Measurement of concentration profiles over ZnO–Cr2O3/CeO2–ZrO2 monolithic catalyst in oxidative steam reforming of methanol

Oxidative steam reforming of methanol (OSRM) reaction was investigated over a novel monolithic ZnO–Cr₂O₃/CeO₂–ZrO₂ catalyst developed in our laboratory. A novel flat-bed reactor was designed to measure the concentration profiles of the monolithic catalyst beds under different operation conditions: water-to-methanol mole ratio (W/M) between 1 and 1.5; oxygen-to-methanol mole ratio (O/M) in the range of 0.1–0.3; space velocity ranging from 1840 to 2890 h^− 1; and reaction temperature in the scale of 400–440 °C. On the basis of these results, reaction pathways for the OSRM were discussed. It is indicated that only three independent reactions dominate in our reaction system, namely, the partial oxidation of methanol, the steam reforming of methanol and the methanol decomposition reaction, whereas the water–gas shift and the reverse water–gas shift reactions should be ignored. In addition, the steam reforming of methanol proceeds along all the catalyst bed, whereas methanol decomposition and oxidation reactions occur mainly at the entrance of the catalyst bed.     

Steam reforming of methanol over a CuO/ZnO/Al2O3 catalyst part II: A carbon membrane reactor

The reaction of methanol steam reforming was studied in a carbon membrane reactor over a commercial CuO/ZnO/Al₂O₃ catalyst (Süd-Chemie, G66 MR). Carbon molecular sieve membranes supplied by Carbon Membranes Ltd. were tested at 150 °C and 200 °C. The carbon membrane reactor was operated at atmospheric pressure and with vacuum at the permeate side, at 200 °C. High methanol conversion and hydrogen recovery were obtained with low carbon monoxide permeate concentrations. A sweep gas configuration was simulated with a one-dimensional model. The experimental mixed-gas permeance values at 200 °C were used in a mathematical model that showed a good agreement with the experimental data. The advantages of using water as sweep gas were investigated in what concerns methanol conversion and hydrogen recovery. The concentration of carbon monoxide at the permeate side was under 20 ppm in all simulation runs. These results indicate that the permeate stream can be used to feed a polymer electrolyte membrane fuel cell.     

Production of H2 for fuel cell applications: methanol steam reforming with sufficiently thorough cleaning of H2 from CO impurity

Methanol steam reforming (MSR) and preferential CO oxidation (PROX) were studied with the view of improving the generation of H₂-rich gases. In MSR, conventional catalysts of methanol synthesis were tested, various Cu-based catalysts were prepared and studied. A theoretic kinetic model (based on the reaction mechanism established using independent methods [1]) is developed and checked out. PROX was studied over various Ru/Al₂O₃ catalysts using a flow “quasi-adiabatic” reactor. On-line recording of gas temperature in the catalyst bed and CO residual concentration at varied reaction conditions allowed to observe ignition and extinction of the catalyst surface and the transition states of the process. It is shown that in the ignition mode a sharp decrease in CO residual concentration can be achieved. The combination of proposed catalyst and the control of the macrokinetic regime of PROX allows high degree of CO removal from gaseous mixtures produced by MSR. Residual CO content in a H₂-rich gaseous mixture can be lowered to < 15 ppm at GHSV∼100 m³/(kg cat)/h and O₂/CO ratio of 1. Obtained data show the possibility of designing a high-throughput set-up for generation of H₂-rich gases from methanol with one-step cleaning from the CO impurity.     

Modeling and simulation for the methane steam reforming enhanced by in situ CO2 removal utilizing the CaO carbonation for H2 production

The transient behavior of catalytic methane steam reforming (MSR) coupled with simultaneous carbon dioxide removal by carbonation of CaO pellets in a packed bed reactor for hydrogen production has been analyzed through a mathematical model with reaction experiments for model verification. A dynamic model has been developed to describe both the MSR reaction and the CaO carbonation-enhanced MSR reaction at non-isothermal, non-adiabatic, and non-isobaric operating conditions assuming that the rate of the CaO carbonation in a local zone of the packed bed is governed by kinetic limitation or by mass transfer limitation of the reactant CO₂. Apparent carbonation kinetics of the CaO pellet prepared has been determined using the TGA carbonation experiments at various temperatures, and incorporated into the model. The resulting model is shown to successfully depict the transient behavior of the in situ CaO carbonation-enhanced MSR reaction. The effects of major operating parameters on the transient behavior of the CaO carbonation-enhanced MSR have been investigated using the model. The bed temperature is the most important parameter for determining the amount of CO₂ removed by carbonation of CaO, and at temperatures of 600°C, 650°C, 700°C and 750°C, the CO₂ uptake is 1.43, 2.29, 3.5 and -CO₂/kg-CaO, respectively. Simultaneously with the increase in CO₂ uptake with increasing temperature, the corresponding amounts of hydrogen produced are 1.56, 2.54, 3.91 and -H₂/kg-CaO, at the same temperatures as above. Operation at high pressure, high steam to methane feed ratio, and the decreased feed rate at a given temperature are favorable for increasing the degree of the overall utilization of CaO pellets in the reactor bed, and for lowering the CO concentration in the product.     

