Application of hydrogen-permselective Pd-based membrane in an industrial single-type methanol reactor in the presence of catalyst deactivation

This work presents application of palladium-based membranes in a conventional single-type methanol reactor. A novel reactor configuration with hydrogen-permselective Pd and Pd–Ag membrane are proposed. In this configuration the reacting synthesis gas is fed to the shell side of reactor while the high pressure product is routed from recycle stream through tubes of the reactor in a co-current mode with reacting gas. The reacting gas is cooled simultaneously with recycle gas in tube and saturated water in outer shell. The permselective palladium layer on inner tube allows hydrogen to penetrate from the tube side to the reaction side. In this work, the results of two types of novel membrane reactors are compared with a conventional methanol synthesis reactor at identical process conditions. Also the effect of key parameters such as membrane thickness, reaction and tube side pressure, ratio of tube side flow rate to reaction side flow rate on performance of reactor are investigated. The steady-state and quasi-steady-state simulations results show that there are favorable profiles of temperature and methanol mole fraction along the reactor in proposed reactor relative to conventional reactor system. Therefore using this novel configuration in industrial single-type methanol reactor improves methanol production rate.     

A Novel Fluidized‐Bed Membrane Dual‐Type Reactor Concept for Methanol Synthesis

A novel fluidized‐bed membrane dual‐type methanol reactor (FBMDMR) concept is proposed in this paper. In this proposed reactor, the cold feed synthesis gas is fed to the tubes of the gas‐cooled reactor and flows in counter‐current mode with a reacting gas mixture in the shell side of the reactor, which is a novel membrane‐assisted fluidized bed. In this way, the synthesis gas is heated by heat of reaction which is produced in the reaction side. Hydrogen can penetrate from the feed synthesis gas side into the reaction side as a result of a hydrogen partial pressure difference between both sides. The outlet synthesis gas from this reactor is fed to tubes of the water‐cooled packed bed reactor and the chemical reaction is initiated by the catalyst. The partially converted gas leaving this reactor is directed into the shell of the gas‐cooled reactor and the reactions are completed in this fluidized‐bed side. This reactor configuration solves some drawbacks observed from the new conventional dual‐type methanol reactor, such as pressure drop, internal mass transfer limitations, radial gradient of concentration, and temperature in the gas‐cooled reactor. The two‐phase theory of fluidization is used to model and simulate the proposed reactor. An industrial dual‐type methanol reactor (IDMR) and a fluidized‐bed dual‐type methanol reactor (FBDMR) are used as a basis for comparison. This comparison shows enhancement in the yield of methanol production in the fluidized‐bed membrane dual‐type methanol reactor (FBMDMR).     

Co‐current and Countercurrent Configurations for a Membrane Dual Type Methanol Reactor

A dynamic model for a membrane dual‐type methanol reactor was developed in the presence of catalyst deactivation. This reactor is a shell and tube type where the first reactor is cooled with cooling water and the second one with feed synthesis gas. In this reactor system, the wall of the tubes in the gas‐cooled reactor is covered with a palladium‐silver membrane which is only permeable to hydrogen. Hydrogen can penetrate from the feed synthesis gas side into the reaction side due to the hydrogen partial pressure driving force. Hydrogen permeation through the membrane shifts the reaction towards the product side according to the thermodynamic equilibrium. Moreover, the performance of the reactor was investigated when the reaction gas side and feed gas side streams are continuously either co‐current or countercurrent. Comparison between co‐current and countercurrent mode in terms of temperature, activity, methanol production rate as well as permeation rate of hydrogen through the membrane shows that the reactor in co‐current configuration operates with lower conversion and also lower permeation rate of hydrogen but with longer catalyst life than does the reactor in countercurrent configuration.     

Fischer‐Tropsch Synthesis: Modeling and Performance Study for Fe‐HZSM5 Bifunctional Catalyst

A water‐cooled fixed bed Fischer‐Tropsch reactor packed with Fe‐HZSM5 catalyst has been modeled in two dimensions (radial and axial) using the intrinsic reaction rates previously developed at RIPI. The reactor is used for production of high‐octane gasoline from synthesis gas. The Fischer‐Tropsch synthesis reactor was a shell and tube type with high pressure boiling water circulating on the shell side. By the use of a two‐dimensional model, the effects of some important operating parameters such as cooling temperature, H₂/CO ratio in syngas and reactor tube diameter on the performance capability of the reactor were investigated. Based on these results, the optimum operating conditions and the tube specification were determined. The model has been used to estimate the optimum operating conditions for the pilot plant to be operated in RIPI.     

