Mathematical Modeling and Optimization of Combined Steam and Dry Reforming of Methane Process in Catalytic Fluidized Bed Membrane Reactor

Mathematical modeling of the methane-combined reforming process (steam methane reforming–dry reforming methane) was performed in a fluidized bed membrane reactor. The model characterizes multiple phases and regions considering low-density phase, high-density phase, membrane, and free board regions that allow study of reactor performance. It is demonstrated that the combined effect of membrane and reaction coupling provides opportunities to overcome equilibrium limits and helps to achieve higher conversion. Additionally, the influence of key parameters on reactor performance including reactor temperature, reactor pressure, steam to methane feed ratio (S/C), and carbon dioxide to methane feed ratio (CO₂/C) were investigated in the multi-objective genetic algorithm to find the optimal operating conditions. Finally, the process of steam reforming was simulated in selected optimal conditions and the results are compared to those of the combined reforming process. Comparison reveals the superiority of the combined reforming process in terms of methane conversion, catalyst activity, and outlet H₂/CO ratio in the syngas product in being close to unity.     

Partial Oxidation of Methane to Syngas in a Packed Bed Catalyst Membrane Reactor

The planar membrane reactor configuration was explored for partial oxidation of methane (POM) to syngas. A supported membrane composed of yttria‐stabilized zirconia and La_0.8Sr_0.2Cr_0.5Fe_0.5O_3‐δ was sealed to a stainless holder, and a Ni/Al₂O₃ catalyst bed was placed under the membrane plane with a small slit between them. This reactor configuration would facilitate the POM reaction via oxidation‐reforming mechanism: the oxidation reaction occurring at the membrane surface and the reforming reaction taking place in the catalyst bed. At 800°C and a methane feed rate of 32 mL min^?1, the reactor attained methane throughput conversion over 90%, CO and H₂ selectivity both over 95%, and an equivalent oxygen permeation rate 1.4 mL cm^?2 min^?1. The membrane and catalyst remained intact after the POM testing. The planar membrane reactor configuration explored in this study may lead to the development of a compact reactor for syngas production. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2170–2176, 2016     

Kinetic study of methane reforming with carbon dioxide over NiCeMgAl bimodal pore catalyst

The kinetic behavior of NiCeMgAl bimodal pore catalyst for methane reforming with CO₂ was investigated after the elimination of external and internal diffusion effects in a fixed‐bed reactor as a function of temperature and partial pressures of reactants and products. Increase in CO₂ partial pressure favors the consumptions of CH₄ and CO₂ but inhibits the formation of H₂ due to the existence of reverse water gas shift (RWGS) reaction. The reforming rate increased first and then reached a horizontal stage with the rise of CH₄ partial pressure. A Langmuir–Hinshelwood model was developed assuming that the carbon deposition is ignorable but the RWGS reaction is non‐ignorable and the removal of adsorbed carbon intermediate is the rate‐determining step. A nonlinear least‐square method was applied to solve the kinetic parameters. The derived kinetic expression fits the experimental data very well with a R² above 0.97, and also predicts the products flow rate satisfactorily. © 2016 American Institute of Chemical Engineers AIChE J, 63: 2019–2029, 2017     

Effect of Oxygen on Methane Steam Reforming in a Sliding Discharge Reactor

Hydrogen‐rich gas can be efficiently produced in compact plasma reformers by the conversion of a variety of hydrocarbon fuels, including natural gas and gasoline. This article describes experimental and modeling progress in plasma reforming of methane using a sliding discharge reactor (SDR). Experiments have been carried out in a compact device operating at low consumed power (1–2 kW). Previous studies of methane steam reforming using a SDR at atmospheric pressure show promising results (H₂ concentration higher than 55 %). In order to study the effect of oxygen on the methane conversion and thus hydrogen production, a small amount of oxygen in the range of 7–20 % was added to the CH₄‐H₂O mixture. An unexpected result was that under our experimental conditions in the SDR oxygen did not have any influence on the methane conversion. Almost the totality of added oxygen is recovered intact. Moreover, part of the H₂ produced was transformed into water by reaction with O₂. A model describing the chemical processes based on classical thermodynamics is also proposed. The results indicate that the reactor design has to be improved in order to increase conversion and hydrogen production.     

