基团贡献方阱链流体状态方程的开发与应用

发布时间：2018-11-02 15:25

【摘要】：化工过程设计、模拟、优化等方面均离不开流体的热物理性质和相平衡数据。利用状态方程模拟流体的热物理性质和相平衡数据对于指导实际工业生产、优化操作条件、完善工艺过程具有极其重要的作用。在缺乏实验数据情况下,开发具有预测功能的状态方程对于拓展理论模型在宽广范围内的应用具有十分重要的现实意义。本文将基团贡献法的思路引入到变阱宽方阱链流体状态方程(SWCF-VR)中,构建了基团贡献方阱链流体状态方程(GC-SWCF),力求通过基团参数获得状态方程的模型参数,以期使状态方程具备预测功能。利用纯物质密度的实验数据得到了8种有机基团和16种金属基团对GC-SWCF方程中模型参数的贡献值,为预测由这些基团构建的物质的热力学性质奠定了基础。研究发现,GC-SWCF方程能满意预测高碳直链烷烃和1-醇的密度,其总的平均偏差分别为2.39%和2.03%。在较宽的温度和压力范围内,GC-SWCF方程能令人满意的预测16种液态金属的密度,总体平均偏差仅为0.16%。不仅如此,在远离临界点时,GC-SWCF方程还能较好预测有机物的蒸发焓,对烯烃和酮类蒸发焓预测的平均误差分别为4.80%和4.88%。采用一个与温度无关的可调参数,GC-SWCF方程能在较宽温度范围内计算二元烷烃混合物以及二元烷烃-醇混合物的密度,其平均误差分别为0.59%和1.16%,并可预测不同温度、压力以及组成下的合金的密度。对于由分子结构比较简单且差异不大的有机物所构成的二元系统,GC-SWCF方程可满意计算气液相平衡,其关联计算得到的温度平均偏差为1.84K,压力平均偏差为3.20kPa,总体气相平均偏差为1.98%。对于存在缔合作用的系统,GC-SWCF方程的计算效果稍差,但能再现实验现象。
[Abstract]:The design, simulation and optimization of chemical processes can not be separated from the thermo-physical properties and phase equilibrium data. It is very important to simulate the thermo-physical properties and phase equilibrium data of the fluid by using the equation of state for guiding the actual industrial production, optimizing the operating conditions and perfecting the technological process. In the absence of experimental data, the development of state equations with predictive function is of great practical significance in expanding the application of the theoretical model in a wide range. In this paper, the group contribution method is introduced into the variable well wide square well chain fluid state equation (SWCF-VR), and the group contribution square well chain fluid state equation (GC-SWCF) is constructed. The model parameters of the equation of state are obtained by the group parameters. It is expected that the equation of state can be predicted. The contribution values of 8 organic groups and 16 metal groups to the model parameters in the GC-SWCF equation were obtained by using the experimental data of pure matter density, which laid a foundation for predicting the thermodynamic properties of the substances constructed from these groups. It is found that the GC-SWCF equation can predict the density of high carbon alkanes and 1-alcohols satisfactorily, and the total average deviations are 2.39% and 2.03%, respectively. In a wide range of temperature and pressure, the GC-SWCF equation can satisfactorily predict the density of 16 liquid metals, and the overall average deviation is only 0.16. Moreover, the GC-SWCF equation can well predict the enthalpy of evaporation of organic matter when it is far away from the critical point. The average error for the prediction of enthalpy of evaporation of olefins and ketones is 4.80% and 4.88%, respectively. Using a temperature-independent adjustable parameter, the GC-SWCF equation can calculate the densities of binary alkane mixtures and binary alkane alcohol mixtures in a wide range of temperatures. The average errors are 0.59% and 1.16%, respectively. The density of alloys at different temperatures, pressures and compositions can be predicted. For the binary system composed of organic compounds with relatively simple molecular structure and little difference, the GC-SWCF equation can satisfactorily calculate the vapor-liquid equilibrium. The average deviation of temperature and pressure is 1.84 KA and 3.20 KPA respectively, and the correlation calculation results show that the average deviation of temperature and pressure are 1.84 KA and 3.20 KPA, respectively. The average deviation of the total gas phase is 1.98. For the system with association interaction, the GC-SWCF equation is less effective, but it can reproduce the experimental phenomena.
【学位授予单位】：华东理工大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TQ021

【参考文献】