MODELING AND SIMULATION OF A NONISOTHERMAL CATALYTIC MEMBRANE REACTOR

A two-dimensional nonisothermal mathematical model has been developed to simulate a tube-and-shell configuration, catalytic membrane reactor. The three-layer membrane consists of an inert large-pore support, an o₂ semipermeable dense perovskite layer and a porous catalytic layer. The model is applied to the simulation of the partial oxidation or methane to syngas (oxyreforming). The membrane reactor simultaneously supplies oxygen to the catalytic reaction along the reactor length, and separates oxygen from the air feed, using a dense perovskite layer which is a mixed conductor, thus allowing rapid oxygen permeation without the use of an external circuit. Two configurations of catalytic membrane reactors are simulated, for both bench-scale and industrial-scale conditions. Comparisons are made to the conventional fixed-bed reactor, and to membrane reactors which are isothermal, adiabatic or wall-cooled. The simulation results imply that the temperature rise in exothermic partial oxidation reactions may be mitigated substantially by the use of a dense membrane reactor,     

Assessment of micro-structured fixed-bed reactors for highly exothermic gas-phase reactions

The application of micro-structured fixed-bed reactors for highly exothermic partial oxidation reactions and their comparison to established multi-tubular fixed-bed reactors was investigated by numerical simulation. As examples, the partial oxidations of butane to maleic anhydride and of o-xylene to phthalic anhydride were chosen. The simulation results revealed that the reactor productivity, i.e. the amount of product per unit of reactor volume, achievable in micro-structured fixed-bed reactors is between 2.5 and 7 times higher than in conventional multi-tubular fixed-bed reactors without the danger of excessive pressure drop. For the partial oxidation of butane to maleic anhydride this can be explained by the increased reactor efficiency caused by lower efficiency losses through heat and mass transfer limitations. In addition, maleic anhydride selectivities and yields are higher in micro-structured fixed-bed reactors. In the case of o-xylene oxidation to phthalic anhydride the main advantage is that egg-shell catalysts in the conventional fixed-bed reactor can be replaced by bulk catalysts in the micro-structured fixed-bed reactor. For this reaction, product selectivities are very similar for all reactor configurations. Thus the catalyst inventory and reactor productivity are strongly increased. This study underlines, that micro-structured fixed-bed reactors exhibit the potential to intensify large scale industrial processes significantly.     

Membrane pilot reactor applied to selective oxidation reactions

The partial oxidation of butane to maleic anhydride was studied in a conventional fixed bed as well as a novel reactor configuration consisting of a porous metallic membrane immersed in a gas–solid fluid bed. The diameter of both reactors was at a commercial scale greater than 30 mm. A range of gas flow rates, temperatures and butane concentrations were tested. Maleic anhydride yield was generally higher in the membrane reactor due to higher butane conversion. Maleic productivity in the fixed bed equalled that observed in the membrane reactor when the gas–solid fluid bed was maintained at a higher temperature of as much as 30 °C. The butane feed rate to the membrane reactor was limited by hot spots. These hot spots were unanticipated and underscore the importance of increasing heat transfer in order to commercialize this technology.     

多孔膜反应器中丙烷催化脱氢制丙烯的模拟研究

针对丙烷高效脱氢制丙烯的多孔膜反应器构建了无量纲数学模型并进行了模拟研究,考察了催化剂活性、透氢膜性能、操作条件对多孔膜反应器中丙烷脱氢的转化率、丙烯收率、氢气收率和纯度的影响。结果表明,移走产物氢气可以有效提升膜反应器的性能,其性能的提升程度由不同温压条件下催化剂和透氢膜性能共同决定。高活性催化剂是丙烷高效转化的基础,催化剂活性越高,膜反应器内的产氢速率越快;其次,膜的选择性和渗透通量越高,氢气的移除效率越高,可在最大程度上打破热力学平衡的限制,使反应向生成丙烯的方向移动。当多孔透氢膜的氢气渗透率在10^-7~10^-6 mol·m^-2·s^-1·Pa^-1,H₂/C₃H₈选择性达到100时,其丙烷转化率可以与Pd膜反应器内的转化率相当,但分离的氢气纯度低于Pd膜反应器。与传统的固定床反应器相比,膜反应器由于促进了化学平衡的移动,可以在较低的反应温度下获得相当高的丙烷转化率,且丙烷转化率随着反应压力的增加呈现出一个最大值。该模拟研究可为实际生产过程中膜反应器用于PDH反应的高效强化提供有益的技术指导。     

