthesis gas for methanol production. A mathematical heterogeneous model has been used to simulate the reactor. The process performance under steady state conditions was analyzed with respect to key operational parameters (inlet temperature, O₂/CH₄, CO₂/CH₄ and steam/CH₄ ratios). The influence of these parameters on gas temperature, methane conversion, hydrogen production and H₂/CO ratio was investigated. Model validation was carried out by comparison of the reforming model results with industrial data of CSR. Differential evolution (DE) method was applied as a powerful method for optimization. Optimum feed temperature and reactant ratios (CH₄/CO₂/H₂O/O₂) are 1100 K and 1/1.3/2.46/0.47 respectively. The optimized TR has enhanced methane conversion by 3.8% relative to industrial reformers in a single reactor. Methane conversion, hydrogen yield and H₂/CO ratio in optimized TR are 97.9%, 1.84 and 1.7 respectively. The optimization results of tri-reformer were compared with the corresponding predictions from process simulation software operated at the same feed conditions.     

Techno-economic and environmental assessment of methanol steam reforming for H2 production at various scales

According to global trend of transition to a hydrogen society, needs for alternative hydrogen (H₂) production methods have been on the rise. Among them, methanol steam reforming (MSR) in a membrane reactor (MR) has received a great attention due to its improved H₂ yield and compact design. In this study, 3 types of economic analysis – itemized cost estimation, sensitivity analysis, and uncertainty analysis – and integrative carbon footprint analysis (iCFA) were carried out to investigate economic and environmental feasibility. Unit H₂ production costs of MSR in a packed-bed reactor (PBR) and an MR for various H₂ production capacities of 30, 100, 300, and 700 m³ h⁻¹ and CO₂ emission rates for both a PBR and an MR in H₂ production capacity of 30 m³ h⁻¹ were estimated. Through itemized cost estimation, unit H₂ production costs of a PBR and an MR were obtained and scenario analysis was carried out to find a minimum H₂ production cost. Sensitivity analysis was employed to identify key economic factors. In addition, comprehensive uncertainty analysis reflecting unpredictable fluctuation of key economic factors of reactant, labor, and natural gas obtained from sensitivity analysis was also performed for a PBR and an MR by varying them both simultaneously and individually. Through iCFA, lowered CO₂ emission rates were obtained showing environmental benefit of MSR in an MR.     

Optimization of hydrogen production via coupling of the Fischer–Tropsch synthesis reaction and dehydrogenation of cyclohexane in GTL technology

In this study, a thermally-coupled reactor containing the Fischer–Tropsch synthesis reaction in the exothermic side and dehydrogenation of cyclohexane in the endothermic side has been modified using a hydrogen perm-selective membrane as the shell of the reactor to separate the produced hydrogen from the dehydrogenation process. Permeated hydrogen enters another section called permeation side to be collected by Argon, known as the sweep gas. This three-sided reactor has been optimized using differential evolution (DE) method to predict the conditions at which the reactants’ conversion and also the hydrogen recovery yield would be maximized. Minimizing the CO₂ and CH₄ yield in the reactor’s outlet as undesired products is also considered in the optimization process. To reach this goal, optimal initial molar flow rate and inlet temperature of three sides as well as pressure of the exothermic side have been calculated. The obtained results have been compared with the conventional reactor data of the Research Institute of Petroleum Industry (RIPI), the membrane dual – type reactor suggested for Fischer–Tropsch synthesis, and the membrane coupled reactor presented for methanol synthesis. The comparison shows acceptable enhancement in the reactor’s performance and that the production of hydrogen as a valuable byproduct should also be considered.     

