Modeling, simulation and control of a methanol synthesis fixed-bed reactor

In this paper, the dynamic behavior and control of the low pressure methanol synthesis fixed bed reactor have been investigated. For simulation purpose, a heterogeneous one-dimensional model has been developed. First, the reactor simulation is carried out under steady-state condition and the effects of several parameters such as shell temperature, feed composition (especially CO₂ concentration) and recycle ratio on the methanol productivity and reactor temperature profile are investigated. Using the steady state model and a trained feedforward neural network that calculates the effectiveness factor, an optimizer which maximizes the reactor yield has been developed. Through the dynamic simulation, the system open loop response has been obtained and the process dynamic is approximated by a simple model. This model is used for the PID controller tuning and the performances of fixed and adaptive PID controllers are compared for load rejection and set point tracking. Finally the proposed optimizer is coupled with a controller for online optimization and hot spot temperature protection.     

一步法合成二甲醚反应器的研究进展

综述了合成气一步法合成二甲醚反应器的发展近况,着重介绍了固定床、浆态床及组合床的研究进展,并根据国内外的研究对几种反应器进行了工艺比较。     

Model predictive control of an industrial pyrolysis gasoline hydrogenation reactor

This study focuses on the implementation of a nonlinear model predictive control (MPC) algorithm for controlling an industrial fixed-bed reactor where hydrogenations of raw pyrolysis gasoline occur. An orthogonal collocation method is employed to approximate the original reactor model consisting of a set of partial differential equations. The approximate model obtained is used in the synthesis of a MPC controller to control the temperature rising across a catalyst bed within the reactor. In the MPC algorithm, a sequential optimization approach is used to solve an open-loop optimal control problem. Feedback information is incorporated in the MPC to compensate for modeling error and unmeasured disturbances. The control studies are demonstrated in cases of set point tracking and disturbance rejection.     

Production of fatty acid methyl esters over a limestone-derived heterogeneous catalyst in a fixed-bed reactor

Production of fatty acid methyl esters (FAME) via the transesterification of different vegetable oils and methanol with a limestone-derived heterogeneous catalyst was investigated in a fixed-bed reactor at 65 °C and ambient pressure. This heterogeneous catalyst, as a 1 or 2 mm cross-sectional diameter extrudate, was prepared via a wet mixing of thermally treated limestone with Mg and Al compounds as binders and with or without hydroxyethyl cellulose (HEC) as a plasticizer, followed by calcination at 800 °C. The physicochemical properties of the prepared catalysts were characterized by various techniques. Palm kernel oil, palm oil, palm olein oil and waste cooking oil could be used as the feedstocks but the FFA and water content must be limited. The extrudate catalyst prepared with the HEC addition exhibited an enhanced formation of FAME due to an increased porosity and basicity of the catalyst. The FAME yield was increased with the methanol/oil molar ratio. The effect of addition of methyl esters as co-solvents on the FAME production was investigated. The structural and compositional change of the catalysts spent in different reaction conditions indicated that deactivation was mainly due to a deposition of glycerol and FFA (if present). The FAME yield of 94.1 wt.% was stably achieved over 1500 min by using the present fixed-bed system.     

浆态床合成二甲醚复合催化剂的研究进展

概述了以合成气为原料合成二甲醚工艺中浆态床反应器使用的双功能催化剂的研究现状和最新进展。介绍了传统双功能催化剂以及对传统催化剂的改性研究,重点介绍了基于使催化材料的制备环境与其使用环境完全一致,以解决催化剂失活问题的完全液相法的研究进展,该方法制备的催化剂具有良好的稳定性和催化性能,并具有广泛的应用前景。     

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.     

Modelling, simulation and control of an industrial, semi-batch, emulsion-polymerization reactor

This paper presents an emulsion-polymerization model that is designed for an industrial, semi-batch reactor. The model consists of a reaction model and a calorimetry model, and as such enables us to predict the reactor temperature and the batch-output parameters, i.e., the conversion, the solids content and the viscosity. The model was validated on real-plant data and used in the analysis and design of the reactants dosing control. The control strategy proposed is valid for cases where evaporative cooling is either the only or an additional way to remove the heat of the reaction. It consists of an initiator and monomer dosing control, using the reactor temperature as a controlled variable. The simulation results and the real-plant testing show that the proposed reactants dosing control significantly reduces the variations in the reactor temperature and at the same time results in more uniform batch results.     

Modeling of an industrial fixed bed reactor based on lumped kinetic models for hydrogenation of pyrolysis gasoline

In this work, a mathematical model of an industrial fixed bed reactor for the catalytic hydrogenation of pyrolysis gasoline produced from olefin production plant is developed based on a lumped kinetic model. A pseudo-homogeneous system for liquid and solid phases and three pseudo-components: diolefins, olefins, and parraffins, are taken into account in the development of the reactor model. Temperature profile and product distribution from real plant data on a gasoline hydrogenation reactor are used to estimate reaction kinetic parameters. The developed model is validated by comparing the results of simulation with those collected from the plant data. From simulation results, it is found that the prediction of significant state variables agrees well with the actual plant data for a wide range of operating conditions; the developed model adequately represents the fixed-bed reactor.     

