Optimization of coproduction of ethyl acetate and n-butyl acetate by reactive distillation☆

Based on a previous investigation, a simulation model was used for optimization of coproduction of ethyl acetate and n-butyl acetate by reactive distil ation. An experimental setup was established to verify the simulated results. The effects of various operating variables, such as ethanol feed location, acetic acid feed location, feed stage of reaction mixture of acetic acid and n-butanol, reflux ratio of ethyl acetate reactive distillation column, and distil-late to feed ratio of n-butyl acetate column, on the ethanol/n-butanol conversions, ethyl acetate/n-butyl acetate purity, and energy consumption were investigated. The optimal results in the simulation study are as follows:ethanol feed location, 15th stage;acetic acid feed location, eighth stage;feed location of reaction mixture of acetic acid and n-butanol, eighth stage;reflux ratio of ethyl acetate reactive distillation column, 2.0;and distillate to feed ratio of n-butyl acetate, 0.6.     

Batch Extractive Distillation in a Column with a Middle Vessel

Batch extractive distillation was studied in a column with a middle vessel. The process was simulated by a constant holdup model and solved by two point implicit method. Acetone and methanol mixture was separated in such a setup using water as solvent. The simulation agrees well with experimental results. The experimental and simulation results show that the solvent at the bottom and the product at the top of the column can be withdrawn simultaneously for a long period of time. It needs more time for the solvent to reach high purity than that required for the more volatile component to reach high purity, so that the time to withdraw solvent from the bottom is delayed.     

带有中间储罐的塔用于间歇萃取精馏

Batch extractive distillation was studied in a column with a middle vessel. The process was simulated by a constant holdup model and solved by two point implicit method. Acetone and methanol mixture was separated in such a setup using water as solvent. The simulation agrees well with experimental results. The experimental and simulation results show that the solvent at the bottom and the product at the top of the column can be withdrawn simultaneously for a long period of time. It needs more time for the solvent to reach high purity than that required for the more volatile component to reach high purity, so that the time to withdraw solvent from the bottom is delayed.     

酯化反应蒸馏过程的模型化及模拟研究

In this paper,a generalized model of the reactive distillation processes was developed via rate-based approach. The homotopy-continuation method was employed to solve the complicated nonlinear model equations efficiently. The simulation on the reactive distillation processes was carried out with the profiles of stage temperature,composition and flow rate for both vapor and liquid phases obtained. Based on careful analysis of the simulation results, the pitfalls in experimental design were detected. Finally, a software package for the simulation of reactive distillation processes was developed.     

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.     

反应精馏过程中的多稳态分析

Reactive distillation processes for synthesis of ethylene glycol （EG） and ethyl tert-butyl ether （ETBE） were modeled with the simulation package ASPEN PLUS. The input multiplicity and output multiplicity were discussed with the method of sensitivity analysis for both cases. In EG production process, steady state multiplicities were studied in terms of effective liquid holdup volume and boil-up ratio. In ETBE synthesis process, the user kinetic subroutine was supplied into ASPEN PLUS firstly, and then the composition, temperature and reaction-rate profiles within the reactive distillation column were presented in detail. A set of stable solution branches based on distinct initial guesses for a range of boil-up ratio were found in EG synthesis. Input multiplicities were observed for a range of reboiler duty at several values of reflux ratio for ETBE synthesis process. These results can be used to avoid excessive energy consumption and achieve optimum design of reactive distillation column.     

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.     

催化精馏塔中乙酸甲酯水解的研究

A nonequilibrium stage model was used to simulate countercurrent multicomponent catalytic distillation processes for methyl acetate hydrolysis. Computations of stage eiliciencies or height equivalent to a theoretical plate (HETP) were entirely avoided by this model. The consistency of simulated results and experimental data in conversions and concentration of each component along a column indicates that the model predicts the actual process well. The influences of operating parameters on hydrolytic conversions, such as feed molar ratios, feed locations, feed and reflux rates, heights of reactive and stripping sections, were analyzed adequately by simulating calcuiations. A good operating mode was then obtained, which is helpful to the development of a new process.     