Ultrasonication for biohydrogen production from food waste

The applicability of ultrasonication for enhancement of hydrogen production from food wastes was evaluated in three different systems. System A is a conventional continuously-stirred tank reactor (CSTR) fed raw food waste; system B is a conventional continuously-stirred tank reactor fed sonicated food waste, and system C (US patent-pending) is the sonicated biological hydrogen reactor (SBHR) which comprised a CSTR connected with an ultrasonic probe at the bottom of the reactor. In this study, the increase in hydrogen production rate relative to the control (system A) due to sonication of the feed before the digestion was 27%, compared to 90% in the SBHR. Similarly, the CSTR with sonicated feed exhibited a 23% increase in hydrogen yield as mol H₂/mol hexose_consumed compared to a 62% increase in the SBHR relative to the control (system A). The VSS destruction in the SBHR was higher than those in the CSTR and CSTR with sonicated feed by 50% and 60%, respectively.     

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.     

Impact of Ni-based catalyst patterning on hydrogen production from MSR: External steam reformer modelling

Wall-coated Methane Steam Reformers (MSR) are commonly used as fuel processing in the hydrogen production chain. In such devices, the catalyst which is generally nickel-based is coated on the walls, and the heat supply influences directly the fuel processing efficiency. In this work, two-dimensional CFD study is carried out to explore an enhancement on MSR thermal behavior. Two configurations in terms of catalyst coating are investigated. The first MSR configuration is equipped with continuous catalytic layer, while in the second, discrete catalyst layers separated by an inert gap are imposed. The effect of the catalyst patterning on the thermal and mass behavior of MSR is discussed. The results show that the MSR efficiency can be improved by extending the catalytic zone and discretizing the catalyst coating. Comparing to conventional MSR with continuous catalytic layers, enhancement of 28.71% in CH₄ conversion and 88.574% in H₂ production is realized by using discretized catalytic layers.     

Multi-objective optimization of hydrogen production process and steam reforming reactor design

This study proposes a multi-objective optimization approach to design a steam methane reforming (SMR) reactor and maximize the efficiency of the hydrogen production process. Out of 1782 possible variable combinations, only 50 iterations were performed, identifying three Pareto optimal that resulted in reactor size reductions of 50.53%, 35.56%, and 20.69%, respectively, compared to the reference reactor. The process efficiency for each optimal design varied slightly, with one achieving a 105.05% increase in efficiency, another remaining stable at 100.48%, and a third experiencing a slight decrease to 86.66% compared to the reference case. The results offer practical insights for planning an on-site distributed hydrogen production system, demonstrating that an increase in overall process efficiency can be achieved even with a reduced reactor size. This work is the first attempt to optimize a hydrogen production system by simultaneously considering overall process efficiency and SMR reactor design.     

Thermal analysis of a micro tubular reactor for methanol steam reforming by optimizing the multilayer arrangement of catalyst bed for the catalytic combustion of methanolr

Packed bed tube reactors are commonly used for hydrogen production in proton exchange membrane fuel cells. However, the hydrogen production capacity of methanol steam reforming (MSR) is greatly limited by the poor heat transfer of packed catalyst bed. The hydrogen production capacity of catalyst bed can be effectively improved by optimizing the temperature distribution of reactor. In this study, four types of reactors including concentric circle methanol steam reforming reactor (MSRC), continuous catalytic combustion methanol steam reforming reactor (MSRR), hierarchical catalytic combustion methanol steam reforming reactor (MSRP) and segmented catalytic combustion reactor with fins (MSRF) are designed, modeled, compared and validated by experimental data. It was found that the maximum temperature difference of MSRC, MSRR, MSRP and MSRF reached 72.4 K, 58.6 K, 19.8 K and 11.3 K, respectively. In addition, the surface temperature inhomogeneity U_f and CO concentration of the MSRF decreased by 69.8% and 30.7%, compared with MSRC. At the same reactor volume, MSRF can achieve higher methanol conversion rate, and its effective energy absorption rate is 4.6%, 3.9% and 2.6% higher than that of MSRC, MSRR and MSRP, respectively. The MSRF could effectively avoid the influence of uneven temperature distribution on MSR compared with the other designs. In order to further improve the performance of MSRF, the influences of methanol vapor molar ratio, inlet temperature, flow rate, catalyst particle size and catalyst bed porosity on MSR were also discussed in the optimal reactor structure (MSRF).     

