Towards further internal heat integration in design of reactive distillation columns—Part IV: Application to a high-purity ethylene glycol reactive distillation column

In the first three papers of this series, it has been shown that strengthening internal heat integration within a reactive distillation column involving reactions with high thermal effect is really effective for the reduction of utility consumption and capital investment besides the improvement in process dynamics and operation. One important issue that remains unstudied so far is the influences of reaction selectivity upon the reinforcement of internal heat integration, since the reaction operation is often accompanied by side-reactions and the maintenance of a high selectivity is extremely necessary in process synthesis and design. A reactive distillation column synthesizing high-purity ethylene glycol through the hydration of ethylene oxide is chosen and studied in this work. Because of the unfavorable physicochemical properties of the reacting mixture separated (e.g., the fairly large volatility between the reactants and the existence of a consecutive side-reaction), the process represents a challenging problem for the reinforcement of internal heat integration. Intensive comparison is conducted between the process designs with and without the consideration of further internal heat integration between the reaction operation and the separation operation involved, and it has been found that seeking further internal heat integration still leads to a substantial reduction of energy requirement, in addition to a further abatement in capital investment. Moreover, a favorable effect is again observed upon the process dynamics and operability. These striking outcomes manifest evidently that seeking further internal heat integration should be considered in process synthesis and design irrespective of what a reaction selectivity has been assigned.     

分壁式精馏塔精制丁二烯流程模拟

丁二烯是一种重要的石油化工烯烃原料,由于其生产过程能耗高,因此节能降耗成为丁二烯生产工艺的研究热点。利用Aspen Plus模拟软件对丁二烯精制工艺的两套流程进行了模拟研究,考察了分壁式精馏塔(DWC)中内部互连物流连接位置、预分离塔气液相流量和回流比对分离效果和热负荷的影响,对比了相同分离条件下DWC分离流程和传统顺序分离流程的能耗,并根据两套分离流程中塔内液相丁二烯浓度分布情况,分析DWC的节能原因。结果表明,当主塔理论板数105,预分离塔理论板数56,进入预分离塔气相流量1020kmol/h,液相流量890kmol/h,回流比7800时,DWC分离效果最好,丁二烯质量分数可达99.7%,这为DWC精制丁二烯工艺的工业化提供了理论依据。由于DWC有效减少了精馏过程中的返混效应,提高了能量利用率,使其冷凝器可节能29.36%,再沸器可节能29.19%,存在明显的节能优势。     

反应精馏隔壁塔内合成乙酸甲酯的模拟

提出了一种应用反应精馏隔壁塔合成乙酸甲酯的新工艺流程,采用反应精馏隔壁塔替代常规反应精馏流程中的反应精馏塔及甲醇回收塔。利用Aspen Plus模拟软件,对反应精馏隔壁塔及常规流程进行了模拟,比较分析了两种流程塔内液相组成分布,并分析了塔顶回流比与气相分配比对反应精馏隔壁塔的影响。结果显示新流程可以节能11.9%,并能降低设备投资费用和操作费用。     

From simulation studies to experimental tests in a reactive dividing wall distillation column

The design and control of thermally coupled distillation sequences have been studied since many years, but the real implementation occurred until middle of the 1980s using a single shell divided by a wall named dividing wall distillation column. In this work, experimental results for the production of ethyl acetate in a reactive dividing wall distillation column are presented for first time. The experimental results are in agreement with those obtained using steady state simulations with AspenONE Aspen plus. These experimental results are important since it is possible to validate most of the previous results generated using simulations.     