Enhancement of Methanol Production in a Membrane Dual‐Type Reactor

In this study, a dynamic model for a membrane dual‐type methanol reactor was developed in the presence of long term catalyst deactivation. The proposed model is used to compare the performance of a membrane dual‐type methanol reactor with a conventional dual‐type methanol reactor. A conventional dual‐type methanol reactor is a shell and tube heat exchanger reactor in which the first reactor is cooled with cooling water and the second one is cooled with synthesis gas. In a membrane dual‐type reactor, the wall of the tubes in the gas‐cooled conventional reactor is covered with a palladium‐silver membrane, which is only permeable to hydrogen. Hydrogen can penetrate from the feed synthesis gas side into the reaction side due to the hydrogen partial pressure driving force. Hydrogen permeation through the membrane shifts the reaction towards the product side according to the thermodynamic equilibrium. The proposed dynamic model was validated against measured daily process data of a methanol plant recorded for a period of four years and a good agreement was achieved. The simulation results show that there is a favorable profile of temperature and activity of the membrane dual‐type reactor relative to single and conventional dual‐type reactor systems. Therefore, the performance of methanol reactor systems improves when a membrane is used in a conventional dual‐type methanol reactor.     

Contribution to emission reduction of CO2 by a fluidized-bed membrane dual-type reactor in methanol synthesis process

In this work, a fluidized-bed membrane dual-type reactor was evaluated for CO₂ removal in methanol synthesis process. The feed synthesis gas is preheated in the tubes of the gas-cooled reactor and flowing in a counter-current mode with reacting gas mixture in the shell side. Due to the hydrogen partial pressure driving force, hydrogen can penetrate from feed synthesis gas into the reaction side through the membrane. The outlet synthesis gas from this reactor is fed to tubes of the water-cooled packed-bed reactor and the chemical reaction is initiated by the catalyst. The methanol-containing gas leaving this reactor is directed into the shell of the gas-cooled reactor and the reactions are completed in this fluidized-bed side. A two-phase dynamic model in bubbling regime of fluidization was developed in the presence of long-term catalyst deactivation. This model is used to compare the removal of CO₂ in a FBMDMR with a conventional dual-type methanol synthesis reactor (CDMR) and a membrane dual-type methanol synthesis reactor (MDMR). The simulation results show a considerable enhancement in the CO₂ conversion due to have a favourable profile of temperature and activity along the fluidized-bed membrane dual-type reactor relative to membrane and conventional dual-type reactor systems.     

Dynamic modeling and operability analysis of a dual-membrane fixed bed reactor to produce methanol considering catalyst deactivation

The goal of this research is dynamic operability analysis of dual-membrane reactor considering catalyst deactivation to produce methanol. A dynamic heterogeneous one-dimensional model is developed to predict the performance of this configuration. In this configuration, a conventional reactor has been supported by a Pd/Ag membrane tube for hydrogen permeation and alumina–silica composite membrane tube to remove water vapor from the reaction zone. To verify the accuracy of the considered model, the results of conventional reactor are compared with the plant data. The main advantages of the dual-membrane reactor are: higher catalyst activity and lifetime, higher CO₂ conversion and methanol production.     

