Effects of particle sizes on performances of the horizontally buried-pipe steam generator using waste heat in a bioethanol steam reforming hydrogen production system

The discrete element geometric model of the horizontally buried-pipe steam generator was set up. The effects of particle size (20 mm–80 mm) on performances of the horizontally buried-pipe steam generator using waste heat in a bioethanol steam reforming hydrogen production system was studied. When the particle size increases, the particle layer flatness decreases, the particle layer flow ununiformity increases. The volatility of the particle residence time distribution increases with the particle size increases, and the standard deviation of the particle residence time increases. When the particle size increases, the voidage of the particle system increases. So the particle thermal resistance in the steam generator increases with the particle size increases, the steam production of the generator decreases, and the system hydrogen production of decreases.     

Effect of the vacancy close to heat exchange wall on the heat transfer performance of the solid particles steam generator using waste heat in a methanol steam reforming hydrogen production system

With the massive consumption of fossil fuels and it resulted in significant carbon emissions, it is urgent to find an alternative clean energy source. Hydrogen has been regarded as one of the most promising energy candidates for the next generation. It is a great approach that methane steam reforming for hydrogen production by rational utilization of industrial waste heat, which significantly minimizes carbon emissions and develops methanol steam reforming technology. A solid particle steam generator based on the primary heat exchange method has been proposed, which can provide the heat and steam in the methanol steam reforming hydrogen production system. The quasi-two-dimensional packing heat transfer model of solid particles steam generator was set up.The effect of distance change between the vacancy and the cold wall and distance change between vacancies on heat transfer performance of the steam generator and hydrogen production capacity were studied. As the distance between the vacancy and the wall increases, the heat transfer performance of the steam generator gradually deteriorates, so the steam production of the steam generator decreases, and the system's hydrogen production capacity is reduced, the maximum of the heat flux and the minimum of the apparent thermal resistance are 34.67 kW/m² and 12.02 K/W, respectively. As the distance between vacancies increases, the heat transfer performance of the steam generator is gradually optimized slightly. To maintain the hydrogen production capacity, vacancies should be avoided to appear 2 layers of particles away from the heat exchange wall in the particles steam generator. From the results of the study, the farther the distance between vacancies, the better the steam production and hydrogen production capacity.     

Effects of fin structure size on methane-steam reforming for hydrogen production in a reactor heated by waste heat

This paper mainly describes the influence of changes in fin structure on the hydrogen production capacity of the methane-steam reforming system. The model of the triangular-fin-tube steam generator was set up. The effects of the fin height (34 mm–46 mm), fin root width (3 mm–6 mm) and the fin-type were studied. As the height of the fin increases (34 mm–46 mm), the CPC temperature at the outlet of the steam generator decreases (the maximum temperature decreases 23.6 K and the average temperature decreases 18.9 K). At the same time, the heat recovery efficiency increased from 96.3% to 98.4%, and so the system hydrogen production increases. As the fin root width increases (3 mm–6 mm), the CPC temperature at the outlet of the steam generator decreases (the maximum temperature decreases 3.7 K and the average temperature decreases 1.2 K). Meanwhile, the heat recovery efficiency increases from 97.5% to 98.1%, and so the system hydrogen production increases. When the fin type is changed from a straight fin to a triangular-fin, the average temperature of the solid particle decreases 30.5 K, the heat recovery efficiency increases by 7.9%, and the system hydrogen production increases.     

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.     

Microwave-activated methanol steam reforming for hydrogen production

Methanol steam reforming (MSR) was carried out in a catalytic packed bed reactor under electrical and microwave heating using the two most common catalysts for this process-CuZnO/Al₂O₃ and PdZnO/Al₂O₃. Significant two-dimensional temperature gradients were found, especially in the latter case. Our results show that for the same average bed temperature, methanol conversion is higher under microwave heating (>10%). On the other hand, the product distribution is not affected by the heating mode. We demonstrate that even in cases where the maximum temperature along the entire height of the bed is significantly higher under electrical heating, conversion is either higher in the microwave case or approximately the same between the two heating modes. Finally, our experimental data indicate that a given methanol conversion can be achieved with lower net heat input to the reactor under microwave heating. This does not mean lower total energy consumption in the microwave process due to the limitations in the magnetron efficiency and the reflected power. However, it may be an implicit indication of higher temperature at metal sites than in bulk phase (microscale hot spot formation) due to the selective heating principle.     

