异丁烯齐聚反应精馏的耦合工艺研究

针对异丁烯齐聚反应和产物提纯过程相分离的工业现状,在自行设计的实验装置上进行了异丁烯齐聚催化反应精馏耦合工艺的研究,分别考察了系统操作状态随时间的变化规律和影响反应精馏过程的主要因素。结果表明:为了得到较高的异丁烯转化率和二聚物选择性,采用全回流操作,进料位置宜设在反应段上方;回流温度过低和塔釜温度过高都对过程不利;添加适当的液相惰性组分,有利于改善填料层的分离效果。在转化率相同的情况下,该反应精馏过程的二聚物选择性大大高于固定床微分反应器和高压釜式反应器的实验结果。     

异丁烯齐聚催化精馏的实验研究

选用工业硅铝小球催化剂,在催化精馏塔内对异丁烯齐聚反应精馏的可行性及操作条件进行了考察。选取了适宜的加热釜温、进科速率、进料位置,并考察了加入惰性组分对异丁烯齐聚反应转化率及齐聚产物分布的影响。异丁烯齐聚反应精馏在工艺上是可行的.     

反应精馏数学模拟研究进展

对反应精馏，特别是非均相催化精馏过程的建模方法以及求解方法的最新研究进展和多定态问题进行了综述。     

叔丁醇催化精馏脱水制异丁烯模拟研究

以质量分数85%叔丁醇(TBA)为原料,对TBA催化精馏脱水制异丁烯工艺进行模拟计算。回归了自制的磺酸阳离子树脂催化剂的动力学数据,并使用Fortran编写了动力学子程序接口。应用Aspen Plus模型系统地讨论了反应段塔板数、操作压力、回流比、精馏段和提馏段塔板数、进料位置对TBA脱水效果的影响。在TBA进料量100 kg/h,反应段每块塔板填装45 kg催化剂,塔顶液相采出异丁烯的条件下进行模拟,结果表明:精馏段4块塔板,反应段5块塔板,提馏段4块塔板,操作压力0.35 MPa,回流比1.5,进料位置在第4块塔板时,TBA转化率达99.5%。     

反应精馏法生产醋酸丁酯动态模拟

目前反应精馏法生产醋酸丁酯工艺发展迅速,但主要集中于对催化剂的探索与研究,在实际生产中仍缺乏较好的控制方法。利用Aspen Dynamics软件对醋酸丁酯反应精馏塔的操作进行了动态模拟,提出了两点温度控制法及温度浓度控制法两种控制方案,对系统进行了进料流量±10%,乙醇及醋酸进料浓度-5%,-10%的扰动测试。研究了不同扰动对产品组成的影响并比较了两种方案分别在面对不同扰动时的控制效果。实验结果表明:进料流量及醋酸进料组成对产品组成影响较大;两点温度控制法在面对不同扰动时均展现出了比温度组成控制法更好的控制效果,该控制方法具有响应速度快,产品组成偏差小的优点。     

反应精馏过程模拟研究进展

对均相反应精馏和非均相催化精馏过程的各种模拟计算方法进行了评述，分析了各种算法的优缺点和适用范围，指明了目前研究中存在的不足和今后的发展方向。     

MTBE转产二异丁烯生产技术及工业实践

在对甲基叔丁基醚(MTBE)及二异丁烯工艺的化学反应、热力学、动力学分析的基础上,讨论了甲基叔丁基醚装置工艺转产二异丁烯工艺的技术方案以及二异丁烯装置的操作控制和工艺指标.工业运行结果表明,以催化裂化装置混合C4为原料,异丁烯的转化率达到98％,二异丁烯在叠合产品中的质量分数为91％,相对于原料的产率为14.9％.理论...     

酯交换合成乙二醇二乙酸酯反应精馏研究

采用反应精馏技术以乙二醇和乙酸仲丁酯为原料,通过酯交换合成乙二醇二乙酸酯。使用Aspen Plus对反应精馏塔进行模拟与优化,其结果为:操作压力为70 kPa,精馏段理论板数为4,反应段理论板数为15,提馏段理论板数为4,酯醇摩尔比为3∶1,回流比为2,该条件下,乙二醇转化率和塔釜乙二醇二乙酸酯质量分数达99%以上。在模拟基础上,进行反应精馏小试实验,最终确定全塔26节塔节,乙二醇和乙酸仲丁酯分别在第4节和第23节进料,全塔操作压力为70 kPa,酯醇摩尔比为3∶1。回流比为2,乙二醇转化率为98.17%,塔釜乙二醇二乙酸酯质量分数为97.54%。实验与模拟结果在误差范围内,验证了模拟计算的可靠性,为工业化提供了理论基础。     

