Modeling, simulation and control of dimethyl ether synthesis in an industrial fixed-bed reactor

Dimethyl ether (DME) as a clean fuel has attracted the interest of many researchers from both industrial communities and academia. The commercially proven process for large scale production of dimethyl ether consists of catalytic dehydration of methanol in an adiabatic fixed-bed reactor. In this study, the industrial reactor of DME synthesis with the accompanying feed preheater has been simulated and controlled in dynamic conditions. The proposed model, consisting of a set of algebraic and partial differential equations, is based on a heterogeneous one-dimensional unsteady state formulation. To verify the proposed model, the simulation results have been compared to available data from an industrial reactor at steady state conditions. A good agreement has been found between the simulation and plant data. A sensitivity analysis has been carried out to evaluate the influence of different possible disturbances on the process. Also, the controllability of the process has been investigated through dynamic simulation of the process under a conventional feedback PID controller. The responses of the system to disturbance and setpoint changes have shown that the control structure can maintain the process at the desired conditions with an appropriate dynamic behavior.     

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.     

A COMPARISON OF A NOVEL RECUPERATIVE CONFIGURATION AND CONVENTIONAL METHANOL SYNTHESIS REACTOR

Coupling energy-intensive endothermic reaction systems with suitable exothermic reactions improves the thermal efficiency of processes and reduces the capital cost of the reactors. In this study, a steady-state heterogeneous model for a novel thermally coupled reactor, containing methanol synthesis reactions and cyclohexane dehydrogenation, was developed. This heat exchanger reactor consists of two fixed beds separated by a wall, where heat is transferred across the surface of the tube from the exothermic into the endothermic side. The co-current mode is investigated, and the simulation results are compared with corresponding data for an industrial methanol fixed bed reactor operated at the same feed conditions. The results show that although methanol productivity in the thermally coupled reactor is not higher than that in the conventional methanol reactor, benzene is also produced as an additional valuable product in a favorable manner, and autothermality is achieved within the reactor. This novel configuration can increase the methanol synthesis temperature at the first part of the reactor for higher process rates and then reduce the temperature at the second part of reactor for increasing thermodynamic equilibrium; those are two key issues in methanol reactor configurations. The influence of inlet temperature, molar flow rate, and shell diameter of the endothermic stream on reactor behavior is investigated. The results suggest that coupling of these reactions in co-current mode could be feasible and beneficial. Experimental proof-of-concept is needed to establish the validity and safe operation of the novel reactor.     

Is heat transfer governing chemical reactions in supercritical fluids?

A high pressure reactor calorimeter has been developed to study chemical reactions in supercritical fluids. Non-dimensional analysis of the heat transfer mechanism in the calorimeter verifies the application of the Nusselt correlation in scCO₂. The reactor's cover and flange have been modified to be fully temperature controlled and their contribution to the dynamic response of the calorimeter is investigated. Finally, the esterification of methanol with acetic anhydride was chosen as a model reaction and the role of heat transfer in chemical reactions in supercritical fluids is discussed.     

Temperature control of highly exothermic batch polymerization reactors

In this article a highly exothermic batch polymerization reactor is considered. The reactor is simplified as a mixing tank with the internal heat generation treated as a disturbance. A fuzzy-hybrid-PID-feedback (FH-PID) control structure is developed in which the output of fuzzy hybrid portion is used to adjust the set point of a PID controller to compensate for the effect of the major disturbance, the heat of reaction. In this way, the hybrid portion of the controller does not influence the stability of the original PID control system. A fuzzy model was constructed to estimate the heat of reaction inside the fuzzy hybrid block. The fuzzy parameters of the hybrid portion do not depend on the process model and can be estimated from the transient response obtained with a conventional PID controller. This FH-PID control strategy has been applied to the temperature control of batch solution and batch inverse emulsion polymerizations of acrylamide in a 1 gallon pilot scale reactor. The results show that this fuzzy hybrid—PID-feedback control strategy improves the control performance of the batch polymerization reactor.     