A comparative study of combination of Fischer–Tropsch synthesis reactors with hydrogen-permselective membrane in GTL technology

This work proposes a one dimensional heterogeneous model to analyze the performance of combination of Fischer–Tropsch synthesis (FTS) reactors in which a fixed-bed reactor is combined with a membrane assisted fluidized-bed reactor. This model is used to compare the performance of the proposed system with a fixed-bed singlestage reactor. In the new concept, the synthesis gas is converted to FT products in two catalytic reactors. The first reactor is water-cooled fixed-bed type while the second reactor is gas-cooled and fluidized-bed. Due to the decrease of H₂/CO to values far from optimum reactants ratio, the membrane concept is suggested to control hydrogen addition. Moreover, a fluidized-bed system has been proposed to solve some observed drawbacks of industrial fixed-bed reactors such as high pressure drop, heat transfer problem and internal mass transfer limitations. This novel concept which has been named fluidized-bed membrane dual-type reactor is used for production of gasoline from synthesis gas. The reactor model is tested against the pilot plant data of the Research Institute of Petroleum Industry. Results show an enhancement in the gasoline yield, a main decrease in CO₂ formation and a favorable temperature profile along the proposed concept.     

新型惰性膜反应器中丁烷氧化脱氢制丁二烯和丁烯

The oxidative dehydrogenation of butane to butadiene and butene was studied using a conventional fixed-bed ractor (FBR), inert membrane reactor (IMR) and mixed inert membrane reactor (MIMR). When IMR and MIMR were employed, a ceramic membrane modified by partially coating with glaze was used to distribute oxygen to a fixed-bed of 24-V-Mg-O catalyst. The oxygen partial pressure in the catalyst bed could be decreased. The effect of feeding modes and operation conditions were investigated. The selectivity of C4 dehydrogenation products (bntene and bntadiene) was found to be higher in IMR than in FBR. The feeding mode with 20% of air mixing with butane in MIMR was found to be more efficient than the feeding mode with all air permeating through ceramic membrane. The MIMR gave the most smooth temperature profile along the bed.     

Simulation and thermodynamic analysis of conventional and oxygen permeable CPO reactors

A one-dimensional steady-state heterogeneous model has been used to simulate the conventional CPO reactor. With the mechanism of O₂ permeable membrane, the model has been developed to simulate O₂ membrane reactor. The output temperature and the mole flow rates of different species in the tube side and the shell side can be calculated. They are the basis for the exergy analysis of the conventional CPO reactor with air, the conventional CPO reactor with pure O₂, and the O₂ permeable membrane CPO reactor. The simulation and exergy analysis results indicate that when the inlet conditions are the same, for a given methane conversion, the exergy efficiencies η₂ and η₁ of conventional CPO reactor with pure oxygen is lowest among the three reactors, because of the large amount of accumulative exergy required for obtaining pure oxygen.The exergy efficiencies η₁ and η₂ of membrane reactor are comparable with conventional CPO reactor with air and much higher than conventional CPO reactor with pure oxygen. As the membrane reactors can carry out simultaneous separation and reaction, in the mean time, removal of nitrogen from the product stream can be accomplished; the membrane reactor has advantages compared to other types of reactors.The operation of the membrane CPO reactor is more favourable when the inlet temperature is increased and the operation pressure is decreased from a thermodynamic point of view.     

