A REACTIVE DISTILLATION PROCESS FOR AN AZEOTROPIC REACTION SYSTEM: TRANSESTERIFICATION OF ETHYLENE CARBONATE WITH METHANOL

A reactive distillation process is proposed for manufacturing dimethyl carbonate (DMC) through the transesterification reaction of ethylene carbonate (EC) with methanol. Modeling and simulation of the reactive distillation column have been carried out to study the effects of operating conditions, such as the reflux ratio, the number of theoretical plates, the feed ratio, the top effluent, the liquid holdup, and the feed location, on EC conversion and product composition at the top of the reactive distillation column. The calculated results show that a complete EC conversion can be achieved. The model reliability is analyzed under different Murphree tray efficiencies, showing no considerable difference between the equilibrium and nonequilibrium models for this system. And the calculated results are verified by experimental data and commercial operation of a dimethyl carbonate plant of 10,000 tons per year.     

催化精馏过程制备碳酸二甲酯的研究

在自制的催化精馏实验装置中 ,以等体积浸渍法负载于碳分子筛上的 1 2 -磷钨酸为催化剂 ,将其捆束型的方式装填于精馏塔中 ,通过碳酸丙烯酯和甲醇之间简单的酯交换反应来进行碳酸二甲酯的制备。通过试验分别考察了原料配比、操作压力、回流比、处理量等工艺参数对催化精馏过程的影响 ,从而确定出适宜的工艺操作条件     

酯交换法合成碳酸二甲酯的催化精馏过程研究

在催化精馏实验装置中 ,以等体积浸渍法负载于是碳分子筛上的 12 磷钨酸为催化剂 ,通过碳酸丙烯酯和甲醇之间的酯交换反应合成碳酸二甲酯。通过实验考察了原料配比、操作压力、回流比、处理量等工艺参数对催化精馏过程的影响。采用神经网络与遗传算法相结合的方法 ,用黑箱模型计算催化精馏过程 ,并进行了全局优化 ;以动力学模型为基础 ,借助ASPEN软件用平衡级模型进行了催化精馏过程的模拟与预测。     

Optimization and control of a reactive distillation process for the synthesis of dimethyl carbonate

Dimethyl carbonate is an environmentally benign and biodegradable chemical. Based on integration of reactive distillation and pressure-swing distillation technologies, a novel process for synthesis of dimethyl carbonate through transesterification with propylene carbonate and methanol has been developed by Huang et al. In this work, the optimization of this process was performed by minimizing the total TAC. The results show that the op-timal design flowsheet can save energy consumption by 18.6％with the propylene carbonate conversion of 99.9％. Then, an effective plant-wide control structure for the process was developed. Dynamic simulation results dem-onstrate that the temperature/flow rate cascade control plus with simple temperature control can keep not only product purity but also the conversion of the reactant at their desired values in the face of the disturbance in re-actant feed flow rate and feed composition.     

隔壁反应精馏合成碳酸甲乙酯节能新工艺

提出了隔壁反应精馏合成碳酸甲乙酯的新工艺,除考虑碳酸二甲酯与乙醇酯交换反应外,还考虑了碳酸二甲酯与碳酸二乙酯反歧化反应的影响,并集成上述反应于一台隔壁反应精馏塔中,优化了碳酸甲乙酯的生产过程。首先,进行了碳酸二甲酯与碳酸二乙酯反歧化反应动力学实验,建立反应动力学模型,并验证了该工艺流程中此模型计算结果的可靠性。然后,运用Aspen Plus对隔壁反应精馏新工艺进行了流程模拟和优化设计,分别确定了酯交换反应段、反歧化反应段、产品精馏段和公共提馏段的理论塔板数,最佳进料位置、回流比等主要操作参数。隔壁反应精馏新工艺与常规反应精馏三塔工艺相比,新工艺将塔釜产品碳酸二乙酯返回隔壁塔内,增加了反歧化反应区,显著提高了碳酸甲乙酯选择性和收率,避免了低价值副产物碳酸二乙酯的产生,并有效减少了设备投资和运行能耗。     

反应精馏合成碳酸苯甲酯的研究

通过对碳酸二甲酯和苯酚酯交换反应精馏合成碳酸苯甲酯的研究,探索出了最优的工艺条件,为以后碳酸二苯酯的工业化奠定了基础。研究表明：以MoO3为催化剂,在1．25MPa下,反应温度200℃,原料中碳酸二甲酯与苯酚的摩尔配比为4：1,催化剂与原料的质量比为0．0005：1,反应时间7h,苯酚总转化率为4853％,碳酸苯甲酯产率为39．75％,苯甲醚产率为8．78％,碳酸苯甲酯的选择性为81．91％。     

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.     

