基于官能团非等活性假设的尼龙66盐溶液聚合动力学模型

doi:10.11949/0438-1157.20200208

化工学报 ›› 2020, Vol. 71 ›› Issue (11): 5208-5215.DOI: 10.11949/0438-1157.20200208

• 催化、动力学与反应器 • 上一篇下一篇

基于官能团非等活性假设的尼龙66盐溶液聚合动力学模型

王颖¹(),林程²,崔晶²,奚桢浩¹(),赵玲^1,³

^1.华东理工大学化工学院，化学工程联合国家重点实验室，上海 200237
^2.中国石化上海石油化工研究院，上海 201208
^3.新疆大学化学与化工学院，石油天然气精细化工教育部重点实验室，新疆乌鲁木齐 830046

收稿日期:2020-02-28 修回日期:2020-05-23 出版日期:2020-11-05 发布日期:2020-11-05
通讯作者: 奚桢浩
作者简介:王颖（1995—），女，硕士研究生，wangying_hola@163.com
基金资助:
十三五国家重点研发计划项目(2016YFB0303001);国家自然科学基金项目(21878256);中央高校基本科研业务费专项资金(22221817014)

New kinetic model for polymerization process of nylon 66 salt solution based on functional group non-isoactivity

Ying WANG¹(),Cheng LIN²,Jing CUI²,Zhenhao XI¹(),Ling ZHAO^1,³

^1.State Key Laboratory of Chemical Engineering, College of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
^2.Sinopec Shanghai Research Institute of Petrochemical Technology, Shanghai 201208, China
^3.The Key Laboratory of Oil and Gas Fine Chemicals, Ministry of Education, College of Chemistry and Chemical Engineering, Xinjiang University, Urumqi 830046, Xinjiang, China

Received:2020-02-28 Revised:2020-05-23 Online:2020-11-05 Published:2020-11-05
Contact: Zhenhao XI

摘要/Abstract

摘要：

尼龙66盐溶液聚合过程属于动力学控制过程。基于官能团非等活性假设，在Mallon酸催化3阶反应动力学模型基础上，引入尼龙盐脱水反应，建立了新的尼龙66盐溶液聚合反应动力学模型，拟合得到了关键反应动力学模型参数，其中盐脱水反应速率常数为8.17×10^-3 kg?mol^-1?h^-1、活化能为19859 cal?mol^-1。与Mallon模型相比，新模型拟合效果更优，可在更宽的温度和水含量范围内准确预测聚合过程的变化。模拟仿真发现，盐脱水反应对聚合过程有重要影响，低温和高水含量下尼龙盐浓度高，聚合效率低；适当提高反应温度或降低初始水含量可以加快尼龙盐脱水反应，从而提高聚合反应效率。新的尼龙盐聚合动力学建模方法不仅适用于尼龙66，也可应用于尼龙1212等盐溶液聚合体系。

关键词: 尼龙66盐, 聚合, 酸催化, 反应, 动力学模型

Abstract:

The polymerization process of nylon 66 salt solution is a dynamically controlled process. Based on the assumption of unequal activity of functional carboxyl and amido groups, a new nylon 66 salt solution polymerization kinetic model was established by introducing the nylon salt dehydration reaction to the acid-catalyzed third-order reaction kinetic model and fitted to obtain the corresponding key kinetic parameters. The fitted salt dehydration reaction rate constant was 8.17×10^-3 kg?mol^-1?h^-1, while the activation energy was 19859 cal?mol^-1, respectively. Compared with Mallon model, the new developed model has a better fitting effect and can accurately predict the change of the polymerization process in a wider range of temperature and water content. Simulation results showed that salt dehydration reaction has an important effect on the polymerization process and the polymerization efficiency was relatively lower with higher concentration of nylon salt, especially under low temperature and high water content. Appropriately increase the reaction temperature or reduce the initial water content can accelerate the nylon salt dehydration reaction, thereby increasing the polymerization reaction efficiency. New nylon salt polymerization kinetics modeling method is not only applicable to nylon 66, but also to nylon 1212 and other salt solution polymerization systems.