反应精馏研究进展及应用前景

对反应精馏技术在工艺和模拟方面的研究进展进行了概述 ,简单介绍了反应精馏的关键技术并对反应精馏的应用前景进行了展望。     

异丁烯制备二异丁烯催化剂研究进展

车用乙醇汽油政策的实施,甲基叔丁基醚今后将无法作为汽油添加剂使用。甲基叔丁基醚生产装置停产,释放大量的异丁烯资源,如何更好地利用异丁烯成为炼油企业面临的重要问题。随着环保要求的提高和油品质量的升级,烷基化油的需求将不断增长。介绍异丁烯的各种用途,综述异丁烯生产二异丁烯所用的催化剂以及在提高二异丁烯选择性方面的研究进展。     

外部环流反应精馏塔的分散控制方案设计

对于具有最不利相对挥发度排序（即反应物为最轻和最重组分，生成物为中间组分）的四元反应分离物系而言，在反应精馏塔的顶部和底部之间引入外部环流能够提高系统的反应分离效率，从而大幅度地降低系统的能量消耗和固定投资成本。以理想四元可逆放热反应的分离为例，研究了外部环流反应精馏塔的分散控制方案的设计问题。结果表明外部环流的引入提高了系统的反应速率，使得外部环流反应精馏塔的闭环控制效果更好（与传统反应精馏塔相比），对干扰的处理能力更强。另外，由于外部环流反应精馏塔比常规反应精馏塔有更多的操作变量（即外部环流流量），利用该变量对出料浓度进行控制，可以进一步提高系统的闭环控制效果。     

Systematic integrated process design and control of binary element reactive distillation processes

Integrated process design and control of reactive distillation processes is considered through a computer‐aided framework. First, a set of simple design methods for reactive distillation column (RDC) that are similar in concept to nonreactive distillation design methods are extended to design‐control of RDCs. These methods are based on the element concept where the reacting system of compounds is represented as elements. When only two elements are needed to represent the reacting system of more than two compounds, a binary element system is identified. It is shown that the same design‐control principles that apply to a nonreacting binary system of compounds are also valid for a reactive binary system of elements for distillation columns. Application of this framework shows that designing the reactive distillation process at the maximum driving force results in a feasible and reliable design of the process as well as the controller structure. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3137–3154, 2016     

Novel eco-efficient reactive distillation process for dimethyl carbonate production by indirect alcoholysis of urea

Dimethyl carbonate is an eco-friendly essential chemical that can be sustainably produced from CO₂,which is available from carbon capture activities or can even be captured from the air.The rapid increase in dimethyl carbonate demand is driven by the fast growth of polycarbonates,solvent,pharmaceutical,and lithium-ion battery industries.Dimethyl carbonate can be produced from CO₂through various chemical pathways,but the most convenient route reported is the indirect alcoholysis of urea.Previous research used techniques such as heat integration and reactive distillation to reduce the energy use and costs,but the use of an excess of methanol in the trans-esterification step led to an energy intensive extractive distillation required to break the dimethyl carbonate-methanol azeotrope.This work shows that the production of dimethyl carbonate by indirect alcoholysis of urea can be improved by using an excess of propylene carbonate(instead of an excess of methanol),a neat feat that we showed it requires only 2.64 kW·h·kg^-1 dimethyl carbonate in a reaction-separation-recycle process,and a reactive distillation column that effectively replaces two conventional distillation columns and the reactor for dimethyl carbonate synthesis.Therefore,less equipment is required,the methanol-dimethyl carbonate azeotrope does not need to be recycled,and the overall savings are higher.Moreover,we propose the use of a reactive distillation column in a heat integrated process to obtain high purity dimethyl carbonate(>99.8 wt-%).The energy requirement is reduced by heat integration to just 1.25 kW·h·kg^-1 dimethyl carbonate,which is about 52%lower than the reaction-separation-recycle process.To benefit from the energy savings,the dynamics and control of the process are provided for
10%changes in the nominal rate of 32 ktpy dimethyl carbonate,and for uncertainties in reaction kinetics.     

