UNIFAC模型关联碳酸酯合成体系的汽液平衡

Correlation of Vapor-Liquid Equilibrium for Carbonates Synthesis System by UNIFAC Model

利用UNIFAC模型对甲醇氧化羰基合成碳酸二甲酯(DMC)体系中的各组分及DMC与苯酚酯交换合成碳酸二苯酯(DPC)体系中的各组分进行了基团划分。根据实验测定的甲醇-DMC、甲醇-草酸二甲酯(DMO)、DMC-DMO、甲醇-苯酚、DMC-苯酚五组二元物系等温汽液平衡数据,拟合了新基团-OCOO-和其他基团间的UNIFAC相互作用参数,扩充了UNIFAC模型的应用范围。与原基团划分的UNIFAC模型关联结果比较,采用新基团划分法推算得到的汽液平衡数据的计算值与实验值偏差较小,说明新基团划分更合理。

Since the vapor-liquid equilibrium （VLE） data which can be used for the design of the dimethyl carbonate （DMC） and diphenyl carbonate （DPC） productions are very limited, the UNIFAC model was considered to be used to predict the VLF data of those binary systems needed for the design of the DMC and DPC synthesis processes. When the UNIFAC method was used to calculate the VLE data of the binary systems of carbonates, a new group division of --OCOO-- was proposed to replace the group division of--O-- and --COO-- for carbonates which was proposed by some other authors, and correspondingly the new interaction parameters of UNIFAC model were regressed by using the experimental VLE data of methanol-dimethyl carbonate （DMC）, methanol-dimethyl oxalate （DMO）, DMC-DMO, methanol-phenol and DMC-phenol binary systems. Using the modified group division and the interaction parameters obtained, the calculated VLE data of the binary systems mentioned above are more coincident with the experimental data than that obtained by using the original group division one, which indicates that with the proposed group division of --OCOO-- and the corresponding interaction parameters, the UNIFAC model extends its application field and can be used to calculate the VLE data of the binary carbonate systems with a good accuracy.