Experiments on hydrogen production from methanol steam reforming in fluidized bed reactor

A novel approach for the hydrogen production which integrated methanol steam reforming and fluidized bed reactor (FBR) was proposed. The reaction was carried out over Cu/ZnO/Al₂O₃ catalysts. The critical fluidized velocities under different catalyst particle sizes and masses were obtained. The influences of the operating parameters, including that of H₂O-to-CH₃OH molar ratio, feed flow rate, reaction temperature, and catalyst mass on the performance of methanol steam reforming were investigated in FBR to obtain the optimum experimental conditions. More uniform temperature distribution, larger surface volume ratio and longer contacting time can be achieved in FBR than that in fixed bed reactor. The results indicate that the methanol conversion rate in FBR can be as high as 91.95% while the reaction temperatures is 330 °C, steam-to-carbon molar ratio is 1.3, and feed flow rate is 540 ml/h under the present experiments, which is much higher than that in the fixed bed.     

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%.     

Effects of particle sizes on performances of the multi-zone steam generator using waste heat in a bio-oil steam reforming hydrogen production system

Hydrogen production by bio-oil steam reforming is an advanced production technology. It is a good method of coupling waste heat utilization with bio-oil steam reforming to produce hydrogen, which increases the cleaning ability of the bio-oil steam reforming system. A multi-zone steam generator using waste heat has been proposed, which can produce the heat source and steam source of the hydrogen system. The DEM model of the multi-zone steam generator was set up. The model has been used to investigate the effects of particle sizes (40 mm–80 mm). With increasing particle size, the flow index and the flow uniformity gradually decrease, the vertical velocity gradient increases in the area on both side with the zone steam generator, and the vertical velocity fluctuation amplitude gradually increases. So, the hydrogen production decreases from the particle size increasing.     

Recent trends in the development of reactor systems for hydrogen production via methanol steam reforming

Hydrogen is currently receiving significant attention as an alternative energy resource, and among the various methods for producing hydrogen, methanol steam reforming (MSR) has attracted great attention because of its economy and practicality. Because the MSR reaction is inherently activated over catalytic materials, studies have focused on the development of noble metal-based catalysts and the improvement of existing catalysts with respect to performance and stability. However, less attention has been paid to the modification and development of innovative MSR reactors to improve their performance and efficiency. Therefore, in this review paper, we summarize the trends in the development of MSR reactor systems, including microreactors and membrane reactors, as well as the various structured catalyst materials appropriate for application in complex reactors. In addition, other engineering approaches to achieve highly efficient MSR reactors for the production of hydrogen are discussed.     

A numerical study on methanol steam reforming reactor utilizing engine exhaust heat for hydrogen generation

Internal combustion engines are used in most vehicles around the world to power the transport sector. Efficiency improvement, emission reduction, and utilization of alternative fuels are the main aspects of current IC engine research. Hydrogen-enhanced combustion proved to be one of the efficient ways to achieve such goals. But the problem lies in the storage of hydrogen for the transportation sector, and on-board fuel reforming is a promising option for solving this issue. It deals with transforming a suitable liquid fuel (methanol) into an H₂-rich gas using a catalytic conversion process. For sustaining the reforming reaction, the required heat energy is taken from engine exhaust waste heat, this process is known as thermochemical recuperation. Number of studies on the reformers utilized for on-board hydrogen generation using engine exhaust heat are limited in the literature. The present study investigates the performance of a reactor that uses the exhaust gas heat energy for sustaining the reforming reaction. A numerical analysis was performed over a selected reactor where exhaust gases were flowing at one side, while on the other, the reforming reaction was taking place with the help of heat provided by high-temperature exhaust gases. A packed bed-type reactor was chosen for the current study and a parametric study was conducted where the effects of various operating parameters on both reacting and heating sides on the reactor's performance were investigated. It was found that temperature was the most influential inlet parameter among others. Steam/Carbon ratio and flow configuration had a negligible effect on the hydrogen yield as well as methanol conversion. Reactant inlet velocity increment revealed a significant drop in methanol conversion as it reduces the residence time for reforming reaction in the catalyst zone.     