Top-down kinetic modeling from power law to elementary steps using KASTER: A methane steam reforming case study

A top-down methodology for kinetic model construction including regression against experimental data is proposed using “KASTER.” As a case study, it is applied in the assessment of methane steam reforming (MSR) including water–gas shift (WGS) on a Ni catalyst at 923 K. The degree of detail in the reaction mechanism and the corresponding model is gradually enhanced, typically ranging from a simple power law to a microkinetic model. The reactor equations are solved transiently, preventing the numerical challenges encountered in the steady-state solution, particularly for microkinetic models. The microkinetic variant indicated that CH₄ dissociative adsorption and CO formation are kinetically relevant steps in MSR, while COOH formation is rate-determining in WGS. However, the model providing the best balance between detail accounted for and parameter significance corresponded to a Langmuir–Hinshelwood–Hougen–Watson (LHHW) mechanism accounting for dissociative adsorption, with CO formation and COOH formation as rate-determining steps for MSR and WGS, respectively.     

Hydrogen production by methanol steam reforming carried out in membrane reactor on Cu/Zn/Mg-based catalyst

The methanol steam reforming (MSR) reaction was studied by using both a dense Pd-Ag membrane reactor (MR) and a fixed bed reactor (FBR). Both the FBR and the MR were packed with a new catalyst based on CuOAl₂O₃ZnOMgO, having an upper temperature limit of around 350 °C. A constant sweep gas flow rate in counter-current mode was used in MR and the experiments were carried out by varying the water/methanol feed molar ratio in the range 3/1–9/1 and the reaction temperature in the range 250–300 °C. The catalyst shows high activity and selectivity towards the CO₂ and the H₂ formation in the temperature range investigated. Under the same operative conditions, the MR shows higher conversions than FBR and, in particular, at 300 °C and H₂O/CH₃OH molar ratio higher than 5/1 the MR shows complete methanol conversion.     

Correlation of activity and stability of CuO/ZnO/Al2O3 methanol steam reforming catalysts with Cu/Zn composition obtained by SEM–EDAX analysis

A series of CuO/ZnO/Al₂O₃ catalysts were prepared and characterized by TPR, surface area, metal area, XRD and SEM–EDAX analysis. These systems were evaluated in the development of a methanol steam reforming catalyst (MSR). A correlation of activity and stability of MSR catalysts with the Cu/Zn ratio derived by SEM–EDAX analysis is observed. The stable activity of these catalysts is also supported by the method of preparation, low temperature reducibility and the presence of reversibly oxidizable Cu species observed by TPR of fresh and used catalysts.     

Kinetic modeling of oxidative coupling of methane over Mn/Na2WO4/SiO2 catalyst

A comprehensive kinetic model for oxidative coupling of methane (OCM) on Mn/Na₂WO₄/SiO₂ catalyst was developed based on a microcatalytic reactor data. The methane conversion and ethylene, ethane, carbon monoxide and carbon dioxide selectivities were obtained in a wide range of operating conditions including 750 < T < 875 °C, 4 < CH₄/O₂ < 7.5 and space time between 30 and 160 kg · s/m³ at P = 657 mmHg. The reaction networks of five kinetic models with appropriate rate equation type were compared together. The kinetics rates parameters of each reaction network were estimated using genetic algorithm optimization method. After comparing the reaction networks, the reaction network presented by Stansch et al. was found to best represent the OCM reaction network and was further used in this work. This kinetic network considers both catalytic and gas-phase as well as primary and consecutive reaction steps to predict the performance of the OCM. Comparing the experimental and predicted data showed that presented model has a reasonable fit between the experimental data and the predicted values with average absolute relative deviation of ± 9.1%.     