Ni Catalysts Supported on Mesoporous Nanocrystalline Magnesium Silicate in Dry and Steam Reforming Reactions

Mesoporous nanocrystalline MgSiO₃ with high surface area was synthesized by a hydrothermal method and employed as support in dry and steam reforming of methane. Ni/MgSiO₃ catalysts were prepared by an impregnation method and characterized by different techniques. N₂ adsorption analysis indicated that addition of nickel shifted the pore size distributions to smaller sizes. Temperature‐programmed reduction analysis revealed that a higher nickel loading enhanced the reducibility of the catalyst. The catalytic performance was improved with increasing the nickel content. The Ni/MgSiO₃ catalyst exhibited high stability in dry reforming but methane conversion declined with time‐on‐stream in the steam reforming reaction. Temperature‐programmed oxidation profiles of spent catalysts indicated that the high amount of carbon deposited on the catalyst surface in dry and steam reforming was assigned to whisker‐type carbon.     

Steam reforming of ethanol over skeletal Ni‐based catalysts: A temperature programmed desorption and kinetic study

An investigation on reaction scheme and kinetics for ethanol steam reforming on skeletal nickel catalysts is described. Catalytic activity of skeletal nickel catalyst for low‐temperature steam reforming has been studied in detail, and the reasons for its high reactivity for H₂ production are attained by probe reactions. Higher activity of water gas shift reaction and methanation contributes to the low CO selectivity. Cu and Pt addition can promote WGSR and suppress methanation, and, thus, improve H₂ production. A reaction scheme on skeletal nickel catalyst has been proposed through temperature programmed reaction spectroscopy experiments. An Eley‐Rideal model is put forward for kinetic studies, which contains three surface reactions: ethanol decomposition, water gas shift reaction, and methane steam reforming reaction. The kinetics was studied at 300–400°C using a randomized algorithms method and a least‐squares method to solve the differential equations and fit the experimental data; the goodness of fit obtained with this model is above 0.95. The activation energies for the ethanol decomposition, methane steam reforming, and water gas shift reaction are 187.7 kJ/mol, 138.5 kJ/mol and 52.8 kJ/mol, respectively. Thus, ethanol decomposition was determined to be the rate determining reaction of ethanol steam reforming on skeletal nickel catalysts. © 2013 American Institute of Chemical Engineers AIChE J 60: 635–644, 2014     

Analysis of hydrogen production from methane autothermal reformer with a dual catalyst-bed configuration

This paper presents a performance analysis of a dual-bed autothermal reformer for hydrogen production from methane using a non-isothermal, one dimensional reactor model. The first section of Pt/Al₂O₃ catalyst is designed for oxidation reaction, whereas the second one based on Ni/MgAl₂O₄ catalyst involves steam reforming reaction. The simulation results show that the dual-bed autothermal reactor provides higher reactor temperature and methane conversion compared with a conventional fixed-bed reformer. The H₂O/CH₄ and O₂/CH₄ feed ratios affect the methane conversion and the H₂/CO product ratio. The addition of steam at lower temperatures to the steam reforming section of the dual-bed reactor can produce the synthesis gas with a higher H₂/CO product ratio.     

Methane partial oxidation to synthesis gas over bimetallic cobalt/tungsten carbide catalysts and integration with a Mn substituted hexaaluminate combustion catalyst

Co_0.2W_0.8C_x and supported Co_0.2W_0.8C_x catalysts are shown to be active for the partial oxidation of methane to synthesis gas. The catalyst stability is improved by operating at elevated pressure, or in the presence of excess methane. At atmospheric pressure the Co_0.2W_0.8C_x catalysts deactivate by oxidation, as seen by X-ray diffraction. Manganese substituted hexaaluminate catalysts with different Mn contents have been tested as catalysts for the total combustion of methane. In particular BaMn₂Al₁₀O₁₉ is active and stable for the combustion reaction. The temperature rise observed in the reactor was up to 300 K, depending on the reaction conditions, and complete conversion of oxygen in the feed was achieved. A process for stabilising the carbide catalysts is demonstrated, combining the manganese substituted hexaaluminate total oxidation catalyst, in series before the carbide reforming catalyst: this process leads to stable operation, with no carbon formation in the reactor and no carbide catalyst oxidation observed.     

