【作者】 徐伟；

【导师】 田宜灵；

【作者基本信息】 天津大学 ， 物理化学， 2008， 博士

【摘要】 本文独创了国内第一套带石英可视窗的可变体积高压釜,利用霍尔探测仪实现体积的准确测量,利用自动控温、恒温法和用手摇泵调节实现宽温度、压力范围的准确调控,用微型高压钢瓶实现高压状态直接取样,因此可方便地实现对高压气液平衡的准确测量。并用文献数据对该装置的可靠性进行了验证。同时还建立了一套操作方便的组分解析装置,对气液相组成进行分析。采用静态分析法测定了二甲醚氧化羰基化反应体系中氧气、一氧化碳、二氧化碳、氮气以及二甲醚分别与碳酸二甲酯组成的二元系统的高压气液相平衡组成、相密度和体积。结果表明五种气体在碳酸二甲酯中的溶解度随着压力的增加而明显加大。碳酸二甲酯在二甲醚气体中随着压力的增加含量逐渐增加,但是在氧气、一氧化碳、二氧化碳和氮气四种气体中却增加不明显。选择PR和PRSV方程分别与van der waals-1型、van der waals-2型、Margules型混合规则和活度系数表达的混合规则搭配成六种不同的计算方法,采用搜索法对上述二元高压气液平衡(GLE)实验数据进行优化计算,系统地分析了状态方程、混合规则、回归方法等对计算结果的影响。结果表明,PRSV方程与van der waals型混合规则组成的方法、PR方程与活度系数表达的混合规则组成的方法的计算结果与实验值符合较好。本文测定的二甲醚氧化羰基化制碳酸二甲酯反应体系中氧气、一氧化碳、二氧化碳、氮气以及二甲醚分别与碳酸二甲酯组成的二元系统的高压气液相平衡数据填补了国内外对这五个体系的研究空白,为研究二元系统的溶液理论和GLE(气液平衡)计算提供了丰富的基础数据,也推进了气液相平衡理论及计算方法的进展。同时为二甲醚氧化羰基化制碳酸二甲酯反应实现工业化生产设计提供了必需的热力学数据数据。本论文还讨论了四氯化碳、氯仿、溴仿、四氯化硅、苯、氯苯、溴苯和硝基苯八种纯物质的熔点曲线,温度范围为226 K到915 K,压力最高为3500 MPa。通过对数据的拟合可以得到熔点方程。熔化过程中的摩尔焓变和摩尔热力学能变化可以同利用所得的熔点方程参数计算得到。更多还原

【Abstract】 A set of variable-volume autoclave with a quartz window has been made domestically for the first time. The accurate volume of a sample could be measured with a hall-effect probe, and the precise adjustment within wide range of temperatures and pressures could be actualized. At high pressure, the samples were taken directly from the autoclave with a small steel vessel. So the accurate vapor-liquid equilibrium data could be obtained. The experiment equipment was proved to be reliable and accurate comparing with literature data. A simple equipment was also built up for analysizing the composition of the vapor and liquid samples. The vapor-liquid equilibrium data (including ingredient, density and volume) of the five binary systems of synthesizing dimethyl carbonate by oxidation carbonylation of dimethyl ether (oxygen+ dimethyl carbonate(O2 + DMC), carbon monoxide+ dimethyl carbonate(CO + DMC), carbon dioxide + dimethyl carbonate(CO2 + DMC), nitrogen+ dimethyl carbonate(N2 + DMC) and dimethyl ether+ dimethyl carbonate(DME + DMC)) have been measured at different temperatures and pressures with isothermal static analytical method. The vapor-liquid equilibrium data show that the solubilities of five gases in dimethyl carbonate increase drastically with increasing pressures at the given temperatures. The contents of dimethyl carbonate in the dimethyl ether gas rise with increasing pressures, but the contents of dimethyl carbonate in other four gases increase faintly.The high-pressure GLE data are also calculated with eight methods for above five systems. The PR and PRSV EOS and four different mixing rules were used. The Suitability of those EOSs and calculated precision were discussed systemically. Three methods showed excellent calculation effects which each other were made up of (PR EOS with activity coefficient and associated theory) and (PR EOS with var der waals mixing rules).The high pressure GLE data of the five binary systems could provide abundant fundamental data for the study of the solution theory and the calculation of GLE, which could develop of the phase equilibrium theory and the calculation methods. At the same time, it could provide the necessary data for the process design of synthesizing dimethyl carbonate by oxidation carbonylation of dimethyl ether.This paper also reports the fusion curves of carbon tetrachloride, chloroform, bromoform, silicon tetrachloride, benzene, nitrobenzene, bromobenzene and chlorobenzene at pressures up to 3500 MPa between 226 K and 915 K. The fusion equations based on the two– and one-phase approaches were used to fit experimental data. The changes of the molar enthalpy and molar thermdynamical energy on fusion were calculated using the parameters of fitted equation.更多还原