Design of mixed conducting ceramic membranes/reactors for the partial oxidation of methane to syngas

The performance of mixed conducting ceramic membrane reactors for the partial oxidation of methane (POM) to syngas has been analyzed through a two‐dimensional mathematical model, in which the material balance, the heat balance and the momentum balance for both the shell and the tube phase are taken into account. The modeling results indicate that the membrane reactors have many advantages over the conventional fixed bed reactors such as the higher CO selectivity and yield, the lower heating point and the lower pressure drop as well. When the methane feed is converted completely into product in the membrane reactors, temperature flying can take place, which may be restrained by increasing the feed flow rate or by lowering the operation temperature. The reaction capacity of the membrane reactor is mainly determined by the oxygen permeation rate rather than by the POM reaction rate on the catalyst. In order to improve the membrane reactor performance, reduction of mass transfer resistance in the catalyst bed is necessary. Using the smaller membrane tubes is an effective way to achieve a higher reaction capacity, but the pressure drop is a severe problem to be faced. The methane feed velocity for the operation of mixed conducting membrane reactors should be carefully regulated so as to obtain the maximum syngas yield, which can be estimated from their oxygen permeability. The mathematical model and the kinetic parameters have been validated by comparing modeling results with the experimental data for the La_0.6Sr_0.4Co_0.2Fe_0.8O_3‐α (LSCF) membrane reactor. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Optimum operation of oxidative coupling of methane in porous ceramic membrane reactors

This paper presents analysis of oxidative coupling of methane on Li/MgO packed porous membrane reactor (PMR) by the fixed-bed reactor (FBR) model with reliable reaction kinetic equations. PMR can improve the selectivity and yield by controlling the oxygen feed to the catalyst bed through manipulating the feed pressure. At a fixed methane feed rate there is an optimal oxygen feed pressure that will achieve the highest yield. With a commercial ultrafiltration ceramic membrane, theoretical analysis shows that PMR can achieve, by operating with both side pressures at 1 bar at 750 °C, a maximal 30% yield at 53% selectivity. The maximal yield achieved in the FBR of identical dimension and temperature is 20.7% at 52.5% selectivity. Parametric study shows that lowering the membrane permeability improves the performance. Higher oxygen feed pressure will reduce the yield as well as the selectivity. Homogeneous reactions at high shell-side pressure can have adverse effect on the performance due to the fact that homogeneous reaction rates are strongly pressure dependent. The shell (oxygen feed) side volume must be minimized to reduce the homogeneous reactions. The results of PMR model calculation fit the published experimental result unexpectedly well.     

Theoretical analysis of oxidative coupling of methane and Fischer Tropsch synthesis in two consecutive reactors: Comparison of fixed bed and membrane reactor

In this paper, theoretical performance of Fischer Tropsch (FT) synthesis is analyzed where its feed comes from an oxidative coupling of methane (OCM) reactor. In this model based analysis, two consecutive reactors are intended that first reactor is OCM and second reactor is FT and FT reactor performance is compared in two conditions of fixed bed and membrane reactor (MR). The parameters concerned, were CH₄/O₂ ratio, contact time, temperature, and amount of N₂ in OCM feed. High CH₄/O₂ ratio gave low yield of C₂₊ in OCM due to insufficient oxygen, but favored FT reaction due to more yield of C₅₊ and other products. Therefore, it was concluded that production and yield of C₅₊ could be more by use of these configurations.     

A novel slurry bubble column membrane reactor concept for Fischer–Tropsch synthesis in GTL technology

