“背包式”反应精馏水解乙酸甲酯的工艺

采用“背包式”反应精馏深度水解乙酸甲酯,考察了工艺条件对水解率和酸水比的影响,并与传统的单塔催化精馏工艺进行了对比。结果表明：提高水酯比可以显著提高乙酸甲酯的水解率;回流进料比的增加有利于提高水解率但会增加能耗,较佳回流比为3.0左右;乙酸甲酯水解率随空速的增加而降低的速度较慢,可以适当提高空速以增加处理能力;增加固定床体积有利于酯的预水解,但是不一定有利于酯的总转化率。采用“背包式”催化精馏工艺可以实现乙酸甲酯的深度水解,且优于传统的单塔催化精馏工艺。     

醋酸甲酯和甲醇热集成变压精馏分离工艺模拟与优化

基于对醋酸甲酯与甲醇二元共沸特性的分析,提出热集成变压精馏分离醋酸甲酯和甲醇的工艺. 利用Aspen Plus软件对该分离过程进行模拟,以NRTL活度系数方程为物性计算方法,其二元相互作用参数由气液相平衡数据回归,分析了加压塔和常压塔的理论板数、进料位置及回流比对分离效果的影响,并进行了能耗比较. 结果表明,该工艺能很好地分离醋酸甲酯和甲醇,较佳的工艺条件为：加压塔操作压力909 kPa,理论板数32,第21块板进料,回流比4.2,塔釜醋酸甲酯纯度99.8%;常压塔操作压力101 kPa,理论板数30,第20块板进料,回流比4.6,塔釜甲醇纯度99.0%. 与常规变压精馏相比,热集成变压精馏可节能达45.8%;与以水为萃取剂的萃取精馏分离工艺相比,热集成变压精馏分离工艺更适合醋酸甲酯与甲醇体系的分离.     

催化精馏塔通用数学模型及其求解方法

建立了醋酸甲酯水解反应精馏实验流程,并探讨了反应精馏的工艺特点和可行性。建立了催化精馏塔通用数学模型,并给出了求解方法。该模型对于化学反应和精馏分离同时进行及交替进行两种形式的催化精馏塔均能适用,且可用于催化精馏塔的动态分析。     

反应与精馏耦合水解醋酸甲酯(英文)

A process composed of a fixed-bed and a distillation column with a side withdraw, mainly methanol, is developed to hydrolyze methyl acetate (MA) as a typical byproduct in polyvinyl alcohol (PVA) and pure terephthalic acid (PTA) factory. The process is simulated by employing the equilibrium stage model RadFrac and plug flow model Rplug in Aspen Plus. Experiments are also carried out in a lab-scale to evaluate the process. The results show that at the molar ratio of water to methyl acetate about 4.0-5.0 in the feed stream and the volume ratio of distillate to feed MA above a critical value, the side product contains more than 80% (by mass) (MeOH) and less than 2% (by mass) MA, while the bottom contains more than 46% (by mass) acetic acid (HAc) and less than 0.5% (by mass) methanol with almost complete conversion of MA. Compared with the old catalytic distillation process we proposed before, this process can cut down 47.6% energy consumption and a distillation column.     

催化精馏合成醋酸甲酯的研究

以强酸型阳离子交换树脂为催化剂,在直径为40 mm的填料塔内对催化精馏合成醋酸甲酯进行了研究。实验塔的三段填料高度分别为810、270、450 mm,填料段之间放置直径为60 mm、高度为175 mm的2节催化剂床层,并在塔釜放置催化剂。采用连续操作,着重考察了醇酸进料摩尔比、醋酸进料位置、甲醇进料位置和回流比对催化精馏合成醋酸甲酯的影响。在选定实验条件下,塔顶醋酸甲酯的质量分数可达到98.43%,醋酸的转化率达到99.13%。     

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%。     

Hydrolysis of methyl acetate via catalytic distillation: Simulation and design of new technological process

An equilibrium stage model was developed for the simulation of the catalytic distillation process of methyl acetate (MeOAc) hydrolysis. In the model, the influences of the reactive kinetics, residence-time, liquid holdup, and separation efficiency of the catalytic packing were considered. The model predicted the conversion of MeOAc and the mass ratio of acetic acid to water in the hydrolysis mixture. The predictions were in good agreement with experimental data. A novel process was designed based on the results of theoretic analysis and the simulation research. This new process had a higher conversion of MeOAc compared with the results in previous research and was found to be energy efficient. Optimal effect parameters and design factors of new technology on energy consumption and conversion were also determined and summarized as the following: the position of side draw is 18th to 19th stages, the catalytic distillation (CD) column pressure is at 350 kPa, the volume ratio of reflux to feed is 6–8, mole ratio of feed water to MeOAc is 3.5–4.5, and the mass ratio of side withdrawal to feed is 0.32–0.34.     