Membrane/sorption-enhanced methanol synthesis process: Dynamic simulation and optimization

In this study, a dynamic mathematical model of a Membrane-Gas-Flowing Solids-Fixed Bed Reactor (Membrane-GFSFBR) with in-situ water adsorption in the presence of catalyst deactivation is proposed for methanol synthesis. The novel reactor consists of water adsorbent and hydrogen-permselective Pd-Ag membrane. In this configuration feed gas and flowing adsorbents are both fed into the outer tube of the reactor. Contact of gas and fine solids particles inside packed bed results in selective adsorption of water from methanol synthesis which leads to higher methanol production rate. Afterwards, the high pressure product is recycled to the inner tube of the reactor and hydrogen permeates to the outer tube which shifts the reaction towards more methanol production. Dynamic simulation result reveals that simultaneous application of water adsorbent and hydrogen permeation in methanol synthesis process contributes to a significant enhancement in methanol production. The notable advantage of Membrane-GFSFBR is the continuous adsorbent regeneration during the process. Moreover, a theoretical investigation has been performed to evaluate the optimal operating conditions and to maximize the methanol production in Membrane-GFSFBR using differential evolution (DE) algorithm as a robust method. The obtained optimization result shows there are optimum values of inlet temperatures of gas phase, flowing solids phase, and shell side under which the highest methanol production can be achieved.     

Application of water vapor and hydrogen-permselective membranes in an industrial fixed-bed reactor for large scale methanol production

Coupling reaction and separation in a membrane reactor improves the reactor efficiency and reduces purification cost in the next stages. In this work a novel reactor consisting two membrane layers has been proposed for simultaneous hydrogen permeation to reaction zone and water vapor removal from reaction zone in the methanol synthesis reactor. In this configuration conventional methanol reactor is supported by a Pd/Ag membrane layer for hydrogen permeation and alumina-silica composite membrane layer for water vapor removal from reaction zone. In this reactor syngas is fed to the reaction zone that is surrounded with hydrogen-permselective membrane tube. The water vapor-permselective membrane tube is placed in the reaction zone. A steady state heterogeneous one-dimensional mathematical model is developed for simulation of the proposed reactor. To verify the accuracy of the model, simulation results of the conventional reactor is compared with the available plant data. The membrane fixed bed reactor benefits are higher methanol production rate, higher quality of outlet product and consequently lower cost in product purification stage. This configuration has enhanced the methanol yield by 10.02% compared with industrial reactor. Experimental proof-of-concept is needed to establish the safe operation of the proposed configuration.     

Non‐Isothermal Non‐Adiabatic Dehydrogenation of Cyclohexane in Catalytic Membrane Reactors

Abstract

This study focuses on modeling and analysis of the non‐isothermal, non‐adiabatic, dehydrogenation of cyclohexane in membrane catalytic reactors. The dehydrogenation reaction is endothermic with a low equilibrium conversion of 0.06 at a temperature of 473 K and pressure of 101 kPa. The membrane reactor removes hydrogen from the reaction mixture and results in increase of the reaction conversion. The analysis is made as a function of feed flow rate, feed temperature, feed composition, inert flow rate in the feed stream, flow rate of sweep gas, pressures of the tube side and shell side, permeability constant of hydrogen, and tube diameter. The analysis also includes a study of the co‐current and the counter‐current flow modes. The results show lower conversion for the counter‐current flow mode, because of the decrease in the driving force for permeation. A comparison of model predictions against previous literature studies shows good agreement.     

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.     

Methanol production in an optimized dual-membrane fixed-bed reactor

Coupling reaction and separation in a membrane reactor improves the reactor efficiency and reduces purification cost in the following stages. This paper focuses on modeling and optimization of methanol production in a dual-membrane reactor. In this configuration, conventional methanol reactor is supported by Pd/Ag membrane tubes for hydrogen permeation and alumina–silica composite membrane tubes for water vapor removal from the reaction zone. A steady state heterogeneous one-dimensional mathematical model is developed to predict the performance of this novel configuration. In order to verify the accuracy of the model, simulation results of the conventional reactor is compared with available industrial plant data. The main advantages of the optimized dual-membrane reactor are: higher CO₂ conversion, the possibility of overcoming the limitation imposed by thermodynamic equilibrium, improvement of the methanol production rate and its purity. Genetic algorithm as an exceptionally simple evolution strategy is employed to maximize the methanol production as the objective function. This configuration has enhanced methanol production rate by 13.2% compared to industrial methanol synthesis reactor.     

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.     

