碳酸二苯酯与低碳醇物系固液平衡研究
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摘要
碳酸二苯酯(Diphenyl Carbonate,以下简称DPC)是酯基交换法合成聚碳酸酯(PC)的单体反应物之一。目前,世界各国对高质量的聚碳酸酯的需求量日益增加,并大力开发PC的非光气法合成工艺,而DPC的纯度又对PC的质量有很大的影响,因此DPC的提纯工艺就成为当前研究的热点。DPC在高温下极易分解,所以冷却结晶法则成为DPC提纯的一种有效方法。固液平衡数据是研究结晶工艺必不可少的基础数据,所以本文对DPC和七种不同低碳醇溶剂的固液平衡进行了研究。
本文采用静态平衡法测定了DPC在甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇和仲丁醇七种溶剂中的固液平衡数据。实验结果表明,DPC在以上溶剂中的溶解度都随温度的升高而增大,所以可以采用冷却结晶法对DPC进行精制。DPC固液平衡数据,是重结晶研究中溶剂选择和工艺条件确定的基础,也是聚碳酸酯合成的动力学研究和工业扩大必不可少的基础数据。
固液平衡模型研究不仅减少了实验量,而且对工业过程设计也具有重要的指导意义。本文采用了三种具有代表性的数学模型,对实验测定物系进行了固液平衡理论研究,且均取得了令人满意的效果。
本文采用具有预测功能的UNIFAC方程对实验测定物系进行研究。在研究中定义了一种新基团C(O)O2,计算了其表面积参数和体积参数,并用实验数据回归了该基团与基团CH3OH、CH2、OH和ACH的相互作用参数。这不仅填充了UNIFAC数据库的空白,也推动了UNIFAC模型在固液平衡研究中的发展。UNIFAC方程对本文所测定溶解度数据的预测值与实验值的最大平均相对误差不超过2.1%,与实验数据符合良好。
本文又分别采用两参数活度系数关联方程Wilson方程和固液平衡简化方程λh方程对各物系实验数据进行了关联。Wilson方程对各物系计算的平均相对误差最大值为0.36%,λh方程的最大平均误差为0.87%。Wilson方程的计算精度稍高些,但总体来说两种模型都取得了令人满意的结果。
Diphenyl carbonate is one of the main monomers of polycarbonate (PC), and we call it DPC for short. At present, the need for PC by the world industry is increasing day by day. The purity of the DPC has an important impact on the quality of the PC, so more study on the purification for DPC is needed. DPC is a substance which is prone to decompose at high temperature, so cooling crystallization is used for the purification.
The solid-liquid equilibrium data is necessary for the study of cooling crystallization, so the solubility of DPC in seven solvents were determined by static method in this paper. The solvents all remain with alcohol, including methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, sec-Butanol. As the result of experiments, cooling crystallization can be used to refine DPC because the solubility of DPC increases as the temperature ascends. The solubility data of DPC is not only the base for the solvents selection and process conditions study of cooling crystallization but also the base data for the study of dynamics and industrial magnification.
The study on solid-liquid equilibrium not only can avoid many unnecessary experiments, but also can provide direction to the industry. The systems in this paper were studied by three solid-liquid equilibrium models, and the results are all very pleasant.
At first, the UNIFAC group contribution method was used in the calculation of the systems in this paper. A new group C(O) O2 was defined in this paper, and the group volume and surface-area parameters were calculated. The interaction parameters of C(O)2O with CH3OH, CH2, OH and ACH were regressed with the data of the seven binary systems in this paper. The systems of this paper were predicted with UNIFAC, and the average correlation error was less than 2.1%.
The experimental data were also correlated by Wilson equation andλh equation. Both of two equations have two parameters that have to be regressed with the experimental data. The largest average correlation error of the two equation were 0.36% and 0.87%, and they both fit the experimental data well.
本文采用静态平衡法测定了DPC在甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇和仲丁醇七种溶剂中的固液平衡数据。实验结果表明,DPC在以上溶剂中的溶解度都随温度的升高而增大,所以可以采用冷却结晶法对DPC进行精制。DPC固液平衡数据,是重结晶研究中溶剂选择和工艺条件确定的基础,也是聚碳酸酯合成的动力学研究和工业扩大必不可少的基础数据。
固液平衡模型研究不仅减少了实验量,而且对工业过程设计也具有重要的指导意义。本文采用了三种具有代表性的数学模型,对实验测定物系进行了固液平衡理论研究,且均取得了令人满意的效果。
本文采用具有预测功能的UNIFAC方程对实验测定物系进行研究。在研究中定义了一种新基团C(O)O2,计算了其表面积参数和体积参数,并用实验数据回归了该基团与基团CH3OH、CH2、OH和ACH的相互作用参数。这不仅填充了UNIFAC数据库的空白,也推动了UNIFAC模型在固液平衡研究中的发展。UNIFAC方程对本文所测定溶解度数据的预测值与实验值的最大平均相对误差不超过2.1%,与实验数据符合良好。
本文又分别采用两参数活度系数关联方程Wilson方程和固液平衡简化方程λh方程对各物系实验数据进行了关联。Wilson方程对各物系计算的平均相对误差最大值为0.36%,λh方程的最大平均误差为0.87%。Wilson方程的计算精度稍高些,但总体来说两种模型都取得了令人满意的结果。
Diphenyl carbonate is one of the main monomers of polycarbonate (PC), and we call it DPC for short. At present, the need for PC by the world industry is increasing day by day. The purity of the DPC has an important impact on the quality of the PC, so more study on the purification for DPC is needed. DPC is a substance which is prone to decompose at high temperature, so cooling crystallization is used for the purification.
The solid-liquid equilibrium data is necessary for the study of cooling crystallization, so the solubility of DPC in seven solvents were determined by static method in this paper. The solvents all remain with alcohol, including methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, sec-Butanol. As the result of experiments, cooling crystallization can be used to refine DPC because the solubility of DPC increases as the temperature ascends. The solubility data of DPC is not only the base for the solvents selection and process conditions study of cooling crystallization but also the base data for the study of dynamics and industrial magnification.
The study on solid-liquid equilibrium not only can avoid many unnecessary experiments, but also can provide direction to the industry. The systems in this paper were studied by three solid-liquid equilibrium models, and the results are all very pleasant.
At first, the UNIFAC group contribution method was used in the calculation of the systems in this paper. A new group C(O) O2 was defined in this paper, and the group volume and surface-area parameters were calculated. The interaction parameters of C(O)2O with CH3OH, CH2, OH and ACH were regressed with the data of the seven binary systems in this paper. The systems of this paper were predicted with UNIFAC, and the average correlation error was less than 2.1%.
The experimental data were also correlated by Wilson equation andλh equation. Both of two equations have two parameters that have to be regressed with the experimental data. The largest average correlation error of the two equation were 0.36% and 0.87%, and they both fit the experimental data well.
引文
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