Thermodynamic analysis of methanol steam reforming to produce hydrogen for HT-PEMFC: An optimization study

A statistical modeling and optimization study on the thermodynamic equilibrium of methanol steam reforming (MSR) process was performed by using Aspen Plus and the response surface methodology (RSM). The impacts of operation parameters; temperature, pressure and steam-to-methanol ratio (H₂O/MeOH) on the product distribution were investigated. Equilibrium compositions of the H₂-rich stream and the favorable conditions within the operating range of interest (temperature: 25–600 °C, pressure: 1–3.0 atm, H₂O/MeOH: 0–7.0) were analyzed. Furthermore, ideal conditions were determined to maximize the methanol conversion, hydrogen production with high yield and to minimize the undesirable products such as CO, methane, and carbon. The optimum corresponding MSR thermodynamic process parameters which are temperature, pressure and H₂O/MeOH ratio for the production of HT-PEMFC grade hydrogen were identified to be 246 °C, 1 atm and 5.6, respectively.     

Cost‐competitive methane steam reforming in a membrane reactor for H2 production: Technical and economic evaluation with a window of a H2 selectivity

Techno‐economic viability studies of employing a membrane reactor (MR) equipped with H₂ separation membranes for methane steam reforming (MSR) were carried out for H₂ production in Korea using HYSYS®, a well‐known chemical process simulator, including economic analysis based on itemized cost estimation and sensitivity analysis (SA). With the reaction kinetics for MSR reported by Xu and Froment, the effect of a wide range of H₂ selectivity (10‐10,000) on the performance in an MR was investigated in this study. Because of the equilibrium shift owing to the Le Chatelier's principle, great performance of enhancement of methane conversion ( ) and H₂ yield and reaction temperature reduction was observed in an MR compared with a packed‐bed reactor (PBR). A window of a H₂ selectivity from 100 to 300 is proposed as a new criterion for better MR performance of MSR depending on potential applications from in‐depth analysis of and H₂ yield enhancements, a H₂ purity, and temperature reduction. In addition, economic analysis to evaluate the feasibility of an MR technology for MSR was carried out focusing on a levelized cost of H₂ based on itemized cost estimation of capital and operating costs as well as SA. Techno‐economic assessment showed 36.7% cost reduction in an MR compared with a PBR and revealed that this MR technology can be possibly opted for a cost‐competitive H₂ production process for MSR.     

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.     

Multi objective optimization of a tri-reforming process with the maximization of H2 production and minimization of CO2 emission & power loss

In this study, the process optimization of a tri-reformer reactor is conducted for the synthesis of hydrogen gas from natural gas using multi-objective optimization (MOO) approach. Specifically, four MOO problems are solved using three objective functions, namely maximization of H₂, minimization of CO₂, and minimization of power loss. It should be noticed that the power loss is an important economic factor due the large pressure drop and flowrates in packed bed reactors. However, it has not been used as an objective function for the optimization based design and/or operation of fixed bed reactor for reforming process to the best of authors’ knowledge. Three of the four MOO problems are 2-objective in nature with all the permutation and combination of the three objectives. The fourth MOO problem is solved considering all the three objectives, simultaneously. For all the MOO problems, feed conditions of O₂, H₂O, and Temperature are considered as the optimization variables. The results obtained with 3 objective functions are observed to be superior to the ones obtained from 2 objective problems.     