Study on Hydrolysis of Methyl Acetate in a Catalytic Distillation Column

A nonequilibrium stage model was used to simulate countercurrent multicomponent catalytic distillation processes for methyl acetate hydrolysis. Computations of stage efficiencies or height equivalent to a theoretical plate (HETP) were entirely avoided by this model. The consistency of simulated results and experimental data in conversions and concentration of each component along a column indicates that the model predicts the actual process well. The influences of operating parameters on hydrolytic conversions, such as feed molar ratios, feed locations, feed and reflux rates, heights of reactive and stripping sections, were analyzed adequately by simulating calculations. A good operating mode was then obtained, which is helpful to the development of a new process.     

Multiple Analysis in a Reactive Distillation Column for the Synthesis of tert‐Amyl Methyl Ether

tert‐Amyl methyl ether (TAME) is produced via reactive distillation. A simulation is set up and controlled on Aspen HYSYS v 8.0 for generating the highest purity of TAME. This simulation includes a plug‐flow reactor and a reactive distillation column. Emphasis was put on finding the optimal operating conditions of the reactive distillation column in order to get the maximum purity of TAME. The operational parameters were reflux ratio, number of reactive stages in the distillation column, and condenser pressure. The results indicated the optimal reflux ratio and condenser pressure which could be adapted to industrial scale.     

反应精馏制备乙酸乙酯的工艺分析

为揭示反应精馏法制备乙酸乙酯的特性及得到较高纯度的产品,并为反应精馏工艺过程的深入研究及工业化提供理论依据,应用Aspen Plus软件模拟分析反应精馏过程。结果表明：给定回流比的情况下,理论塔板数、精馏段塔板数及进料位置、进料比、催化剂用量等参数均对产品纯度及分离效果产生影响。     

用于分离三氯氢硅合成过程中主副产品的隔壁塔模拟

以三氯氢硅合成过程中得到的主副产品混合物二氯二氢硅-三氯氢硅-四氯化硅为分离物系,提出采用隔壁塔代替常规精馏序列分离的新工艺.利用Aspen Plus软件对隔壁塔进行模拟,考察回流比、隔板位置、进料位置、侧线采出位置、液相分配比以及气相分配比对塔顶、侧线以及塔釜产品摩尔分数的影响,得到隔壁塔的最佳工艺参数,并通过模拟比较隔壁塔与常规精馏序列分离此混合物的能耗情况.模拟结果表明:当回流比为6、隔板位置为主塔的第8块板和第24块板、进料位置为预分馏塔的第10块板、侧线采出位置为主塔的第15块板、液相分配比为0.21、气相分配比为0.5时,隔壁塔的分离效果最佳,主产品三氯氢硅的摩尔分数为99.999%;相比于常规精馏序列,隔壁塔再沸器节能29.09%以上,冷凝器节能29.48%以上.     

乙酰丙酸乙酯的反应精馏模型及隔壁塔节能优化设计

乙酰丙酸乙酯是一种潜在的生物质基平台化合物,在工业上具有很高的应用价值。乙酰丙酸乙酯传统的生产方法主要为间歇反应法,效率较低,产物分离困难且工艺流程较长。因此,本文提出了反应精馏工艺生产乙酰丙酸乙酯,在以中试实验结果为依据的基础上,使用Aspen Plus模拟软件建立了工艺流程,并考察了回流比、进料位置、进料摩尔比以及理论塔板数等关键参数,得到了常规单塔反应精馏工艺生产乙酰丙酸乙酯的最优配置。而后,为了得到纯度大于99.9%的乙酰丙酸乙酯,本文进一步提出了反应精馏双塔精制流程以及反应精馏隔壁塔流程,并通过对两种流程所得到的产品纯度以及能耗的对比,验证了反应精馏隔壁塔工艺生产乙酰丙酸乙酯的有效性以及在节能方面较大的优势。     

