The aromatic enhancement in the axial‐flow spherical packed‐bed membrane naphtha reformers in the presence of catalyst deactivation

Because of some disadvantages of conventional tubular reactors (CTRs), the concept of spherical membrane reactors is proposed as an alternative. In this study, it is suggested to apply hydrogen perm‐selective membrane in the axial‐flow spherical packed‐bed naphtha reformers. The axial flow spherical packed‐bed membrane reactor (AF‐SPBMR) consists of two concentric spheres. The inner sphere is supposed to be a composite wall coated by a thin Pd‐Ag membrane layer. Set of coupled partial differential equations are developed for the AF‐SPBMR model considering the catalyst deactivation, which are solved by using orthogonal collocation method. Differential evolution optimization technique identifies some decision variables which can manipulate the input parameters to obtain the desired results. In addition to lower pressure drop, the enhancement of aromatics yield by the membrane layer in AF‐SPBMR adds additional superiority to the spherical reactor performance in comparison with CTR. © 2011 American Institute of Chemical Engineers AIChE J, 2011     

A novel dynamic membrane reactor concept with radial‐flow pattern for reacting material and axial‐flow pattern for sweeping gas in catalytic naphtha reformers

Naphtha reforming units are of high interest for hydrogen production in refineries. In this regard, the application of membrane concept in radial‐flow tubular naphtha reactors for hydrogen production is proposed. Because of the importance of the pressure drop problem in catalytic naphtha reforming units, the radial‐flow reactors are proposed. A radial‐flow tubular membrane reactor (RF‐TMR) with the radial‐flow pattern of the naphtha feed and the axial‐flow pattern of the sweeping gas is proposed as an alternative configuration for conventional axial‐flow tubular reactors (AF‐TR). The cross‐sectional area of the tubular reactor is divided into some subsections in which walls of the gaps between subsections are coated with the Pd‐Ag membrane layer. A dynamic mathematical model considering radial and axial coordinates ((r, z)‐coordinates) has been developed to investigate the performance of the new configuration. Results show ～300 and 11 kg/h increase in aromatic and hydrogen production rates in RF‐TMR compared with AF‐TR, respectively. Furthermore, smaller catalyst particles with higher efficiency can be used in RF‐TMR due to a slight pressure drop. The enhancement in aromatics (octane number) and hydrogen productions owing to applying simultaneously the membrane concept and radial‐flow pattern in naphtha reactors motivates the application of RF‐TMR in refineries. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Methanol synthesis in a novel axial-flow, spherical packed bed reactor in the presence of catalyst deactivation

Since in the foreseeable future liquid hydrocarbon fuels will play a significant role in the transportation sector, methanol might be used potentially as a cleaner and more reliable fuel than the petrochemical-based fuels in the future. Consequently, enhancement of methanol production technology attracts increasing attention and, therefore, several studies for developing new methanol synthesis reactors have been conducted worldwide. The purpose of this research is to reduce the pressure drop and recompression costs through the conventional single-stage methanol reactor. To reach this goal, a novel axial-flow spherical packed bed reactor (AF-SPBR) for methanol synthesis in the presence of catalyst deactivation is developed. In this configuration, the reactor is loaded with the same amount of catalyst in the conventional single-stage methanol reactor. The reactants are flowing axially through the reactor. The dynamic simulation of the spherical reactors has been studied in the presence of long-term catalyst deactivation for four reactor configurations and the results are compared with the achieved results of the conventional tubular packed bed reactor (CR). The results show that the three and four stages reactor setups can improve the methanol production rate by 4.4% and 7.7% for steady state condition. By utilizing the spherical reactors, some drawbacks of the conventional methanol synthesis reactors such as high pressure drop, would be solved. This research shows how this new configuration can be useful and beneficial in the methanol synthesis process.     

A comparison of auto-thermal and conventional methanol synthesis reactor in the presence of catalyst deactivation

This study proposed a one-dimensional dynamic plug flow model to analyze and compare the performance of an auto-thermal and a conversional methanol synthesis reactor in the presence of catalyst deactivation. An auto-thermal two-stage industrial methanol reactor type is a system with two catalyst beds instead of one single catalyst bed. In the first catalyst bed, the synthesis gas is partly converted to methanol in a water-cooled reactor. In the second bed which is a gas-cooled reactor, the reaction heat is used to preheat the feed gas to the first bed. To analyze the effect of important control variables on the rector performance, steady state and dynamic simulations are utilized to investigate effect of operating parameters on the performance of reactors. The simulation results show that there is a favorable profile of temperature along the two-stage auto-thermal reactor type in comparison with conventional single stage reactor type. In this way the catalysts are exposed to less extreme temperatures and, catalyst deactivation via sintering is reduced. Overall, this study resulted in beneficial information about the performance of the reactor over catalyst life-time.     

