A fundamental principle and systematic procedures for process intensification in reactive distillation columns

A fundamental principle is developed for process intensification through internal mass and energy integration in reactive distillation columns and three systematic procedures are devised for process synthesis and design. For reactive distillation columns involving reactions with highly thermal effect, process intensification can be achieved with an exclusive consideration of internal energy integration between the reaction operation and separation operation involved. However, in the case of a highly endothermic reaction with an extremely low reaction rate and/or small chemical equilibrium constant, internal mass integration has also to be considered between the reactive section and stripping section. For reactive distillation columns involving reactions with negligibly or no thermal effect, process intensification can be performed with an exclusive consideration of internal mass integration. For reactive distillation columns involving reactions with moderately thermal effect, process intensification must be conducted with a careful trade-off between internal mass and energy integration. Five hypothetical and two real reactive distillation systems are employed to evaluate the principle and procedures proposed. It is demonstrated that intensifying internal mass and energy integration is really effective for process intensification. Not only can the thermodynamic efficiency be improved substantially, but also the capital investment can be further reduced.     

从裂解碳五分离聚合级异戊二烯的一段萃取工艺

裂解碳五两段萃取精馏工艺存在流程长等问题。本文研究了采用反应精馏的一段萃取工艺,确定了二聚过程中的主要反应及其Arrhenius方程。Aspen Plus软件模拟计算结果表明,反应精馏过程与90 ℃下停留3.5 h的热二聚过程相比,异戊二烯聚合损失率减少40.68％,生成的共二聚体降低35.41%,异戊二烯和间戊二烯的自二聚体降低72.29%,环戊二烯二聚的选择性提高。先反应精馏脱除重组分再脱除炔烃可使进入萃取单元的炔烃降低,满足异戊二烯产品中炔烃质量分数小于50×10^－6,在萃取和解析过程后通过精馏使环戊二烯质量分数小于1×10^－6,得到聚合级异戊二烯产品。本研究提出的一段萃取分离流程短,投资和操作费用低,异戊二烯损失少,再生溶剂要求低。     

多效反应精馏过程生产氯化苄的能量集成

以甲苯氯化生产氯化苄为研究对象,对带侧反应器的反应精馏与精制塔串联工艺(CSRRT)进行研究及能量分析,建立了分段反应精馏与精制塔串联生产氯化苄的新工艺。利用精制塔塔顶蒸汽潜热加热第一段反应精馏塔的塔釜,建立了多效反应精馏(MERD);进一步利用侧反应器的甲苯氯化反应热加热第一段反应精馏塔的塔板物料,建立了多效透热反应精馏(MEDRD)。在相同生产要求下,对3种工艺的能耗进行比较。结果表明,MERD和MEDRD过程实现了能量的优化利用,与CSRRT过程相比,塔釜总再沸器热负荷分别降低16.8%和33.7%。     

差压热耦合反应精馏塔的模拟研究

为了降低反应精馏塔能耗,将差压热耦合技术与反应精馏技术结合,提出了一种新型的差压热耦合反应精馏的流程,并将其应用于乙酸正丁酯的合成中。应用Aspen Plus模拟软件对新工艺流程以及常规反应精馏流程进行了模拟,通过考察压缩比、进料位置、进料醇酸摩尔比等因素对差压热耦合反应精馏合成乙酸正丁酯工艺的影响,得到最优条件。同时,将该工艺与常规反应精馏工艺进行比较,结果显示,新工艺能够大幅度降低能耗,与常规反应精馏装置相比可节能40%左右。     

Reactive distillation for synthesis of glycerol carbonate via glycerolysis of urea

This study developed a new process for synthesis of glycerol carbonate via glycerolysis of urea by reactive distillation. Missing thermodynamic parameters were estimated by various group contribution methods. The results of Gibbs free energy showed that Gani's method provided the lowest deviation. Equilibrium and kinetic model parameters of the glycerolysis obtained from batch experiments were employed for the simulation of the reactive distillation using Aspen Plus^® software. High conversion of glycerol was achieved by reducing reactant loss in distillate through an increase in the number of stripping and reaction stages and a decrease in the number of rectifying stages. Moreover, glycerol and urea in distillate were recycled to the reactive section by increasing reflux ratio to a reasonable value. The suitable design and operating parameters were achieved at 3 stripping stages, 3 reactive stages, no rectifying stage, reboiler heat duty of 15 kW and reflux ratio of 2. This offered 93.6% conversion of glycerol, and 90.0% yield of glycerol carbonate with 100% purity in the final product. Compared with conventional in vacuo process, reactive distillation promoted glycerol conversion by 29.1% and saved in energy consumption by 37.1%.     

