苯氯化侧反应精馏过程的模拟优化与系统实现方法

针对侧反应精馏集成过程反应能力与分离能力最佳匹配条件设计问题,提出基于独立反应量的非线性解耦优化设计方法.研究以综合生产成本最小且反应能力最大为优化目标的多约束混合整型非线性规划问题,并给出了集成优化与模拟系统程序实现方法.将该方法应用到苯氯化侧反应精馏过程集成优化设计中,实现了反应能力与分离能力的最佳匹配,证明所提出的优化设计方法是有效的.

反应精馏过程图解设计法研究进展

反应精馏是伴有化学反应的精馏过程 ,具有设备紧凑、能量集成等优点。文章总结介绍了 80年代中期以来国内外有关反应精馏过程设计的研究进展 ,重点分析了图解设计法理论研究的现状和局限性 ,指出了反应精馏过程图解设计法的发展方向。

反应精馏过程模拟——ASPEN PLUS应用范例

本文利用 ASPEN PL US软件对环氧丙烷水解生成丙二醇的反应精馏过程进行模拟计算 ,对有关物系的相行为进行预测 ,并进行物性计算和流程模拟 ,指明了该反应过程的主反应区及其形成原因。

反应精馏过程控制虚拟仿真实验系统

以化工反应精馏过程为对象,将Unity3D技术、Matlab和工业操作系统相结合,采用动稳结合方式模拟典型高危化工生产流程,以“模+感+控+智”为架构开发了反应精馏过程控制虚拟仿真系统,包含三维虚拟仿真、实验模型和数据交互等模块,解决危险工艺难以开展过程控制实验和综合实践教学难题,为过程控制课程教学和控制算法研究提供了更接近实际的平台,有利于提升学生工程设计能力和创新实践能力。

反应精馏过程设计研究

介绍连续反应精馏过程设计的两种研究方法 :静态分析法和有限元正交搭配OCFE法 .静态分析法是对反应精馏图进行热力学和拓扑学分析 ,鉴定反应精馏过程的基本可能性 ,此方法不需要依靠确定的对象的特性 ,要求最少量反应混合物的物理化学特性 ,有限元正交搭配技术应用了把整级评估模型转变成连续的模型 .OCFE能精确地吻合逐板模型的优化设计 ,而只是使用一套较小的模型公式和避免使用与塔级数有关的总决策变量 .用静态分析寻找一个最大转化率稳定态 .用OCFE确定反应精馏塔的级数 (塔级数 )及进料级 (塔板 )位置 .

侧反应与精馏集成过程的故障动态特性模拟研究

针对甲苯氯化侧反应与精馏集成生产过程,在对实际生产过程合理简化与假设基础上,研制了该生产过程含控制策略的动态模拟系统。在动态模拟系统中合理设置引起反应能力与分离能力不匹配故障因素,如反应器进料配比失调、回流量过低和塔釜加热量不足等过程扰动,进行故障动态仿真研究。分析在故障扰动下整个系统的故障动态特性,获得有效的故障数据,解决了在实际生产装置上无法进行故障实验研究获取系统故障信息的难题。

利用反应精馏的一段萃取分离裂解碳五馏分的方法

申请人：中国石油化工股份有限公司；中国石油化工股份有限公司北京化工研究院 摘要：本发明公开了利用反应精馏的一段萃取分离裂解碳五馏份的方法，包括：①裂解碳五原料在预脱轻塔1中分离出碳四和炔烃等轻组分，然后在预脱重塔2中经反应精馏过程使环戊二烯二聚成双环戊二烯，并得到包含异戊二烯的物流；②包含异戊二烯的物流经过萃取塔3和解析塔4，得到异戊二烯物流；③并戊二烯物流在脱重塔5中经过反应精馏过程得到聚合级异戊二烯产品。本发明的方法具有流程短，能耗低，建设和运行成本低，产品质量高等优点。