Highly active and stable Rh/MgOAl2O3 catalysts for methane steam reforming

Highly active and coke-resistant Rh catalysts were developed for methane steam reforming in microchannel chemical reactors. Rh loading was optimized on a stable MgOAl₂O₃ support to improve the volumetric productivity for methane conversion. Catalyst activities were stable over a wide range of steam/carbon ratios. In particular, experimental results demonstrated that Rh/MgOAl₂O₃ catalysts are extremely active for methane steam reforming and are resistant to coke formation at stoichiometric steam/carbon ratio of 1 for over 14 h time-on-stream with no sign of deactivation. Methane steam reforming activities on this catalyst is compared in both a microchannel reactor and a conventional micro-tubular reactor. Significant performance enhancement was observed in microchannel reactors owing to improved heat and mass transfer.     

Study of the performance of Mo2C for iso-octane steam reforming

In the present work, the performance of commercial molybdenum carbide (Mo₂C) for isooctane steam reforming has been investigated in order to determine the effects of major operating parameters (temperature, space velocity, and steam to carbon ratio) on the catalytic activity. While the results obtained indicate an onset reforming temperature of 850 °C, high concentrations of H₂ in the reforming environment were found to reduce the onset temperature to 750 °C. The catalytic activity at 850 °C was sufficient to produce hydrogen yields greater than 90% and carbon conversions close to 100%, with a low selectivity to CH₄ and CO₂. In addition, and consistent with thermodynamic predictions, a steam to carbon ratio of 1 appeared to optimize the reforming rates. Finally, based on experimental observations, a reaction mechanism was formulated and used to interpret the results obtained during catalytic activity measurements. This mechanism involves continuous oxidation and reduction of Mo metal, which can provide activity and stability to the catalyst when occurring at similar rates.     

A Kinetic Study of Ethanol Steam Reforming Using a Nickel Based Catalyst

A kinetic study of ethanol steam reforming to produce hydrogen within the region of kinetic rate control was carried out. A Ni(II)–Al(III) lamellar double hydroxide as catalyst precursor was used. H₂, CO, CO₂ and CH₄ were obtained as products. Using the Langmuir–Hinshelwood (L–H) approach, two kinetic models were proposed. The first was a general model including four reactions, two of them corresponding to ethanol steam reforming and the other two to methane steam reforming. When high temperatures and/or high water/ethanol feed ratios were used, the system could be reduced to two irreversible ethanol steam reforming reactions.     

Production of hydrogen by steam reforming of bio-oil over Ni/Al2O3 catalysts: Effect of addition of promoter and preparation procedure

Catalytic steam reforming of bio-oil was investigated in a fixed bed tubular reactor for production of hydrogen. Two series of nickel/alumina (Ni/Al₂O₃) supported catalysts promoted with ruthenium (Ru) and magnesium (Mg) were prepared. Each catalyst of the first series (Ru–Ni/Al₂O₃) was prepared by co-impregnation of nickel and ruthenium on alumina. They were examined to investigate the effect of adding ruthenium on the performance of the catalysts for hydrogen production. The effect of the temperature, the most effective parameter in the steam reforming of bio-oil, on the activity of the catalysts was also investigated. Each catalyst of the second series (Ni–MgO/Al₂O₃) was prepared by consecutive impregnation using various preparation procedures. They were tested to determine the effect of adding magnesium as well as the effect of the preparation procedure on the outlet gas concentrations. It was shown that in both series, the catalysts were more efficient in hydrogen production as well as carbon conversion than Ni/Al₂O₃ catalysts. The highest hydrogen yield was 85% which was achieved over Ru–Ni/Al₂O₃ at 950 °C. It was also found that the effect of adding a small amount of ruthenium was superior to that of nickel on the yield of hydrogen when the nickel content was equal to or greater than 10.7%.     

Hydrogen generation and separation using Gd0.2Ce0.8O1.9−δ–Gd0.08Sr0.88Ti0.95Al0.05O3±δ mixed ionic and electronic conducting membranes

Decomposition of steam under a chemical driving force at moderate temperatures offers a simple and economical way to generate hydrogen. A significant amount of hydrogen can be generated and separated by splitting steam and removing the oxygen using Gd_0.2Ce_0.8O_1.9−δ (GDC)–Gd_0.08Sr_0.88Ti_0.95Al_0.05O_3±δ (GSTA) mixed oxygen ionic and electronic conducting membranes. Hydrogen generation experiments for the self-supported thick membranes and porous supported thin membranes were conducted at different oxygen partial pressure gradients across the membrane established using H₂–H₂O mixture gas. Experimental results indicate that the hydrogen generation from steam using GDC–GSTA MIEC membranes at elevated temperatures is mainly controlled by the bulk diffusion of oxygen for the self-supported thick membranes, while the permeation process for the porous supported thin membranes is mixed controlled, i.e. the hydrogen generation/oxygen permeation process is controlled by the surface exchange reactions and bulk diffusion of oxygen through the MIEC membrane. A mathematical model for the calculation of the area specific hydrogen generation rate is proposed in this paper based on the measured oxygen partial pressures, gas compositions, and gas flow rates of the inlet and outlet gases on feed side of the membrane, as well as the permeation area of the membrane.     

