Investigation on catalytic distillation for ethyl acetate production with different catalytic packing structures

The catalytic packing is the core component of the catalytic distillation, and how the catalyst exists in the packing has significant influence on the process. To investigate the effect of catalyst packings on the catalytic distillation process, the classical ethyl acetate reactive distillation system was utilized, and a supported catalytic packing(SCP) was prepared in comparison with the conventional tea-bag catalytic packing(TBP). Laboratory scale experiments showed that the ethyl acetate conv...     

催化反应精馏技术连续制备乙酸乙酯

在直径３０ｍｍ的催化反应精馏塔中进行合成乙酸乙酯的研究，考察了酸醇比、进料流量、回流比、进料位置等因素对过程的影响，在本实验最优条件下，塔顶可获得酯含量大于９４％的产品。     

Determination of catalytic packing characteristics for reactive distillation

Catalytic distillation still expands its field of applications. New structured catalytic column internals have been developed in recent years and new studies have been reported. A modern structured catalytic packing MULTIPAK^® is a subject of the investigations presented in this paper.

Important parameters of MULTIPAK^® have been examined experimentally in a 250 mm ID laboratory column: pressure drop for dry, prewetted and irrigated packings, flooding line and mass transfer coefficients for the gas and liquid phases.

The correlations obtained have been incorporated into a software tool for the simulation of catalytic distillation processes and simulations have been performed assuming methyl acetate synthesis as a model process. The calculations have been verified using the experiments performed for the same synthesis in a 50 mm ID catalytic distillation column operating continuously and thus reflecting industrial applications. It is concluded that the model represents the real process with satisfactory accuracy, although some deviations can be observed, especially within the reactive zone.     

反应蒸馏塔中固体催化剂的装填结构

反应蒸馏是集化学反应与蒸馏分离两个过程于一体的新化工单元过程 ,反应蒸馏塔中固体催化剂的装填结构既要满足汽液两相对流流动的需要 ,又要使反应介质与催化剂能够良好接触。简述了对反应蒸馏塔中固体催化剂装填结构的基本要求 ,分类介绍了国内外开发的有特色与应用前景的催化剂装填结构的特点、局限性与应用范围 ,指出了开发新型催化剂装填结构的必要性     

Experiments and dynamic modeling of a reactive distillation column for the production of ethyl acetate by considering the heterogeneous catalyst pilot complexities

Great effort has been applied to model and simulate the dynamic behavior of the reactive distillation as a successful process intensification example. However, very little experimental work has been carried out in transient conditions. The work presents a series of experiments for the production of ethyl acetate from esterification of acetic acid and ethanol in a reactive distillation pilot column. The steady-state approach performed experiments with both excess of alcohol and stoichiometric feed configuration. Predicted and measured results show good agreement and reveal a strong dependency of the structured packing catalyst activity on the pilot geometry and its operating conditions. The transient process behavior of the heterogeneously catalyzed system was deeply investigated and continuous and dynamic data were collected for an equilibrium model validation, after different perturbations on parameters. The experimental validation is shown to be essential to provide realistic hydrodynamic parameters, to understand the sensitive parameters such as heat losses and to adapt values for the catalyst holdup as a function of the system.     

Design and control of reactive distillation for ethyl and isopropyl acetates production with azeotropic feeds

Reactive distillations for the production of ethyl acetate (EtAc) and isopropyl acetate (IPAc) are classified as the type-II process where the first column consists of a reactive zone and a rectifying section followed by a stripper [Tang et al., 2005. Design of reactive distillations for acetic acid esterification with different alcohols. A.I.Ch.E. Journal 51, 1683-1699]. Instead of using pure alcohols and acetic acid as reactants, this paper studies the effects of reactant purity on the design and control of reactive distillation. This offers significant economical incentives (by reducing raw materials costs), because ethanol forms an azeotrope with water at 90 mol% and isopropanol/water has an azeotrope at 68%. The purities of the acid is set to 95% for acetic acid (industrial grade), 87% for ethanol, and 65% for isopropanol. The results show that the total annual costs (TAC) increase by a factor of 5% for EtAc and 8% for IPAc production using reactive distillation. Next, the operability of the reactive distillations with azeotrope feeds is explored. Three disturbances, feed flow, acid feed purity, and alcohol feed composition, are introduced to assess control performance using dual-temperature control and one-temperature-one-composition control. Simulation results indicate good control performance can be achieved for reactive distillation with azeotropic feeds.     

催化精馏合成乙酸乙酯的工业试验

以固体酸为催化剂,在中试催化精馏塔中进行了乙酸与乙醇反应制备乙酸乙酯的工业试验,试验塔的精馏段塔径为600 mm,内装陶瓷规整填料,反应精馏段塔径为1 000mm,内装7层立体催化精馏塔板.采用连续操作,考察了不同的回流比、釜酸质量分数、进料流量对反应和分离过程的影响,同时测定了塔板上气液相质量分数的分布.通过试验得到...     