基于MVR热泵精馏的混合醇热集成分离工艺

机械蒸汽再压缩(MVR)热泵技术是把低品位的蒸汽通过压缩转变为高品位的蒸汽,循环用于热源的供热以减少能耗。而热集成技术则是合理的匹配冷热物流的换热,以提高物流的有效能利用率。鉴于精馏过程的高能耗和低热力学效率,本文以四元混合醇的分离为研究对象,把基于MVR热泵技术的热集成精馏工艺应用于该体系的分离,提出并研究了该体系带热集成与不带热集成各种MVR精馏工艺;以能耗和年总费用(TAC)为评价指标,采用Aspen Plus 软件对各分离工艺进行模拟与优化,确定各分离工艺的操作参数与设备参数。研究结果表明,与常规顺序分离工艺相比,MVR精馏工艺节约能耗50%以上,节约年总费用约61%。带热集成MVR精馏工艺与不带热集成MVR精馏工艺相比,在能耗和年总费用方面,优势相当,但前者热力学效率提高了约9.5%。     

考虑反应热的乙氧基化反应精馏塔能量内部集成与优化

以正丁醇和环氧乙烷为原料合成乙二醇正丁醚(EGMBE)为例,利用数学模型和模拟分析方法,研究了包含大量反应热效应的乙氧基化反应精馏(ERD)塔中反应热的利用及系统能量优化问题。研究表明,当采用常规的、将反应段直接叠加于提馏段之上的塔设计时,反应热并没有贡献于分离操作或减小再沸器的热负荷,而只是被冷凝器中的冷却介质移走。分析了反应热的可利用途径,提出一种将反应段和提馏段分割、从反应段移出反应热供提馏段加热的内部热集成乙氧基化反应精馏结构--IHIERD。模拟结果表明,IHIERD 将使再沸器的温度从462.5 K降低到420.0 K,冷凝器负荷降低11%,外部能量输入降低14%,节能效果显著。     

考虑内部热集成的乙二醇反应精馏系统设计与优化

针对环氧乙烷水合制乙二醇反应精馏过程反应热的利用和系统能量更大集成问题,提出一种将反应段和提馏段分割、从反应段移出热量供提馏段加热的内部热集成反应精馏塔（R-HIDiC）的设计。利用Aspen Plus模拟软件,分析了内部热集成的可能性,优化了内部热交换量及其分布,给出了一种不需要再沸器的能量最大集成方案。研究表明,与传统的反应精馏塔相比,通过对内部热集成进行优化,乙二醇反应精馏塔可取消再沸器,系统需要的能量只由环氧乙烷水合反应热和外部压缩机提供,其操作费用将降低约47.2%,总费用将降低约39.1%,体现了其技术和经济优越性。     

Design and control of transesterification reactive distillation with thermal coupling

In the study, the design and control strategies of a reactive distillation process with partially thermal coupling for the production of methanol and n-butyl acetate by transesterification reaction of methyl acetate and n-butanol are investigated. Since methanol and methyl acetate formed an azeotrope, the products of a reactive distillation column include n-butyl acetate and the mixture of methanol and methyl acetate, which must be separated by an additional column. Partially thermal coupling can be used to eliminate the condenser of the second column. Not only energy reduction but also better operability and controllability can be obtained for the thermally coupled reactive distillation process. Proper selection and pairing of controlled and manipulated variables chosen for three control objectives were determined by using steady-state analysis. A simple control scheme with three temperature control loops is sufficient to maintain product purities and stoichiometric balance between the reactant feeds.     

