【作者】 许文友；

【导师】 袁希钢；

【作者基本信息】 天津大学 ， 化学工程， 2005， 博士

【摘要】 无机盐作盐析剂分离恒沸有机水溶液体系是一种行之有效的分离方法,有重要的工业应用背景。该方法基于盐析效应的原理,将无机盐加入到恒沸有机水溶液体系中时,由于无机盐的盐析效应,使得有机物在水中的溶解度减少,以致于形成有机物富集相和盐水富集相。当水相中盐浓度较高时形成的有机物富集相中含有少量水和极少量盐、盐水富集相中含有极少量的有机物,使大部分水在盐水相中脱去,得到较高的分离因子。目前,采用无机盐作盐析剂分离恒沸有机水溶液体系的相平衡数据较为缺乏,给采用无机盐分离恒沸有机水溶液体系的研究和开发工作带来很多困难。因此,进行有机物-水-无机盐体系液-液相平衡的研究工作具有较高的学术价值和实用价值。本文采用氟化钾和碳酸钾作盐析剂,以乙醇、正丙醇、异丙醇、正丁醇、仲丁醇、叔丁醇、丙烯腈、丁酮、四氢呋喃、吡啶水溶液体系为研究对象,主要完成了如下四方面的工作:1.盐析剂的选择:通过比较文献及实验测定的乙醇-水-无机盐体系的两相组成,选择出对乙醇-水体系分离效果好的盐析剂。在已知的能与水形成恒沸体系的有机物中乙醇的极性是最强的,因此,对乙醇-水体系分离效果好的盐析剂,一般也对其它有机物-水体系具有较好的分离效果。2.有机物-水-无机盐体系液-液相平衡数据的测定:系统测定了乙醇、正丙醇、异丙醇、正丁醇、仲丁醇、叔丁醇、丙烯腈、丁酮、四氢呋喃、吡啶水溶液分别与氟化钾和碳酸钾形成的有机物-水-无机盐体系的液-液相平衡数据,为采用无机盐分离恒沸有机水溶液体系的工艺设计提供了基础数据。3.有机物-水-无机盐体系液-液相平衡的数学模型研究:采用Pitzer的电解质溶液理论分别与Wilson、NRTL或UNIQUAC方程相结合建立了计算乙醇、正丙醇、异丙醇、正丁醇、仲丁醇、叔丁醇、丙烯腈、丁酮、四氢呋喃、吡啶水溶液分别与氟化钾和碳酸钾形成的有机物-水-无机盐体系液-液相平衡的数学模型,为采用无机盐分离恒沸有机水溶液体系提供了理论依据和计算依据。4.工业应用研究:以吡啶废水的治理和乙醇-丙酮-正丁醇-水体系的分离为例,论证了采用易于回收及循环使用的浓盐水为盐析剂分离恒沸有机水溶液体系的可行性,确定了采用浓盐水治理吡啶废水、分离乙醇-丙酮-正丁醇-水体系的操作条件,并将该研究结果应用于吡啶废水的治理及乙醇-丙酮-正丁醇-水体系的分离。更多还原

【Abstract】 Phase separation procedure based on the salting-out principle for organics/watermixtures separation has been proven to be effective and has the important industryapplication background. When inorganic salts are added into the organics/watermixtures, due to the salting-out effect of the inorganic salts, the organicssolubility in water decreases and two phases are formed: the organics-rich phasecontained negligible salt and the water-rich phase contained negligible organics whenthe concentration of inorganic salts in water phase is higher,consequently water isseparated efficiently from the organics/water mixtures,and high separation factorcould be obtained. At present it is quite short of the liquid-liquid equilibrium data forseparation of azeotropic organics/water mixtures by using inorganic salts as salting-out agents,this brings many difficulties to research and development of processesfor separation of azeotropic organics/water mixtures using inorganic salts. Someasurement and calculation of liquid-liquid equilibrium data for organic-water-inorganic salts have high academic and practical value. The phase separation ofethanol-water , 1-propanol-water , 2-propanol-water , 1-butanol-water , 2-butanol-water , tert-butanol-water , acrylonitrile-water , butanone-water ,tetrahydrofuran-water and pyridine-water using KF and K₂CO₃ has been studied,the following research works have been performed in this paper.1. Selection of salting-out agents:By comparing the composition data of the twophases of the ethanol-water-inorganic salts from the literatures with those obtainedfrom our experiments, the salting-out agents are selected for separating theethanol-water system. The polarity of the ethanol is the most intensive comparingwith most other organics forming the azeotropes with water, so the salting-outagents that have good separation effect for the ethanol-water system should be alsogood for the other organics-water systems.2. The determination of liquid-liquid equilibrium for organics-water-inorganic saltsystems :The liquid-liquid equilibrium data for systems of ethanol-water-KF,ethanol-water-K₂CO₃ , 1-propanol-water-KF , 1-propanol-water-K₂CO₃ , 2-propanol-water-KF,2-propanol-water-K₂CO₃,1-butanol-water-KF,1-butanol-water-K₂CO₃,2-butanol-water-KF,2-butanol-water-K₂CO₃,tert-butanol-water-KF , tert-butanol-water-K2CO3 , acrylonitrile-water-KF , acrylonitrile-water-K2CO3 , butanone-water-KF , butanone-water-K2CO3 , tetrahydrofuran-water-KF , tetrahydrofuran-water-K2CO3 , pyridine-water-KF and pyridine-water-K2CO3 were experimentally determined,providing basic data for processes designof separating azeotropic organics/water mixtures by using phase separationprocedure.3. The liquid-liquid equilibrium model research for organics-water-inorganic salts:For modeling liquid-liquid equilibrium for systems of ethanol-water-KF,ethanol-water-K2CO3 , 1-propanol-water-KF , 1-propanol-water-K2CO3 , 2-propanol-water-KF , 2-propanol-water-K2CO3 , 1-butanol-water-KF , 1-butanol-water-K2CO3 , 2-butanol-water-KF , 2-butanol-water-K2CO3 , tert-butanol-water-KF , tert-butanol-water-K2CO3 , acrylonitrile-water-KF , acrylonitrile-water-K2CO3 , butanone-water-KF , butanone-water-K2CO3 , tetrahydrofuran-water-KF , tetrahydrofuran-water-K2CO3 , pyridine-water-KF and pyridine-water-K2CO3,the Pitzer’s electrolyte solution theory was adopted and applied tocalculate water activity in the water phase, and the Wilson, NRTL or theUNIQUAC equation were selected to calculate water activity in the organics phaserespectively. The thermodynamics model for organic-water-inorganic salt systemswere then obtained,providing theoretical and computational basis for separatingazeotropic organics/water mixtures by using phase separation procedure.4. Industrial application research: The feasibility of separating of azeotropicorganics/water mixtures was demonstrated by two processes: treatment ofazeotropic pyridine waste water and separation of ethanol-acetone-1-butanol-water.In these two processes,brine was used as salting-out agents, which could beeasily recovered and recycled. The operating conditions were determined by usingthe brine,and the pyridine waste water was treated and ethanol-acetone-1-butanol-water was separated by using this research results.更多还原