Mathematical simulation of hydrogen production via methanol steam reforming using double-jacketed membrane reactor

The hydrogen production and purification via methanol reforming reaction was studied in a double-jacketed Pd membrane reactor using a 1-D, non-isothermal mathematical model. Both mass and heat transfer behavior were evaluated simultaneously in three parts of the reactor, annular side, permeation tube and the oxidation side. The simulation results exhibited that increasing the volumetric flow rate of hydrogen in permeation side could enhance hydrogen permeation rate across the membrane. The optimum velocity ratio between permeation and annular sides is 10. However, hydrogen removal could lower the temperature in the reformer. The hydrogen production rate increases as temperature increases at a given Damköhler number, but the methanol conversion and hydrogen recovery yield decrease. In addition, the optimum molar ratio of air and methanol was 1.3 with three air inlet temperatures. The performance of a double-jacketed membrane reactor was compared with an autothermal reactor by judging against methanol conversion, hydrogen recovery yield and production rate. Under the same reaction conditions, the double-jacketed reactor can convert more methanol at a given reactor volume than that of an autothermal reactor.     

Experimental evaluation of methanol steam reforming reactor heated by catalyst combustion for kW-class SOFC

The distributed power generation of methanol steam reforming reactor combined with solid oxide fuel cell (SOFC) has the characteristics of outstanding economic advantages. In this paper, a methanol steam reforming reactor was designed which integrates catalyst combustion, vaporization and reforming. By catalyst combustion, it can achieve stable operation to supply fuel for kW-class SOFC in real time without additional heating equipment. The optimal operating condition of the reforming reactor is 523–553 K, and the steam to carbon ratio (S/C) is 1.2. To study the reforming performance, methanol steam reforming (MSR), methanol decomposition (MD), water-gas shift (WGS) were considered. Operating temperature is the greatest factor affecting reforming performance. The higher the reaction temperature, the lower the H₂ and CO₂, the higher the CO and the methanol conversion rate. The methanol conversion rate is up to 95.03%. The higher the liquid space velocity (LHSV), the lower the methanol conversion rate, the lowest is 90.7%. The temperature changes of the reforming reactor caused by the load change of stack takes about 30 min to reach new balance. Local hotspots within the reforming reactor lead to an excessive local temperature to test a small amount of CH₄ in the reforming gas. The methanation reaction cannot be ignored at the operating temperature. The reforming gas contains 70–75% H₂, 3–8% CO, 18–22% CO₂ and 0.0004–0.3% CH₄. Trace amounts of C₂H₆ and C₂H₄ are also found in some experiments. The reforming reactor can stably supply the fuel for up to 1125 W SOFC.     

Performance assessment and evaluation of catalytic membrane reactor for pure hydrogen production via steam reforming of methanol

