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.     

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.     

A complete miniaturized microstructured methanol fuel processor/fuel cell system for low power applications

A complete miniaturized methanol fuel processor/fuel cell system was developed and put into operation as compact hydrogen supplier for low power application. The whole system consisting of a micro-structured evaporator, a micro-structured reformer and two stages of preferential oxidation of CO (PROX) reactor, micro-structured catalytic burner, and fuel cell was operated to evaluate the performance of the whole production line from methanol to electricity. The performance of micro methanol steam reformer and PROX reactor was systematically investigated. The effect of reaction temperature, steam to carbon ratio, and contact time on the methanol steam reformer performance is presented in terms of catalytic activity, selectivity, and reformate yield. The performance of PROX reactor fed with the reformate produced by the reformer reactor was evaluated by the variation of reaction temperature and oxygen to CO ratio. The results demonstrate that micro-structured device may be an attractive power source candidate for low power application.     

Integrated methanol reforming and oxidation in wash-coated microreactors: A three-dimensional simulation

A microreactor consisting of two parallel channels is numerically simulated where methanol steam reforming takes place in one channel, and the required heat is supplied by methanol oxidation in the other channel. Effects of different parameters on methanol conversion, hydrogen yield and CO concentration are examined. Results from the parametric study are then used to propose conditions for high methanol conversion and hydrogen yield. A microreactor with enhanced output conditions is thus designed which is capable of producing a gas stream consisting of 74% hydrogen (dry). CO concentration in the generated synthesis gas stream is low enough to require only a PROX reactor for CO clean-up, eliminating the need for a bulky water–gas shift reactor. The produced hydrogen from an assembly of such microreactors can feed a low-power PEM fuel cell. A cluster of these microreactors would take a volume of about 91 cm³ to feed a typical 30-watt PEM fuel cell.     

H2 production in silica membrane reactor via methanol steam reforming: Modeling and HAZOP analysis

The main aim of this work is the presentation of both qualitative safety and quantitative operating analyses of silica membrane reactor (MR) for carrying out methanol steam reforming (MSR) reaction to produce hydrogen. To perform the safety analysis, HAZOP method is used. Before the HAZOP analysis, a comprehensive investigation of most important operating parameters effects on silica MR performance is required. Therefore, for a quantitative analysis, a 1-dimensional and isothermal model is developed for evaluating the reaction temperature, reaction pressure, feed molar ratio (steam/methanol) and feed flow rate effects on silica MR performance in terms of methanol conversion and hydrogen recovery. The model validation results show good agreement with experimental data from literature. As a consequence, simulation results indicate that the reaction pressure and feed molar ratio have dual effect on silica MR performance. In particular, it is found that methanol conversion is decreased by increasing the reaction pressure from 1.5 to 4.0 bar, whereas over 4.0 bar, it is improved. Moreover, the hydrogen recovery is decreased by increasing the feed molar ratio from 1 to 5, while over 5, it was approximately constant. After the evaluation of modeling results, the HAZOP analysis for silica MR is carried out during MSR reaction. The analysed operating parameters in the modeling study have been considered as key parameters in the HAZOP analysis. The safety assessment results are presented in tables as check list. By considering the HAZOP results, safety pretreatment works are recommended before or during the experimental tests of MSR reaction in silica MR. According to different parameters consequences, reaction temperature is the most critical parameter in MSR reaction for the silica MR studied in this work. In particular, to avoid the consequences of temperature deviation, it is recommended to use a PID temperature controller in the silica MR for MSR reaction.     

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%.     

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.     

A combined methanol autothermal steam reforming and PEM fuel cell pilot plant unit: Experimental and simulation studies

An integrated system for hydrogen production via autothermal steam reforming of methanol and consequent power generation in a polymer electrolyte membrane (PEM) fuel cell has been developed and operated at C.P.E.R.I. The pilot plant comprises an autothermal reforming reactor to produce hydrogen, a preferential oxidation reactor (PROX) to reduce CO concentration below 50 ppm and a PEM fuel cell for power generation.The present paper deals with the study of this system, both from an experimental and a theoretical point of view. The experimental work aims to: (a) examine the effect of the reforming temperature on methanol conversion and on the effluent stream concentration, (b) investigate the effect of reaction temperature and O₂/CO ratio on the performance of the PROX reactor, and (c) evaluate the operation of a 10-cell PEM fuel cell, using pure hydrogen and air at three temperature levels. The experimental data are subsequently utilized for the validation of one-dimensional pseudo-homogeneous models that have been developed for the two reactors and also for the identification of the voltage–current characteristic curve of the PEM fuel cell. The validated models are then used to investigate the behavior and explore the interactions, both static and dynamic, among the various process subsystems.     