Fixed‐Bed Multi‐Tubular Reactors for Oxidative Dehydrogenation in Ethylene Process

An industrial‐scale reactor for ethylene production was modeled using the oxidative dehydrogenation of ethane (ODHE) in a multi‐tubular reactor system, examining a variety of parameters affecting reactor performance. The model showed that a double‐bed multi‐tubular reactor with intermediate air injection scheme was superior to a single‐bed design, due to the increased ethylene selectivity while operating under lower oxygen partial pressures. The optimized reactor length for 100 % oxygen conversion was theoretically determined for both reactor designs. The use of a distributed oxygen feed with a limited number of injection points indicated a significant improvement on the reactor performance in terms of ethane conversion and ethylene selectivity. This concept also overcame the reactor runaway temperature problem and enabled operations over a wider range of conditions to obtain enhanced ethylene production.     

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.     

Dynamic simulation of a cascade fluidized-bed membrane reactor in the presence of long-term catalyst deactivation for methanol synthesis

In this work, a dynamic model for a cascade fluidized-bed hydrogen permselective membrane methanol reactor (CFBMMR) has been developed in the presence of long-term catalyst deactivation. In the first catalyst bed, the synthesis gas is partly converted to methanol in a water-cooled reactor, which is a fluidized-bed. In the second bed, which is a membrane assisted fluidized-bed reactor, the reaction heat is used to preheat the feed gas to the first bed. This reactor configuration solves some observed drawbacks of new conventional dual type methanol reactor (CDMR) and even fluidized-bed membrane dual type methanol reactor (FBMDMR) such as pressure drop, internal mass transfer limitations, radial gradient of concentration and temperature in both reactors. A dynamic two-phase theory in bubbling regime of fluidization is used to model and simulate the proposed reactor. The proposed model has been used to compare the performance of a cascade fluidized-bed membrane methanol reactor with fluidized-bed membrane dual-type methanol reactor and conventional dual-type methanol reactor. The simulation results show a considerable enhancement in the methanol production due to the favorable profile of temperature and activity along the CFBMMR relative to FBMDMR and CDMR systems.     

Modeling of Multi‐Tubular Reactors for Fischer‐Tropsch Synthesis

The results of the simulation of multi‐tubular Fischer‐Tropsch reactors based on a two‐dimensional pseudo‐homogeneous model are presented. The model takes into account the intrinsic kinetics of two commercial iron and cobalt catalysts, intraparticle mass transfer limitations, and the radial heat transfer within the fixed bed and to the cooling medium (boiling water). The effective rate with Co is slightly higher than with Fe. Hence, a temperature level can be used for Co that is 20 °C lower compared to Fe. The conversion and product selectivies are then almost the same and the reactor can be operated safely without a temperature runaway. The results of the simulations are consistent with literature data and show that there is still room for improvement of fixed bed FT reactors, e.g., by an enhanced heat transfer.     

Temperature response to reactant concentration perturbations in a packed‐bed reactor

Unsteady‐state operations are known to enhance the performance of some packed‐bed reactor systems. However, negative effects of this type of operation should not be neglected. Temperature excursions developed during transients may accelerate some deactivation mechanisms, reducing catalyst lifetime and selectivity. Temperature response to perturbations in reactant concentration was studied for CO oxidation over Pt/Al₂O₃ in a packed‐bed reactor. Experiments were conducted in the CO concentration range for which multiple steady states are observed. Temperature and concentration profiles in the packed‐bed reactor at steady state were found to depend on the dynamic history of the reactor prior to the steady‐state condition.     

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.     

Optimal design of a thermally coupled fluidised bed heat exchanger reactor for hydrogen production and octane improvement in the catalytic naphtha reformers