Time optimal start-up strategies for reactive distillation columns

In this contribution, a rigorous process model to simulate the start-up of a cold and empty reactive distillation (RD) column is developed and experimentally validated with a transesterification process. Strategies for time optimal start-up of an RD column are presented. The mostly used strategy for conventional distillation of total reflux for RD is only recommendable with limitations. New, alternative strategies, like the recycling of the off-spec bottom and top product or the initial charging with product, to minimize the necessary start-up time are presented. Suitable strategies can save up to 82% of the needed time for the column start-up.     

响应面法优化一水硫酸氢钠流化催化精馏生产乙酸乙酯工艺条件

以新型的一水硫酸氢钠为催化剂,采用粉末状催化剂混合乙酸一起进料的加入方式,即流化催化精馏工艺,并利用响应面法优化乙酸乙酯催化精馏过程条件.首先,通过单因素灵敏度分析法对乙酸进料量、酸醇进料摩尔比、回流比、催化剂用量、釜底加热功率5个因素进行实验考察,确定了乙酸进料量、酸醇摩尔进料比、回流比3个关键因素的优化值及取值范围.根据单因素实验结果与精馏塔设备要求,塔釜加热功率和催化剂用量分别设定为68 W和2.0%(质量分数)乙酸,采用中心组合设计原则对乙酸进料量、酸醇进料摩尔比和回流比3个关键因素进行实验设计.以乙醇转化率为响应值,基于响应实验结果,利用响应面法对实验结果进行了方程回归,得到3个关键因素与响应值的二次关联模型.通过方差分析和平行实验,证明该模型准确可用.优化后的乙酸乙酯流态化催化精馏工艺条件为乙酸进料量3.2 mol·h^-1,酸醇进料摩尔比为3.1,回流比为3.3,在此优化条件下进行实验,乙醇转化率为88.67%,比基于单因素灵敏度分析法得到的优化工艺条件下乙醇转化率高1.0%.     

高通量催化精馏填料的停留时间分布研究

介绍了高通量催化精馏规整填料(HCCP),是一种模块化催化精馏规整填料。停留时间分布(RTD)是催化精馏填料的重要性能参数,同时影响着填料的分离效果和塔内化学反应的进行,着重研究了高通量催化精馏填料的RTD问题。实验在内径为400 mm的冷模塔内进行,常温常压下以空气-水为介质,氯化钠水溶液作为示踪剂,通过脉冲注入的扰动-响应技术获得RTD曲线。采用轴向扩散模型分析RTD曲线,可得出模型参数彼克列数PeL及填料的持液量、轴向扩散因子Dax。结果表明,该填料内的返混现象较轻微。分析计算的结果即可用于填料性能的评价,为填料的进一步改进提供理论基础;也可用于催化精馏塔的设计和优化。     

Esterification of acetic acid with ethanol: Reaction kinetics and operation in a packed bed reactive distillation column

The reaction kinetics of the esterification of acetic acid with ethanol, catalyzed both homogeneously by the acetic acid, and heterogeneously by Amberlyst 15, have been investigated. The reactions were carried out at several temperatures between 303.15 and 353.15 K and at various starting reactant compositions. Homogeneous and heterogeneous reactions have been described using the models proposed by Pöpken et al. [T. Pöpken, L. Götze, J. Gmehling, Reaction kinetics and chemical equilibrium of homogenously and heterogeneously catalyzed acetic acid esterification with methanol and methyl acetate hydrolysis, Ind. Eng. Chem. Res. 39 (2000) 2601–2611]. These models use activities instead of mole fractions. Activity coefficients have been calculated using ASOG [K. Kojima, K. Tochigi, Prediction of Vapor–liquid Equilibria by the ASOG Method, Elsevier, Tokyo, 1979] and UNIFAC (Aa. Fredenslund, J. Gmehling, P. Rasmussen, Vapor–liquid Equilibria Using UNIFAC. A Group Contribution Method, Elsevier, Amsterdam, 1977] methods.

A packed bed reactive distillation column filled with Amberlyst 15 has been employed to obtain ethyl acetate. The influence of feed composition and reflux ratio have been analyzed.     

Comparative control study of ideal and methyl acetate reactive distillation

The control of an ideal reactive distillation column is compared with that of a similar, but somewhat different, real chemical system, the production of methyl acetate. Similarities and differences are observed. Three control structures are evaluated for both systems. A control structure with one internal composition controller and one temperature controller provides effective control of both systems for both high and moderate conversion designs. A two-temperature control structure is effective when the system is overdesigned in terms of number of reactive trays, holdup and/or catalyst load. Direct control of product purity for the high-conversion/high-purity design is difficult because of system nonlinearity and interaction. Tray temperature control avoids the nonlinearity problem.     

