Thermodynamic modeling with new UNIFAC groups for solubility of nylon66-salt in water system

doi:10.11949/j.issn.0438-1157.20151235

Abstract

Abstract:

Modeling of PA66 polymerization process requires accurate solubility computation of nylon66-salt in water system. The UNIFAC activity coefficient method with new groups was applied to predict the solubility. The new groups were -CH₂COO^-·⁺H₃NCH₂- and -CH₂COOH, which characterized the component's special structure. The pure parameters of new UNIFAC groups and interaction parameters between new groups were obtained by regression with melting point and molar fusion enthalpy of PA66-salt as well as the solubility data of PA66-salt in water obtained by experiments. The UNIFAC model with new groups was used to simulate the solubility of PA66-salt in aqueous solution, giving a relative error of 2.1% from the experimental data. The model was further employed to simulate the concentration of PA66-salt under the industrial conditions (120℃) and gave a relative error as low as 5%, compared with 20% from the UNIFAC model with default groups in Aspen.

Key words: nylon66-salt, aqueous solution, solubility, UNIFAC model, UNIFAC groups

摘要：

尼龙66(PA66)盐在水中溶解度的准确计算是尼龙66 聚合过程模型化基础。选择UNIFAC 活度系数方法,针对PA66 聚合体系对组分进行基团划分,定义的新基团为羧基和氨基形成的缔合基团(-CH₂COO^-·⁺H₃NCH₂-)、羧基与其相邻的亚甲基(-CH₂COOH)。利用PA66 盐-水的固液平衡实验数据以及PA66 盐的熔点和熔化焓,回归得到UNIFAC 模型的基团交互作用参数。基于构建的UNIFAC 物性模型预测了0~100℃范围内PA66 盐在水中的溶解度,与实验数据的平均相对误差为2.1%;采用该模型进一步计算工业操作条件(120℃)下的盐浓度,与Aspen 自带参数的UNIFAC 模型比较,其误差从20%左右降到5%以下。

关键词: 尼龙66 盐, 水溶液, 溶解度, UNIFAC 模型, UNIFAC 基团

CLC Number:

TQ028.8

GU Xueping, TIAN Lulu, FENG Lianfang, ZHANG Cailiang. Thermodynamic modeling with new UNIFAC groups for solubility of nylon66-salt in water system[J]. CIESC Journal, 2016, 67(2): 435-441.

顾雪萍, 田璐璐, 冯连芳, 张才亮. 基于新UNIFAC基团的尼龙66盐溶解度的计算方法[J]. 化工学报, 2016, 67(2): 435-441.

References 20

[1]	华阳, 刘振明, 刘权毅, 等. 尼龙66国内外生产现状及发展建议[J]. 弹性体, 2010, 20(6):78-82. HUA Y, LIU Z M, LIU Q Y, et al. Present situation and development suggestion of nylon-66[J]. China Elastomerics, 2010, 20(6):78-82.
[2]	顾凯, 黄继红. 聚合过程模拟与优化——基于Polymer Plus[M]. 北京:化学工业出版社, 2010:125. GU K, HUANG J H. Simulation and Optimization of Polymerization Process-Based on Polymer Plus[M]. Beijing:Chemical Industry Press, 2010:125.
[3]	SCHAFFER M A, MCAULEY K B, CUNNINGHAM M F, et al. Experimental study and modeling of nylon polycondensation in the melt phase[J]. Industrial & Engineering Chemistry Research, 2003, 42(13):2946-2959.
[4]	CHEN C C. A segment-based local composition model for the Gibbs energy of polymer solutions[J]. Fluid Phase Equilibria, 1993, 83:301-312.
[5]	RENON H, PRAUSNITZ J M. Local compositions in thermodynamic excess functions for liquid mixtures[J]. AIChE Journal, 1968, 14(1):135-144.
[6]	SEAVEY K C, KHARE N P, LIU Y, et al. A new phase-equilibrium model for simulating industrial nylon-6 production trains[J]. Industrial & Engineering Chemistry Research, 2003, 42(17):3900-3913.
[7]	FREDENSLUND A, JONES R L, PRAUSNITZ J M. Group-contribution estimation of activity coefficients in nonideal liquid mixtures[J]. AIChE Journal, 1975, 21(6):1086-1099.
[8]	GONG X, LÜ Y, ZHANG Y, et al. Liquid-liquid equilibria of the quaternary system water + caprolactam +1-octanol + ammonium sulfate[J]. Journal of Chemical & Engineering Data, 2007, 52(3):851-855.
[9]	GMEHLING J G, ANDERSON T F, PRAUSNITZ J M. Solid-liquid equilibria using UNIFAC[J]. Industrial & Engineering Chemistry Fundamentals, 1978, 17(4):269-273.
[10]	LÜ Y C, LIN Q, LUO G S, et al. Solubility of berberine chloride in various solvents[J]. Journal of Chemical & Engineering Data, 2006, 51(2):642-644.
[11]	LOHMANN J, RÖPKE T, GMEHLING J. Solid-liquid equilibria of several binary systems with organic compounds[J]. Journal of Chemical & Engineering Data, 1998, 43(5):856-860.
[12]	BONDI A. van der Waals volumes and radii[J]. The Journal of Physical Chemistry, 1964, 68(3):441-451.
[13]	孙晓波. 混合二元酸综合利用工程基础研究[D]. 郑州:郑州大学, 2007. SUN X B. Study on engineering foundation of comprehensive utilization of mixed dibisic acids[D]. Zhengzhou:Zhengzhou University, 2007.
[14]	曾思. 工业聚酯装置酯化过程的建模与流程模拟[D]. 杭州:浙江大学, 2010. ZENG S. Modeling and simulation of esterification section in industrial poly(ethylene terephthalate) process[D]. Hangzhou:Zhejiang University, 2010.
[15]	WU H S, SANDLER S I. Use of ab initio quantum mechanics calculations in group contribution methods (Ⅰ):Theory and the basis for group identifications[J]. Industrial & Engineering Chemistry Research, 1991, 30(5):881-889.
[16]	赵亚军, 司继林, 夏力, 等. 基于元素和化学键的快速计算分子体积和表面积的方法[J]. 计算机与应用化学, 2013, 30(7):739-742. ZHAO Y J, SI J L, XIA L, et al. A new method based on elements and chemical bonds for fast calculation of moleculer volume and surface[J]. Computers and Applied Chemistry, 2013, 30(7):739-742.
[17]	陈明鸣. 对苯二甲酸生产中相关相平衡的测定与研究[D]. 天津:天津大学, 2003. CHEN M M. Determination and study on the corresponding phase equilibria in terephthalic acid manufacture[D]. Tianjin:Tianjin University, 2003.
[18]	STEPHEN H, STEPHEN T. Solubilities of Inorganic and Organic Compounds[M]. Oxford:Pergamon Press, 1963.
[19]	张朝晖. 国内外尼龙66盐市场分析及需求预测[J]. 化工技术经济, 2002, 20(4):26-28. ZHANG Z H. Market analysis and forecast of nylon66 salt[J]. Chemical Techno-Economics, 2002, 20(4):26-28.
[20]	己二酸、己二胺、尼龙66盐[J]. 合成纤维工业, 1983, (3):60-63. Adipic acid, hexamethylene diamine and PA66-salt[J]. China Syntehtic Fiber Industry, 1983, (3):60-63.

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