Key words: nylon 66 salt, polymerization, acid-catalyzed, reaction, kinetic modeling

中图分类号:

TQ 316.4

王颖,林程,崔晶,奚桢浩,赵玲. 基于官能团非等活性假设的尼龙66盐溶液聚合动力学模型[J]. 化工学报, 2020, 71(11): 5208-5215.

Ying WANG,Cheng LIN,Jing CUI,Zhenhao XI,Ling ZHAO. New kinetic model for polymerization process of nylon 66 salt solution based on functional group non-isoactivity[J]. CIESC Journal, 2020, 71(11): 5208-5215.

图/表 10

图1 水桥

Fig.1 Water bridge

图2 “成盐”反应

Fig.2 Salting-like reaction

表1 模型参数估计结果

Table 1 Parameters of new model

反应动力学模型参数	参数估计结果	Mallon等^[12]模型参数值
A/ (kg²?mol^-2)	1.50×10^-10	1.81×10^-10
?H′/ (cal?mol^-1)	-18333	-18300
?H″/(cal?mol^-1)	-233.04	404.13
?S″/(cal?mol^-1?K^-1)	10.20	12.50
k_0,s / (kg?mol^-1?h^-1)	8.17×10^-3	—
E_s,a /( cal?mol^-1)	19859	—
k_0,f /( kg²?mol^-2?h^-1)	2.01×10³	7.17×10^-3
E_a / (cal?mol^-1)	7716.65	8578
C/( cal?mol^-1)	40761.50	40716
A_e	0.06678	0.06681

图3 不同温度和初始水/盐摩尔比条件下模拟值与实验值的比较

Fig.3 Comparison of simulated values with experimental data of different initial water/salt molar ratios at different temperatures

图4 初始水/盐摩尔比为6.23时不同温度下两模型模拟值与实验值比较

Fig.4 Comparison of simulated values of two models and experimental data with the initial water/salt mole ratio of 6.23 at different temperatures

图5 220℃不同初始水含量下两模型模拟值与实验值比较

Fig.5 Comparison of simulated values of two models and experimental data at 200℃ with different initial water/salt mole ratios

图6 不同反应条件下模拟值与实验值比较

Fig.6 Comparison of simulated values and experimental data under different reaction conditions

图7 不同温度下不同初始水/盐摩尔比时尼龙盐浓度及水含量随时间的变化情况

Fig.7 Changes of nylon salt and water concentration with time at different temperatures under different initial water/salt molar ratio

表2 拓展的模型参数估计结果

Table 2 Parameters of modified model

反应动力学模型参数	参数估计结果
A/ (kg²?mol^-2)	1.79×10^-10
?H′/ (cal?mol^-1)	-18263
?H″/( cal?mol^-1)	-832.07
?S″/ (cal?mol^-1?K^-1)	13.79
k_0,s /( kg?mol^-1?h^-1)	1.02 $×$ 10^-2
E_s,a /( cal?mol^-1)	15013
k_0,f / (kg²?mol^-2?h^-1)	2.35×10³
E_a /( cal?mol^-1)	3141
C/( cal?mol^-1)	40624
A_e	0.06554

表2 拓展的模型参数估计结果

Table 2 Parameters of modified model

反应动力学模型参数	参数估计结果
A/ (kg²?mol^-2)	1.79×10^-10
?H′/ (cal?mol^-1)	-18263
?H″/( cal?mol^-1)	-832.07
?S″/ (cal?mol^-1?K^-1)	13.79
k_0,s /( kg?mol^-1?h^-1)	1.02 $×$ 10^-2
E_s,a /( cal?mol^-1)	15013
k_0,f / (kg²?mol^-2?h^-1)	2.35×10³
E_a /( cal?mol^-1)	3141
C/( cal?mol^-1)	40624
A_e	0.06554

图8 拓展模型在不同反应条件下模拟值与实验值的比较

Fig.8 Comparison of simulated values with experimental data under different reaction conditions of new model

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基于官能团非等活性假设的尼龙66盐溶液聚合动力学模型

New kinetic model for polymerization process of nylon 66 salt solution based on functional group non-isoactivity

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