Fischer–Tropsch synthesis (FTS) plays an important role in the production of ultra-clean transportation fuels, chemicals, and other hydrocarbon products. In this work, a novel combination of fixed-bed and slurry bubble column membrane reactor for Fischer–Tropsch synthesis has been proposed. In the first catalyst bed, the synthesis gas is partially converted to hydrocarbons in a water-cooled reactor which is fixed bed. In the second bed which is a membrane assisted slurry bubble column reactor, the heat of reaction is used to preheat the feed synthesis gas to the first reactor. Due to the decrease of H₂/CO to values far from optimum reactants ratio, the membrane concept is suggested to control hydrogen addition. A one-dimensional packed-bed model has been used for modeling of fixed-bed reactor. Also a one-dimensional model with plug flow pattern for gas phase and an axial dispersion pattern for liquid-solid suspension have been developed for modeling of slurry bubble column reactor. Proficiency of a membrane FTS reactor (MR) and a conventional FTS reactor (CR) at identical process conditions has been used as a basis for comparison in terms of temperature, gasoline yield, H₂ and CO conversion as well as selectivity. Results show a favorable temperature profile along the proposed concept, an enhancement in the gasoline yield and, thus a main decrease in undesirable product formation. The results suggest that utilizing this type of reactor could be feasible and beneficial. Experimental proof of concept is needed to establish the validity and safe operation of the proposed reactor.     

Xylene Isomerization in a ZSM-5/SS Membrane Reactor

A membrane reactor containing different types of ZSM-5/porous SS membranes was used to perform the xylene isomerization reaction. The parent Na-ZSM-5 layer was synthesized by secondary growth on top of porous stainless steel tubes. The xylene isomerization reaction was carried out at different temperatures in the membrane reactor and in a fixed-bed reactor of identical geometry for comparison. Two different kinds of membranes were prepared by ion exchange: a Pt/H-ZSM-5 catalytic membrane and two Ba-ZSM-5 composites with different Ba²⁺ concentration. The p-xylene production using 100% exchanged Ba-membrane was about 28% higher than the fixed-bed reactor at 370 °C, when m-xylene was fed.     

Simulation of ethylene epoxidation in a multitubular transport reactor

It has been demonstrated that increased yields of ethylene oxide are obtained with a fixed-bed reactor operating with multiple injection of oxygen and cyclic adsorption-desorption of the desired reaction product. In certain conditions, this reactor simulates the operation of a larger two-tube transport reactor; the latter reactor may, in turn, be used to simulate large-scale commercial multitubular transport reactors. The small fixed-bed reactors may also be used for optimization of the process. The reaction of ethylene epoxidation on a silver catalyst is a good illustration of the advantages of a multitubular transport reactor and of this new method of simulation and optimization.     

Catalytic Dehydrogenation of Ethanol in Ru-Modified Alumina Membrane Reactor

Abstract

Ru-modified alumina composite membranes were prepared by the sol-gel method. The pore size distribution from nitrogen adsorption showed that average pore diameters were 3.1–4.5 nm, and the ideal separation factor was obviously higher than that of a pure γ-AI₂O₃ membrane. Ethanol dehydrogenation was carried out in the Ru-modified alumina membrane reactors. The effects of the reaction temperature, feed rate, and argon sweep flow rate on acetaldehyde yield were investigated. The results showed that the yield of acetaldehyde increased by 25–28% at the same conditions in a Ru-modified alumina membrane reactor. The reduced temperature of the Ru-modified alumina composite membrane was measured by temperature-programmed reduction, and the morphology of the membrane was characterized by SEM, TEM, and XRD.     

Ammonia oxidation in Ba0.5Sr0.5Co0.8Fe0.2O3−δ membrane reactor

Selective oxidation of ammonia to NO was studied in a dense mixed ion electron conducting Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ membrane reactor, which integrates the separation and catalytic reaction process in a single reactive separation unit. The influence of the temperature and feed concentration on the membrane reaction performance were investigated in detail. Under reaction conditions, the oxygen permeation flux through the dense membrane increases with increasing temperature and ammonia flow rate. The lower temperature and ammonia concentration can favor the formation of NO, in which higher catalytic performance is obtained, suggesting that the membrane reactor operation is much beneficial for selective oxidation of ammonia.     