Ultra-rapid synthesis of syngas by the catalytic reforming of methane enhanced byin-situ heat supply through combustion

Development in highly active catalysts for the reforming of methane with CO₂ and partial oxidation of methane was conducted to produce hydrogen and carbon monoxide with high reaction rates. An Ni-based four-components catalyst, Ni-Ce₂O₃-Pt-Rh, supported on an alumina wash-coated ceramic fiber in a plate shape was suitable for the objective reaction. By combining the catalytic combustion of ethane or propane, methane conversion was markedly enhanced, and a high space-time yield of syngas, 25,000 mol/l·h was obtained at a catalyst temperature of 700 ‡C or furnace temperature of 500 ‡C. The extraordinary high space-time yield of syngas was also confirmed even under the very rapid flow rate conditions as a contact time of 3 m-sec by using a monolithic shape of catalyst bed without back pressure.     

Catalytic Performance of Coal Char for the Methane Reforming Process

A new concept of combined coal gasification and methane reforming in a single reactor was proposed as an alternative path for syngas production using coal and coalbed methane. Here, the results of this process are summarized. The experimental work was carried out in a fixed‐bed reactor. Methane cracking, CO₂/steam reforming of methane over coal char, and the effects of chars made from different types of parent coal on methane conversion were examined. The catalytic effect of coal char on methane cracking and reforming increased with decreasing coalification degree. A synergistic effect was observed in that, while the coal char catalyzed the methane reforming reactions, gasification of the coal char took place simultaneously, which counter‐balanced the deposition of carbon especially for the methane‐steam‐char system.     

Dual-membrane reactor for methane oxidative coupling and dry methane reforming: Reactor integration and process intensification

A novel dual-membrane reactor concept was introduced for integrating the oxidative coupling of methane (OCM) and CO₂ methane reforming (dry reforming) reactors. The OCM reactions occur in a conventional porous packed bed membrane reactor structure and a portion of the undesired produced CO₂ and generated heat are transferred through a molten-carbonate perm-selective membrane and consumed in the adjacent dry methane reforming catalytic bed. This integrated reactor provides a very promising thermal performance by controlling the temperature peak to be below 50 °C in reference to the average operating temperature in the OCM section. This was achieved even for the low methane-to-oxygen ratio 2 by introducing 10% CO₂ as the diluent agent and reactant in this integrated reactor structure. This contributed to the improved selective performance of 32% methane conversion and 25% C₂-yield including 21% C₂H₄-yield in the OCM section which also enhances the performance of the downstream units consequently. Around half of the unconverted methane leaving the OCM section was converted to syngas in the DRM section.The dual-membrane reactor alone can utilize a significant amount of the carbon dioxide generated in the OCM catalytic bed. In combination with adsorption unit in the downstream of the integrated process, 90% of the produced CO₂ can be recovered and further converted to valuable syngas products. The experimental data, obtained from a mini-plant scale experimental facility, were exploited to verify the performance of the OCM reactor and the CO₂ separation section.     

A comparative computational study of diesel steam reforming in a catalytic plate heat‐exchange reactor

A two‐dimensional steady‐state model of a catalytic plate reactor for diesel steam reforming is developed. Heat is provided indirectly to endothermic reforming sites by flue gas from a SOFC tail‐gas burner. Two experimentally validated kinetic models on diesel reforming on platinum (Pt) catalyst were implemented for a comparative study; the model of Parmar et al., Fuel. 2010;89(6):1212–1220 for a Pt/Al₂O₃ and the model of Shi et al., International Journal of Hydrogen Energy. 2009;34(18):7666–7675 for a Pt/Gd‐CeO₂ (GDC). The kinetic models were compared for: species concentration, approach to equilibrium, gas hourly space velocity and effectiveness factor. Cocurrent flow arrangement between the reforming and the flue gas channels showed better heat transfer compared to counter‐current flow arrangement. The comparison between the two kinetic models showed that different supports play significant role in the final design of a reactor. The study also determined that initial 20% of the plate reactor has high diffusion limitation suggesting to use graded catalyst to optimize the plate reactor performance. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1102–1113, 2017     

Effects of promoters on catalytic activity and carbon deposition of Ni/γ‐Al2O3 catalysts in CO2 reforming of CH4