Analysis of the Start‐up Process for Reactive Distillation

The start‐up procedure of a distillation column is a time‐ and energy‐consuming process. Further, the products during the start‐up time are off specification and cannot easily be recycled as for conventional distillation but must costly be disposed of. In this paper, a process model to simulate the barely analyzed start‐up procedure for a reactive distillation from the cold and empty state to steady state is presented. The start‐up of a reactive distillation column has been modeled with gPROMS. The advantage of a cold and empty start‐up is the consistent and reproducible initialization. Commercial simulators do not give the opportunity to start form a cold and empty state, e.g., a column modeled with Hysys must be shut down from a steady state to be able to model the complete start‐up process, which is not possible, for example, for a batch process. Also, a change in the describing equations and discontinuities in process variables is difficult to handle within the simulation. In this paper, the start‐up strategies normally used for distillation without reaction are examined and applied to reactive distillation. It will be shown that the widely used strategy of total reflux is not suitable for reactive distillation. A simplified model to derive a time constant which describes the influence of parameter setting changes, like heating power, reflux ratio and feed composition on the start‐up time, is introduced and validated.     

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。     

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.     

异氰酸正丁酯工艺优化

通过正交实验,研究低温、高温光气化反应的影响因素,通过稳定性实验确定反应的最佳条件。对光气化工艺和精馏方案优化,使得产品纯度达到99.5%以上。     

酶反应精馏耦合技术研究进展

酶反应精馏是将酶催化反应与精馏过程进行耦合,可有效打破反应化学平衡的限制,提高酶反应转化率和选择性,是一种新型化工过程强化技术。本文分别从酶催化剂及其催化反应机制、酶催化剂装填方式、酶催化反应与精馏耦合型式、酶反应精馏耦合技术的应用案例等方面综述了酶反应精馏耦合技术的研究进展,分析表明：目前酶反应精馏耦合技术的开发尚不成熟,且与化学催化剂催化的反应精馏过程不同,酶反应精馏工艺过程开发还需考虑酶催化反应温度、底物浓度等因素对酶催化活性影响。在后续研究中,可分别从研究体系、酶的固定化技术、酶催化剂装填方式、酶反应精馏理论研究、酶反应精馏耦合工艺开发等方面开展强化研究。     

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。     

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.     

多目标遗传算法在反应精馏优化中的应用

反应精馏是反应与精馏的复合过程,因其具有选择性强、投资少、能耗低等优点而受到研究者们的广泛关注,并且在工业生产中得到广泛的应用。利用人工神经网络（ANN）模型来模拟反应精馏过程。在建立ANN模型时,首先用ASPEN软件模拟计算出多组数据以弥补实验数据不多的不足,并在此基础上用多目标遗传算法（GA）进行操作条件的优化。优化结果表明,多目标遗传算法结合ANN对反应精馏进行优化是可行的,而且具有很高的精度。以合成乙酸乙酯的反应精馏过程为例说明上述模拟和优化方法。     

A techno‐economic comparison of various process options for the production of 1,1‐diethoxy butane

BACKGROUND: Acetals can be considered important bio‐based diesel additives. The production of most of these compounds, from an alcohol and an aldehyde, suffers from low conversion due to thermodynamic limitations. These limitations can be overcome through the removal of the by‐product water. Previous studies showed that the in situ dehydration options of reactive distillation and pervaporation membrane reactor integration offer little advantage or at least not at reasonable unit dimensions. The aim of the present work is the development of a membrane based process and comparison with other alternatives (based on experimental data). RESULTS: Three different membrane processes were developed. The one in which the reaction mixture is recycled over a first dehydration membrane module and subsequently through a simple distillation column, was found to give the highest overall conversion (100%) at low recycle rates and reasonable membrane area. This process was techno‐economically compared with other possible alternatives: (1) a process based on a conventional tubular reactor and several distillation columns; and (2) a process based on reactive distillation. CONCLUSIONS: Efficient water removal by membranes avoids possible azeotropes in downstream distillation units making them much simpler, reducing considerably the unit sizes and the energy demand (40% lower). Copyright © 2012 Society of Chemical Industry     

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%。     

反应精馏合成醋酸正丁酯的模拟和优化

利用Aspen Plus模拟了合成醋酸正丁酯的反应精馏过程,并分析各工艺参数对产品纯度和再沸器热负荷影响。通过优化得出最佳工艺参数为:理论塔板数为16;精馏段、反应段和提馏段塔板数分别为5、7和4;醋酸和正丁醇的进料塔板数分别为5和7;酸醇进料比为1:1;回流比为1。在此条件下产品醋酸正丁酯的纯度达99.55%;乙酸的转化率达99.71%,再沸器的能耗较低。