The present study combines simultaneously the definition of fluidisation and process intensification (thermally coupled heat exchanger reactor) concept and determines the optimum operational conditions in both sides of the reactor, using Differential Evolution (DE) optimisation approach. The exothermic hydrogenation of nitrobenzene to aniline takes place in a set of tubular reactors which is placed inside the naphtha reactors and thermally handle the endothermic reaction of reforming. A single objective function consists of four terms including aromatic mole fraction of the reformate and hydrogen production from each reactor in the endothermic side as well as the total molar flow rate of aniline and nitrobenzene conversion in the exothermic side is defined. Seven decision variables such as inlet temperature of exothermic and endothermic sides, exothermic molar flow rates for the first and the second reactors and the number of tubes are considered during the optimisation procedure. Temperature constraints have been considered in both sides during the optimisation in order to reduce the possibility of rapid catalyst deactivation by sintering. Results show approximately 464.4 and 598.9 kg/h increase in aromatic and aniline production rates in optimised thermally coupled fluidised bed naphtha reactor (OTCFBNR) compared with non‐optimised case (TCFBNR), respectively. Such a theoretical study is necessary prior to designing new pilot plants and revamping industrial units. © 2011 Canadian Society for Chemical Engineering     

Computer Simulation of the Performance of a Downer‐Regenerator CFB for the Partial Oxidation of n‐Butane to Maleic Anhydride

A reactor model for a downer‐regenerator circulating fluidized‐bed (CFB) during the partial oxidation of n‐butane to maleic anhydride is presented. Upflow reactors (risers) suffer from severe solids back mixing and gas‐solids‐separation, in comparison down flow reactors exhibit a more uniform gas‐solids flow and reduced backmixing, resulting in narrower residence time distributions. Due to the sensitivity of the VPO catalyst to over‐reduction, downer reactors present an interesting alternative to riser reactors. The reactor models for the downer and the regenerator fluidized‐bed are coupled with reduction and oxidation kinetics for the catalyst, respectively. The influence of the solids residence time distributions for the combined system of both reactors on the oxidation state of the catalyst is explored by a novel newly developed oxygen loading distribution. Simulation results suggest the limited solids‐flux in downers restrict the maximum butane concentrations, while the scale‐up is predicted to be uncritical.     

Combustion of methane lean mixtures in reverse flow reactors: Comparison between packed and structured catalyst beds

The scope of this work is to compare systematically the performance of particle beds and monolithic beds in catalytic reverse flow reactors used for combustion of lean methane/air mixtures, using alumina-supported palladium as catalyst. Different values of gas surface velocity (0.1–0.3 m/s), particle diameter (3–6 mm, for particle bed), cell density (200–400 cpsi, for structured bed) and catalyst/inert ratio (0.4–1) were used for the simulation of the combustion of 3500 ppm methane in both kinds of reverse flow reactor. An unsteady one-dimensional heterogeneous model has been developed and solved using a MATLAB code. The model, physical parameters and transport properties used had been experimentally validated in a previous work, operating with a particle bed reverse flow reactor. Results obtained indicate that the reverse flow reactor is more stable when the catalyst particle beds are use, although the difference with the monolith bed decreases as surface velocity increases. In contrast, pressure drops in the bed are higher for the particle bed.     

Production of optically pure L‐valine in fluidized and packed bed reactors with immobilized L‐aminoacylase

A process to obtain L ‐valine has been developed using fluidized and packed bed reactors with L ‐aminoacylase (from hog kidney) immobilized by covalent binding. L ‐Valine production using the immobilized derivative of L ‐aminoacylase in fluidized and packed bed reactors was studied at three different substrate concentrations and two different flow rates. Higher productions were obtained in the packed bed reactor in all cases. The different solubilities of L ‐valine and acetyl‐D ‐valine in ethanol were used to purify L ‐amino acid from the reactor effluents. The amount of added ethanol did not influence the separation yields, although the purity of L ‐valine was strongly affected by this parameter. The last step involved was racemization of the unhydrolyzed acetyl‐D ‐valine, which was then used as substrate in a new reaction cycle. © 1999 Society of Chemical Industry     

Dynamic mathematical modeling of a novel dual-type industrial ethylene oxide (EO) reactor

In this paper, the dynamic behavior of a novel dual-type industrial ethylene oxide reactor has been proposed with taking catalyst deactivation into account. The configuration of two catalyst beds instead of one single catalyst bed is developed for conversion of ethylene to ethylene oxide. In the first reactor which is an industrial fixed-bed water-cooled reactor, the feed gas is partly converted to ethylene oxide. This reactor functions at very high yield and at a higher than normal operating temperature. In the second converter, the reaction heat is used to preheat the feed gas to the first reactor and a milder temperature profile is observed. The potential possibilities of a two-stage catalyst bed system are analyzed using a 1D heterogeneous dynamic model to obtain necessary comparative estimates. A differential evolution (DE) algorithm is applied as an effective and robust method to optimize the reactors length ratio. The results obtained from the simulation demonstrate that there is a desirable catalyst temperature profile along the dual-type reactor (DR) compared with the conventional single-type reactor (SR). In this way, the catalysts are exposed to less extreme temperatures and thus, diminishing the catalyst deactivation via sintering. Results from this study provided beneficial information about the effects of reactors configuration on catalyst lifetime and ethylene oxide production rate simultaneously.     

