甲醛+1,3,5-三聚甲醛+硫酸+水体系汽液相平衡实验和理论研究

doi:10.11949/0438-1157.20191242

化工学报 ›› 2020, Vol. 71 ›› Issue (1): 216-224.DOI: 10.11949/0438-1157.20191242

甲醛+1,3,5-三聚甲醛+硫酸+水体系汽液相平衡实验和理论研究

张先明^1,²(),胡玉峰¹()

1. 中国石油大学(北京)重质油国家重点实验室和高压流体相平衡实验室，北京 102249
2. 鄂尔多斯应用技术学院化学工程系，内蒙古鄂尔多斯 017000

收稿日期:2019-10-23 修回日期:2019-10-30 出版日期:2020-01-05 发布日期:2020-01-05
通讯作者: 胡玉峰
作者简介:张先明（1984—），男，博士，副教授，zhangxianming84@163.com
基金资助:
国家自然科学基金重大项目(21890763);国家自然科学基金项目(21776300);中国石油化工集团公司项目(ZX20180062);校级科研项目(KYYB2019006)

Experimental and theoretical studies on vapor liquid equilibrium for formaldehyde + 1,3,5-trioxane + sulphuric acid + water system

Xianming ZHANG^1,²(),Yufeng HU¹()

1. State Key Laboratory of Heavy Oil Processing and High Pressure Fluid Phase Behavior & Property Research Laboratory, China University of Petroleum, Beijing 102249, China
2. Department of Chemical Engineering, Ordos Institute of Technology, Ordos 017000, Inner Mongolia, China

Received:2019-10-23 Revised:2019-10-30 Online:2020-01-05 Published:2020-01-05
Contact: Yufeng HU

摘要/Abstract

摘要：

工业上利用甲醛水溶液在硫酸催化下的反应精馏工艺生产1,3,5-三聚甲醛，因此，1,3,5-三聚甲醛生产工艺的优化和新型催化剂的开发受到了广泛关注。这需建立反应体系的汽-液相平衡模型，研究1,3,5-三聚甲醛合成过程中催化剂可能发挥的多重作用。为此，测定了(甲醛+1,3,5-三聚甲醛+硫酸+水)体系的汽-液相平衡数据，采用扩展型UNIFAC模型对汽-液相平衡数据进行了关联，确定了模型参数，并对该体系进行了系统的计算，揭示了硫酸催化剂在该反应精馏工艺中的三重作用。上述成果对优化1,3,5-三聚甲醛生产工艺和开发1,3,5-三聚甲醛新型催化剂具有重要意义。

关键词: 1,3,5-三聚甲醛反应体系, 汽液平衡, 活度系数, 催化作用

Abstract:

1,3,5-Trioxane is industrially produced from aqueous formaldehyde solutions through reaction distillation catalyzed by sulfuric acid. Optimizing industrial process of the synthesis and developing new catalysts have attracted extensive attention. It is necessary to establish a vapor-liquid equilibrium model of the reaction system and reveal the multiple functions that the catalyst may play in the synthesis of 1,3,5-trioxane. For this reason, experimental data for the vapor-liquid equilibrium of (formaldehyde + 1,3,5-trioxane + H₂SO₄ + water) system are measured. The extended UNIFAC model is used for correlating the vapor-liquid equilibrium data, and the model parameters are determined, whereby systematic calculation is made. The results show that the sulfuric acid catalyst has triple functions in the reaction distillation process. The above results are of great significance for optimizing the production process of 1,3,5-trioxane and developing new catalysts.

Key words: 1,3,5-trioxane reaction system, vapor liquid equilibria, activity coefficient, catalysis

中图分类号:

TQ 013.1

张先明, 胡玉峰. 甲醛+1,3,5-三聚甲醛+硫酸+水体系汽液相平衡实验和理论研究[J]. 化工学报, 2020, 71(1): 216-224.

Xianming ZHANG, Yufeng HU. Experimental and theoretical studies on vapor liquid equilibrium for formaldehyde + 1,3,5-trioxane + sulphuric acid + water system[J]. CIESC Journal, 2020, 71(1): 216-224.

图/表 1

参考文献 37

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甲醛+1,3,5-三聚甲醛+硫酸+水体系汽液相平衡实验和理论研究

Experimental and theoretical studies on vapor liquid equilibrium for formaldehyde + 1,3,5-trioxane + sulphuric acid + water system

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