用新离子交换树脂催化剂优化连续催化精馏塔中乙基叔丁基醚的合成(英文)

Liquid phase synthesis of one of the important fuel oxygenate, ethyl tert-butyl ether （ETBE）, from etha-nol and tert-butyl alcohol （TBA） has been studied in catalytic distillation column （CDC） using ion exchange resin catalyst CT-145H. A packed CDC of 1.2 m height and 50 mm diameter with indigenously developed reactive sec-tion packing was used to generate experimental data. Effect of different key variables on product purity in distillate, was investigated to find the optimum operating conditions for ETBE synthesis. The optimum conditions for 0.2 kg·s-1 of ethanol feed were found：reboiler duty of 375 W, molar feed ratio of 1︰1.3 of reactants, and reflux ratio of 7. Concentration profiles for each component along each column section at optimum conditions were also drawn. Neither output nor input multiplicity was observed at experimental conditions.     

用于生产TAEE的反应精馏和全蒸发的混合过程

In this study, a reactive distillation column in which chemical reaction and separation occur simultaneously is applied for the synthesis of tert-amyl ethyl ether （TAEE） from ethanol （EtOH） and tert-amyl alcohol （TAA）. Pervaporation, an efficient membrane separation technique, is integrated with the reactive distillation for enhancing the efficiency of TAEE production. A user-defined Fortran subroutine of a pervaporation unit is developed, allowing the design and simulation of the hybrid process of reactive distillation and pervaporation in Aspen Plus simulator. The performance of such a hybrid process is analyzed and the results indicate that the integration of the reactive distillation with the pervaporation increases the conversion of TAA and the purity of TAEE product, compared with the conventional reactive distillation.     

乳酸提纯反应精馏新工艺非平衡级稳态模拟

Purification of lactic acid by reactive distillation (RD) is a novel technology which has many excellent characteristics compared with traditional technologies. This paper presented a non-equilibrium model for lactic acid purification RD pilot column. An Improved Separation Efficiency Function (ISEF) was proposed based on de-coupling and pseudo-homogenous assumptions, which greatly improved the solving efficiency and made this model suitable for practical application. Simulation results were consistent with the experiments in different conditions, and the simulation results outperformed the simulator ASPEN PLUS in which the equilibrium stage assumptions were adopted. The static characteristics of the pilot setup were also investigated. The analysis result could help to accelerate the commercialization of the lactic acid purification RD technology.     

反应精馏合成乙酸丁酯的实验和模拟(英文)

In this paper, a reactive distillation (RD) column was applied for synthesis n-butyl acetate from n-butanol and acetic acid. The Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic model and an equilibrium stage model for separation were employed to study the RD process. The results obtained from the equilibrium stage model agreed well with the experiments. The effects of operating variables on the n-butanol conversion and n-butyl acetate purity were further investigated. The optimal column configuration for the production of n-butyl acetate was designed with 5 rectifying stages, 8 reaction stages and 13 stripping stages by the simulation study. According to the simulation results, n-butanol conversion and n-butyl acetate purity all reached greater than 96%.     

用离子液体作催化剂和夹带剂时在反应萃取精馏塔中乙酸甲酯和正丁醇酯交换反应的模拟

A new reactive and extractive distillation process with ionic liquids as entrainer and catalyst (RED-IL) was proposed to produce methanol and n-butyl acetate by transesterification reaction of methyl acetate with n-butanol. The RED-IL process was simulated via a rigorous model, and high purity products of methanol and n-butyl acetate can be obtained in such a process. The effects of reflux ratio, feed mode, holdup, feed location, entrainer ratio and catalyst concentration on RED-IL process were investigated. The conversion of methyl acetate and purities of products increase with the holdup in column, entrainer ratio and catalyst content. An optimal reflux ratio exists in RED-IL process. Comparing to the mixed-feed mode, the segregated-feed mode is more effective, in which the optimal feed locations of reactants exist.     

反置式间歇蒸馏塔的设计程序(Ⅰ)多组分理想物系

Inverted batch distillation column(stripper) is opposed to a conventional batch distillation column(rectifier). It has a storage vessel at the top and products leave the column at the bottom. The batch stripper is favourable to separate mixtures with a small amount of light components by removing the heavy components as bottom products. In this paper, we are presenting a shortcut procedure based on our earlier work for design and simulation of the inverted batch distillation column, which is equivalent to the Fenske-Underwood-Gilliland procedure for continuous distillation. Given a separation task, we propose to compute the minimum number of stages(Nbmin) and the minimum reboil ratio(Rbmin) required in a batch stripper,which are the stages and reboil ratio required in a hypothetical inverted batch distillation column operating in total reboil ratio or having an infinite number of stages,respectively. Then, it is shown that the performance of inverted batch columns with a finite number of stages and reboil ratios could be correlated in Gilliland coordinates with the minimum stages Nbmln and the minimum reboil ratio Rbmin.     