Simulation of fixed bed reactor for dimethyl ether synthesis

Dimethyl Ether (DME) is considered as one of the most promising candidates for a substitute for LPG and diesel fuel. We analyzed one-step DME synthesis from syngas in a shell and tube type fixed bed reactor with consideration of the heat and mass transfer between catalyst pellet and reactants gas and effectiveness factor of catalysts together with reactor cooling through reactor wall. Simulation results showed strong effects of pore diffusion. We compared two different arrangements of catalysts, mixture of catalyst pellets (methanol synthesis catalyst and methanol dehydration catalyst) and hybrid catalyst. Hybrid catalyst gave better performance than a mixture of pellets in terms of CO conversion and DME productivity, but more difficulties with reactor temperature control. Use of inert pellets and inter-cooling was also simulated as a means of controlling maximum reactor temperature.     

Passivity-based control of the phthalic anhydride fixed-bed reactor

The control of tubular fixed-bed reactors with highly exothermic reactions is approached from a passivity-based control perspective. The proposed controller solves dynamic tracking of the reactor exit conversion and stabilization of the reactor temperature by exploiting the passivity properties of the process. The model-based control structure proposed in this paper provides a suitable framework for developing the passivity-based control law and the state predictor. The integrated controller is designed and its performance in the face of parameter variation and model uncertainty is tested by numerical simulation. Digital simulation on an industrial phthalic anhydride fixed-bed reactor shows that the proposed control scheme can give satisfactory dynamic tracking ability and disturbance rejection performance, which is robust in the presence of process variation and model uncertainty. This paper provides a basic insight into the characterization and solution of control problems that are particular to tubular fixed-bed reactor systems and constitutes the application of passivity-based control theory to complex chemical processes.     

Pattern formation in models of fixed-bed reactors

This work reviews and compares spatiotemporal patterns in three models of adiabatic fixed catalytic beds for reactions with oscillatory kinetics: homogeneous and heterogeneous models, which are studied using generic first-order kinetics, and a detailed model of CO oxidation in the monolithic reactor. These three models describe reactors with one, two or all three phases (fluid-, solid- and adsorbed-phases), respectively. Pattern selection is based on the oscillatory or bistable nature of the kinetics and on the nature of fronts. The heterogenous and detailed models may exhibit local bistability while the homogeneous model does not admit this property: a simple conversion between the parameters of the homogeneous and heterogeneous models is suggested.

The spatiotemporal patterns in the reactor can be predicted from the sequence of phase planes spanned by the reactor. Stationary or oscillatory front solutions, oscillatory states that sweep the whole surface or excitation fronts may be realized in the homogeneous and heterogeneous models. The detailed model of the converter may exhibit oscillatory motion, which may be periodic or chaotic, in which typically a hot domain enters the reactor exit and moves quickly upstream; the following extinction occurs almost simultaneously due to strong coupling by convection.     

工业级错流列管式固定床反应器的CFD模拟

工业级大型列管式固定床反应器壳程温度场与流场的均匀程度与反应的转化率及选择性密切相关。通过添加阻力源项和分散热源项,对工业级全尺寸错流列管式固定床壳程流场及温度场进行了CFD模拟研究,并进一步考察了折流板窗口区大小及其位置对壳程压降与温度分布的影响。结果表明,模拟得到壳程压降与由经验公式计算得到的压降较为接近,且壳程温度分布与工业实际数据吻合;增大窗口区面积,壳程压降呈现指数下降,同时高温差区（径向温差大于2 K）的范围与径向温差变大;随着第1块折流板位置降低,高温差区范围及径向温差均减小,但压降并不呈现规律性变化。模拟方法可用于工业级大型列管式固定床反应器的优化及设计。     

Performance of a multi-slit packed bed microstructured reactor in the synthesis of methanol: Comparison with a laboratory fixed-bed reactor

The performance of a multi-slit Integrated Micro Packed Bed Reactor-Heat Exchanger (IMPBRHE) for methanol synthesis from synthesis gas over Cu/ZnO/support commercial catalyst was experimentally investigated from a reaction engineering perspective. Through establishment of a systematic comparison strategy, performance comparison with a laboratory scale tubular Fixed-Bed Reactor (FBR) with three different dilution ratios was made to evaluate the IMPBRHE. The productivity, thermal behavior, activity of body materials, pressure drop and residence time distribution (RTD) of the two reactor types were investigated. The IMPBRHE outperformed the undiluted FBR and gave CO conversions comparable to the diluted FBRs. The main difference is ascribed to superior heat exchange properties of the IMPBRHE, which can improve reactor performance for an exothermic reaction such as methanol synthesis. The results reveal advantages of the IMPBRHE for robust scale up.     

