乙酸乙烯与乙烯混合物亥姆霍兹自由能状态方程及应用  

Development and Application of Helmholtz Free Energy Equations ofStatefor Vinyl Acetate and Its Mixture with Ethylene

作　　者：高克慧 王建安[1] 卢昌存 吕倩 余小玲 毕胜山[1] GAO Kehui;WANG Jian’an;LU Changcun;L Qian;YU Xiaoling;BI Shengshan(MOE Key Laboratory of Thermo-Fluid Science and Engineering,Xi’an Jiaotong University,Xi’an 710049,China;Beijing Yanshan Branch,China Petroleum and Chemical Corporation,Beijing 102500,China;School of Chemical Engineering and Technology,Xi’an Jiaotong University,Xi’an 710049,China)

机构地区：[1]西安交通大学热流科学与工程教育部重点实验室,西安710049 [2]中国石油化工股份有限公司北京燕山分公司,北京102500 [3]西安交通大学化学工程与技术学院,西安710049

出　　处：《西安交通大学学报》2024年第7期50-61,共12页Journal of Xi'an Jiaotong University

基　　金：国家自然科学基金资助项目(52076166);中国石油化工股份有限公司资助项目(222051)。

摘　　要：为向高压聚乙酸乙烯生产过程提供全面可靠的热力学性质数据及预测模型,在搜集文献中热力学性质实验数据及添加合理趋势限制条件的基础上,采用Powell直接拟合算法开发了乙酸乙烯及乙酸乙烯与乙烯混合物的多参数亥姆霍兹自由能经验状态方程。结果表明:乙酸乙烯状态方程适用范围为三相点温度到650 K,压力可外推至100 MPa;乙酸乙烯与乙烯混合物状态方程适用温度为104~520 K,压力为0.1~200 MPa。经与实验数据比较分析,乙酸乙烯状态方程计算密度的总体偏差为0.3%;混合物状态方程计算压力50~195 MPa内密度的偏差在±4%内,在高压区域内计算精确度表现良好;乙酸乙烯与乙烯混合物的压缩因子与实验数据吻合较好,偏差总体分布在±3%。分析表明所开发状态方程可满足工程设计需求。To provide comprehensive and reliable thermodynamic property data and prediction models for the production of polyvinyl acetate under high-pressure conditions,the multi-parameter Helmholtz free energy empirical equations of state(EoS)for vinyl acetate and its mixture with ethylene are developed with Powell direct fitting algorithm on the basis of collecting published experimental data of thermodynamic properties in the literature and adding reasonable constraints.The results show that the EoS for vinyl acetate is valid from the triple-point temperature to 650 K with pressures from 0.1 MPa to 100 MPa,and the EoS for the mixture of vinyl acetate and ethylene is valid from 104 K to 520 K with pressures from 0.1 MPa to 200 MPa.Compared with experimental data,the deviation of EoS for vinyl acetate in density is 0.3%;the deviations in density at pressures between 50 MPa and 195 MPa calculated from the mixture EoS are within±4%,and the calculated accuracy performs better with increasing pressure;the compression factors for the mixture of vinyl acetate and ethylene are calculated and fit well with the experimental data,with deviations generally distributed within±3%.The developed EoS in this paper can meet the engineering design requirements.

关 键 词：乙酸乙烯 乙烯 状态方程 混合物 热力学性质 

分 类 号：TK123[动力工程及工程热物理—工程热物理]