Analysis of attainable reactor performance for the oxidative methane coupling process

In this work, a comparative analysis of attainable performance is presented for three different reactor structures including a fixed-bed reactor, and two different feeding structures of packed bed membrane reactors. For this purpose, three types of kinetic models, namely La₂O₃/CaO, Mn/Na₂WO₄/SiO₂, and PbO/Al₂O₃ have been used under a wide range of operating conditions. Thus, the effect of several variables such as operating temperature, membrane thickness, methane-to-oxygen ratio, feed flow rate, gas streams composition, and reactor length are investigated.Moreover, kinetic-analysis based on a proposed graphical approach enables determination of the suitable operational condition range and allows analysis of the feasible and optimal performance that corresponds to the effect of several dependent operating variables. The results show that tracking the optimum area of operation has a monotonic direction under some range of operating conditions, while it reflects qualitative trade-offs under some other ranges of operating conditions. For all investigated reactor concepts and catalysts, optimal operating conditions and the best corresponding performance are presented.     

A comparison of co-current and counter-current modes of operation for a novel hydrogen-permselective membrane dual-type FTS reactor in GTL technology

In this work, a comparison of co-current and counter-current modes of operation for a novel hydrogen-permselective membrane reactor for Fischer-Tropsch Synthesis (FTS) has been carried out. In both modes of operations, a system with two-catalyst bed instead of one single catalyst bed is developed for FTS reactions. In the first catalytic reactor, the synthesis gas is partly converted to products in a conventional water-cooled fixed-bed reactor, while in the second reactor which is a membrane fixed-bed reactor, the FTS reactions are completed and heat of reaction is used to preheat the feed synthesis gas to the first reactor. In the co-current mode, feed gas is entered into the tubes of the second reactor in the same direction with the reacting gas stream in shell side while in the counter-current mode the gas streams are in the opposite direction. Simulation results for both co-current and counter-current modes have been compared in terms of temperature, gasoline and CO₂ yields, H₂ and CO conversion, selectivity of components as well as permeation rate of hydrogen through the membrane. The results showed that the reactor in the co-current configuration operates with lower conversion and lower permeation rate of hydrogen, but it has more favorable profile of temperature. The counter-current mode of operation decreases undesired products such as CO₂ and CH₄ and also produces more gasoline.     

Non-catalytic hydrodesulfurization and hydrodemetallization of residua

Non-catalytic hydrodesulfurization (NHDS) and hydrodemetallization (NHDM) i.e. hydrothermal desulfurization and demetallization of heavy crude and atmospheric residue was studied in two different bench-scale units equipped with fixed-bed reactors in series operated in adiabatic and isothermal modes. The reactors were loaded with inert material (silicon carbide). Different feedstocks were used for thermal hydrodesulfurization tests: 13°API heavy crude oil, 21°API crude oil, atmospheric residue from the 13°API heavy crude oil, and atmospheric residue from the 21°API crude oil. The effects of pressure, residence time, temperature and type of feed on NHDS and axial reactor temperature profiles were examined. The effect of reaction variables is explained in terms of quenching of the reaction by hydrogen addition and changes in reaction selectivity. The results indicate that selectivity toward the reaction of NHDS as compared with NHDM do not show important changes when the temperature was increased. Temperature was found to be the main variable that affected the extent of thermal desulfurization and demetallization reactions. The different reactor temperature profiles were explained with the type of reaction occurring in the different sections of the reacting system.     

CFD modeling of gas flow in porous medium and catalytic coupling reaction from carbon monoxide to diethyl oxalate in fixed-bed reactors

A comprehensive two-dimensional heterogeneous reactor model was developed to simulate the flow behavior and catalytic coupling reaction of carbon monoxide (CO)–diethyl oxalate (DEO) in a fixed-bed reactor. The two-temperature porous medium model, which was revised from a one-temperature porous medium model, as well as one equation turbulent model, and exponent-function kinetic model was constructed for the turbulent velocity scale comparing with laminar flow and simulation of the catalytic coupling reaction. The simulation results were in good agreement with the actual data collected from certain pilot-plant fixed bed reactors in China. Based on the validated approach and models, the distributions of reaction parameters such as temperature and component concentrations in the reactor were analyzed. The simulations were then carried out to understand the effects of operating conditions on the reactor performance which showed that the conduction oil temperature in the reactor jacket and the CO concentration are the key impact factors for the reactor performance.