混合离子液体催化反应精馏合成乙酸正己酯

离子液体催化反应精馏是提高酯交换平衡反应转化率的一种绿色有效方法。以离子液体1-丙基磺酸-3-甲基咪唑三氟甲烷磺酸盐（［PSO₃HMIm］［OTf］）和离子液体1-辛基-2,3-二甲基咪唑双（三氟甲烷磺酰）亚胺盐（［OMMIm］［Tf₂N］）的混合物作为乙酸甲酯和正己醇进行酯交换反应合成乙酸正己酯的催化剂,测定了酯交换反应动力学。探讨了混合比、反应温度、反应物初始摩尔比、催化剂浓度对反应速率和乙酸甲酯转化率的影响,考察了催化剂的回收性能。利用实验数据回归得出混合离子液体催化酯交换反应动力学方程。在反应动力学的基础上进行了乙酸甲酯和正己醇的酯交换反应精馏流程模拟,分析了理论板数、回流比、进料位置及反应段塔板数、催化剂用量、持液量等参数对反应精馏塔的影响。在优化的操作条件下,获得纯度为0.9993的乙酸正己酯产品。     

醋酸甲酯水解动力学及催化剂包效率因子的测定

测定了用SK—1A离子交换树脂催化的醋酸甲酯水解的宏观动力学,设计了能反映流体在催化剂包中实际流动情况的循环式间歇恒温反应流程,测定了醋酸甲酯水解催化精馏中试塔所用催化剂捆扎包的效率因子,并得到效率因子与液体流量和进料水酯摩尔比的关联式．     

乙酸甲酯催化精馏水解工艺研究

采用阳离子交换树脂为催化剂 ,研究了乙酸甲酯催化精馏水解工艺。反应区充填离子交换树脂催化剂捆束包 ,提馏段充填Mo Ti金属板波纹丝网填料。在小试、中试 (塔径为 2 0 0mm)和工业化 (塔径为1 0 0 0mm)实验中 ,系统地研究了水酯摩尔比、回流进料比和空速对酯分解率和分解液中酸水质量比的影响 ,获得不改变现有聚乙烯醇生产中乙酸甲酯分解回收工艺流程的最佳分解率为 50 %— 60 % ,由此导致比原工艺节能约 30 %和原有设备利用率成倍提高     

Investigations on the Synthesis of Methyl Acetate in a Heterogeneous Reactive Distillation Process

The production of methyl acetate in a reactive distillation process – prior art for 15 years – is often used as an example to study the basic phenomena of reactive distillation. The present paper deals with a theoretical and experimental analysis of methyl acetate synthesis in a reactive distillation column. A design method based on the interpretation of reactive distillation line diagrams is used to identify the main process parameters and to provide a foundation for experimental investigation. The significant influence of the reflux ratio on the conversion in the column is shown by mini plant experiments using supported ion exchanger in the form of Raschig rings as a heterogeneous catalyst. These experiments demonstrate the catalytic quality of this packing material. To simulate the reactive distillation column with a simple stage-to-stage method, the separation efficiency of the catalytic rings is investigated. Comparison of experimental and simulation results reveals that a simple model based on the assumption of simultaneous chemical and phase equilibrium describes the experimental data quite well over a wide range of reflux ratios. Furthermore, simulation results show that the conversion depends less on the number of reactive stages than on the use of two feed stages.     