The steam reforming of methanol was investigated in a catalytic Pd–Ag membrane reactor at different operating conditions on a commercial Cu/ZnO/Al₂O₃ catalyst. A comprehensive two-dimensional non-isothermal stationary mathematical model has been developed. The present model takes into account the main chemical reactions, heat and mass transfer phenomena in the membrane reactor with hydrogen permeation across the PdAg membrane in radial direction. Model validation revealed that the predicted results satisfy the experimental data reasonably well under the different operating conditions. Also the impact of different operating parameters including temperature, pressure, sweep ratio and steam ratio on the performance of reactor has been examined in terms of methanol conversion and hydrogen recovery. The modeling results have indicated the high performance of the membrane reactor which is related to continuous removal of hydrogen from retentate side through the membrane to shift the reaction equilibrium towards formation of hydrogen. The obtained results have confirmed that increasing the temperature improves the kinetic properties of the catalyst and increase in the membrane's H₂ permeance, which results in higher methanol conversion and hydrogen production. Also it is inferred that the hydrogen recovery is favored at higher temperature, pressure, sweep ratio and steam ratio. The model prediction revealed that at 573 K, 2 bar and sweep ratio of 1, the maximum hydrogen recovery improves from 64% to 100% with increasing the steam ratio from 1 to 4.     

Qualitative investigation on effects of manifold shape on methanol steam reforming for hydrogen production

Fluid velocity distribution among microchannels plays important role on the reaction performances. In this work, the velocity distribution among microchannels with two different manifold structures is compared by a three-dimensional CFD model under two situations respectively, no reaction and methanol steam reforming occurs. Then the performances of methanol steam reforming in both plates are experimentally investigated, and the effect of manifold shape on the hydrogen production performances is qualitatively analyzed by the combination of simulation results of velocity distribution. It is found that the microchannel plate with right-angle manifold enables narrow velocity distributions under different entrance velocities and reaction temperatures, whether no reaction occurs or methanol steam reforming is progressing, which can be the critical element results in better conversion rate and selectivity of process than that of the microchannel plate with oblique-angle manifold. Optimizing the structural parameters to facilitate a relatively uniform velocity distribution to increase the hydrogen production performances may be a key factor to be considered.     

Numerical investigation of a multichannel reactor for syngas production by methanol steam reforming at various operating conditions

A novel multichannel reactor with a bifurcation inlet manifold, a rectangular outlet manifold, and sixteen parallel minichannels with commercial CuO/ZnO/Al₂O₃ catalyst for methanol steam reforming was numerically investigated in this paper. A three-dimensional numerical model was established to study the heat and mass transfer characteristics as well as the chemical reaction rates. The numerical model adopted the triple rate kinetic model of methanol steam reforming which can accurately calculate the consumption and generation of each species in the reactor. The effects of steam to carbon molar ratio, weight hourly space velocity, operating temperature and catalyst layer thickness on the methanol steam reforming performance were evaluated and discussed. The distributions of temperature, velocity, species concentration, and reaction rates in the reactor were obtained and analyzed to explain the mechanisms of different effects. It is suggested that the operating temperature of 548 K, steam to carbon ratio of 1.3, and weight hourly space velocity of 0.67 h⁻¹ are recommended operating conditions for methanol steam reforming by the novel multichannel reactor with catalyst fully packed in the parallel minichannels.     

Structural design and performance research of methanol steam reforming microchannel for hydrogen production based on mixing effect

To improve hydrogen production performance of reforming, a plate-type microchannel carrier plate with a ridge structure was designed based on the mixing effect. The mixing effect of the ridge structure on the hydrogen production performance of reforming was analyzed. Then the effects of geometric parameters (shape, size, spacing, and tilt angle) of the ridge structure on heat, mass transfer, and the hydrogen production performance of the reforming process were modelled and simulated. Finally, data analysis and structural optimisation of microchannels with the ridge structure were conducted via methanol steam reforming hydrogen production experiments. The experimental results show that the trapezoidal ridge structure microchannel (T-type0) achieved the best hydrogen production performance, whose methanol conversion rate was 60.8%, under the gas hourly space velocity of 48,757 mL/(g&h). Especially compared with the ordinary rectangular microchannel structure (O-type0), the methanol conversion rate of the trapezoidal ridge structure microchannel increased by 25.2%. Moreover, the pressure drop of this microchannel did not increase significantly, indicating that the structure did not significantly increase the pressure drop loss while enhancing the heat and mass transfer. Therefore, the ridge structure proposed in this paper can effectively improve heat and mass transfer performance and the hydrogen production efficiency of the microchannel.     