Modeling-based optimization of a fixed-bed industrial reactor for oxidative dehydrogenation of propane

An industrial scale propylene production via oxidative dehydrogenation of propane(ODHP)in multi-tubular reactors was modeled.Multi-tubular fixed-bed reactor used for ODHP process,employing 10000 of small diameter tubes immersed in a shell through a proper coolant flows.Herein,a theory-based pseudo-homogeneous model to describe the operation of a fixed bed reactor for the ODHP to correspondence ole fin over V_2O_5/γ-Al_2O_3catalyst was presented.Steady state one dimensional model has been developed to identify the operation parameters and to describe the propane and oxygen conversions,gas process and coolant temperatures,as well as other parameters affecting the reactor performance such as pressure.Furthermore,the applied model showed that a double-bed multitubular reactor with intermediate air injection scheme was superior to a single-bed design due to the increasing of propylene selectivity while operating under lower oxygen partial pressures resulting in propane conversion of about 37.3%.The optimized length of the reactor needed to reach 100%conversion of the oxygen was theoretically determined.For the single-bed reactor the optimized length of 11.96 m including 0.5m of inert section at the entrance region and for the double-bed reactor design the optimized lengths of 5.72m for the first and 7.32 m for the second reactor were calculated.Ultimately,the use of a distributed oxygen feed with limited number of injection points indicated a signi ficant improvement on the reactor performance in terms of propane conversion and propylene selectivity.Besides,this concept could overcome the reactor runaway temperature problem and enabled operations at the wider range of conditions to obtain enhanced propylene production in an industrial scale reactor.     

三相床中合成气一步法制二甲醚

在反应温度 2 30～ 2 70℃、压力 2～ 5MPa下 ,以医药用石蜡油为惰性液相介质 ,使用C30 2铜基催化剂和CM - 3- 1改性分子筛组成的复合催化剂 ,在三相搅拌釜中研究了合成气 (CO、CO2 、H2 )一步法合成二甲醚的反应。结果表明随着温度的升高 ,碳的转化率增加 ,二甲醚的选择性提高 ,甲醇的选择性降低 ;随着压力的增加 ,碳的转化率升高 ,二甲醚的选择性提高 ,甲醇的选择性降低     

二甲醚精馏塔实验研究与模拟计算

建立了用于二甲醚精制的精馏塔实验流程,实验测定了在操作工艺条件下的精馏结果。以平衡级理论为依据建立二甲醚精馏过程的数学模型,根据研究体系在通常情况下沸点相差较大、液相非理想性的特点,建立序贯收敛的循环嵌套迭代计算方法对模型进行求解,模拟计算结果与实验数据结果吻合较好。对二甲醚精馏塔的模拟分析结果表明：塔顶要得到含量不小于99 %(mol)二甲醚产品,维持操作压力1 MPa、在精馏塔中部进料的情况下,进料量不超过22 mol·h^-1为宜;回流比要根据进料液中二甲醚组分含量控制在一定范围内;进料液中二氧化碳含量高低对产品二甲醚纯度和收率影响显著,在进入精馏塔之前尽可能地将二氧化碳除去是必要的。     

能源化工与催化固定床一步法制二甲醚催化剂性能

采用固定床反应装置,以共沉淀法制备甲醇催化剂和一步法合成二甲醚催化剂,采用BET、XRD和SEM对催化剂进行表征。在反应压力2.5 MPa、反应温度260 ℃和空速(500~900) h^-1条件下,催化剂催化活性最好,其中,CO转化率≥90%,二甲醚收率≥60%,二甲醚选择性≥65%。     

Changes in char reactivity due to char-oxygen and char-steam reactions using Victorian brown coal in a fixed-bed reactor

This study was to examine the influence of reactions of char–O2 and char–steam on the char reactivity evolution. A newly-designed fixed-bed reactor was used to conduct gasification experiments using Victorian brown coal at 800 °C. The chars prepared from the gasification experiments were then collected and subjected to reactivity characterisation (ex-situ reactivity) using TGA (thermogravimetric analyser) in air. The results indicate that the char reactivity from TGA was generally high when the char experienced intensive gasification reactions in 0.3%O2 in the fixed-bed reactor. The addition of steam into the gasification not only enhanced the char conversion sig-nificantly but also reduced the char reactivity dramatical y. The curve shapes of the char reactivity with involve-ment of steam were very different from that with O2 gasification, implying the importance of gasifying agents to char properties.     

A modeling study of the effect of reactor configuration on the cycle length of heavy oil fixed-bed hydroprocessing

This article analyses how the configuration of an industrial fixed-bed reactor affects the cycle length of a heavy oil hydroprocessing unit. It is well-known that during the hydroprocessing of heavy feeds, catalyst aging is counterbalanced by continuously increasing reaction temperature. In addition, the exothermality of the reaction provokes a huge temperature rise along the reactor, which is why quenching is necessary. Thus, there is an increasing temperature profile that evolves with time until a maximum allowable temperature is reached and then the operation is shut down. For this reason, there is an optimum reactor configuration (i.e. number of quenches and their positions) that must be established when designing new processes in order to maximize unit run length. To evaluate this problem, a reactor performance model with time varying catalyst activity was constructed. Kinetic and catalyst aging data were obtained from bench-scale tests. The model showed to reproduce sufficiently well the experimental data set. The analysis of various reactor designs indicated that for this process the use of single-bed or double-bed reactors is unpractical in terms of cycle length. A more complex configuration consisting of multiple beds of increasing lengths is necessary to delay shut down.