乳酸提纯新工艺动态建模仿真和控制系统设计

基于非平衡级和拟均相假设,建立了乳酸提纯反应精馏新工艺实验装置的动态机理模型.通过改进的数值计算方法提高了模型的求解效率,设计并实现了包含物性估算系统的模型仿真平台,以促进新工艺的工业化应用.利用仿真平台对新工艺装置进行了动态特性分析,在此基础上设计了两种单端质量控制方案:直接物料平衡和间接物料平衡方案.在不同类型和幅度的过程扰动下,分析比较了两种控制方案的调节性能.结果表明直接物料平衡方案控制品质优于间接物料平衡方案,可在不同扰动情况下满足过程的产品质量和转化率的联合控制要求.非平衡级动态机理模型能够反映反应精馏过程的动态特性,分析发现反应精馏过程有着独特的过程特性,基于机理模型的仿真平台是分析反应精馏特性的有效工具.     

变压精馏分离甲醇-丙酮的工艺模拟及优化

采用Aspen Plus软件,以塔釜能耗为目标,以甲醇、丙酮纯度为约束函数,对双效变压精馏分离甲醇-丙酮工艺过程进行模拟。分析了操作压力、理论板数、回流比、进料位置和进料温度等参数对精馏过程的影响。确定了最优工艺参数：减压塔操作压力40 kPa,理论板数37,回流比2.4,进料塔板数26,进料温度25 ℃;常压塔理论板数30,回流比4.2,进料塔板数23。减压塔所得甲醇质量分数为99.0%,常压塔所得丙酮质量分数为99.7%。对比变压精馏和萃取精馏过程,变压精馏更容易得到高纯度丙酮产品,节能约13.4%。模拟结果对工业设计和设备改造具有一定指导意义。     

二异丁烯反应精馏生产过程控制策略设计

二异丁烯是一种重要的化工中间体,近年来研究者提出了以催化裂化C₄为原料、采用反应精馏技术同时生产高纯二异丁烯和汽油添加剂的新工艺。由于反应精馏过程中非线性程度高,稳定控制困难,使得采用反应精馏技术生产二异丁烯过程的控制策略研究较少。采用Aspen dynamic软件进行动态模拟,针对反应精馏生产二异丁烯过程开发了温度控制方案、组分温度联合控制方案和组分温度串级控制方案。对3个控制系统进行（±10）%的进料流量扰动和（±5）%组成扰动测试并进行对比。结果表明：组分温度串级控制方案在添加扰动的情况下依然保证了二异丁烯质量分数99%,三异丁烯质量分数小于10%以及异丁烯转化率大于99%的要求,并且最终稳定时间约5 h,具有更好的抗干扰性能。研究结果能够为二异丁烯产品的生产工艺工业化应用提供设计依据。     

联合精馏分离四氢呋喃-水共沸物的实验及优化模拟

由于四氢呋喃与水会生成沸点64 ℃的最低共沸物,采用三塔联合精馏的方法对其进行分离。根据文献资料选择乙二醇作为萃取精馏过程的萃取剂,并在脱水塔中对萃取精馏塔产物进行脱水。选择Aspen Plus软件对工艺流程进行模拟。选择Wilson模型及RadFrac模块对单塔工艺参数进行模拟及优化,确定了各塔进料板与回流比等最适宜参数。经实验考察的项目结果均与模拟结论一致。脱水塔产物四氢呋喃含水量可低至170 μg/g。根据优化后的参数在Aspen Plus中进行全工艺流程的闭合与模拟,终产物四氢呋喃的质量分数可达0.9995,收率为0.9988。其质量分数优于常见双塔萃取精馏流程。     

侧反应器反应精馏方法生产醋酸甲酯的模拟

采用强酸性阳离子交换树脂催化醋酸与甲醇反应精馏生成醋酸甲酯,可避免硫酸作为催化剂的不足。但该非均相催化反应受平衡限制,且达到平衡时间较长,采用传统反应精馏塔难以提供足够反应空间。文中设计侧反应器与精馏塔耦合新工艺,采用Aspen Plus软件模拟研究了侧反应器数量、位置,原料进料位置,回流比,醇酸比等对反应精馏过程的影响。结果表明,当装置具有7个侧反应器,反应器间隔4块板,在优化的操作条件下,醋酸甲酯质量分数可达99.1%。