Selection of internals for reactive distillation column—case-based reasoning approach

The design of reactive distillation (RD) systems is considerably more complex than design of the individual, conventional reactors and distillation columns. One of the main issues in the design of RD column is a definition of type and specification of geometric features of the internal devices. In this work, there is described a design supporting tool for pre-selection of packing type for RD column. Case-based reasoning has been applied as a basic method for decision support. The computer system for pre-design of reactive column internals has been built as an implementation of developed methodology. The acid catalysed reaction of 2-methylpropylacetate synthesis was used to test the system. The CBR system can significantly reduce the development time for design of reactive distillation column and suggests a good start points for further design activity.     

An integrated reactive distillation process for biodiesel production

An integrated reactive distillation process for biodiesel production is proposed. The reactive separation process consists of two coupled reactive distillation columns (RDCs) considering the kinetically controlled reactions of esterification of the fatty acids (FFA) and the transesterification of glycerides with methanol, respectively. The conceptual design of the reactive distillation columns was performed through the construction of reactive residue curve maps in terms of elements. The design of the esterification reactive distillation column consisted of one reactive zone loaded with Amberlyst 15 catalyst and for the transesterification reactive column two reactive zones loaded with MgO were used. Intensive simulation of the integrated reactive process considering the complex kinetic expressions and the PC-SAFT EOS was performed using the computational environment of Aspen Plus. The final integrated RD process was able to handle more than 1% wt of fatty acid contents in the vegetable oil. However, results showed that the amount of fatty acids in the vegetable oil feed plays a key role on the performance (energy cost, catalyst load, methanol flow rate) of the integrated esterification–transesterification reactive distillation process.     

Evaluation of configuration alternatives for multi-product polyester synthesis by reactive distillation

Reactive distillation (RD) combines reaction and separation in an integrated setup that is able to reduce the energy use, improve productivity and selectivity, and increase the efficiency. In previous work, we showed the design, modeling and experimental validation of a RD process for synthesis of unsaturated polyesters. The results of our previous work clearly demonstrated that reactive distillation is indeed a very promising alternative for the polyesters synthesis.This study explores the best suitable internals and various feed configurations of a reactive distillation process for unsaturated polyester synthesis. Multi-product simulations were performed to find the operational parameters for producing different grades of polyester in the same equipment. The product transition time during product changeover is determined for various configurations and product grades. The selection criteria for the best configuration are the minimum requirements of volume and energy to produce 100 ktpy polyesters.The results of the rigorous simulations carried out in Aspen Custom Modeler shows that the best configuration has the reactive stripping section as a packed or trayed bubble column, and the reactive rectifying section as a packed column. With respect to the feed configuration, the feeding of monoesters to the RD column significantly intensifies the polyester process as compared to an anhydrous reactant fed to the column. Moreover, the product transition time in this configuration is also significantly reduced as compared to the other configurations.     

“背包式”反应精馏集成过程研究进展

“背包式”反应精馏是一种反应器与精馏塔既相互独立又相互耦合的离散集成技术。由于反应与分离处于不同空间位置,能够突破传统反应精馏对工况的限制,拓宽应用范围,且便于工程放大。本文综述了国内外“背包式”反应精馏从基础到应用的研究概况。从转化率、选择性、塔内温度、组成分布等方面,分析了“背包式”反应精馏与传统反应精馏的等效性,指出“背包式”反应精馏的优势在于工况的灵活选择利于实现反应与分离能力的最佳匹配。介绍了“背包式”反应精馏在稳态模拟与优化、动态模拟及控制等方面的研究进展,并从不同工况反应与精馏集成技术的应用、便捷的催化剂装填与反应器设计应用两个角度归纳了该技术的应用进展。最后,从优化设计理论、先进控制方法、能量综合利用以及强化酶催化反应等方面对“背包式”反应精馏进一步的研究与应用进行展望。     

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%.     

Reactive distillation with KATAPAK

KATAPAK-SP and -S are structured catalytic packings for reactive distillation or gas–liquid reactors available from laboratory to industrial scale. Applying the KATAPAK-SP concept, the ratio of catalyst volume fraction to separation efficiency can be varied over a wide range, therefore the design of a reactive distillation column can be further optimized to fit each reaction system best.

Pressure drop, separation efficiency, dynamic liquid hold-up and residence time distribution have been investigated for KATAPAK-SP in a diameter of 250 mm. Results for different gas and liquid loads are presented. The findings are compared with results for the structured laboratory scale packing KATAPAK-S and the industrial scale packing KATAPAK-S 170.Y.

The dehydration of tert-butyl alcohol was selected as a sample reaction to illustrate the influence of different catalytic structures on the performance of the reactive distillation column. The setups are compared with respect to dimensions and economics.     