萃取精馏法精制碳酸二甲酯的过程模拟研究

利用化工模拟软件Aspen Plus采用萃取精馏,以N,N-二甲基甲酰胺(DMF)为萃取剂,对碳酸二甲酯生产中的产品精制进行模拟计算,详细分析了理论板数、进料位置、溶剂比和回流比对产品浓度的影响,结果表明,最佳工艺方案为:理论板数36,粗酯进料位置27,萃取剂进料位置4,回流比2.6,溶剂比2.4,产品碳酸二甲酯含量达到99.8%,为分离过程的优化操作和设计提供依据。     

考虑水力学可行性的反应精馏塔板持液量设计及优化

以筛板塔为塔板基础构型,以原料转化率最大为目标,以塔径和出口堰高为主要调节参数,以塔板水力学可行性为约束条件,建立了一种可优化塔板液相持液量的塔板结构设计方法. 塔模拟计算在Aspen Plus平台上进行,化学反应采用动力学方程表达,塔板水力学计算采用Cup-Tower软件. 结果表明,本设计方法应用于DPC反应精馏过程,在满足流体力学可行性条件下,塔板上液相持液量比基础设计提高了1.39倍,苯酚转化率提高了33.6%.     

酯交换法合成碳酸二甲酯工艺研究

通过酯交换法,以甲醇和碳酸丙烯酯为原料,反应精饱同最佳剂,确定了其用量,考察了原料配比等对反应转化率的影响。同时,采用萃取精馏法对甲醇＝碳酸二甲酯二元恒沸物进行了分离研究,得到了适宜的萃取剂,研究了萃取剂的配比和回流比对分离性能的影响。并考察了催化剂和萃取剂的回收及循环使用对反应和分离性能的影响。对副产品丙二醇的回收及回流比对其纯度的影响也进行了考察。     

尿素醇解法合成碳酸二甲酯催化精馏工艺模拟

在AspenPlus平台上对尿素醇解法合成碳酸二甲酯反应精馏工艺进行模拟,针对反应精馏塔塔顶冷凝器结晶堵塞问题,优化了采出方式,提高了塔顶温度,以防止结晶。     

加压–常压精馏分离甲醇–碳酸二甲酯的相平衡和流程模拟

变压精馏是分离共沸混合物的有效方法. 本文在计算机模拟和分析的基础上, 提出了加压–常压串联分离甲醇–碳酸二甲酯共沸体系的工艺方法. 采用UNIQUAC方程来表征甲醇–碳酸二甲酯二元共沸体系的气液平衡. 根据实验数据，回归了该热力学模型中的交互作用参数，模型的计算结果与实际数据吻合. 模型的适用范围为：压力0.1~1.5 MPa, 温度337~440 K. 基于平衡级模型，对加压精馏塔进行了模拟计算, 分析了各主要操作参数对分离效率、产品纯度及操作费用的影响. 在对加压–常压串联流程模拟的基础上，得到了最佳分离操作工艺参数. 模拟结果对工业过程的设计和改造具有一定的指导意义.     

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 distil ation and extractive distil ation. The perfor-mance of solvents in separating DMC-methanol azeotrope and the effects of operation parameters on the reactive distillation process are investigated experimental y. 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%.     

浆料催化精馏合成碳酸二甲酯的模拟研究

以浆料催化精馏酯交换合成碳酸二甲酯实验为基础,应用Aspen Plus软件建立了浆料催化精馏合成过程的稳态模型并进行研究。研究结果表明,模型的计算值与实验值吻合良好。通过计算机模拟还得到了实验难以测定的塔内温度分布、塔内气液相流率及组成和碳酸二甲酯在各板的生成速率的变化规律。     

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.     

