乙苯液相无溶剂氧化体系中的相平衡及其应用研究

发布时间：2018-02-12 13:30

本文关键词： 液液相平衡固液相平衡汽液相平衡乙苯苯乙酮模拟与优化　出处：《湖南大学》2015年硕士论文　论文类型：学位论文

【摘要】：苯乙酮是重要的化工原料,广泛用于香皂、香料及医药等行业。传统苯乙酮生产工艺中,以三氯化铝为催化剂,苯和乙酰氯酰基化反应制备苯乙酮,该法产生强酸,易腐蚀设备和污染环境。本文研究的工艺背景为以氧气为氧化剂,选择性氧化乙苯合成苯乙酮。该工艺舍弃了传统生产工艺的乙酰氯和三氯化铝,改用氧气为氧化剂的无溶剂参与的绿色氧化制备苯乙酮的新工艺,既节省了原料成本、三废处理费用,也降低了设备腐蚀。以氧化剂为氧气,直接氧化乙苯制备苯乙酮的反应过程中,主产物为苯乙酮,副产物主要有1-苯乙醇、苯甲酸、水等。设计的工艺过程主要包括反应液分离、萃取精馏、减压精馏等分离系统。设计合理的分离条件,涉及到的、必不可少的是该体系的基础热力学数据。该工艺相关的液液平衡数据和固液平衡数据是重要的热力学基础数据。本论文针对针对乙苯液相氧化液的分离工艺进行流程设计、模拟与优化,完善相关的基础数据,为该工艺提供思路和依据,主要对以下几方面内用进行研究:相平衡数据研究1.液液相平衡:测定常压下括水+乙苯+苯乙酮、水+乙苯+1-苯乙醇和水+苯乙酮+1-苯乙醇三个三元体系的液液平衡数据。并用NRTL和UNIQUAC活度系数模型,对所有液液平衡数据进行模型参数拟合,得到对应模型的二元相互作用参数。利用得到的模型参数,对四元体系水+乙苯+苯乙酮+1-苯乙醇的液液平衡数据进行预测和验证。2.固液相平衡:建立固液相平衡实验装置,分别测定苯甲酸在1-苯乙醇、苯乙酮和乙苯等溶剂中的溶解度,用NRTL模型对苯甲酸在不同溶剂中的溶解度进行关联,得到二元相互作用参数。建立苯甲酸在多元混合溶剂中的溶解度预测模型,实现苯甲酸在多元混合溶剂中溶解度的预测和验证。3.汽液相平衡:利用文献已有的汽液平衡数据,进行热力学模型关联。分离工艺优化研究设计了乙苯氧化产物的分离工艺,并运用ASPEN PLUS软件中的灵敏度分析工具对反应物分离、苯甲酸分离、1-苯乙醇与苯乙酮分离工艺进行了模拟,对分离反应物、分离苯甲酸、分离1-苯乙醇与苯乙酮的精馏塔进行了回流比、进料位置和塔板数的灵敏度分析,找出了单元操作的最佳操作条件,得到优化的分离条件和对应的模拟结果。
[Abstract]:Acetophenone is an important chemical raw material, which is widely used in soap, perfume, medicine and other industries. In the traditional production process of acetophenone, acetophenone is prepared by the reaction of benzene with acetyl chloride acylation with aluminum trichloride as catalyst, which produces strong acid. The technological background of this paper is selective oxidation of ethylbenzene to acetophenone with oxygen as oxidant. The process has abandoned the traditional production process of acetyl chloride and aluminum trichloride. The new process of producing acetophenone by using oxygen as oxidant in green oxidation with no solvent can not only save the cost of raw material, but also reduce the cost of waste treatment, and reduce the corrosion of equipment. In the process of direct oxidation of ethylbenzene to acetophenone, the main product is acetophenone, the by-products are mainly 1-phenylethanol, benzoic acid, water and so on. Separation systems, such as vacuum distillation, design of reasonable separation conditions, The basic thermodynamic data of the system are essential. The liquid-liquid equilibrium data and the solid-liquid equilibrium data are important thermodynamic basic data. In this paper, the separation process of ethylbenzene liquid-phase oxidation solution is designed. Simulation and optimization, improvement of the basic data, provide ideas and basis for the process, mainly for the following aspects of the study: phase equilibrium data study 1.Liquid-liquid equilibrium: determination of ethylphenyl acetophenone in water at atmospheric pressure, The liquid-liquid equilibrium data of three ternary systems of water ethylbenzene 1-phenylethanol and water-acetophenone 1-phenylethanol were obtained. All the liquid-liquid equilibrium data were fitted by NRTL and UNIQUAC activity coefficient models. The binary interaction parameters of the corresponding model were obtained. Using the obtained model parameters, the liquid-liquid equilibrium data of water ethylphenyl acetophenone 1-phenylethyl alcohol was predicted and verified .2.Solid-liquid equilibrium: a solid-liquid equilibrium experimental device was established. The solubility of benzoic acid in 1-phenylethanol, acetophenone and ethylbenzene was determined, and the solubility of benzoic acid in different solvents was correlated with NRTL model. The solubility prediction model of benzoic acid in multicomponent mixed solvents was established to predict and verify the solubility of benzoic acid in multicomponent mixed solvents. The separation process of ethylbenzene oxidation product was studied and designed. The sensitivity analysis tool of ASPEN PLUS software was used to separate the reactants. The separation process of 1-phenylethyl alcohol and acetophenone by benzoic acid was simulated. The reflux ratio, feed position and tray number of the distillation column for separation of benzoic acid, benzoic acid and 1-phenylethanol were analyzed. The optimal operating conditions of the unit operation are found, and the optimized separation conditions and the corresponding simulation results are obtained.
【学位授予单位】：湖南大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TQ013.1

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