Catalytic reforming of methane with carbon dioxide was studied in a fixed‐bed reactor using unpromoted and promoted Ni/γ‐Al₂O₃ catalysts. The effects of promoters, such as alkali metal oxide (Na₂O), alkaline‐earth metal oxides (MgO, CaO) and rare‐earth metal oxides (La₂O₃, CeO₂), on the catalytic activity and stability in terms of coking resistance and coke reactivity were systematically examined. CaO‐, La₂O₃‐ and CeO₂‐promoted Ni/γ‐Al₂O₃ catalysts exhibited higher stability whereas MgO‐ and Na₂O‐promoted catalysts demonstrated lower activity and significant deactivation. Metal‐oxide promoters (Na₂O, MgO, La₂O₃, and CeO₂) suppressed the carbon deposition, primarily due to the enhanced basicities of the supports and highly reactive carbon species formed during the reaction. In contrast, CaO increased the carbon deposition; however, it promoted the carbon reactivity. © 2000 Society of Chemical Industry     

Temperature profiles of the monolith catalyst in CO<Subscript>2</Subscript> reforming of methane with<Emphasis Type="Italic">in-situ</Emphasis> combustion of methane and ethane

The temperature profiles in a monolith reactor were measured in CO₂ reforming of CH₄ within-situ combustion of methane and ethane in order to find out in what sequence the reactions are occurring. The reaction gas flowed both upward and downward. A hot spot was observed at low furnace temperatures, and it tended to disappear as the furnace temperature increased. This is due to natural extinguishment of the flame caused by the endothermic reforming reactions occurring. The hot spot disappeared at a lower temperature with the up-flow when compared with the down-flow. When the hot spot appears, H₂O and CO₂ are produced by complete oxidation and accordingly the steam reforming and the CO₂ reforming occur competitively in the rear part of the monolith. If the hot spot does not appear, it is considered that the partial oxidation of methane occurs predominantly over the complete oxidation, resulting in more efficient CO₂ removal.     

Effect of carbon deposition over carbonaceous catalysts on CH4 decomposition and CH4-CO2 reforming

An investigation was made using a continuous fixed bed reactor to understand the influence of carbon deposition obtained under different conditions on CH₄-CO₂ reforming. Thermogravimetry (TG) and X-ray diffraction (XRD) were employed to study the characteristics of carbon deposition. It was found that the carbonaceous catalyst is an efficient catalyst in methane decomposition and CH₄-CO₂ reforming. The trend of methane decomposition at lower temperatures is similar to that at higher temperatures. The methane conversion is high during the initial of stage of the reaction, and then decays to a relatively fixed value after about 30 min. With temperature increase, the methane decomposition rate increases quickly. The reaction temperature has significant influence on methane decomposition, whereas the carbon deposition does not affect methane decomposition significantly. Different types of carbon deposition were formed at different methane decomposition reaction temperatures. The carbon deposition Type I generated at 900°C has a minor effect on CH₄-CO₂ reforming and it easily reacts with carbon dioxide, but the carbon deposition Type II generated at 1000°C and 1100°C clearly inhibits CH₄-CO₂ reforming and it is difficult to react with carbon dioxide. The results of XRD showed that some graphite structures were found in carbon deposition Type II.     

Stable equilibrium shift of methane steam reforming in membrane reactors with hydrogen‐selective silica membranes

Equilibrium shifts of methane steam reforming in membrane reactors consisting of either tetramethoxysilane‐derived amorphous hydrogen‐selective silica membrane and rhodium catalysts, or hexamethyldisiloxane‐derived membrane and nickel catalysts is experimentally demonstrated. The hexamethyldisiloxane‐derived silica membrane showed stable permeance as high as 8 × 10^?8 mol m^?2 s^?1 Pa^?1 of H₂ after exposure to 76 kPa of vapor pressure at 773 K for 60 h, which was a much better performance than that from the tetramethoxysilane‐derived silica membrane. Furthermore, the better silica membrane also maintained selectivity of H₂/N₂ as high as 10³ under the above hydrothermal conditions. The degree of the equilibrium shifts under various feedrate and pressure conditions coincided with the order of H₂ permeance. In addition, the equilibrium shift of methane steam reforming was stable for 30 h with an S/C ratio of 2.5 at 773 K using a membrane reactor integrated with hexamethyldisiloxane‐derived membrane and nickel catalyst. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Carbon dioxide reforming of methane with a free energy minimization approach