乙酸甲酯与甲醇共沸物催化精馏水解工艺

以乙酸甲酯与甲醇共沸物为原料,采用阳离子交换树脂为催化剂,研究了乙酸甲酯催化精馏水解工艺。在实验中以捆扎包作为催化剂的装填方式,系统地研究了催化精馏段和提馏段的高度、进料位置、进料中含甲醇、水酯物质的量比、回流进料比和空速等对酯分解率的影响,获得了最佳的工艺条件。分析了传统的水解分离工艺,提出了可行的新工艺。在最佳工艺条件下,新工艺系统的能耗比传统的固定床工艺降低39.99%。     

侧反应器反应精馏过程合成醋酸甲酯的模拟

采用Aspen Plus模拟了合成醋酸甲酯的侧反应器反应精馏过程,研究进料位置、回流比、酸醇比、侧反应器数量等对反应精馏过程的影响,得到优化的工艺条件。该研究结果与传统反应精馏装置对比表明,2种精馏装置性能接近,侧反应器反应精馏技术具有工艺流程环保、塔结构简单等优点。模拟研究结果可为合成醋酸甲酯侧反应器精馏塔提供基础理论和设计数据,为在类似反应精馏体系应用该装置提供技术支持。     

用人工神经网络模型模拟催化精馏塔

尝试用人工神经网络模型模拟醋酸甲酯水解催化精馏塔的操作过程,并寻求最佳工艺条件。以进料水酯比、回流进料比和醋酸甲酯的体积流率与催化剂体积比作为输入层的三个节点,醋酸甲酯的转化率和塔釜中的酸水比为输出层的两个节点,采用ＢＰ算法结合模拟退火算法,利用小试实验数据训练网络并检验训练结果;内插或外推一系列假想的工艺条件,让网络预测操作结果,最后确定最佳操作目标,通过网络模型寻找一组最佳工艺条件。结果表明：以充足可靠的实验数据为基础,神经网络模型能精确预测实验结果;利用人工神经网络模型对工艺条件进行优化,可取得令人满意的结果。     

反应精馏法制备醋酸甲酯的研究

以醋酸、甲醇为原料,以浓硫酸为催化剂,对反应精馏法制备醋酸甲酯的过程进行了实验研究。着重考察了回流比、进料中醋酸摩尔分率、塔板数及混酸进料位置等因素对反应转化率和塔顶产品中醋酸甲酯含量的影响,并得出最佳的工艺条件。     

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.     

离子液体反应萃取精馏合成乙酸乙酯

采用离子液体1-磺酸丁基-3-甲基咪唑硫酸氢盐([HSO₃bmim][HSO₄])和1-丁基-3-甲基咪唑双三氟甲磺酰亚胺盐([BMIM][Tf₂N])分别作为催化剂和萃取剂,对乙酸甲酯与乙醇合成乙酸乙酯和甲醇的反应萃取精馏(RED)过程进行了模拟计算。在反应动力学和汽液相平衡分析基础上建立了反应萃取精馏流程,研究了理论板数、回流比、持液量、进料位置、溶剂比(萃取剂进料与原料进料摩尔流量的比值)、催化剂进料流量等参数对反应萃取精馏过程的影响。在优化的操作条件下,甲醇纯度为0.9922,乙酸乙酯纯度为0.9905,乙酸甲酯转化率为0.9922。     

乙酸甲酯水解工艺设计

在分析目前国内乙酸甲酯水解工艺的基础上,提出采用福州大学催化精馏水解技术代替传统的固定床水解反应器进行水解的新工艺。着重从工程设计方面对其工艺过程进行探讨。     

醋酸甲酯催化精馏水解过程模拟

利用醋酸甲酯水解体系热力学、水解反应动力学以及催化填料的基础数据,采用化工流程模拟与分析的方法,系统地对醋酸甲酯催化精馏水解过程进行了模拟研究。通过与实验数据进行对比,验证了该模拟方法的正确性。通过对工艺条件的灵敏度分析,获得该过程较优的工艺参数。在对现有工艺流程模拟的基础上,结合工业实际操作,提出两种工艺改进方案。     

浆料催化精馏制备醋酸甲酯

在内径为76 mm的常压玻璃塔内,精馏段填充θ环,反应段为筛板,以甲醇与醋酸酯化反应合成醋酸甲酯为模型反应,采用平均粒径为4μm的强酸性大孔型离子交换树脂为催化剂,对浆料催化精馏工艺制备醋酸甲酯进行了试验研究。考察了催化剂浓度、进料比、进料总流量和回流比等因素对该过程的影响。在选定的试验条件下,醋酸甲酯收率可达86.4%,塔顶酯的纯度可达92.95%(质量分数)。