Steady-state design of thermally coupled reactive distillation process for the synthesis of diphenyl carbonate

Diphenyl carbonate, a precursor in the production of polycarbonate, is traditionally synthesized by the transesterification reaction of dimethyl carbonate and phenol. In this study, phenyl acetate was used instead of phenol to react with dimethyl carbonate and yield diphenyl carbonate, due to its higher reaction conversion and the absence of side reactions and azeotropes. A plant-wide process with a reactive distillation (RD) column and a separation column was optimized by minimizing the total annual cost. The performance of the thermal coupling between these two columns was also investigated. RD with thermal coupling was demonstrated to provide better energy efficiency than conventional RD. The remixing phenomenon associated with thermodynamic inefficiency in conventional distillation sequences could be greatly reduced by implementing thermal coupling between columns. Reactant concentrations that were closer to stoichiometric balance in the reaction zone were given for the thermally coupled RD column.     

离子液体催化反应精馏合成乙酸乙酯工艺模拟

为研究离子液体在反应精馏中的作用,采用离子液体1-丁基-3-甲基咪唑硫酸氢盐（[BMIM]HSO₄）作为催化剂,对乙酸和乙醇合成乙酸乙酯的反应精馏流程进行了计算模拟。在确定了参数的酯化反应动力学的基础上,用Aspen Plus软件建立了反应精馏流程,研究了催化剂用量、精馏段理论板数、反应段理论板数、乙醇进料位置、进料摩尔比、持液量及回流比等参数对反应精馏过程的影响。研究结果表明,塔顶乙酸乙酯的质量分数随催化剂用量、精馏段理论板数、反应段理论板数和持液量增大而增大,工艺流程存在最佳回流比以及最佳进料酸醇摩尔比。得到的优化条件如下：离子液体与乙酸摩尔比为1：2.5,进料酸醇摩尔比为4：1,理论塔板数为21块,乙酸和催化剂在第7块理论塔板进料,乙醇在第19块理论塔板进料,塔板持液量0.1L,回流比为4,塔顶乙酸乙酯的质量分数可以达到98.73%。     

甲苯氯化连串反应的RD和SRC过程分析与比较

侧反应器与精馏塔集成(SRC)是塔内耦合反应精馏(RD)的新拓展,同时适用于反应与精馏处于相同工况和不同工况两种情形。以甲苯氯化连串反应为研究对象,分别建立了RD和SRC过程的数学模型,在相同总塔板数和塔釜上升蒸气量条件下,计算了相同工况下(反应与精馏压力均为101.3 kPa),RD与SRC过程的气/液流率、温度、组成分布,发现两者性能具有一致性。在此基础上,以产品氯化苄的生产成本为目标函数、标志系统产能的氯气进料流率和分配比例为优化变量,对甲苯氯化连串反应的相同工况RD与SRC过程、不同工况SRC过程(反应压力为101.3 kPa、精馏压力为10 kPa)进行优化,结果表明,相同压力工况下,优化得到的RD与SRC的装置产能与产品质量一致;但在不同压力工况下,SRC的产能明显提升、产品质量也有所提高,反映出不同工况SRC明显的优势。     

Design of entrainer-enhanced reactive distillation for the synthesis of butyl cellosolve acetate

An innovative entrainer-enhanced reactive distillation (RD) process is presented, which aims to the production of high-purity butyl cellosolve acetate from butyl cellosolve and acetic acid via an esterification reaction. This entrainer-enhanced RD process can procure technical advantages from both heterogeneous azeotropic distillation and RD. Solvents such as cyclohexane, ethylene dichloride, toluene, and octane are considered as candidates in this esterification RD process. The function of entrainers is to simplify the separation between water and acetic acid. For this purpose, the proper entrainer to use is thus evaluated based on its mutual solubility with water in two liquid phases. Simulation results reveal that total annual cost can be substantially reduced when cyclohexane, toluene, and octane are used as entrainers in the RD column. The octane-enhanced RD provides the most economical design in this studied case.     

反应精馏隔壁塔的模拟研究

以乙酸甲酯酯转换体系为例提出了一种反应精馏隔壁塔的设计和优化方法,应用该方法可将常规双塔反应精馏序列转化为反应精馏隔壁塔并保证各操作参数的最优值.首先通过在反应精馏塔与甲醇塔之间交换汽液相物流来实现反应精馏隔壁塔的简捷设计;然后利用Aspen Plus模拟软件,对常规反应精馏序列和反应精馏隔壁塔进行了模拟分析;最终以2...     

基于(火用)损失分析的反应精馏塔板上反应体积的优化设计

针对以选择性为主要目标的反应精馏塔设计中反应段塔板上反应体积或催化剂的分配问题,提出一种基于热力学(火用)损失分析和流程模拟计算相结合的优化设计策略。为了深层次分析反应精馏塔板上(火用)损失的原因并为制定调优方向提供理论依据,将塔板上的总(火用)损失区分为物理(火用)损失和化学(火用)损失两部分并分别进行计算。在此基础上,将建立的(火用)损失计算方法和流程模拟技术相结合,将反应段塔板上的反应体积的分配和对应的(火用)损失分布相关联,以再沸器热负荷最小为目标,通过建立的方法对反应体积的分配逐步调优,可实现反应精馏塔的优化设计。方法的有效性通过环氧乙烷水合制乙二醇反应精馏体系进行了验证。结果表明,与普遍采用的塔板上等反应体积分配的设计方法相比,通过本文建立的优化分配方法,可使系统的能耗降低18%以上,同时结果优于文献值。     

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.     