生物燃料乙醇分壁塔萃取精馏新工艺的研究

针对生物燃料乙醇生产中的"蒸馏-脱水"过程,建立基于分壁式萃取精馏塔的三塔工艺和两塔工艺,对2种工艺进行模拟计算,比较其分离效果和过程能耗。结果显示,在满足产品质量的前提下,三塔工艺比两塔工艺节约66.6%的冷凝器热负荷和77.9%的再沸器热负荷。对三塔工艺的分壁式萃取精馏塔的工艺条件进行优化,优化结果为,主塔回流比1.5,溶剂比1.0,原料进料位置为第22块板,隔板底端位置在第28块板,气相分配比为8.4。在优化工艺条件下对三塔工艺进行全流程模拟,可得到质量分数99.96%生物燃料乙醇和99.49%的水,回收萃取剂乙二醇质量分数为99.97%。     

内部热耦合对理想反应蒸馏塔动态特性的影响

基于理想型强放热反应蒸馏塔研究了3项内部热耦合策略对系统动态特性及可控性的影响.其中,实现反应段与提馏段间正耦合作用的措施能够有效提高系统热力学效率,但同时减弱了提馏段的传质推动力,不利于系统动态操作.为改善系统的动态特性及可控性,需要在提馏段补充一定量的分离塔板.下移上进料位置提高了系统热力学效率,但也引入了逆耦合作用,严重影响系统动态操作,故在过程强化中应该回避.     

Towards further internal heat integration in design of reactive distillation columns—Part III: Application to a MTBE reactive distillation column

According to the principle introduced in the first two papers of this series, seeking further internal heat integration between reaction operation and separation operation during the synthesis, design, and operation of a reactive distillation column synthesizing methyl tertiary butyl ether (MTBE) from methanol and isobutylene is investigated. Although the MTBE reactive distillation column is characterized by complicated thermodynamic properties and multiple steady states, a substantial reduction of energy requirement and capital investment can still be achieved with the consideration of further internal heat integration between the reaction operation and the separation operation in the two existing steady states. Dynamics and operation of the resultant process designs are then examined in terms of static and dynamic analysis and sharp improvement in process dynamics and controllability is clearly identified through intensive comparison against the simple process design without the consideration of further internal heat integration between the reaction operation and the separation operation involved. It is demonstrated that the more synergistic relationship evolved during the reinforcement of internal heat integration should account for the dramatic improvement in process dynamics and controllability.     

基于优化的反应精馏塔简捷设计

基于G ibbs自由能最小原理达到反应和相平衡的假设,提出了一种适用于初步设计的新的设计方法。以甲基叔丁基醚和碳酸二乙酯的反应精馏过程为例,应用Aspen软件模拟,经分析发现,通过改变理论级数和回流比,可得到合理的塔内温度分布,从而使塔底产品组成得到最大程度的提高,为此提出基于优化的设计法:以产品组成最大为目标函数,以回流比、精馏段和提馏段理论板数为决策变量,采用遗传算法进行优化计算。结果表明,2个设计实例均能在保证低能耗的同时得到较高的产品纯度,说明该设计方法可以设计出较好的反应精馏塔。     

反应精馏回收糠醛生产中产生的甲酸和醋酸

二步法甲酸/醋酸催化玉米芯生产糠醛工艺的水解过程会产生少量的醋酸和甲酸,因此水解液中醋酸和甲酸的质量分数不断增加。为了使糠醛生产中甲酸和醋酸质量分数适合工艺条件,文中采用反应精馏法回收该工艺中过量的醋酸和甲酸。分别考察了回流比、酸水进料流量、甲醇与醋酸进料摩尔比、醋酸质量分数和甲酸质量分数等因素对反应精馏回收甲酸和醋酸效果的影响。通过实验得出了适宜的工艺条件:对甲酸质量分数在0.5%以上、醋酸质量分数20%以下的水解液,酸水进料流量在9.0 mL/min、甲醇醋酸进料摩尔比为3∶1和回流比为5等条件下的处理效果最佳。最佳反应条件下对于醋酸质量分数为20%的水解液,醋酸转化率为50.4%,同时甲酸质量分数降低到0.5%。实验证明此方法在满足二步法生产糠醛工艺对水解液甲酸和醋酸质量分数的要求的同时,可回收过量的甲酸和醋酸。     