中国石油大学（华东）碳酸二乙酯新工艺研制成功

中国石油大学（华东）化学化工学院研制成功一种生产碳酸二乙酯的工艺方法及设备。 该项技术是将反应精馏过程应用于隔壁塔中，是一种高度集成的化工生产工艺。在一个反应精馏隔壁塔内同时完成酯交换反应、碳酸二乙酯产品分离等任务。

碳酸二乙酯新工艺研制成功

中国石油大学（华东）化学化工学院日前开发出一种生产碳酸二乙酯的工艺方法及设备。该技术是将反应精馏过程应用于隔壁塔中．在一个反应精馏隔壁塔流程中。与常规反应精馏流程相比。省去了两个隔壁塔、一个冷凝器与两个再沸器，因此可有效降低能耗和设备投资。产品中碳酸二乙酯质量分数达到99．5％．碳酸二甲酯转化率达到99％，选择性达到99％，而能耗则比常规反应精馏流程减少20％～50％。

Comparison of Two Types of Control Structures for Benzene Chlorine Reactive Distillation Systems

The ＂neat＂ operation of the two-reactant reactive distillation column has Oetter steady-state economics, while It presents a challenge for design, optimization, and control of the process. Based on the optimal economic design, the dual-composition control structure and dual-temperature control structure are designed respectively for the benzene chlorine consecutive reactive distillation process. The effectiveness and robustness are analyzed comparably for the disturbance resistance in terms of changes of production rate and feed composition. Results show that dual-temperature control with propose selection of tray temperatures and the optimal profile of the set point can provide better transient process performance than the composition control structure.

Hybrid Process of Reactive Distillation and Pervaporation for the Production of Tert-amyl Ethyl Ether

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.

Kinetic-Thermodynamic Analysis of the Reactive Distillation Process of the Cyclohexene Hydration Using the Zeolite Catalyst

Reactive distillation could be utilized to produce cyclohexanol through the cyclohexene hydration. By means of highly active zeolite catalyst HZSM-5, the kinetic-thermodynamic analysis of this reactive distillation has been carried out to get the characteristics of the reactive distillation. Results from kinetic and thermodynamic analysis indicate that the optimal pressure of this reactive distillation process should be set to higher pressure such as 0.3 or 0.4 MPa. To avoid the recovery of cyclohexanol at the top of the column, an unreactive section should be allocated at the upper column. In addition, the inert component benzene is more unfavorable to the reactive distillation process in comparison with the inert cyclohexane.

Intrinsic Kinetic Modeling of Thermal Dimerization of C5 Fraction

This work aims to investigate the intrinsic kinetics of thermal dimerization of C_5 fraction in the reactive distillation process. Experiments are conducted in an 1000-m L stainless steel autoclave under some selected design conditions. By means of the weighted least squares method, the intrinsic kinetics of thermal dimerization of C_5 fraction is established, and the corresponding pre-exponential factor as well as the activation energy are determined. For example, the pre-exponential factor A is equal to 4.39×105 and the activation energy E4 a is equal to 6.58×10J/mol for the cyclopentadiene dimerization reaction. The comparison between the experimental and calculated results shows that the kinetics model derived in this work is accurate and reliable, which can be used in the design of reactive distillation columns.

Production of glycerol carbonate via reactive distillation and extractive distillation: An experimental study

A process for the production of glycerol carbonate(GC) is proposed with the transesterification of glycerol(GL)and dimethyl carbonate(DMC) with CaO as catalyst by reactive distillation and extractive distillation. The performance of solvents in separating DMC-methanol azeotrope and the effects of operation parameters on the reactive distillation process are investigated experimentally. The results indicate that both the GL conversion and GC yield increase with the DMC/GL molar ratio, reflux ratio, final temperature of tower bottom, and CaO/GL molar ratio and decrease as the recycle number of CaO increases. The calcium concentration in the residual reaction mixture also decreases remarkably as the DMC/GL molar ratio increases. At DMC/GL molar ratio 4.0, reflux ratio 1.0, final temperature of tower bottom 358 K, and CaO/GL molar ratio 0.05, both the GL conversion and GC yield can reach above 99.0%, and the mass concentration of calcium in the product is less than 0.08%.

