CAJ | 학술논문

混合物汽液相平衡通常需要引入合适的混合法则才能更好地进行关联。针对目前混合法则中协体积项b的改进提出了一种新的修正协体积项b的方法。该方法以Mie势能理论、London色散力理论为基础，同时引入Leach等分子形状系数进行修正，这样协体积项b中的交互作用参数lij形式上是纯组分分子形状系数θ和φ及临界参数的函数，无需实验数据拟合得到，从而真实反映了二元混合物的实际混合情况。将修正的协体积项b运用于MHV1、LCVM及HV混合法则并结合PR+NRTL模型对不同种类的16个体系汽液相平衡进行了计算，并与采用b=∑xibi的 MHV1、LCVM 及 HV 混合法则结合 PR+NRTL 模型计算的结果进行比较，结果表明运用修正的协体积项 b的混合法则+PR+NRTL模型所得的计算结果精度优于采用b=∑xibi的MHV1、LCVM及HV混合法则+PR+NRTL模型的计算结果。
혼합물기액상평형통상수요인입합괄적혼합법칙재능경호지진행관련。침대목전혼합법칙중협체적항b적개진제출료일충신적수정협체적항b적방법。해방법이Mie세능이론、London색산력이론위기출，동시인입Leach등분자형상계수진행수정，저양협체적항b중적교호작용삼수lij형식상시순조분분자형상계수θ화φ급림계삼수적함수，무수실험수거의합득도，종이진실반영료이원혼합물적실제혼합정황。장수정적협체적항b운용우MHV1、LCVM급HV혼합법칙병결합PR+NRTL모형대불동충류적16개체계기액상평형진행료계산，병여채용b=∑xibi적 MHV1、LCVM 급 HV 혼합법칙결합 PR+NRTL 모형계산적결과진행비교，결과표명운용수정적협체적항 b적혼합법칙+PR+NRTL모형소득적계산결과정도우우채용b=∑xibi적MHV1、LCVM급HV혼합법칙+PR+NRTL모형적계산결과。
To get better correlation results of vapor liquid equilibrium (VLE) of mixture systems, it is usually necessary to select the suitable mixing rule. The modifications of force parameter a have obtained good results in both theory and application. However, the research on co-volume parameter b is less and usually empirical. A new modified method for co-volume b was presented. In the revised mixing rule, the molecular shape factors obtained from Leach et al were introduced to amend co-volume b on the basis of Mie potential-energy and London dispersion theory. Thus, the interactive parameter lij in co-volume b was dependent on the molecular shape factorsθ , φ, and critical parameters of the components. Without experimental data, molecular shape factors and interactive parameter lij could be obtained, which could be used to reflect the actual situations of mixture systems. The VLE calculation results for 16 kinds of different systems were given by using modified co-volume parameter b in MHV1/LCVM/HV mixing rules combined with PR EOS and NRTL models, and the results were compared with the results of using b=∑xibi in MHV1/LCVM/HV mixing rule combined with PR EOS and NRTL models. The models with the modified co-volume b were better than those with b=∑xibi to some extent.