苯氯化侧反应精馏过程的系统设计与控制(英文)

The distillation column with side reactors (SRC) can overcome the temperature/pressure mismatch in the traditional reactive distillation, the column operates at temperature/pressure favorable for vapor-liquid separation, while the reactors operate at temperatures/pressures favorable for reaction kinetics. According to the smooth operation and automatic control problem of the distillation column with side reactors (SRC), the design, simulation calculation and dynamic control of the SCR process for chlorobenzene production are discussed in the paper. Firstly, the mechanism models, the integrated structure optimal design and process simulation systems are established, respectively. And then multivariable control schemes are designed, the controllability of SRC process based on the optimal steady-state integrated structure is explored. The dynamic response performances of closed-loop system against several disturbances are discussed to verify the effectiveness of control schemes for the SRC process. The simulating results show that the control structure using conventional control strategies can effectively overcome feeding disturbances in a specific range.     

Process intensification and energy saving of reactive distillation for production of ester compounds

Reactive distillation(RD) process is an innovative hybrid process combining reaction with distillation, which has recently come into sharp focus as a successful case of process intensification. Considered as the most representative case of process intensification, it has been applied for many productions, especially for production of ester compounds. However, such problems existing in the RD system for ester productions are still hard to solve,as the removal of the water which comes from the esterification, and the separation of the azeotropes of ester–alcohol(–water). Many methods have been studying on the process to solve the problems resulting in further intensification and energy saving. In this paper, azeotropic–reactive distillation or entrainer enhanced reactive distillation(ERD) process, reactive extractive distillation(RED) process, the method of co-production in RD process, pressure-swing reactive distillation(PSRD) process, reactive distillation–pervaporation coupled process(RD–PV), are introduced to solve the problems above, so the product(s) can be separated efficiently and the chemical equilibrium can be shifted. Dividing-wall column(DWC) structure and novel methods of loading catalyst are also introduced as the measures to intensify the process and save energy.     

ABSTRACTS

Simulation and Optimization of Extraction Dislillation Separation Process for Methyl Acetate - Methanol
In this paper, the simulation software ASPEN PLUS is used for the simulation calculation of methyl acetate - methanol extraction distillation process. Using NRTL thermodynamic model and RADFKAC rigorous method calculates the number of theoretical plates, the impact of feed location, solvent ratio, extraction solvent temperature, reflux ratio of extraction distillation process so as to find the optimum operating oarameters.     

Systematic exploration of the applicability of the idiomatic vapor balance rule to distillation column consolidation

For N-component distillation(N ≥ 3), consolidation between different column sections is an inevitable manipulation when synthesizing complex distillation configurations. In the consolidation, the idiomatic vapor balance(IVB) rule, in which the larger vapor flowrate in the two columns before consolidation will be chosen as the balanced vapor flowrate at the consolidation point, has been widely used. However, the applicability of the IVB rule has not been verified, which is of essential importance to the accuracy of the distillation configuration synthesis.In the present study, the applicability of the IVB rule to distillation column consolidation was systematically explored by rigorous method for the first time. First, the separation of ideal and non-ideal three-component mixtures with variable compositions was studied, and the optimized configurations before and after consolidation were determined by a rigorous method. The results indicated that for the separation of an ideal mixture, the IVB rule was applicable for the whole composition range, while for the separation of a non-ideal mixture, the IVB rule was only applicable for very limited composition range. Finally, two cases of synthesizing distillation configurations for the separation of non-ideal mixtures were studied to verify the remarkable deviations the IVB rule may cause. The results indicated that the applicability of the shortcut method using the IVB rule to the distillation configuration synthesis depended on the composition of the non-ideal mixture, and a remarkable error might result and the truly optimal configuration might be missed if the IVB rule is applied to a non-ideal mixture.     

Production of ethyltert-butyl ether fromtert-butyl alcohol and ethanol catalyzed byβ-zeolite in reactive distillation

The synthesis of ethyl tert-butyl ether (ETBE) from a liquid phase reaction between tert-butyl alcohol (TBA) and ethanol (EtOH) in reactive distillation has been studied.β-Zeolite catalysts with three compositions (Si/Al ratio=13, 36 and 55) were compared by testing the reaction in a semi-batch reactor. Although they showed almost the same performance, the one with Si/Al ratio of 55 was selected for the kinetic and reactive distillation studies because it is commercially available and present in a ready-to-use form. The kinetic parameters of the reaction determined by fitting parameters with the experimental results at temperature in the range of 343–363 K were used in an ASPEN PLUS simulator. Experimental results of the reactive distillation at a standard condition were used to validate a rigorous reactive distillation model of the ASPEN PLUS used in a simulation study. The effects of various operating parameters such as condenser temperature, feed molar flow rate, reflux ratio, heat duty and mole ratio of H₂O : EtOH on the reactive distillation performance were then investigated via simulation using the ASPEN PLUS program. The results were compared between two reactive distillation columns: one packed withβ-zeolite and the other with conventional Amberlyst-15. It was found that the effect of various operating parameters for both types of catalysts follows the same trend; however, the column packed withΒ-zeolite outperforms that with Amberlyst-15 catalyst due to the higher selectivity of the catalyst.     