Simultaneous utilization of two different membranes for intensification of ultrapure hydrogen production from recuperative coupling autothermal multitubular reactor

The potential of simultaneous hydrogen production and in situ water removal in a thermally coupled multitubular two-membrane reactor (TCTMR) were studied numerically. Methanol synthesis is carried out in exothermic side with H-SOD membrane and supplies the necessary heat for the endothermic side. Dehydrogenation of cyclohexane is carried out in endothermic side with hydrogen-permselective Pd/Ag membrane wall. Therefore, the proposed reactor consists of two membranes, one for separation of pure hydrogen from endothermic side and another one for separation of water from exothermic side. The motivation for in situ H₂O removal during methanol synthesis by using H-SOD membranes is to displace the water-gas shift equilibrium to enhance conversion of CO₂ to improve methanol productivity. A steady-state heterogeneous model is developed to analyze the operation of the coupled methanol synthesis. The proposed model has been used to compare the performance of a TCTMR with conventional reactor (CR) and thermally coupled membrane reactor (TCMR) at identical process conditions. This comparison shows that TCTMR in addition to possessing advantages of a TCMR has a more favorable profile of temperature and increased productivity compared with other reactors. Furthermore, lower water production rate in TCTMR reduces catalyst re-crystallization.     

Hydrogen,nuclear energy,and the advanced high-temperature reactor

Nuclear energy has been proposed as an energy source to produce hydrogen (H₂) from water. An examination of systems issues in this paper indicates that the infrastructure of H₂ consumption is now compatible with the production of H₂ by nuclear reactors. Alternative H₂ production processes were examined to define the requirements such processes would impose on the nuclear reactor. These requirements include supplying heat at a near-constant high temperature, providing a low-pressure interface with the H₂ production processes, isolating the nuclear plant from the chemical plant, and avoiding tritium contamination of the H₂ product. A reactor concept—the advanced high-temperature reactor—was developed to match these requirements for H₂ production.     

Flow pattern analysis and multi-objective optimization of helically corrugated tubes used in the intermediate heat exchanger for nuclear hydrogen production

Using the heat of the very-high-temperature gas-cooled reactor (VHTR) for large-scale and carbon-free hydrogen production provide an excellent option for a new sustainable energy economy. The intermediate heat exchanger (IHX) is a crucial component to realize this new hydrogen production mode. To supply sufficient heat for hydrogen production, the heat transfer of IHX needs to be enhanced. In this study, helically corrugated tubes (HCTs) were used to enhance the heat transfer of IHX. The flow pattern of HCTs was analyzed and a multi-objective optimization was then performed. First, the numerical experiment design with two objectives and three factors was conducted by Box-Behnken design in the response surface methodology (RSM). Second, the significant regression models for Nusselt number, friction factor, and performance evaluation criteria were obtained by the analysis of variance. Combining the analysis of turbulence kinetic energy and flow dead zone, a more comprehensive mechanism for the effect of corrugation parameters on flow and heat transfer was proposed. Finally, the fast-elitist non-dominated sorting genetic algorithm (NSGA Ⅱ) was adopted to conduct the multi-objective optimization of HCTs. The technique for order of preference by similarity to ideal solution (TOPSIS) was adopted for multi-objective decision-making. The CFD validation and comparison with RSM experimental design confirmed that the obtained Pareto optimal set and Pareto front can provide a comprehensive and effective design strategy for the IHX used for nuclear hydrogen production.     

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.     

Performance of gas-phase photocatalytic reactors on hydrogen production

Three types of high-performance photocatalytic reactors were developed for gas-phase photocatalytic hydrogen (H₂) production from hydrogen sulphide (H₂S) and effective photocatalytic decomposition of gaseous H₂S at a very low concentration is investigated. In this paper, three lab-scale photocatalytic reactors viz., packed bed photocatalytic reactor, catalyst coated fixed bed photocatalytic reactor and catalyst dispersed photocatalytic reactors were developed to study the performance of reactors on hydrogen production. The novel photocatalyst (CdS + ZnS)/Fe₂O₃ and the optimized catalyst dosage, H₂S gas flow rate, pollutant concentration, light irradiations were used. The experimental result indicates that packed bed photocatalytic reactor can effectively splits the H₂S into hydrogen (i.e. 98%) and rapidly decompose H₂S toward zero concentration than the other two reactors. Hence the bench-scale photocatalytic reactor was fabricated in packed bed reactor and the maximum hydrogen conversion achieved from hydrogen sulphide was found to be 98%.     

