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

doi:10.7652/xjtuxb202407005

您当前的位置：

首页 >

文章列表页 >

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

更新时间：2025-07-28

- Development and Application of Helmholtz Free Energy Equations of Statefor Vinyl Acetate and Its Mixture with Ethylene
- Vol. 58, Issue 7, Pages: 50-61(2024)
- 作者机构：
  
  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
- 作者简介：
- 基金信息：
- DOI：10.7652/xjtuxb202407005
  CLC： TK123
- Published：2024
- 稿件说明：
移动端阅览
Development and Application of Helmholtz Free Energy Equations of Statefor Vinyl Acetate and Its Mixture with Ethylene[J]. 2024, 58(7): 50-61.
DOI：

Development and Application of Helmholtz Free Energy Equations of Statefor Vinyl Acetate and Its Mixture with Ethylene[J]. 2024, 58(7): 50-61. DOI： 10.7652/xjtuxb202407005.

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。

Abstract

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

Keywords

references

肖铭. 乙酸乙烯酯的供需现状及未来发展趋势 [J]. 精细与专用化学品, 2021, 29(4): 5-8.

XIAO Ming. Supply and demand status of vinyl acetate and its development trend [J]. Fine and Specialty Chemicals, 2021, 29(4): 5-8.

柳杰. 简述高压聚乙烯装置压缩机管道支架设计 [J]. 当代化工研究, 2022(9): 141-143.

LIU Jie. Briefly describe the design of the pipeline support for the compressor of the high pressure polyethylene plant [J]. Modern Chemical Research, 2022(9): 141-143.

SÜLZNER U, LUFT G. Viscosity of alcohol-ethene mixtures at pressures up to 195 MPa [J]. International Journal of Thermophysics, 1998, 19(1): 43-69.

CLAPEYRON E. Memoire sur la puissance motrice de la chaleur [J]. Journal de I'Ecole Polytechnique, 1834, ⅪⅤ: 153-190.

PENG Dingyu, ROBINSON D B. A new two-constant equation of state [J]. Industrial Engineering Chemistry Fundamentals, 1976, 15(1): 59-64.

SOAVE G. Equilibrium constants from a modified Redlich-Kwong equation of state [J]. Chemical Engineering Science, 1972, 27(6): 1197-1203.

SPAN R. Multiparameter equations of state: an accurate source of thermodynamic property data [M]. Berlin, Germany: Springer, 2000.

SMUKALA J, SPAN R, WAGNER W. New equation of state for ethylene covering the fluid region for temperatures from the melting line to 450 K at pressures up to 300 MPa [J]. Journal of Physical and Chemical Reference Data, 2000, 29(5): 1053-1121.

SCHMIDT R, WAGNER W. A new form of the equation of state for pure substances and its application to oxygen [J]. Fluid Phase Equilibria, 1985, 19(3): 175-200.

JACOBSEN R T, STEWART R B, JAHANGIRI M. A thermodynamic property formulation for nitrogen from the freezing line to 2 000 K at pressures to 1 000 MPa [J]. International Journal of Thermophysics, 1986, 7(3): 503-511.

KUNZ O, WAGNER W. The GERG-2008 wide-range equation of state for natural gases and other mixtures: an expansion of GERG-2004 [J]. Journal of Chemical and Engineering Data, 2012, 57(11): 3032-3091.

DOLLIVER M A, GRESHAM T L, KISTIAKOWSKY G B, et al. Heats of organic reactions: Ⅵ Heats of hydrogenation of some oxygen-containing compounds [J]. Journal of the American Chemical Society, 1938, 60(2): 440-450.

DAUBERT T E, JALOWKA J W, GOREN V. Vapor pressure of 22 pure industrial chemicals [J]. AIChE Symposium Series, 1987, 83(256): 128-156.

STEVENS R M M, BAKX A, VAN DER NEUT P R H, et al. High-pressure vapor-liquid equilibria of the ternary system carbon dioxide + vinyl acetate + 2-butanol. Experimental and modeling results [J]. Journal of Chemical Engineering Data, 1997, 42(6): 1280-1284.

ANTOINE C. Tensions des vapeurs: nouvelle relation entre les tensions et les temperatures [J]. Comptes Rendus Hebdomadaires Des Séances De Lacadémie Des Sciences, 1888, 107: 681-684.

FROST A A, KALKWARF D R.A semi-empirical equation for the vapor pressure of liquids as a function of temperature [J]. The Journal of Chemical Physics, 1953, 21(2): 264-267.

RIEDEL L A. A new universal vapor pressure formula [J]. Chemie Ingenieur Technik, 1954, 26(5): 259-264.

MILLER D G. Derivation of two equations for the estimation of vapor pressures [J]. The Journal of Physical Chemistry, 1964, 68(6): 1399-1408.

THEK R E, STIEL L I. A new reduced vapor pressure equation [J]. AIChE Journal, 1966, 12(3): 599-602.

GOODWIN R D. Nonanalytic vapor pressure equation with data for nitrogen and oxygen [J]. Journal of Research of the Notional Bureau of Standards: A Physics and Chemistry, 1969, 73A(5): 487-491.