Separation of ethyl tert-butyl ether-ethanol by combined pervaporation and distillation

A cellulose derivative membrane (30 wt.% cellulose acetate butyrate (CAB) combined with 70 wt.% cellulose acetate propionate (CAP)) was prepared, and its properties were evaluated by the pervaporation separation of mixtures of ethyl tert-butyl ether (ETBE) and ethanol. The experimental results showed that the selectivity and permeability of the membrane were dependent on the blend composition, the processed feed and the experimental temperature. With respect to the temperature, the fluxes obeyed the Arrhenius equation. On the basis of these results, a separation process for the production of ETBE was developed by combining pervaporation and distillation. The distillation column was designed with the software ASPEN PLUS, and the liquid-vapour equilibria were predicted by the UNIFAC method. The area of the membrane was calculated according to the production capacity. It may be concluded that the combined process for the separation of mixtures of ETBE and ethanol is simple with high recovery of the ETBE product.     

Control System Design for a Single Feed ETBE Reactive Distillation Column

Reactive distillation (RD) is advantageous for the Ethyl Tert‐Butyl Ether (ETBE) synthesis. The steady state model of an ETBE reactive distillation column created using the simulator HYSYS is analyzed to synthesize effective control structures. Since the column exhibits input multiplicity with the dual process objectives of ETBE RD (isobutene conversion and ETBE purity), inferential variables are selected. A control structure that organizes a sensitive tray temperature in the stripping section using the reboiler duty and maintains the temperature difference of reactive trays using the reflux flow, is found to be most suitable. A decentralized PI controller and constrained Model Predictive Controller (MPC) are implemented, and performances are compared for set point tracking and disturbance rejection. MPC control algorithms are implemented in MATLAB and interfaced with HYSYS. Constrained MPC (CMPC) is found to be effective for load disturbance rejection, which frequently occurs in the single feed configuration.     

A generalized framework for computing bifurcation diagrams using process simulation programs

Interest in discovering multiple steady-state solutions for reaction and separation processes grew exponentially in the 1990s. Process simulators like ASPEN PLUS, CHEMCAD, HYSYS, and PRO/II are designed to obtain at best one solution. Simulation programs can find multiple solutions only by the expenditure of much effort. Here, a bifurcation technique using arclength continuation is presented that can be incorporated as an add-in subroutine to a simulation program to automatically trace a solution path, including turning points, to obtain multiple solutions with respect to a user-selected parameter. The technique is illustrated with applications to the ASPEN PLUS process simulator. The algorithms are based on a predictor–corrector implementation where the predictors reside in add-in FORTRAN routines and the existing nonlinear equation solvers in ASPEN PLUS equipment models serve as the correctors. Furthermore, the existing physical property packages in ASPEN PLUS are also utilized. The method was tested successfully on an adiabatic CSTR example using the ASPEN RCSTR model, and homogeneous azeotropic, heterogeneous azeotropic, and reactive distillation examples using the ASPEN RADFRAC model. Two of these examples are presented here. In all four examples, the range of the selected bifurcation parameter covers a region that produces three multiple solutions.     

反应精馏技术的研究进展

针对国内外反应精馏技术及其应用的最新研究情况,较全面地归纳和分析了反应精馏工艺的研究进展,并介绍了SYNTHESISER、ASPEN PLUS等计算机模拟软件在反应精馏工艺的应用情况。     

氯乙烯生产过程的节能

用ASPEN PLUS 软件对某氯乙烯装置进行了严格的数学模拟,并进行了全过程的节能研究。通过减小VC1#塔的回流比,节省了高压蒸汽;通过提高EDC2#塔压,获得了高品位的热源,分别为EDC1#塔、脱水塔、EDC回收塔及HCl塔的再沸器供热,并为EDC2#塔的进料预热。提出的方案可节省低压蒸汽11 450.75 kg/h,中压蒸汽4738.07 kg/h,高压蒸汽6153.51 kg/h,冷却水11 746 343.9 kg/h,年节省费用为2566.0万元。     

甲缩醛反应精馏过程模拟

通过实验取得了甲醛和甲醇合成甲缩醛的反应参数;建立了其连续生产工艺的数学模型,利用ASPEN PLUS软件对甲醛和甲醇缩合生成甲缩醛进行了模拟,结果表明反应精馏连续生产甲缩醛的工艺是可行的,转化率高达99%,并得到含甲缩醛99%的产物,同时确定了进料板和反应区.     

甲醇精馏过程的模拟及优化

应用化工流程模拟软件ASPEN PLUS,对甲醇三塔精馏过程进行模拟,所得结果与生产操作数据基本吻合。对精馏塔的回流比及进料块位置进行了优化,优化后的产量和产品质量都有提高,效益增加1.3%。     

反应精馏与渗透蒸发膜分离耦合法合成乙基叔丁基醚

以乙醇和叔丁醇为原料 ,通过催化反应、精馏与渗透蒸发膜分离三单元耦合过程合成了乙基叔丁基醚(ETBE) ,建立了相关五元高度非理想体系的耦合过程数学模型 ,以改进的超松弛法对模型求解 ,并进行了模型校验和工艺操作参数的模拟寻优