Design of process and control scheme for cyclohexanol production from cyclohexene using reactive distillation

Cyclohexanol is a commonly used organic compound. Currently, the most promising industrial process for synthesizing cyclohexanol, by cyclohexene hydration, suffers from a low conversion rate and difficult separation. In this paper, a three-column process for catalytic distillation applicable in the hydration of cyclohexene to cyclohexanol was established to solve these. Simulation with Aspen Plus shows that the process has good advantages, the conversion of cyclohexene reached 99.3%, and the product purity was ≥99.2%. The stable operation of the distillation system requires a good control scheme. The design of the control scheme is very important. However, at present, the reactive distillation process for cyclohexene hydration is under investigation experimentally and by steady-state simulation. Therefore, three different plant-wide control schemes were established (CS1, CS2, CS3) and the position of temperature sensitive stage was selected by using sensitivity analysis method and singular value decomposition method. The Tyreus-Luyben empirical tuning method was used to tune the controller parameters. Finally, Aspen Dynamics simulation software was used to evaluate the performance of the three control schemes. By introducing ΔF ±20% and x_ENE ±5%, comparison the changes in product purity and yield of the three different control schemes. By comparison, we can see that the control scheme CS3 has the best performance.     

Inter-integration reactive distillation with vapor permeation for ethyl levulinate production: Equipment development and experimental validating

Ethyl levulinate, one of the main derivatives of levulinic acid (LA), is of significant potential as platform chemicals for bio-based materials. The esterification of LA was generally carried out in a conventional batch reactor or in a conventional reactive distillation column. However, traditional methods are hard to deal with equilibrium limited reactions and azeotropic issues. Therefore, the inter-integration reactive distillation with vapor permeation (R-VP-D) process, which integrated reaction, vapor permeation, and distillation into one single unit, is proposed in this paper and validated in the pilot-scale experiments. A comparative study is made between a pilot-scale RD column with and without VP module. Owing to the water-selective VP membrane and the ingenious design of related apparatuses, the R-VP-D process reveal a superiority in LA conversion of 21.9% maximum higher than RD without VP process and removing of product water about 53.6% from VP module, which indicates its promising industrial application in process intensification field.     

Design and optimization of reactive distillation: a review

Reactive distillation process, a representative process intensification technology, has been widely applied in the chemical industry. However, due to the strong interaction between reaction and separation, the extension of reactive distillation technology is restricted by the difficulties in process analysis and design. To overcome this problem, the design and optimization of reactive distillation have been widely studied and illustrated for plenty of reactive mixtures over the past three decades. These design and optimization methods of the reactive distillation process are classified into three categories: graphical, optimization-based, and evolutionary/heuristic methods. The primary objective of this article is to provide an up-to-date review of the existing design and optimization methods. Desired and output information, advantages and limitations of each method are stated, the modification and development for original methodologies are also reviewed. Perspectives on future research on the design and optimization of reactive distillation method are proposed for further research.     

用于生产TAEE的反应精馏和全蒸发的混合过程

In this study, a reactive distillation column in which chemical reaction and separation occur simultaneously is applied for the synthesis of tert-amyl ethyl ether （TAEE） from ethanol （EtOH） and tert-amyl alcohol （TAA）. Pervaporation, an efficient membrane separation technique, is integrated with the reactive distillation for enhancing the efficiency of TAEE production. A user-defined Fortran subroutine of a pervaporation unit is developed, allowing the design and simulation of the hybrid process of reactive distillation and pervaporation in Aspen Plus simulator. The performance of such a hybrid process is analyzed and the results indicate that the integration of the reactive distillation with the pervaporation increases the conversion of TAA and the purity of TAEE product, compared with the conventional reactive distillation.     

乙酸戊酯酯化反应精馏过程系统控制模拟及分析

反应精馏技术是将反应和精馏两个单元操作耦合在一个设备中同时进行,其非线性给反应精馏过程的平稳操作和过程控制提出了更高的要求。目前,反应精馏过程控制研究都是针对特定反应体系进行的有针对性的研究,对于乙酸戊酯反应体系的控制研究少有报道。本文利用Aspen Plus和Aspen Dynamic 软件对乙酸戊酯的反应精馏过程进行动态模拟,针对塔釜产品组成要求提出温度控制和组成控制两种不同的控制方案,对两个控制系统分别进行±10%的进料流量扰动测试和酸醇比为1:1、1.2:1的进料组成扰动测试。研究了不同扰动对产品质量的影响并比较了两种方案在不同扰动干扰下的控制效果。结果表明:进料组成扰动会对两个控制方案造成较大影响;温度控制方案的控制稳定性要好于组成控制方案。