Progress research in preparation of adiponitrile

doi:10.16085/j.issn.1000-6613.2024-0892

Abstract

Abstract:

Adiponitrile, as one of the main raw materials for producing polyamide (nylon 66), has been long monopolized by foreign companies. In recent years, the research on the high efficiency production methods of adiponitrile has gradually become a hot topic because the increasing demand of nylon 66 helped bring about the growing gap between adiponitrile supply and demand. The basic research, process characteristics and development direction of the preparation methods for adiponitrile were introduced in the article, such as butadiene method, acrylonitrile electrolytic dimerization method and adipic acid ammoniation method. In addition, the application feasibility of process intensification technology in acrylonitrile electrolytic dimerization method and adipic acid ammoniation method were discussed in depth from the view of reaction mechanism in the review. Finally, the kinetics and thermodynamics of adipic acid ammoniation were summarized. The application of the process intensification technology would be the key to promoting efficient and green production of adiponitrile, which was of great significance for the improvement and autonomy of adiponitrile production technology.

Key words: adipic acid ammoniation method, butadiene method, acrylonitrile electrolytic dimerization method, adiponitrile, process intensification, organic compounds, chemical processes, reaction kinetics

摘要：

己二腈作为生产聚酰胺（尼龙66）的主要原料之一，其生产工艺长期被国外公司垄断。近年来，随着尼龙66需求量的增加，己二腈的供需缺口逐渐增大，其高效的生产技术逐渐成为研究热点。本文介绍了己二腈的制备方法如丁二烯法、丙烯腈电解二聚法和己二酸氨化法的基础研究、工艺特点及发展方向等；从机理出发探讨了过程强化技术在丙烯腈电解二聚法和己二酸氨化法中的应用可行性，并对己二酸氨化法的动力学和热力学进行了总结。将过程强化技术应用于己二腈生产过程是推动己二腈高效绿色生产的关键，对己二腈生产技术的提升和自主化具有重要意义。

关键词: 己二酸氨化法, 丁二烯法, 丙烯腈电解二聚法, 己二腈, 过程强化, 有机化合物, 化学过程, 反应动力学

CLC Number:

TQ226.6

DU Lei, CAO Zhitao, XU Lang, ZHANG Yingjie, SUN Baochang, ZOU Haikui, CHU Guangwen, CHEN Jianfeng. Progress research in preparation of adiponitrile[J]. Chemical Industry and Engineering Progress, 2025, 44(7): 3683-3696.

杜磊, 曹志涛, 许浪, 张英杰, 孙宝昌, 邹海魁, 初广文, 陈建峰. 己二腈制备方法的研究进展[J]. 化工进展, 2025, 44(7): 3683-3696.

Figures/Tables 14

时间/年	阴极材料	阳极材料	支撑电解质种类	电流密度/kA·m^-2	己二腈选择性/%	参考文献
1964	汞池/铅	铂丝	四乙基对甲苯磺酸铵	—	—	[25]
1984	铅	镀铂钛	四乙基硫酸铵	50	93	[26]
1990	铬	软钢	EDTA和四丁基氢氧化铵乳液	2	78	[37]
2011	铅	DSA-O₂^①	四甲基氯化铵乳液	1	65	[35]
2012	铅	DSA-O₂	四甲基氯化铵乳液	4	78	[29]
2020	铬	铂网	EDTA和TAA	-20	93	[34]

物质	Δ_fH $m ⊖$ /kJ·mol^-1
己二酸	-983.298
氨气	-46.99
己二酰胺	-596.528
水	-242.66
己二腈	68.2

物质	Δ_fH $m ⊖$ /kJ·mol^-1
己二酸	-983.298
氨气	-46.99
己二酰胺	-596.528
水	-242.66
己二腈	68.2

反应过程	Δ_rH $m ⊖$ /kJ·mol^-1
中和反应	-4.57
脱水反应	179.408
总反应过程	174.838

反应过程	Δ_rH $m ⊖$ /kJ·mol^-1
中和反应	-4.57
脱水反应	179.408
总反应过程	174.838

物质	Δ_fH $m ⊖$ /kJ·mol^-1
己二酸（液体）	-870.048
氨气	-36.49
己二酰胺（液体）	-503.28
水（气体）	-233.85
己二腈	139.45

物质	Δ_fH $m ⊖$ /kJ·mol^-1
己二酸（液体）	-870.048
氨气	-36.49
己二酰胺（液体）	-503.28
水（气体）	-233.85
己二腈	139.45

反应过程	Δ_rH $m ⊖$ /kJ·mol^-1
中和反应	-27.95
脱水反应	175.03
总反应过程	147.08

反应过程	Δ_rH $m ⊖$ /kJ·mol^-1
中和反应	-27.95
脱水反应	175.03
总反应过程	147.08

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