摘要
针对己二腈传统生产工艺存在的污染环境、安全隐患大及原料不可持续等问题,提出以5-羟甲基糠醛为原料,通过呋喃二甲腈合成与转化反应制备生物基己二腈的新方法.采用吉布斯自由能、原子利用率、本质安全指数三参量表征反应的热力学可行性、原子经济性及本质安全性.构建化学反应的三参量综合评价体系,通过"三参量差"判据计算,得到该反应体系适宜的氮载体为离子液体型羟胺盐,氢载体为甲酸;反应路径为5-羟甲基糠醛和离子液体型羟胺盐制呋喃二甲腈反应集成及其进一步和甲酸制己二腈反应集成.通过多反应集成,可以明显减小"三参量差"值,接近理想化学反应.理性设计的合成生物基己二腈新方法具有绿色和安全特征,建立的反应三参量综合评价体系具有通用性.
Adiponitrile is a key presursor to synthesize hexamethylenediamine that is specifically used for the production of nylon 66 and hexamethylene diisocyanate(HDI). Both nylon 66 and HDI are dispensible to chemical industries: Nylon 66 is widely used for chemical fibers and engineering plastics, towards clothing, electrical appliances, automobiles, and military industry;while HDI is important for the synthesis of high-grade polyurethane for automotive and coatings industries. In addition, HDI is also used as a curing agent for rocket propellant, highlighting the significance of adiponitrile production.Current production of adiponitrile mainly involves ammoniation-dehydration of adipic acid, electrolytic dimerization of acrylonitrile, or hydrocyanation of 1,3-butadiene. All of these involve high energy consumption processes that utilize highly toxic raw materials with unavoidable side reactions, leading to great concerns on cost, safety, environrment and sustainability. Therefore, it is urgent to develop a novel, safe and green method for the synthesis of adiponitrile. On the other hand, it is of equal importance for modern chemical industry to evaluate if a synthetic route is not only economic but also environmentally benigh, safe, and sustainable.Herein, a novel synthetic strategy is designed for adiponitrile preparation using biomass resource of 5-hydroxymethylfurfural through a conversion reaction of intermediate furandicarbonitrile. This strategy can avoid the safety risks and pollution issues in the present adiponitrile production industry. More importantly, it is a green and sustainable processs toproduce adiponitrile, especially considering the increasing shortage of petroleum resources. More specifically, when the furandicarbonitrile was synthesized from 5-hydroxymethylfurfural and nitrogen carrier compounds,hydroxylamine ionic liquid salts was the best served nitrogen carrier compounds, followed by ammonium carbonate,ammonium formate, ammonia and ammonium chloride. If the adiponitrile was synthesized from furandicarbonitrile and hydrogen carrier compounds, formic acid was the best-served hydrogen carrier compounds, followed by methanol, ethanol and hydrogen. The another one-step reaction route uisng 5-hydroxymethylfurfural and ammonium formate as raw materials was dominant.Besides, a "three-parameter evaluation system" is proposed for the first time and established, where Gibbs free energy,atom utilization efficiency, and intrinsic safety index determine the thermodynamic feasibility, atom economy, and reliability of chemical reactions, respectively. The synthetic strategy for bio-based adiponitrile production is evaluated by the "three-parameter evaluation system" and shows significantly reduced "three-parameter difference" value and is close to the ideal chemical reactions, when using hydroxylamine ionic liquid salts as the nitrogen carrier, formic acid as the hydrogen carrier, and integrating multi-reactions of 5-hydroxymethylfurfural and hydroxylamine ionic liquid salts and its further reaction with formic acid to produce adiponitrile.Such a novel synthesis of bio-based adiponitrile from 5-hydroxymethyl furfural, hydroxylamine ionic liquid salts and formic acid is green and safe, while the established "three-parameter evaluation system" is versatile and paves a new route towards validating efficient chemical productions.
作者
丁晓墅
邬长城
王延吉
Xiaoshu Ding;Changcheng Wu;Yanji Wang(Tianjin Key Laboratory of Inherent Safety Chemical Process,School of Chemical Engineering,Hebei University of Technology,Tianjin 300130,China)
出处
《科学通报》
EI
CAS
CSCD
北大核心
2020年第5期401-409,共9页
Chinese Science Bulletin
关键词
生物基己二腈
合成方法
热力学
原子利用率
本质安全
评价方法
bio-based adiponitrile
synthetic route
thermodynamics
atomic utilization
intrinsic safety
evaluation method