AMBROSE D, COUNSELL J F, DAVENPORT A J. The use of Chebyshev polynomials for the representation of vapour pressures between the triple point and the critical point [J]. The Journal of Chemical Thermodynamics, 1970, 2(2): 283-294.

WAGNER W. New vapour pressure measurements for argon and nitrogen and a new method for establishing rational vapour pressure equations [J]. Cryogenics, 1973, 13(8): 470-482.

WU J T, LIU Z G. An accurate vapor pressure equation with good extrapolation characteristics [J]. International Journal of Thermophysics, 2005, 26(3): 767-784.

LEMMON E W, SPAN R. Short fundamental equations of state for 20 industrial fluids [J]. Journal of Chemical Engineering Data, 2006, 51(3): 785-850.

LEMMON E W, JACOBSEN R T. A new functional form and new fitting techniques for equations of state with application to pentafluoroethane(HFC-125)[J]. Journal of Physical and Chemical Reference Data, 2005, 34(1): 69-108.

DIKY V, MUZNY C D, SMOLYANITSKY A Y, et al. Thermodata engine(TDE)version 10.1(pure compounds, binary mixtures, ternary mixtures, and chemical reactions): NIST standard reference database 103b [EB/OL].(2016-07-14)[2023-12-01]. https://www.nist.gov/publications/thermodata-engine-tde-version-101-pure-compounds-binary-mixtures-ternary-mixtures-and.

FIGURSKI G, MUHLENBRUCH M. Liquid-gas equilibrium of an acetone(1)+vinylacetate(2)system at 760 torr [J]. Zeitschrift Fur Physikalische Chemie-International Journal of Research in Physical Chemistry Chemical Physics, 1978, 259(2): 357-362.

OSCARSON J L, LUNDELL S O, CUNNINGHAM J R. Phase equilibria for ten binary systems [J]. AIChE Symposium Series, 1987, 83(256): 1-17.

STEVENS R M M, VAN ROERMUND J C, JAGER M D, et al. High-pressure vapour-liquid equilibria in the systems carbon dioxide + 2-butanol, + 2-butyl acetate, + vinyl acetate and calculations with three EOS methods [J]. Fluid Phase Equilibria, 1997, 138(1/2): 159-178.

SWAMY P A, VAN WINKLE M. Vapor-liquid equilibria at 760 Mm. mercury for the system vinyl acetate-2,4-Dimethyl pentane [J]. Journal of Chemical and Engineering Data, 1965, 10(3): 214-215.

ZERNOV V S, KOGAN V B, LYUBETSKII S G. Liquid-vapor phase equilibria in binary systems: Ⅲ liquid-vapor equilibrium in the ethylene-vinyl acetate system [J]. Zhurnal Prikladnoi Khimii, 1971, 44: 1819-1823.

KAPOOR S, RATTAN V K. Vapor-liquid equilibria and excess properties of the binary system vinyl acetate + p-xylene [J]. Journal of Chemical Engineering Data, 2005, 50(6): 1897-1901.

RAFIEE H R, FROUZESH F, MIRI S. Volumetric properties for binary mixtures of ethyl acetate, vinyl acetate and tert-butyl acetate with 1-propanol and iso-butanol at T=(293.15—313.15)K and P=0.087 MPa [J]. Journal of Molecular Liquids, 2016, 213: 255-267.

RUDOI-KOLKER V M, GRIGORYAN K A. Density and viscosity of ternary system of acetaldehyde + acetic acid + vinyl acetate [J]. Zhurnal Prikladnoi Khimii, 1964, 37: 1622-1623.

WISNIAK J, CORTEZ G, PERALTA R D, et al. Density, excess volume, and excess coefficient of thermal expansion of the binary systems of dimethyl carbonate with butyl methacrylate, allyl methacrylate, styrene, and vinyl acetate at T=(293.15, 303.15, and 313.15)K [J]. The Journal of Chemical Thermodynamics, 2008, 40(12): 1671-1683.

ZERNOV V S, KOGAN V B, LYUBETSKII S G, et al. Compressibility of an ethylene-vinyl acetate system [J]. Zhurnal Prikladnoi Khimii, 1973, 48(8): 1829-1831.

Views

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Simulation Study on the Effect of Hydrogen/Nitrogen Addition on Soot Formation in Ethylene Diffusion Flames

Equation of State for Normal Hydrogen

A New Equation of Liquid and Gaseous Densities for Dimethyl Ether

Turbulent Kinetic Energy Dissipation Mechanism of Supercritical Carbon Dioxide Leakage Flow in a Scallop Bionic Seal Cavity

A Structure-Semantics-Residual Collaborative Image Compression Framework：Towards Privacy Protection and High-Fidelity Reconstruction

Related Author

YAN Zhiyu

SHI Congling

XIONG Xinyi

LEI Bohan

LI Qianqian

WANG Jinhua

HUANG Zuohua

吴江涛

Related Institution

西安交通大学绿色氢电全国重点实验室，710049，西安State Key Laboratory of Multiphase Flow in Power Engineering, Xi'an Jiaotong University, Xi'an 710049, China

中国安全生产科学研究院城市安全研究所，100012，北京Urban Security Institute, China Academy of Safety Science and Technology, Beijing 100012, China

Key Laboratory of Thermo-Fluid Science and Engineering of MOE, Xi 'an Jiaotong University

⁰