配备不同类型控制器CSTR反应器的动态模拟

为了提高CSTR反应器操作的安全稳定性,本文以水合法制丙二醇为例,分析了当CSTR反应器进料温度受到扰动后,配备比例控制器(P)、积分控制器(I)和微分控制器(D),以及它们的组合对CSTR操作状态的影响。动态模拟结果表明:P型、I型、D型、PI型和PID型控制器均能有效避免CSTR由高稳态跌落至低稳态的现象,而PID型控制器是提高CSTR反应器安全稳定性的最佳选择。     

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.     

乙炔加氢反应器全周期操作优化

乙炔加氢反应器作为乙烯工业流程的重要环节,其运行会很大程度上影响到乙烯产品的产量和纯度。在一个运行周期内,乙炔加氢反应器内催化剂活性会随时间推移而缓慢降低,使操作点偏移,乙烯产量会随之降低。为了实现全周期操作优化,通过研究催化剂的失活机理,提出了考虑绿油累积效果的催化剂失活动力学模型,进而改进了乙炔加氢反应器二维非均相模型。通过在gPROMS平台模拟反应器全周期运行验证了改进模型的正确性,在上层运用Matlab优化器与gPROMS平台交互求解一个运行周期的操作优化问题。优化结果表明,与定值温度补偿方案相比,全周期操作优化在经济效益和反应器再生周期两方面都要优于定值温度补偿方案,且同时优化入口温度与入口加氢量的全周期操作优化方案具有更大的优势。     

ADAPTIVE FUZZY MODEL BASED PREDICTIVE CONTROL OF AN EXOTHERMIC BATCH CHEMICAL REACTOR*

An adaptive fuzzy model based predictive control (AFMBPC) approach is presented to track the desired temperature trajectories in an exothermic batch chemical reactor. The AFMBPC incorporates an adaptive fuzzy modeling framework into a model based predictive control scheme to derive analytical controller output. This approach has the flexibility to cope with different fuzzy model structures whose choice also lead to improve the controller performance. In this approach, adaptation of fuzzy models using dynamic process information is carried out to build a predictive controller, thus eliminating the determination of a predefined fixed fuzzy model based on various sets of known input-output relations. The performance of the AFMBPC is evaluated by comparing to a fixed fuzzy model based predictive controller (FFMBPC) and a conventional PID controller. The results show the better suitability of AFMBPC for the control of highly nonlinear and time varying batch chemical reactors.     

Dynamic modeling and simulations of the behavior of a fixed‐bed reactor‐exchanger used for CO2 methanation

A multidimensional heterogeneous and dynamic model of a fixed‐bed heat exchanger reactor used for CO₂ methanation has been developed in this work that is based on mass, energy and momentum balances in the gas phase and mass and energy balances for the catalyst phase. The dynamic behavior of this reactor is simulated for transient variations in inlet gas temperature, cooling temperature, gas inlet flow rate, and outlet pressure. Simulation results showed that wrong‐way behaviors can occur for any abrupt temperature changes. Conversely, temperature ramp changes enable to attenuate and even fade the wrong‐way behavior. Traveling hot spots appear only when the change of an operating condition shifts the reactor from an ignited steady state to a non‐ignited one. Inlet gas flow rate variations reveal overshoots and undershoots of the reactor maximum temperature. © 2017 American Institute of Chemical Engineers AIChE J, 64: 468–480, 2018     

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.     

Kinetic study of the methanol to olefin process on a SAPO-34 catalyst

In this paper, a new kinetic model for methanol to olefin process over SAPO-34 catalyst was developed using elementary step level. The kinetic model fits well to the experimental data obtained in a fixed bed reactor. Using this kinetic model, the effect of the most important operating conditions such as temperature, pressure and methanol space-time on the product distribution has been examined. It is shown that the temperature ranges between 400 °C and 450 °C is appropriate for propene production while the medium temperature (450 °C) is favorable for total olefin yield which is equal to 33%. Increasing the reactor pressure decreases the ethylene yield, while medium pressure is favorable for the propylene yield. The result shows that the ethylene and propylene and consequently the yield of total olefins increase to approximately 35% with decreasing the molar ratio of inlet water to methanol.     