Hybrid reactive distillation systems for n-butyl acetate production from dilute acetic acid

The recovery of dilute acetic acid, regarding as a waste stream in many chemical and petrochemical processes, becomes an important issue due to economic and environmental awareness. In this work, a simulation study on the direct utilization of dilute acetic acid to produce n-butyl acetate via esterification with butanol in a reactive distillation is presented by using Aspen Plus. The performance of a hybrid reactive distillation with a pretreatment unit, i.e., a conventional distillation or a pervaporation, is investigated. For a single reactive distillation system, it is found that higher overall energy of the system is required when the concentration of acetic acid is lowered. By considering the enrichment of acetic acid in the reactive distillation column feed from 35 to 65 wt.%, a hybrid pervaporation–reactive distillation requires lower energy than both the conventional distillation–reactive distillation system and the single reactive distillation.     

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%。     

催化蒸馏技术的应用进展

综述了催化蒸馏技术的应用进展情况，介绍了催化蒸馏技术的特点及装填方式，并从醚化、酯化，烷基化、缩合等几个方面简要叙述了近年来催化蒸馏技术的应用与发展。     

Reactive distillation for methyl acetate production

We describe a hierarchy of methods, models, and calculation techniques that support the design of reactive distillation columns. The models require increasingly sophisticated data needs as the hierarchy is implemented. The approach is illustrated for the production of methyl acetate because of its commercial importance, and because of the availability of adequate published data for comparison. In the limit of reaction and phase equilibrium, we show (1) the existence of both a minimum and a maximum reflux, (2) there is a narrow range of reflux ratios that will produce high conversions and high purity methyl acetate, and (3) the existence of multiple steady states throughout the entire range of feasible reflux ratios. For finite rates of reaction, we find (4) that the desired product compositions are feasible over a wide range of reaction rates, up to and including reaction equilibrium, and (5) that multiple steady states do not occur over the range of realistic reflux ratios, but they are found at high reflux ratios outside the range of normal operation. Our calculations are in good agreement with experimental results reported by Bessling et al., [Chemical Engineering Technology 21 (1998) 393].     

催化精馏塔中催化剂填装技术的研究述评

按气、液、固三相间不同的接触方式,将催化精馏技术中的瓶颈问题之一的催化剂填装技术分为两大类作了系统的介绍,即气、液、固三相混合接触式和液、固与气、液分别接触式。阐明了各类填装方式的优缺点及其可能的应用领域,指出了催化剂填装技术未来多元化的发展趋势。     

一种适用于催化反应精馏的新型填料

为适应催化反应精馏填料需要高持液量及高效率的应用特点,开发了一种新型多层丝网填料PACTU-800,并通过设计中试装置对其进行了流体力学性能测试及传质性能测试。以空气-水为测试物系的冷模实验表明,F因子为0—0.55时,喷淋密度增大则压降增大,F>0.55时,压降变化没有明显规律;并经拟合得到泛点气速公式,与贝恩-霍根公式计算值相对误差为9.1%;以正庚烷-甲基环己烷为测试物系的热模实验表明:该填料理论板数较高,且F因子对其影响不大;F>2.3时,压降开始急剧增大。结果说明:PACTU-800操作弹性大,持液量大,适合高气液负荷下操作;其通量大,压降变化小,停留时间长,效率较高且较恒定。     

高通量催化精馏规整填料的流体力学性能

介绍了一种可应用于催化精馏工艺的高通量催化精馏规整填料(HCCP),并对其流体力学性能进行了研究与讨论。以空气-水物系为介质在内径为400 mm的冷模精馏塔内进行实验,测量了该填料的干湿塔压降、持液量等流体力学性能。高通量催化精馏规整填料在结构方面进行了改进,使催化剂装填量可控,实验结果表明:填料在降低塔内压降、增加通量方面具有明显优势。最后对实验数据进行回归,获得经验关联式;实验测量值与公式计算结果吻合较好,这表明,数据回归获得的关联式可用于预测一定操作条件下填料的流体力学性能,用于工业实践及设备放大。     

Reactive dividing-wall column for the co-production of ethyl acetate and n-butyl acetate

Reactive dividing-wall column (RDWC) technology plays a critical role in the energy saving and high efficiency of chemical process. In this article, the process of co-producing ethyl acetate (EA) and n-butyl acetate (BA) with RDWC was studied. BA was not only the product, but also acted as entrainer to remove the water generated by the two esterification reactions. Experiments and simulations of the co-production process were carried out. It was found that the experimental results were in good agreement with the simulation results. Two kinds of RDWC structures (RDWC-FC and RDWC-RS) were proposed, and the co-production process operating parameters of the two types of RDWC were optimized by Aspen Plus respectively. The optimal operating parameters of the RDWC-FC were determined as follows: 0.6 of the reflux ratio of aqueous phase (RR), 0.66 of the vapor split (R_V) and 0.51 of the liquid split (R_L). And the optimal operating parameters of the RDWC-RS were shown as follows: RR was 0.295 and R_V was 0.61. Furthermore, the energy saving analysis of the co-production process was based on the annual output of 10000 tons of EA, compared with the traditional reaction distillation (RD) to prepare EA and BA, the reboiler duty of the RDWC-FC column could save 20.4%, TAC saving 23.6%; RDWC-RS reboiler energy consumption could save 17.0%, TAC 22.2%.