Selective Oxidation of Methanol to Green Oxygenates – Feasibility Study of Fixed-Bed and Membrane Reactors

A feasibility study of a conventional fixed-bed reactor and a packed-bed membrane reactor (PBMR) in distributor configuration is carried out for the selective oxidation of methanol to the oxygenates dimethoxymethane and methyl formate on a VO_x/TiO₂ catalyst. Kinetic experiments provided the reaction network and a reliable kinetic model of six main reactions involved. The PBMR offers significant advantages and potential for the formation of both target products due to an effective kinetic coupling of the oxidative dehydrogenation of methanol and the consecutive reaction steps to dimethoxymethane and methyl formate in a broad range of operation conditions.     

Hydrogen production from urea wastewater using a combination of urea thermal hydrolyser-desorber loop and a hydrogen-permselective membrane reactor

This work presents novel application of palladium-based membrane in a wastewater treatment loop of urea plant for hydrogen production. Urea wastewater treatment loop is based on combined thermal hydrolysis-desorption operations. The wastewater of urea plant includes ammonia and urea which in the current treatment loop; urea decomposes to ammonia and carbon dioxide. The catalytic hydrogen-permselective membrane reactor is proposed for hydrogen production from desorbed ammonia of urea wastewater which much of it discharges to air and causes environmental pollution. Therefore hydrogen is produced from decomposition of ammonia on nickel-alumina catalyst bed simultaneously and permeates from reaction side to shell side through thin layer of palladium-silver membrane. Also a sweep gas is used in the shell side for increasing driving force. In this way, 4588 tons/yr hydrogen is produced and environmental problem of urea plant is solved. The membrane reactor and urea wastewater treatment loop are modeled mathematically and the predicted data of the model are consistent with the experimental and plant data that show validity of the model. Also the effects of key parameters on the performance of catalytic hydrogen-permselective membrane reactor such as the temperature, pressure, thickness of Pd-Ag layer, configuration of flow and sweep gas flow ratio were examined.     

Simulation of an Industrial Pyrolysis Gasoline Hydrogenation Unit

A model is developed based on a two‐stage hydrogenation of pyrolysis gasoline to obtain a C₆–C₈ cut suitable for extraction of aromatics. In order to model the hydrogenation reactors, suitable hydrodynamic and reaction submodels should be solved simultaneously. The first stage hydrogenation takes place in a trickle bed reactor. The reaction rates of different di‐olefines as well as hydrodynamic parameters of the trickle bed (i.e., catalyst wetting efficiency, pressure drop, mass transfer coefficient and liquid hold‐up) have been combined to derive the equations to model this reactor. The second stage hydrogenation takes place in a two compartment fixed bed reactor. Hydrogenation of olefines takes place in the first compartment while sulfur is eliminated from the flow in the second compartment. These reactions occur at relatively higher temperature and pressure compared to the first stage. The key component in this stage is considered to be cyclohexene, of which the hydrogenation was found to be the most difficult of the olefines present in the feed. The Langmuir‐Hinshelwood kinetic expression was adopted for the hydrogenation of cyclohexene and its kinetic parameters were determined experimentally in a micro‐reactor in the presence of the industrial catalyst. The model was solved for the whole process of hydrogenation, including hydro‐desulfurization. The predictions of the model were compared with actual plant data from an industrial scale pyrolysis gasoline hydrogenation unit and satisfactory agreement was found between the model and plant data.     

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     

A comparative study of two different configurations for exothermic–endothermic heat exchanger reactor

The coupling of the energy intensive endothermic reaction systems with appropriate exothermic reactions reduces the size of the reactors and can improve the thermal efficiency of processes. One type of a suitable reactor for such a kind of coupling is the heat exchanger reactor. In this study, the catalytic methanol synthesis is coupled with the catalytic dehydrogenation of cyclohexane to benzene in an integrated reactor formed from two fixed beds separated by a wall where heat is transferred across the surface of the tube. A steady-state heterogeneous model of the two fixed beds predicts the performance of the two different configurations of the thermally coupled reactor. The co-current mode is investigated and the simulation results are compared with the corresponding predictions for the industrial methanol fixed bed reactor operating in the same feed conditions. The results of the study reveal that should the exothermic and endothermic reactions be located in the shell side and tube side, respectively, the methanol production rate will increase in comparison with the conventional methanol synthesis reactor as well as the case where the exothermic reaction is located in the tube side and endothermic reaction in the shell side.     

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.     

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.