Microfibrous structured catalytic packings for miniature methanol fuel processor: Methanol steam reforming and CO preferential oxidation

The microfibrous structured catalytic packings for miniature fuel processor consisting of a methanol steam reformer and a subsequent CO cleanup train has been investigated experimentally. A highly void and tailorable sinter-locked microfibrous carrier consisting of 3.5 vol% 8 μm diameter Ni-fibers is used to entrap 35 vol% 150-250 μm catalyst particulates for both methanol steam reforming (MSR) and CO preferential oxidation (PROX). We demonstrate a microfibrous entrapped Pd-ZnO/Al₂O₃ catalyst packings for high efficiency hydrogen production by the MSR reaction. The use of microfibrous entrapment technology significantly enhances the catalyst utilization efficiency by a 4-fold improvement of the weight hourly space velocity (WHSV), compared to the single Pd-ZnO/Al₂O₃ particulates as keeping the methanol conversion at >98%. The microfibrous entrapped Pt-Co/Al₂O₃ catalyst packings can drive the CO from 2% down to <50 ppm at 150 °C with O₂/CO ratio of 1 using a gas hourly space velocity (GHSV) of 32,000 h⁻¹. Finally, a prototype fuel processor system integrating MSR reformer and CO PROX train is demonstrated as three reactors in series. Such test rig is capable of producing roughly 1700 standard cubic centimeter per minute (sccm) PEMFC-grade H₂ (equivalent to ∼163 W of electric power) in a longer-term test, in which the MSR reactor is operated at 300 °C using a methanol/water (1/1.1, mole) mixture WHSV of 9 h⁻¹ and CO PROX reactors at 150 °C using an O₂/CO molar ratio of 1.3, respectively. In the test of this prototype system, MSR reactor delivers >97% methanol conversion throughout the entire 1200-h test; the CO cleanup train placed in line after 800-h MSR illustrates the capability to decrease the CO concentration from ∼3.5% to ∼1% at PROX-1 and then to less than 20 ppm at PROX-2 until to the end of test.     

An integrated system for hydrogen and methane production during landfill leachate treatment

The patent-pending integrated waste-to-energy system comprises both a novel biohydrogen reactor with a gravity settler (Biohydrogenator), followed by a second stage conventional anaerobic digester for the production of methane gas. This chemical-free process has been tested with a synthetic wastewater/leachate solution, and was operated at 37 °C for 45 d. The biohydrogenator (system (A), stage 1) steadily produced hydrogen with no methane during the experimental period. The maximum hydrogen yield was 400 mL H₂/g glucose with an average of 345 mL H₂/g glucose, as compared to 141 and 118 mL H₂/g glucose for two consecutive runs done in parallel using a conventional continuously stirred tank reactor (CSTR, System (B)). Decoupling of the solids retention time (SRT) from the hydraulic retention time (HRT) using the gravity settler showed a marked improvement in performance, with the maximum and average hydrogen production rates in system (A) of 22 and 19 L H₂/d, as compared with 2–7 L H₂/d in the CSTR resulting in a maximum yield of 2.8 mol H₂/mol glucose much higher than the 1.1–1.3 mol H₂/mol glucose observed in the CSTR. Furthermore, while the CSTR collapsed in 10–15 d due to biomass washout, the biohydrogenator continued stable operation for the 45 d reported here and beyond. The methane yield for the second stage in system (A) approached a maximum value of 426 mL CH₄/gCOD removed, while an overall chemical oxygen demand (COD) removal efficiency of 94% was achieved in system (A).