The discrete residence time distribution of a distillation colum operated with microprocessor controlled periodic cycling

The fluid flow in a distillation column was studied by measurements of the discrete residence time distribution. The column, 100 mm in diameter was fitted with 5 sieve plates of 14.8% free area with a 6.1 mm hole diameter on a 635 mm plate spacing. The periodic control was obtained using a JOLT microprocessor system. An analysis of the discrete residence time distribution yielded the parameters in the (2S) model that describes the fluid flow. Modifications to the column internals are required to alter these parameters, if the maximum separation improvements are to be obtained.     

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.     

Transesterification of palm oil with methanol in a reactive distillation column

The higher feedstock and processing costs for biodiesel production can be reduced by applying reactive distillation (RD) in transesterification process. The effects of reboiler temperature, amount of KOH catalyst, methanol to oil molar ratio and residence time on the methyl ester purity were determined by using a simple laboratory-scale RD packed column. The results indicated that from the empty column, the system reached the steady state in 8 h. Too high reboiler temperature and the amount of catalyst introduce more soap from saponification in the process. The optimal operating condition is at a reboiler temperature 90 °C, a methanol to oil molar ratio of 4.5:1.0, KOH of 1 wt.% respect to oil and 5 min of residence time in the column. This condition requires the fresh feed methanol 25% lower than in the conventional process and produces 92.27% methyl ester purity. Therefore this RD column can be applied in small or medium biodiesel enterprise.     

A novel process for the synthesis of unsaturated polyester

Traditionally polyester production is done in a batch reactor equipped with a separation column for a batch distillation. A promising alternative for the intensification of this process is reactive distillation. The aim of this paper is to study the conceptual design of reactive distillation and to find out whether reactive distillation is potentially interesting compared to batch reactor process. Therefore, a reactive distillation model is developed and sensitivity analysis is used to obtain the design and operational parameters for the reactive distillation process. These parameters are the required number of stages, required residence time, feed ratio, reflux ratio and temperature of feed stream. The model predicts the polymer attribute, isomerization and saturation composition of the polymer in the range of industrial polyester production data. The simulation study shows that the total production time of polyester in a continuous reactive distillation system is reduced from 12 h to 1.5-2 h compared to the industrial batch reactor process. The equilibrium conversion is also raised by 7% compared to the conventional process. The model demonstrated that reactive distillation has the potential to intensify the process by factor of 6-8 in comparison to the batch reactor.     

A review on process intensification in internally heat-integrated distillation columns

Internally heat-integrated distillation column (HIDiC) is the most radical approach of a heat pump design, making efficient use of internal heat-integration: the rectifying section of a distillation column operating at a higher pressure becomes the heat source, while the stripping part of the column acts as a heat sink. Remarkably, a HIDIC can bring up to 70% energy savings compared to conventional distillation columns. This is highly appealing regarding the fact that distillation is one of the most energy intensive operations in the chemical process industry accounting for over 40% of the energy usage. This review paper describes the latest developments concerning this promising but difficult to implement process intensification technology, covering all the major aspects related to the working principle, thermodynamic analysis, potential energy savings, various design configurations and construction options (ranging from inter-coupled or concentric columns, shell and tube and plate–fin heat exchanger columns to SuperHIDiC), design optimization, process control and operation issues, as well as pilot-scale and potential industrial applications. Further advancement, i.e., development of HIDiC technology for multi-component mixture separations is an extremely challenging research topic, especially when HIDiC becomes associated with other technologies such as dividing-wall column (DWC) or reactive distillation (RD).     

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.     

Simulation studies on reactive distillation for synthesis oftert-amyl ethyl ether

In this work, a reactive distillation column in which chemical reactions and separations occur simultaneously is applied for the synthesis of tert-amyl ethyl ether (TAEE) from ethanol (EtOH) and tert-amyl alcohol (TAA). A rate-based kinetic model for liquid-phase etherification and an equilibrium stage model for separation are employed to study the reactive distillation. The calculation is carried out using the commercial software package, Aspen Plus. Simulations are performed to examine the effects of design variables, i.e., a number of rectifying, reaction and stripping stages on the performance of reactive distillation column. It has been found that an optimal column configuration for the TAEE production under the study is designed with no rectifying, 4 reaction and 8 stripping stages. With such an appropriate specification of the reactive distillation column, the effects of various operating variables on the TAA conversion and TAEE selectivity are further investigated and the results have shown that the reflux ratio and operating pressure are the most important factors to the operation of the reactive distillation.