【作者】 朱云庆；

【导师】 李青松； 李发永；

【作者基本信息】 中国石油大学 ， 化学工程， 2008， 硕士

【摘要】 长期以来,醋酸废水的处理一直是困扰许多企业的技术难题。研究醋酸、水的有效分离不仅可以带来经济和社会效益,同时对于化工分离、化工环保等学科的发展也具有重要作用。在工业生产中,大量精确可靠的流体相平衡数据是实现萃取精馏工艺的设计改造、挖潜创新及选择最佳工艺条件的基础条件,同时在化学工程领域,流体相平衡数据的测定和热力学模型的研究也是十分重要的内容。本研究中,采用改进ROSE釜测定了常压下醋酸/醋酸乙烯酯、醋酸/醋酸乙烯酯/水体系(互溶区内)的汽液相平衡数据,并绘制了汽液相平衡的x-y相图和T-x-y相图。对实验数据进行关联和预测时,由于醋酸是强缔合的物质,相平衡关系非常复杂,不仅存在各组分单体之间的相平衡,同时存在缔合体之间的相平衡以及缔合体与缔合组分之间的化学平衡,因此在关联过程中,我们综合考虑了汽液两相中醋酸的二缔合、三缔合作用,分别采用修正UNIQUAC方程计算液相表观活度系数,并由此推算出液相逸度,同时对于汽相的非理想性,我们则采用修正维里方程、R-K方程来校正,从而计算汽相的真实逸度系数。通过关联实验测定的醋酸/醋酸乙烯酯二元汽液相平衡数据,得到计算温度和汽液两相组成,并算出关联的温度偏差及汽液相组成偏差,得到了修正UNIQUAC方程的交互作用能量参数Δu 12和Δu21,绘制了汽液相平衡的x-y相图和T-x-y相图。同时用关联的二元模型参数,汽相分别采用修正维里方程、R-K方程,液相则采用修正Wilson方程和修正UNIQUAC方程对三元汽液相平衡数据进行了预测,并计算了推算值与实测值的平均误差与均方根误差。醋酸物系的液液相平衡体系中也存在缔合现象,因此本研究中同时对常压下正癸烷/醋酸/水体系、减压渣油(正癸烷)/醋酸/水体系30℃、50℃、70℃做了液液相平衡实验研究,得到了相关相平衡实验数据,并绘制了醋酸在两相中的分配系数变化曲线,为后续实验研究打好了基础。更多还原

【Abstract】 For a long time, the treatment of acetic-acid contained wastewater has been a technical problem that plagued many enterprises. Study of the effective separation of water and acetic acid can not only bring economic and social benefits, but also play an important role in the development of chemical separation, chemical industry and environmental protection disciplines.In industrial production, a large number of accurate and reliable data of fluid phase equilibrium are a required condition of the design, reconstruction, innovation, and choosing optimum process condition, meanwhile, in the field of chemical engineering, the measurement of fluid equilibrium data and the study of thermodynamic model is also very important content.In this study, we adopt the improved ROSE kettle to measure the VLE(Vapor-liquid equilibrium) data of acetic acid / vinyl acetate system and acetic acid / vinyl acetate / water system (immiscible region) at normal pressure. Also we protract the x-y phase diagram and the T-x-y phase diagram.When we associate and forecast the experimental data, we are faced a problem, as acetic acid is a strong associated material, the equilibrium relations are very complex that not only contained the phase equilibrium relationship between the components monomers, but also contained the relationship between associations and the chemical equilibrium between associated components and its monomers. So in the progress of association, we synthesized the two-molecule-association and three-molecule-association in the phase equilibrium. And we adopted the modified UNIQUAC equation to calculate the apparent activity coefficient of liquid phase, finally to calculate the fugacity. Meanwhile, we proofread the non-ideal property of gas phase by modified VIRIAL equation and R-K equation to calculate the real fugacity coefficient. As a result, we associated the experimental VLE data of AC(acetic acid)/VAC(vinyl acetate) system and calculated the equilibrium temperature and the composition of the two phase, also we protracted the x-y figure and T-x-y figure. By the way, we also calculated the temperature deviations and the deviations of two phase composition, and got the coefficients and of modified UNIQUAC equation. On the other hand, we forecasted the VLE data of AC/VAC/Water system by modified-VIRIAL-equation andΔu 12Δu21 modified-R-K-equation used in vapor phase and by modified-Wilson-equation and modified-UNIQUAC-equation respectively, also calculated the the average error and RMS error.The association phenomena also exited in liquid-liquid phase equilibrium system, so in this investigation we measured the LLE(Liquid-liquid equilibrium) data of n-decane/AC/water system, vacuum residue(n-decane solution)/AC/water system at 30℃,50℃,70℃and drew the curve of AC distribution coefficients in oil and water phases.更多还原