Simulation of activity loss of fixed bed catalytic reactor of MTO conversion using percolation theory

In this investigation, a reactor model for prediction of the deactivation behavior of MTO's porous catalyst in a fixed bed reactor is developed. Effect of coking on molecular transport in the porous structure of SAPO-34 has been simulated using the percolation theory. Thermal effects of the reaction were considered in the model and the temperature profile of the gas stream in the reactor was predicted. The predicted loss in catalyst activity with time-on-stream was in very good agreement with the experimental data. The resulting coke deposition and gas temperature profiles along the length of reactor suggested a reaction front moving toward the outlet of the fixed bed reactor at the operating experimental conditions of 1 h⁻¹ and 723 K for methanol space velocity and inlet temperature, respectively. Effects of space time, coordination of Bethe network, and effective diffusivity of component in reaction mixture on the reactor performance are presented.     

OPTIMIZING THE FEED CONDITIONS IN A DIMETHYL ETHER PRODUCTION PROCESS TO MAXIMIZE METHANOL CONVERSION USING A HYBRID FIRST PRINCIPLE NEURAL NETWORK APPROACH

Modeling is a fundamental step in plant optimization and simulation. In this work, a new technique for modeling a gas-solid heterogeneous fixed-bed reactor is developed. Gas diffusion into the solid catalyst pellets requires solving the mass balance equations inside the catalyst. The computational load needed can be quite time-consuming due to system complexities and nonlinearities. This bottleneck prevents on-line optimization of the process. In this work, a trained three-layer neural network model is used to replace major parts of these computations. The model is then incorporated within the overall model of an adiabatic fixed-bed reactor to produce dimethyl ether (DME) from methanol dehydration over solid acidic catalysts. The performance of the reactor simulated using this procedure indicated good agreement with its experimental operation. Then an optimizer is employed to determine the best feed conditions. The proposed strategy can be applied to any heterogeneous fixed-bed reactor.     

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.     

Dynamic optimization of membrane dual-type methanol reactor in the presence of catalyst deactivation using genetic algorithm

This paper presents a study on optimization of a membrane dual-type methanol reactor in the presence of catalyst deactivation. A theoretical investigation has been performed in order to evaluate the optimal operating conditions and enhancement of methanol production in a membrane dual-type methanol reactor. A mathematical heterogeneous model has been used to simulate and compare the membrane dual-type methanol reactor with conventional methanol reactor. An auto-thermal dual-type methanol reactor is a shell and tube heat exchanger reactor 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 reactor is covered with a pd–Ag membrane, which is only hydrogen-permselective. The simulation results have been shown that there are optimum values of reacting gas and coolants temperatures to maximize the overall methanol production. Here, genetic algorithms have been used as powerful methods for optimization of complex problems. In this study, the optimization of the reactor has been investigated in two approaches. In the first approach, the optimal temperature profile along the reactor has been studied and then a stepwise approach has been followed to determine the optimal profiles for saturated water and gas temperatures in three steps during the time of operations to maximize the methanol production rate. The optimization methods have enhanced 5.14% and 5.95% additional yield throughout 4 years of catalyst lifetime for first and second optimization approaches, respectively.     

基于神经网络PID控制器的辊道窑温度控制仿真系统研究

在深入分析辊道窑特点及其热工过程的基础上,运用新型智能神经网络PID控制器设计开发了"基于神经网络PID控制器的辊道窑温度控制仿真系统",通过对辊道窑温度控制仿真和电炉模拟实验,证明设计开发的PID控制器是可行的。     

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.     

Simulation d'un réacteur catalytique à lit fixe (Oxydation du propène)

A bidimensional pseudo homogeneous model is developed to explain the behaviour of a fixed bed catalytic reactor for oxydation of propene to acrolein. The rate of the main reaction and of side reaction are expressed as power fonctions of partial pressures of oxygene and propene. Heat transfer parameter (Pe_hr et Bi) necessary for simulation are obtained by the help of temperature profiles in the absence of reaction. The integration of the model has been done by orthogonal collocation and the results i.e. temperature profiles and outlet concentration are compared with experimental data.