Kinetic studies on the dimerization of isobutene with Ni/Al_2O_3 as a catalyst for reactive distillation process

Isooctane is a promising gasoline additive that could be produced by dimerization of isobutene(IB) with subsequent hydrogenation.In this work,the dimerization of IB has been carried out in a batch reactor over a temperature range of 338-383 K in the presence of laboratory prepared Ni/Al_2O_3 as a catalyst and n-pentane as solvent.The influence of various parameters such as temperature,catalyst loading and initial concentration of IB was examined.A Langmuir-Hinshelwood kinetic model of IB dimerization was established and the parameters were estimated on the basis of the measured data.The feasibility of oligomerization of IB based on the reactive distillation was simulated in ASPEN PLUS using the kinetics developed.The simulation results showed that the catalyst of Ni/Al_2O_3 had higher selectivity to diisobutene(DIB) and slightly lower conversion of IB than ion exchange resin in the absence of polar substances.

Conceptual Design of a Butyl-levulinate Reactive Distillation Process by Incremental Refinement

Butyl-levulinate has been identified as a promising fuel candidate with high oxygen content. Its com- bustion in diesel engines yields very low soot and NOx emissions. It can be produced by the esterification of butanol and levulinic acid, which themselves are platform chemicals in a biorenewables-based chemical supply chain. Since the equilibrium of esterification limits the conversion in a conventional reactor, reactive distillation can be applied to overcome this limitation. The presence of the high-boiling catalyst sulfuric acid requires a further separation step downstream of the reactive distillation column to recover the catalyst for recycle. Optimal design specifications and an optimal operating point are determined using rigorous flowsheet optimization. The challenging optimization problem is solved by a favorable initialization strategy and continuous reformulation. The design identified has the potential to produce a renewable transportation fuel at reasonable cost.

Simulation of Reactive Distillation Process for Monosilane Production via Redistribution of Trichlorosilane

The reactive distillation process for producing high purity monosilane via trichlorosilane redistribution reaction was simulated. Rigorous RadFrac block was employed in Aspen Plus simulation package. Accurate results could be given when the chemical kinetics was taken into account in the equilibrium stage model. A single column process was used for the verification of previous studies. The results showed that 99.9% purity monosilane could be achieved in the reactive distillation. A pumparound block was employed to reduce the condenser duty with inexpen-sive coolant. The effects of operating pressure, feed stage location, liquid holdup per stage and pumparound location were also investigated. The energy consumption was limited, but the refrigerant temperature was too low, which is the fatal disadvantage. Therefore, a double columns process was developed to increase the condenser tem-perature. The simulation results demonstrated that a reasonable temperature could be achieved by varying the recycle stream location.

Design of reactive distillation processes for the production of butyl acrylate:Impact of bio-based raw materials

The chemical industry is nowadays predominantly using fossil raw materials,but the alternative use of bio-based resources is investigated to account for the foreseeable scarcity of fossil feedstocks.A main challenge of using biobased feedstocks is the complexity of the impurity profile.For an economic production of bio-based chemicals,the use of intensified processes is inevitable and approaches are needed for the various process intensification techniques to identify their applicability to be used for the production of bio-based components.In the presented study,an approach is shown for the reactive distillation(RD) technology to identify the most critical bio-based impurities and their impact on the reactive distillation process.The investigated case-study is the production of n-butyl acrylate from acrylic acid and n-butanol.Among all initially identified impurities,the key impurities,having the biggest impact on the product purity in the reactive distillation process,are found.These impurities are then studied in more detail and an operating window depending on the impurity concentration is identified for the reactive distillation column.Furthermore,an integrated design of upstream and downstream processes is facilitated,as the presented results can be used in the development of the fermentation processes for the production of the bio-based reactants by decreasing the concentration of the critical impurities.

化学工程

DMC和丙醇酯交换合成MPC反应的热力学;一氯甲烷热裂解的热力学分析;气固相催化反应动力学方程的推导新思路;Mo／ZSM-5催化剂上NO催化还原反应机理与动力学研究;干气制乙苯反应精馏过程的数值模拟;甲烷自热转化工艺的模拟计算;