Steam reforming of ethanol over Pt/ceria with co-fed hydrogen

Metal/ceria catalysts are receiving great interest for reactions involving steam conversion, including CO for low-temperature water–gas shift, and the conversion of chemical carriers of hydrogen, among them methanol, and ethanol. The mechanism by which ROH model reagents are activated on the surface of the Pt/partially reduced ceria catalyst was explored using a combination of reaction testing and infrared spectroscopy. In this particular investigation, the activation and turnover of ethanol were explored and compared with previous investigations of methanol steam reforming and low-temperature water–gas shift under H₂-rich conditions, where the surface of ceria is in a partially reduced state. Under these conditions, activation of ethanol was found to proceed by dissociative adsorption at reduced defect sites on ceria (i.e., Ce surface atoms in the Ce³⁺ oxidation state), yielding an adsorbed type II ethoxy species and an adsorbed H species, the latter identified to be a type II bridging OH group. In the presence of steam, the ethoxy species rapidly undergoes molecular transformation to an adsorbed acetate intermediate by oxidative dehydrogenation. This is analogous to the conversion of type II methoxy species to formate observed in previous investigations of methanol steam reforming. In addition, although formate then decomposes in steam to CO₂ and H₂ during methanol steam reforming, in an analogous pathway for ethanol steam reforming, the acetate intermediate decomposes in steam to CO₂ and CH₄. Therefore, further H₂ production requires energy-intensive activation of CH₄, which is not required for methanol conversion over Pt/ceria.     

Development of new nickel based catalyst for biomass tar steam reforming producing H2-rich syngas

Mayenite (Ca₁₂Al₁₄O₃₃ or 12CaO.7Al₂O₃) was previously developed and applied as Ni support for biomass tar steam reforming in the absence and presence of H₂S by our group because of its high oxygen restoring property in the structure [C. Li et al., Appl. Catal., B. 2008]. In this study, catalyst Ni/mayenite (mayenite as support) was prepared by impregnation method with nickel nitrate hexahydrate. Experiments were tested in a fixed-bed reactor, toluene as a tar model compound. The influence of the catalyst preparation and operating parameters (reaction temperature, steam to carbon ratio and space time) on catalyst activity and products selectivity were studied, and a long-time evaluation (more than 76 h) also exhibited excellent resistance to coking. These results were compared to these obtained by commercial-like catalysts: Ni/CaO_x/MgO_1−x and our previous NiO/mayenite, showing that Ni/mayenite exhibited excellent property for biomass tar reforming, with higher H₂ yield than that of Ni/CaO_x/MgO_1−x, and higher CO selectivity than that of NiO/mayenite. For kinetic model, the first order reaction used for toluene with activation energy of 80.24 kJ.mol^− 1 was coincident with literature data.     

CO/FTIR Spectroscopic Characterization of Pd/ZnO/Al2O3 Catalysts for Methanol Steam Reforming

An as-synthesized 8.8wt% Pd/ZnO/Al₂O₃ catalyst was either pretreated under O₂ at 773 K followed by H₂ at 293 K or under H₂ at 773 K to obtain, respectively, a supported metallic Pd° catalyst (Pd°/ZnO/Al₂O₃) or a supported PdZn alloy catalyst (PdZn/ZnO/Al₂O₃). Both catalysts were studied by CO adsorption using FTIR spectroscopy. For the supported PdZn alloy catalyst (PdZn/ZnO/Al₂O₃), exposure to a mixture of methanol and steam, simulating methanol steam reforming reaction conditions, does not change the catalyst surface composition. This implies that the active sites are PdZn alloy like structures. The exposure of the catalyst to an oxidizing environment (O₂ at 623 K) results in the break up of PdZn alloy, forming a readily reducible PdO with its metallic form being known as much less active and selective for methanol steam reforming. However, for the metallic Pd°/ZnO/Al₂O₃ catalyst, FTIR results indicate that metallic Pd° can transform to PdZn alloy under methanol steam reforming conditions. These results suggest that PdZn alloy, even after an accidental exposure to oxygen, can self repair to form the active PdZn alloy phase under methanol steam reforming conditions. Catalytic behavior of the PdZn/ZnO/Al₂O₃ catalyst also correlates well with the surface composition characterizations by FTIR/CO spectroscopy.     

