基团贡献状态方程的开发与热力学模型参数的理论预测

屈绍广; 王昶昊; 施云海; 彭昌军; 刘洪来; 胡英

doi:10.11949/0438-1157.20191149

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基团贡献状态方程的开发与热力学模型参数的理论预测

热力学 | 更新时间：2026-07-24

- 基团贡献状态方程的开发与热力学模型参数的理论预测
- Development of group-contribution equation of state and theoretical prediction of thermodynamic model parameters
- 化工学报 2020年71卷第1期页码：200-208
- 作者机构：
  
  1. 华东理工大学化学与分子工程学院，上海 200237
  2. 华东理工大学化工学院，上海 200237
- 作者简介：
  
  屈绍广(1990—), 男,硕士，18818211686@126.com
  彭昌军（1964—）,男,博士，教授，cjpeng@ecust.edu.cn
- 基金信息：
  
  国家重点基础研究计划项目(2015CB251401);国家自然科学基金项目(21476070;21776069)
- DOI：10.11949/0438-1157.20191149
  中图分类号： TQ 013.1
- 收稿：2019-10-09，
  
  修回：2019-11-15，
  
  网络首发：2020-08-12，
  
  纸质出版：2020-01-05
- 稿件说明：
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屈绍广, 王昶昊, 施云海, 彭昌军, 刘洪来, 胡英. 基团贡献状态方程的开发与热力学模型参数的理论预测[J]. 化工学报, 2020, 71(1): 200-208

QU Shaoguang, WANG Changhao, SHI Yunhai, PENG Changjun, LIU Honglai, HU Ying. Development of group-contribution equation of state and theoretical prediction of thermodynamic model parameters[J]. CIESC Journal, 2020, 71(1): 200-208
屈绍广, 王昶昊, 施云海, 彭昌军, 刘洪来, 胡英. 基团贡献状态方程的开发与热力学模型参数的理论预测[J]. 化工学报, 2020, 71(1): 200-208 DOI： 10.11949/0438-1157.20191149.

QU Shaoguang, WANG Changhao, SHI Yunhai, PENG Changjun, LIU Honglai, HU Ying. Development of group-contribution equation of state and theoretical prediction of thermodynamic model parameters[J]. CIESC Journal, 2020, 71(1): 200-208 DOI： 10.11949/0438-1157.20191149.

摘要

热力学模型是研究流体相行为和热力学性质的重要工具。理论模型的有效应用离不开模型参数的确定。为赋予热力学模型的预测功能，目前的策略一是建立基团贡献(GC)状态方程(EOS)，二是探索热力学模型参数的理论预测方法。围绕先前开发的变阱宽方阱链流体状态方程(SWCF-VR)，采用基团贡献法思路获得了不同基团对模型参数的贡献值，建立了GC-SWCF方程，证实GC-SWCF方程能满意预测纯物质的密度。进一步将似导体屏蔽模型(COSMO)与SWCF结合，基于COSMO方法获得了192种有机化合物的SWCF方程的模型参数，这是一种不依赖实验数据确定模型参数的理论方法。发现COSMO+SWCF能较好地预测纯物质的密度。引入一个与温度无关的二元交互作用可调参数后，GC-SWCF与COSMO+SWCF都可应用于二元混合物密度与气液相平衡的计算中。

Abstract

Thermodynamic model is an important tool to study fluid phase behaviour and thermodynamic properties.The effective application of theoretical model is inseparable from the determination of model parameters. To endow the prediction function of the thermodynamic model

the current strategy is to establish the group contribution(GC) equation of state(EOS)

and to explore the theoretical prediction method of the parameters of the thermodynamic model. Based on the previously developed equations of state for square-well chain fluids with variable well-width range(GC-SWCF-VR )

the group contribution equations of state for square-well chain fluids(GC-SWCF) were established

and the contribution values of different groups to model parameters were obtained by using group contribution method. It was proved that the density of pure substences can be predicted satisfactorily by GC-SWCF. Combining conductor-like screening model(COSMO) with SWCF

the model parameters of SWCF equation for 192 organic compounds were obtained based on COSMO method

which is a theoretical method to determine model parameters without relying on experimental data. It is found that COSMO+SWCF can predict the density of pure substences. Using one temperature-independent binary interaction adjustable parameter

both GC-SWCF and COSMO+SWCF can be applied to the calculation of densities and vapor-liquid equilibrium for binary mixture.

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Keywords

references

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