隔板塔共沸精馏分离二氯甲烷-乙腈-水-硅醚体系

以二氯甲烷-乙腈-水-硅醚为分离体系,采用自制隔板塔小试装置,研究了共沸剂回流比和液相分配比等操作参数对隔板塔分离效果的影响。实验结果表明,当气相分配比R_v为0.5,共沸剂回流比为3时,液相分配比R_l在[0.12,0.2]范围内,隔板塔分离效果较好。在实验的基础上,采用Aspen Plus软件对隔板塔共沸精馏工艺进行模拟,考察了隔板塔共沸精馏工艺最佳操作区域及节能效果。模拟结果表明,特定分离要求下,隔板塔存在一个使再沸器热负荷最小的最佳操作区域,在此最佳操作区域内,R_l和R_v相互关联,呈一一对应关系;与三塔串联简单精馏工艺相比,完成相同的分离任务,隔板塔共沸精馏工艺再沸器节能32.74%,冷凝器热负荷减少33.70%,乙腈回收率由66.47%提高到96.01%,且大幅降低设备投资。     

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。     

碳五隔壁反应精馏预处理工艺模拟及多目标优化

针对碳五综合利用预处理工段能耗较高的现状,在反应精馏(RD)预处理流程基础上提出了隔壁反应精馏(RDWC)预处理流程。首先,利用化工模拟软件Aspen Plus搭建RDWC四塔等效严格模型,并对其进行自由度和单变量分析。在此基础上,以响应面Box-Behnken Design(BBD)方法作为模型拟合工具,拟合出目标变量与决策变量之间的函数关系,并对拟合结果进行方差分析(ANOVA)。最后采用基于分解的多目标进化算法(MOEA/D)对RDWC预处理流程进行多目标优化,得到一系列Pareto最优解,选出其中年总成本(TAC)最小的一组解与RD预处理流程进行对比。结果显示：与RD预处理流程相比,RDWC预处理流程可以节约TAC 12.8%,节省再沸器负荷27.8%,选择性也有所提高。     

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。     

反应精馏隔壁塔生产乙酸正丁酯的优化与控制

对反应精馏隔壁塔生产乙酸正丁酯过程进行了模拟、优化与控制的系统研究。利用Aspen Plus软件模拟乙酸甲酯与正丁醇的酯交换反应过程,以年总费用（TAC）为目标函数进行过程优化,通过稳态敏感性分析及相对增益矩阵（RGA）判据得到不同的操纵变量与控制变量匹配关系,以此为基础,在Aspen Dynamics平台建立了若干控制结构并进行分析对比。结果表明,利用两股反应物呈比例进料可较为有效地抵抗进料扰动,最后提出的无再沸器热负荷与混合物进料量比值（Q_r/F）控制的改进控制结构CS3,在降低反应精馏隔壁塔控制过程超调量方面有较大的优越性。     

Experimental operation of a reactive dividing wall column and comparison with simulation results

Reactive dividing wall columns (RDWC) are a special type of distillation column that allow for the targeted realization of chemical reactions and the separation into multiple product fractions in one shell. However, despite their huge economical and ecological potentials for certain fields of application, this innovative technology has not found its way into industrial production processes yet. The very limited availability of experimental research studies verifying the prediction capabilities of respective modeling concepts for this type of distillation column might be one decisive reason for that. Therefore, the present study puts its focus on the detailed comparison between experimental operation of RDWC and the corresponding simulation results for steady‐state. For the first time, the mentioned comparison is carried out for a chemical system with non‐negligible side reactions. It is shown that even for this highly complex system, the mathematical model is capable of predicting the column operation. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1036–1050, 2017     

Enzymatic catalyzed reactive dividing wall column: Experiments and model validation