A hybrid fuel cell system integrated with methanol steam reformer and methanation reactor

In this paper, a hybrid fuel cell system integrated with methanol steam reformer and methanation reactor is demonstrated. Methanol steam reformer employed in this system is to produce hydrogen-rich reformate in connection with a methanation reactor to reduce the carbon monoxide content effectively, and the reformate gas is sent into a low-temperature polymer electrolyte fuel cell for direct electric power generation. The optimum conditions (temperature, water to methanol ratio, and space velocity) for methanol steam reforming (MSR) reaction and methanation (MET) reaction are verified by experiments. A comparison between pure hydrogen, reformate surrogate, and actual reformate is performed. The results show that the power density of this hybrid system achieves 245.2 mW/cm² while it achieves 268.8 mW/cm² when employing pure hydrogen as the fuel. An alternative novel method to solve the problem of hydrogen storage and transportation is provided and the in-situ hydrogen production and utilizing through low-temperature fuel cell system is realized, which is helpful to accelerate the commercialization process of the fuel cell.     

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.     

Methanol steam reforming in a planar wash coated microreactor integrated with a micro-combustor

A numerical simulation of methanol steam reforming in a microreactor integrated with a methanol micro-combustor is presented. Typical Cu/ZnO/Al₂O₃ and Pt catalysts are considered for the steam reforming and combustor channels respectively. The channel widths are considered at 700 μm in the baseline case, and the reactor length is taken at 20 mm. Effects of Cu/ZnO catalyst thickness, gas hourly space velocities of both steam reforming and combustion channels, reactor geometry, separating substrate properties, as well as inlet composition of the steam reforming channel are investigated. Results indicate that increasing catalyst thickness will enhance hydrogen production by about 68% when the catalyst thickness is increased from 10 μm to 100 μm. Gas space velocity of the steam reforming channel shows an optimum value of 3000 h⁻¹ for hydrogen yield, and the optimum value for the space velocity of the combustor channel is calculated at 24,000 h⁻¹. Effects of inlet steam to carbon ratio on hydrogen yield, methanol conversion, and CO generation are also examined. In addition, effects of the separating substrate thickness and material are examined. Higher methanol conversion and hydrogen yield are obtained by choosing a thinner substrate, while no significant change is seen by changing the substrate material from steel to aluminum with considerably different thermal conductivities. The produced hydrogen from an assembly of such microreactor at optimal conditions will be sufficient to operate a low-power, portable fuel cell.     

High-purity hydrogen production by sorption-enhanced methanol steam reforming over a combination of Cu–Zn–CeO2–ZrO2/MCM-41 catalyst and (Li–Na–K) NO3·MgO adsorbent

In this study, sorption-enhanced methanol steam reforming (SEMSR) was applied to generate high-purity hydrogen. The mesoporous MCM-41 as support and CuO, ZnO, CeO₂, ZrO₂ as active agents and promoters were employed for the catalyst preparation. In addition, (Li–Na–K) NO₃·MgO as a CO₂ adsorbent was prepared by the wet mixing method. The fresh and used catalysts were characterized by XRD, BET, FTIR, FESEM, TEM, H₂-TPR and TGA analyses. Also, the CO₂ sorbent was studied by XRD, BET, FESEM, TEM and TGA analyses before and after the reaction. The SEMSR performances of the synthesized catalyst and adsorbent were evaluated experimentally in a fixed-bed reactor. The effect of various conditions such as temperature, WHSV, feed molar ratio and sorbent/catalyst ratio were investigated. The best results were obtained at 300 °C, a feed molar ratio (water/methanol) of 2:1, a WHSV of 1.62 h^?1, and the sorbent/catalyst ratio of 8:1, which produced 99.8% hydrogen, 25% more than the hydrogen production during conventional methanol steam reforming. Moreover, the cyclic stability of the catalyst and the sorbent was studied for 10 cycles.