Carbon dioxide reforming of methane to syngas is one of the primary technologies of the new poly-generation energy system on the basis of gasification gas and coke oven gas. A free energy minimization is applied to study the influence of operating parameters (temperature, pressure and methane-to-carbon dioxide ratio) on methane conversion, products distribution, and energy coupling between methane oxidation and carbon dioxide reforming methane. The results show that the methane conversion increases with temperature and decreases with pressure. When the methane-to-carbon dioxide ratio increases, the methane conversion drops but the H₂/CO ratio increases. By the introduction of oxygen, an energy balance in the process of the carbon dioxide reforming methane and oxidation can be realized, and the CO/H₂ ratio can be adjusted as well without water-gas shift reaction for Fischer-Tropsch or methanol synthesis. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Effect of carbon deposition over carbonaceous catalysts on CH<Subscript>4</Subscript> decomposition and CH<Subscript>4</Subscript>-CO<Subscript>2</Subscript> reforming

An investigation was made using a continuous fixed bed reactor to understand the influence of carbon deposition obtained under different conditions on CH₄-CO₂ reforming. Thermogravimetry (TG) and X-ray diffraction (XRD) were employed to study the characteristics of carbon deposition. It was found that the carbonaceous catalyst is an efficient catalyst in methane decomposition and CH₄-CO₂ reforming. The trend of methane decomposition at lower temperatures is similar to that at higher temperatures. The methane conversion is high during the initial of stage of the reaction, and then decays to a relatively fixed value after about 30 min. With temperature increase, the methane decomposition rate increases quickly. The reaction temperature has significant influence on methane decomposition, whereas the carbon deposition does not affect methane decomposition significantly. Different types of carbon deposition were formed at different methane decomposition reaction temperatures. The carbon deposition Type I generated at 900°C has a minor effect on CH₄-CO₂ reforming and it easily reacts with carbon dioxide, but the carbon deposition Type II generated at 1000°C and 1100°C clearly inhibits CH₄-CO₂ reforming and it is difficult to react with carbon dioxide. The results of XRD showed that some graphite structures were found in carbon deposition Type II.     

Comparison of the performance of a direct-contact bubble reactor and an indirectly heated tubular reactor for solar-aided methane dry reforming employing molten salt

A theoretical approach is presented for the comparison of two different atmospheric pressure reactors—a direct-contact bubble reactor (DCBR) and an indirectly heated tubular reactor (IHTR)—to evaluate the reactor performance in terms of heat transfer and available catalytic active surface area. The model considers the catalytic endothermic reactions of methane dry reforming that proceeds in both reactors by employing molten salts at elevated temperatures (700–900 °C) in the absence of catalyst deactivation effects. The methane conversion process is simulated for a single reactor using both a reaction kinetics model and a heat transfer model. A well-tested reaction kinetics model, which showed an acceptable agreement with the empirical observations, was implemented to describe the methane dry reforming. In DCBR, the heat is internally transferred by direct contact with the three phases of the system: the reactant gas bubbles, the heat carrier molten salts and the solid catalyst (Ni-Al₂O₃). In contrast, the supplied heat in the conventional shell-and-tube heat exchanger of the IHTR is transferred across an intervening wall. The results suggest a combination system of DCBR and IHTR would be a suitable configuration for process intensification associated with higher thermal efficiency and cost reduction.     

Experimental Study of Internal Reforming on Large‐area Anode Supported Solid Oxide Fuel Cells

The effect of endothermic internal steam reformation of methane and exothermic fuel cell reaction on the temperature of a planar‐type anode‐supported solid oxide fuel cell was experimentally investigated as a function of current density and fuel utilization. We fabricated a large‐area (22 × 33 cm²) cell and compared temperature profiles along the cell using 30 thermocouples inserted through the cathode end plate at 750 °C under various conditions (Uf ∼50% at 0.4 A cm⁻²; Uf ∼70% at 0.4 A cm⁻²; Uf ∼50% at 0.2 A cm⁻²) with hydrogen fuel and methane‐steam internal reforming. The endothermic effect due to internal reforming mainly occurs at the gas inlet region, so this process is not very effective to cool down the hot spot created by the exothermic fuel cell reaction. This eventually results in a larger temperature difference on the cell. The most moderate condition with regards to thermal gradient on the cell corresponds to high fuel utilization (Uf ∼70%) and low current density (∼0.2 A cm⁻²). The electrochemical performance was also measured, and it was found that the current–voltage characteristics are comparable for the cell operated under hydrogen fuel and internal steam reforming of methane because of lower polarization resistance with high partial pressure of water vapor.