【作者】 宣爱国；

【导师】 马沛生； 吴元欣；

【作者基本信息】 天津大学 ， 化学工艺， 2007， 博士

【摘要】 碳酸二苯酯是一种重要的有机碳酸酯。本课题选择合成碳酸二苯酯相关物系即选择一氧化碳、氧气、苯酚、碳酸二甲酯、甲醇、乙醇等物料作为研究对象,进行高压气液相平衡基础研究。利用一套测定高压气液相平衡的实验装置,采用循环法测定了一氧化碳和氧气在2.0~9.0 MPa压力范围内、在各种纯溶剂和混合溶剂中的溶解度数据。实验结果表明,一氧化碳和氧气在单一溶剂和混合溶剂中溶解度均随压力的升高而增大,而随温度的变化不大。用各种不同的立方型状态方程如SRK、PR和PRSV方程,加上几种不同形式的混合规则如传统的二次型混合规则、Wong-Sandler混合规则、MHV1混合规则、NRTL混合规则以及van Laar混合规则,对实验的三元体系进行了关联。计算了一氧化碳、氧气在单一溶剂和混合溶剂中的亨利系数。由一氧化碳-苯酚-乙醇、一氧化碳-碳酸二甲酯-甲醇、氧气-苯酚-乙醇、氧气-碳酸二甲酯-甲醇三元体系的实验溶解度数据,回归出相应的二元交互作用参数kij和二元交互作用能量参数Δgij。关联结果表明,改进的计算模型(方法八)与实验值有较好的吻合,平均误差小于2%。一氧化碳、氧气在溶剂中的逸度f? iL与压力呈线性关系。关联得到了恒温恒压条件下f? CLO与混合溶剂浓度xi的模型。进一步选用UNIFAC法对苯酚-乙醇、氧气-碳酸二甲酯等二元体系研究组分的活度系数。定义了新的基团-碳酸基团,利用实验数据关联出碳酸基团的UNIFAC参数,补充了文献中这个基团所缺少的数据。计算结果表明用活度系数法研究高压气液相平衡,对苯酚-乙醇、氧气-碳酸二甲酯二元体系的估算与实验值能很好地吻合。关联的平均误差为0.675 %。对氧气在碳酸二甲酯-甲醇、苯酚-乙醇混合溶剂溶解度的预测也有较好的结果。利用DA-505U型振动管密度仪测定了苯酚-乙醇体系在五个不同温度下的密度。通过对Redich-Kister方程进行修正,得出了过剩摩尔体积的计算模型,同时回归出苯酚-乙醇体系在298.15K~348.15K温度范围内的模型参数。为了能预测苯酚-乙醇体系的热力学性质,选用SRK方程和HVOS混合规则计算了该体系的AE,为进一步地研究该溶液的活度系数奠定了一些基础。总而言之,论文所测定的一氧化碳和氧气在高压下于纯溶剂和混合溶剂中的溶解度和提供的计算模型,是碳酸二苯酯的合成、分离等工程化应用所必需的数据。碳酸基团的定义及其回归的参数,将使得用基团贡献法的对该体系的计算更为可能。苯酚-乙醇体系过剩体积、过剩AE自由能研究以及活度系数的估算,也提供一批热力学数据。更多还原

【Abstract】 Diphenyl carbonate is an important aromatic carbonate. Its related reactants such as carbonate monoxide, oxygen, phenol, dimethyl carbonate, methanol and ethanol and so on, were chosen as the systems that were studied on phase equilibrium at high pressure.The solubilities of CO and O2 in some above solvents and their mixed solvents were determined at the pressure range from 2.0 MPa to 9.0 MPa by a set of the experimental apparatus through cycle method for gas liquid equilibria systematically. The experimental results show that all the solubilities of CO and O2 in unitary solvents and their mixed solvents are increased along with the rise of pressure.The calculation of gas liquid equilibrium for the ternary systems can be figured up using various cubic equation of state, ie SRK, PR and PRSV EOS etc. At the same time, the diversity mixing rules, for example, the traditional quadratic form mixing rules, Wong-Sandler mixing rules, MHV1mixing rules, NRTL mixing rules and van Laar mixing rules, were coupled with the expression of the constant of EOS. Henry’s constants of CO and O2 in the single solvent and mixing solvents were fitted to the experimental data .The binary interaction parameters kij and the binary interaction energy parametersΔgij were regressed from the solubilities for the experimental systems for CO-C6H5OH-C2H5OH、CO-(CH3O)2CO-CH3OH、O2-C6H5OH-C2H5OH and O2-(CH3O)2CO-CH3OH, respectively. It is fairly obvious from the correlated results that the agreement between experimental data of solubility and calculated ones with the proposed model (method 8) was rather satisfactory. The mean error is less than 2 %. The fugacity f? iL for the components CO and O2 has a good linear function. At the constant temperature and pressure, the new model can be presented on the relationship between the fugacity f? iL and the mole fraction of component (1) x1 in the mixed solvents.Furthermore, the activity coefficientsγi for the component i in the binary systems such as phenol-ethanol, oxygen-dimethyl carbonate can be computed by employing UNIFAC method. A new group carbonate-group has been defined in dimethyl carbonate and its group volume parameter, group surface area parameter and group interaction energy parameters in the studied systems were derived from the experimental data. It should be noted that these parameters is a supplement because carbonate-group is lack in the UNIFAC method literatures. According to the calculated results, they have an approving agreement with the experimental solubilities. The mean error calculated is 0.675%。Besides, the prediction of solubility can be suitable for O2 in C6H5OH-C2H5OH and (CH3O)2CO-CH3OH mixed solvents, respectively. But the calculated accuracy for the gas liquid equilibrium at high pressure is inferior to one obtained from EOS method.On the other hand, the densities were measured by a vibrating densimeter and the excess molar volumes VE were calculated at five temperatures and atmospheric pressure for phenol-ethanol. By the improved Redlich-Kister equation, the model parameters of VE were fitted to the experimental density data at the temperature range from 298.15 K to 348.15 K.For prediction of the thermodynamic property for phenol-ethanol, the AE was discussed by SRK EOS coupled with HVOS mixing rules. It can be concluded that EOS method can be used for the calculated of the liquid solution by matching the mixing rules. Hence these works are an investigated basis of the activity coefficient.In a word, firstly the measured solubilities of CO and O2 in unity solvent and mixed solvents and its computed model may be an essential data provided for the synthesis technology and separation process of diphenyl carbonate. Secondly, the definition and the regressive parameters of new carbonate-group will make the calculation of group contribution more realiable. Finally, the excess molar volume and the excess Helmholtz free energy were studied, and a series of activity coefficient were first presented so that it makes the prediction of the thermodynamic property for phenol-ethanol becomes possible.更多还原