A novel process for the integration of chemical reaction and product separation is proposed: the enzymatic catalyzed reactive dividing wall column (eRDWC). The eRDWC combines the highly integrated and complex reactive dividing wall column (RDWC) with the use of a very selective enzymatic catalyst. This apparatus enables the simultaneous production and separation of up to 4 pure product streams. Comprehensive experiments with the reference system of a hexanol and butyl acetate transesterification in a DN 65 pilot scale column show the feasibility of stable steady state operations for this process. A rigorous model for the plant design of an eRDWC wall column is developed. The reaction kinetics and vapor‐liquid‐equilibria for the reference system are measured and implemented in the model. The model is successfully validated using the acquired experimental data. The application of enzymes in continuous reactive distillation processes has the potential to increase the selectivity at milder process conditions. © 2016 American Institute of Chemical Engineers AIChE J, 63: 2198–2211, 2017     

Design and optimization of a dividing wall column for debottlenecking of the acetic acid purification process

The dividing wall column (DWC) has gained increasing application in a variety of chemical processes because of its potentiality in energy and capital cost savings in multicomponent separations. The main objective in this work is investigation of its use for removing the bottleneck phenomenon within the column when increasing the throughput of an existing distillation process, particularly, the acetic acid (AA) purification process. Optimal column sequence design, involving both conventional and DWC, is considered. The internal recycle flow distribution around the dividing wall was investigated as a primary optimizing variable. Several column arrangements were analyzed to show that the DWC requires less investment and energy costs than conventional distillation, the Petlyuk column, or the prefractionator arrangement.     

间壁塔萃取精馏制取植物油抽提溶剂的研究

针对植物油抽提溶剂萃取精馏系统存在的萃取剂结焦问题展开研究,分析了萃取剂结焦的原因,提出了间壁塔萃取精馏制取植物油抽提溶剂的思路,并应用工艺模拟软件对比了间壁塔萃取精馏工艺和常规精馏工艺。模拟结果表明,间壁塔主塔合适的理论塔板数为30,侧线塔塔板数为10,剂油比为1.1(体积比),侧线采出位置为第27块板。与常规两塔精馏相比,再沸器热负荷降低约10%,冷凝器热负荷降低15%,且设备投资也有所减少。     

Simulated annealing-based optimal design of energy efficient ternary extractive dividing wall distillation process for separating benzene-isopropanol-water mixtures

This article investigates the performances of different extractive distillation processes intensified with dividing-wall column for separating benzene-isopropanol-water ternary mixtures. All the processes with ethylene glycol as solvent are optimized with the minimal total annual cost (TAC) as target. In order to get the global optimal solution intelligently, an improved simulated annealing algorithm is adopted, which is programmed in MATLAB and linked to Aspen Plus. The results show that the extractive dividing wall column-solvent (EDWC-S) process consisting of an extractive dividing wall column and a solvent recovery column is the best scheme. It can reduce the TAC by 28.65％and CO2 emissions by 32.84％com-pared to the conventional triple-column extractive distillation process.     

渗透汽化-隔壁塔精馏耦合初步分离费托合成水的过程研究

费托合成水中含有醇、酮、酸等多种高附加值含氧有机物可提取出来作为高附加值产品,但由于费托合成水处量大,共沸体系复杂,通常需要首先对其进行初步分离。设计了直接两塔精馏、渗透汽化-两塔精馏、直接隔壁塔精馏、渗透汽化-隔壁塔精馏四种可供选择的初步分离工艺。根据渗透汽化实验数据在Aspen Plus中构建渗透汽化过程模型并进行模拟,结合灵敏度分析得到精馏过程的最佳工艺参数和模拟结果,并对四种工艺的能耗和有效能损失进行对比。结果表明,渗透汽化-隔壁塔精馏工艺具有明显的节能优势,其能耗较直接两塔精馏可降低15.85%,有效能损失降低45.74%。经渗透汽化膜预浓缩后,溶液的浓度可进入隔壁塔的适宜分离浓度区间,以充分发挥隔壁塔优势。由于渗透汽化所需能量可由余热等低品位热源提供,在余热充足的煤化工领域中可显著降低有效能损失。对于该过程而言,当渗透汽化膜价格低于438元/m²时,渗透汽化-隔壁塔精馏耦合工艺将会表现出较高的经济性。