Coupling reaction and azeotropic distillation for the synthesis of glycerol carbonate from glycerol and dimethyl carbonate

A new process, coupling reaction and azeotropic distillation was proposed for the synthesis of glycerol carbonate (GC) from glycerol (G) and dimethyl carbonate (DMC). The bench scale experimental investigation was systematically conducted for this new process. With calcium oxide (CaO) as the solid catalyst, the high yield of glycerol carbonate can be obtained at a low molar ratio of dimethyl carbonate to glycerol with the method of coupling reaction and azetropic distillation. The effect of azeotropic agents on glycerol carbonate yield was explored, and indicated that benzene was the most effective azeotropic agent. The effects of the process parameters, tower height, amount of added benzene, final temperature of tower bottom and reflux ratio were investigated. Glycerol carbonate yield can be as high as 98% under the conditions at molar ratio of dimethyl carbonate to glycerol 1:1, final temperature of tower bottom 85 °C, 1.5 mass ratio of added benzene to that in the azeotrope with methanol theoretically produced and reflux ratio 4. By continuously removing methanol from reaction system with the method of coupling reaction and azeotropic distillation, the yield of glycerol carbonate can be retained at high level using the recycled catalyst.     

Simulation study on a reactive distillation process of methyl acetate hydrolysis intensified by reaction of methanol dehydration

Methyl acetate (MeOAc) recovery from the polyvinyl alcohol (PVA) production is a difficult and heavy energy consuming process. In this work, a reactive distillation (RD) process of MeOAc hydrolysis intensified by methanol (MeOH) dehydration, as an auxiliary reaction, was proposed. Two different feeds with the mole ratio of MeOAc to MeOH at 1:1 and 1:9 were studied, and the effect of the operating pressure, the feed location and the reflux ratio on the RD column was analyzed. The simulations of reactive distillation were performed using a three phase non-equilibrium model implemented by gPROMS. As the limit of the reaction rate of MeOH dehydration, it is impossible to get 100% conversion of MeOAc and MeOH by a single RD column. Therefore, two novel processes for recovery of methyl acetate in PVA production were developed. The simulation results show that the high purity of dimethyl ether (DME) could be achieved with a complete conversion of MeOAc, and a large amount of energy demand and equipment costs can be reduced.     

Stable Organic Titanium Catalysts and Reactive Distillation Used for the Transesterification of Dimethyl Carbonate with Phenol

The transesterification of dimethyl carbonate with phenol to methyl phenyl carbonate (MPC) was investigated on novel catalysts such as titanium diisopropoxide bis(ethyl acetoacetate) and titanium dibutoxide bis(ethyl acetoacetate) in a closed batch reactor at 185–206 °C under high pressure. The produced methanol could be removed efficiently by reactive distillation in order to overcome the equilibrium. The prepared catalysts have higher resistance to water than titanium alkoxides. Phenol conversion as high as 86.4 % with an MPC selectivity of 99.4 % was achieved under optimal reaction conditions within 9 h. Most of the catalytic activity was retained after repeated use for ten times.     

常压下甲醇-碳酸二甲酯汽液平衡测定及其萃取剂选择

甲醇( MeOH)与尿素催化合成碳酸二甲酯的工艺路线是目前最有发展前途的一种合成方法,但该过程中由于使用了过量的甲醇,在合成中形成了碳酸二甲酯和甲醇的共沸物,分离困难.已报道的分离方法中萃取精馏,在经济效益、操作和安全方面都优于其他方法.草酸二甲酯,碳酸乙烯酯,碳酸丙烯酯均可作为萃取精馏分离DMC的萃取剂,但MeOH-...     

Investigations on the Synthesis of Methyl Acetate in a Heterogeneous Reactive Distillation Process

The production of methyl acetate in a reactive distillation process – prior art for 15 years – is often used as an example to study the basic phenomena of reactive distillation. The present paper deals with a theoretical and experimental analysis of methyl acetate synthesis in a reactive distillation column. A design method based on the interpretation of reactive distillation line diagrams is used to identify the main process parameters and to provide a foundation for experimental investigation. The significant influence of the reflux ratio on the conversion in the column is shown by mini plant experiments using supported ion exchanger in the form of Raschig rings as a heterogeneous catalyst. These experiments demonstrate the catalytic quality of this packing material. To simulate the reactive distillation column with a simple stage-to-stage method, the separation efficiency of the catalytic rings is investigated. Comparison of experimental and simulation results reveals that a simple model based on the assumption of simultaneous chemical and phase equilibrium describes the experimental data quite well over a wide range of reflux ratios. Furthermore, simulation results show that the conversion depends less on the number of reactive stages than on the use of two feed stages.