A Review of Process Aspects and Modeling of Ebullated Bed Reactors for Hydrocracking of Heavy Oils

The main characteristics of ebullated bed reactors have been reviewed in this work. Key factors of the application of these reactors to hydrocracking of heavy petroleum fractions, such as sediments formation, catalyst attrition and catalyst deactivation, have been clearly discussed. Mathematical representation of ebullated bed systems has been organized into hydrodynamics, scaling down and reactor modeling. Only a few reports dealing with the topic of this review were found in the literature, which employ different levels of sophistication to establish the model equations. These literature reports were summarized and properly discussed, from which it has been recognized that modeling of ebullated bed reactors is a complex task and deserves more attention.     

Advantages of Forced Non‐steady Operated Trickle‐Bed Reactors

Trickle‐bed reactors are usually operated in the steady state trickle flow regime. Uneven liquid distribution and the formation of hot spots are the most serious problems experienced during trickle flow operation. In this paper, we advocate the use of non‐steady state operation of trickle‐bed reactors. Based on a square‐wave cycled liquid feed, several operation modes are developed that involve the artificial induction of natural pulses and control of the catalyst wetting efficiency over longer times. The operation modes aim at increasing the mass transfer rate of the limiting reactant and simultaneous prevention of flow maldistribution and hot spot formation. The operation modes are distinguished by a relatively fast and slow cycling of the liquid feed. The potential advantages of the developed feed strategies on reactor performance are evaluated.     

Dynamic Simulation and Optimization of a Dual‐Type Methanol Reactor Using Genetic Algorithms

In this investigation, a dynamic simulation and optimization for an auto‐thermal dual‐type methanol synthesis reactor was developed in the presence of catalyst deactivation. Theoretical investigation was performed in order to evaluate the performance, optimal operating conditions, and enhancement of methanol production in an auto‐thermal dual‐type methanol reactor. The proposed reactor model was used to simulate, optimize, and compare the performance of a dual‐type methanol reactor with a conventional methanol reactor. An auto‐thermal 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. The proposed model was validated against daily process data measured of a methanol plant recorded for a period of 4 years. Good agreement was achieved. The optimization was achieve by use of genetic algorithms in two steps and the results show there is a favorable profile of methanol production rate along the dual‐type reactor relative to the conventional‐type reactor. Initially, the optimal ratio of reactor lengths and temperature profiles along the reactor were obtained. Then, the approach was followed to get an optimal temperature profile at three periods of operation to maximize production rate. These optimization approaches increased by 4.7 % and 5.8 % additional yield, respectively, throughout 4 years, as catalyst lifetime. Therefore, the performance of the methanol reactor system improves using optimized dual‐type methanol reactor.     

Periodic operation of transport reactors for catalytic reactions

Based on plug flow of gas and catalyst particles and concentration dependent deactivation kinetics, the performance of transport reactors under a periodic (rectangular pulse) inlet concentration is analysed for improvement in conversion and extent of catalyst decay. The effects of reaction and deactivation orders, reaction and deactivation constant groups, and γ (cycle split) on the performance of the reactors are evaluated theoretically. For reaction orders greater than one, periodic operation improves conversion. Resonance behaviour is observed for certain combinations of parameters. For identical operating conditions vertical upflow, downflow and horizontal flow reactors are compared. Conversion in upflow reactors is higher than that in either horizontal flow or downflow reactors. However, catalyst decay is the least in downflow reactors.     

Simulation and Optimization of an Adiabatic Multi‐Bed Catalytic Reactor for the Oxidation of SO2

A software package was developed for the simulation and optimization of a multi‐bed adiabatic reactor for the catalytic oxidation of SO₂, using a heterogeneous plug flow model. The orthogonal collocation (OC) technique with up to eight collocation points was used for the solution of a nonlinear, two‐point boundary value differential equation for the catalyst particle, and it was shown that the use of the OC technique with two collocation points can describe the system well. Because of the nonlinear behavior of the effectiveness factor along the bed, optimal catalyst distribution between the beds and corresponding inlet temperatures were determined by two methods, including: the use of (1) intrinsic or (2) actual rate of reaction in the optimization criteria. The results showed that for the second case, the minimum amount of the catalyst can be reached at lower temperatures, the amount of catalyst required is always less, and the number of beds is greater than or equal to that of the first case.