Simulating and Optimizing Auto-Thermal Reforming of Methane to Synthesis Gas Using a Non-Dominated Sorting Genetic Algorithm II Method

Conventional synthesis gas production plants consist of a natural gas steam reforming to CO + 3H₂ on Ni catalysts in a furnace. An alternative method for highly endothermic steam reforming is auto-thermal reforming. In this work, synthesis gas production by auto-thermal reforming was simulated based on a heterogeneous and one-dimensional model in two cases. The first case was the auto-thermal reformer of Dias and Assaf's study. The present work was validated by the reported experimental results. The second case was the fixed-bed catalytic auto-thermal reactor operated at high pressure, which was suitable for methanol production and Fischer–Tropsch reactions (baseline case). Then, the effect of operating variables on the system behavior was studied. Finally, Pareto-optimal solutions were determined by non-dominated sorting genetic algorithm II. The objectives included obtaining a H₂/CO ratio of 2 in the produced synthesis gas and the maximum methane conversion. The adjustable parameters were the feed temperature, mass flux, and O₂/CH₄ and H₂O/CH₄ ratios in the feed.     

Hydrogen generation in a Pd membrane fuel processor: assessment of methanol-based reaction systems

The feasibility of a Pd membrane fuel processor that integrates several methanol-based chemistries and hydrogen purification steps is assessed. The assessment involves membrane reactor simulations to determine the effects of operating and design parameters on performance metrics including hydrogen utilization, hydrogen productivity, device volume, and Pd requirements. Methanol decomposition (direct and oxidative) on Pd/SiO₂, methanol steam reforming (MSR) on Cu/ZnO/Al₂O₃, and methanol partial oxidation (MPOX) on Cu/Al₂O₃ are evaluated. The membrane reactor model includes detailed treatments of the catalytic kinetics from the literature, accounts for reaction on the Pd membrane and hydrogen permeation inhibition by site blockage, among other features. The simulations reveal that a maximum in the hydrogen productivity occurs at an intermediate value of the space velocity, implying a trade-off between reactor size, methanol conversion and hydrogen utilization. The assessment involves a determination of the Pd membrane surface to reactor volume ratio that maximizes productivity and the requisite Pd to realize that productivity. We show that MSR on Cu/ZnO and MPOX on Cu are promising reaction systems to practice the membrane concept for fuel processing, whereas direct methanol decomposition is reaction limited, making it infeasible. Several approaches for improving membrane fuel processor performance are evaluated and discussed. We show that oxygen addition can increase the hydrogen productivity in the Pd system, while water addition is beneficial for the MPOX system. The extent of enhancement in both cases depends on supply rate and kinetic factors.     

Low-level CO in hydrogen-rich gas supplied by a methanol processor for PEMFCs

The present study developed a low-CO methanol processor for the online supply of hydrogen to a proton exchange membrane fuel cell (PEMFC) composed of a steam reformer, a catalytic combustor and a reactor for the removal of CO. Commercial Cu/ZnO/Al₂O₃- and Pt/Al₂O₃-based catalysts were used in the methanol steam reforming and the preferential oxidation (PROX) reactor, respectively. The steam reformer was successfully heated with a catalytic combustor at room temperature without any additional electrical power supply. Hydrogen gas was obtained at a flow rate of 43.0 L h⁻¹ using a feed flow rate of 39.5 ml h⁻¹ (S/C=1.1) and an operation temperature of 250 °C, corresponding to a power output of 59 W_e. The CO concentration could be maintained at 4–5 ppm for stable operation.     

Hydrogen production by steam reforming of LNG over Ni/Al2O3-ZrO2 catalysts: Effect of ZrO2 and preparation method of Al2O3-ZrO2

An Al₂O₃-ZrO₂ support was prepared by grafting a zirconium precursor onto the surface of commercial γ-Al₂O₃. A physical mixture of Al₂O₃-ZrO₂ was also prepared for the purpose of comparison. Ni/Al₂O₃-ZrO₂ catalysts were then prepared by an impregnation method, and were applied to the hydrogen production by steam reforming of liquefied natural gas (LNG). The effect ZrO₂ and preparation method of Al₂O₃-ZrO₂ on the performance of supported nickel catalysts in the steam reforming of LNG was investigated. The Al₂O₃-ZrO₂ prepared by a grafting method was more efficient as a support for nickel catalyst than the physical mixture of Al₂O₃-ZrO₂ in the hydrogen production by steam reforming of LNG. The well-developed tetragonal phase of ZrO₂ and the high dispersion of ZrO₂ on the surface of γ-Al₂O₃ were responsible for the enhanced catalytic performance of Ni/Al₂O₃-ZrO₂ prepared by way of a grafting method.