Zinc oxide nanorods based catalysts for hydrogen production by steam reforming of methanol

Zinc oxide (ZnO) nanorods were epitaxially grown on porous cordierite support by a hydrothermal process and utilized for catalyzing methanol steam reforming (MSR) reaction. Catalytic activity of ZnO nanorods for MSR process was correlated to the terminated surfaces of ZnO crystallites. Copper (Cu), palladium (Pd) and gold (Au) nanoparticles infused ZnO nanorods were prepared by in-situ precipitation of the metals on the nanorods. 28% hydrogen selectivity was observed with Cu/ZnO nanorods (Cu/10Zn), while Pd/ZnO nanorods and (Pd/10Zn) showed slightly lower activity. Higher catalytic activity of copper and palladium impregnated ZnO nanorods can be attributed to the synergistic combination of bimetallic oxides. In contrast, Au/ZnO nanorods (Au/10Zn) showed very high activity for methanol dehydrogenation and higher than 97% methanol conversion was achieved for operating temperatures as low as 200 °C.     

Robust multi-objective optimization of methanol steam reforming for boosting hydrogen production

Methanol steam reforming (MSR) has been considered as a promising method for producing pure hydrogen in recent decades. A comprehensive two-dimensional steady-state mathematical model was developed to analyze the MSR reactor. To improving high purity hydrogen production, a triple-objective optimization of the MSR reactor is performed. Non-dominated Sorting Genetic Algorithm-II (NSGA-II) is employed as a robust optimization approach to maximize the three objectives, termed as, methanol conversion, CO selectivity, and H₂ selectivity. The Pareto optimal frontier has also been provided and the ultimate solution of the Pareto front has been found by the three decision-making methods (TOPSIS, LINMAP, and Shannon's Entropy). Among the three distinct decision-making approaches, LINMAP presents better results according to the deviation index parameter. It has been shown that a perfect agreement is available between the plant and simulation data. Operating under the optimum values based on the LINMAP method confirms an almost 47.04% enhancement of H₂ mass fraction compared to the conventional industrial MSR reactor. The predicted results advocate that the key superiority of the optimized-industrial reactor is the remarkable higher production rate of hydrogen compared to the conventional MSR reactor which makes optimized-industrial reactor both feasible and beneficial.     

Synergetic integration of a methanol steam reforming cell with a high temperature polymer electrolyte fuel cell

In this work an integrated unit, combining a methanol steam-reforming cell (MSR-C) and a high temperature polymer electrolyte membrane fuel cell (HT-PEMFC) was operated at the same temperature (453 K, 463 K and 473 K) allowing thermal integration and increasing the system efficiency of the combined system. A novel bipolar plate made of aluminium gold plated was built, featuring the fuel cell anode flow field in one side and the reformer flow field on the other. The combined unit (MSR-C/HT-PEMFC) was assembled using Celtec^® P2200N MEAs and commercial reforming catalyst CuO/ZnO/Al₂O₃ (BASF RP60). The water/methanol vaporisation originates oscillations in the vapour flowrate; reducing these oscillations increase the methanol conversion from 93% to 96%. The MSR-C/HT-PEMFC showed a remarkable high performance at 453 K. The integrated unit was operated during ca. 700 h at constant at 0.2 A cm^?2, fed alternately with hydrogen and reformate at 453 K and 463 K. Despite the high operating temperature, the HT-PEMFC showed a good stability, with an electric potential difference decreasing rate at 453 K of ca. 100 μV h^?1. Electrochemical impedance spectroscopy (EIS) analysis revealed an overall increase of the ohmic resistances and charge transfer resistances of the electrodes; this fact was assigned to phosphoric acid losses from the electrodes and membrane and catalyst particle size growth.