己二腈工业合成工艺的研究进展及原子经济量化分析  

A review of adiponitrile industrial production processes and associated atom economies

作　　者：朱云峰[1] 郜亮[1] 温朗友[1] 宗保宁[1] 

机构地区：[1]中国石化石油化工科学研究院,北京100083

出　　处：《科学通报》2015年第16期1488-1501,1,共14页Chinese Science Bulletin

基　　金：国家重点基础研究发展计划(2012CB224804)资助

摘　　要：己二腈是一种重要的基本有机化工原料,工业上主要用于加氢生产尼龙66的单体己二胺.目前己二腈的合成技术主要被巴斯夫、英威达、旭化成、首诺等国外公司垄断,严重限制了我国尼龙66产业的发展.受技术垄断的限制,我国的己二腈的市场格局在很长一段时间内不会有大的变化,己二腈产业也将长期面临挑战.己二腈的工业合成方法主要包括丙烯腈电解二聚法、丁二烯氢氰化法、己二酸氨化脱水法等.丙烯腈法早期采用隔膜法,考虑到丙烯腈不参与阳极反应,后改进工艺取消了隔膜,其优势在于过程简单,反应一步完成,但反应需要消耗大量的电能,且反应条件需严格控制,丙烯腈的浓度、电解液的p H、电流密度、电解液流速都会对反应的选择性及收率产生影响;己二酸法分为液相法和气相法,其优点在于设备投资低,对设备的标准要求低,但反应需要较高的温度,副反应多且原子经济性差;丁二烯法具有原料成本低、生产能耗低、工艺路线短、产品收率高、原子经济性高的优点,是比较理想的工业化路线,但原料氰化氢毒性大,潜在风险高,对生产设备、操作及管理具有极高的要求.本文针对现有的己二腈合成工艺的技术要点、反应机理及原子经济性进行了分析,并指出传统的己二腈生产工艺亟待绿色化改造,开发具有自主知识产权的己二腈工艺对我国尼龙66产业发展具有重要意义.Adiponitrile（ADN） is an important raw material in the chemical industry, and is primarily used in the synthesis of 1,6-hexamethylenediamine（HMDA）, a component of nylon 6,6. In present-day China, the technology required for the synthesis of ADN has been monopolized by several foreign corporations, including BASF, Invista, Asha and Solutia, which has hampered the development of a domestic nylon 6,6 industry. Based on this scenario, it is anticipated that the ADN market patterns in China will remain unchanged for a significant time span, suggesting that the domestic ADN industry will face long-term challenges. There are three main methods of producing ADN： electrolytic hydrodimerization of acrylonitrile, hydrocyanation of 1,3-butadiene and catalytic dehydration of adipic acid and ammonia. In the case of the electrohydrodimerization process, earlier versions employed the diaphragm method. Considering acrylonitrile do not participate in the anodic reaction, process improvements have removed the need for a diaphragm, thus allowing a simplified, one-step reaction process. However, the electrohydrodimerization method still consumes large amounts of electric energy, and the associated reaction parameters, such as the acrylonitrile concentration, electrolyte p H, current density and electrolyte flow rate, must be strictly controlled, as they may potentially affect both the selectivity and yield of the reaction. The dehydration process is typically conducted in either the liquid or vapor phase, and has the advantages of requiring minimal investment and equipment. However, the atom economy associated with this process is unsatisfactory as a result of the high reaction temperature and uncontrollable side reactions. The hydrocyanation process is comparatively superior, with the advantages of low raw-material costs, reduced energy consumption, short process flows and higher atom economy. However, the raw material hydrogen cyanide is highly toxic and its use involves significant risk, thus requiring extremely rigorous

关 键 词：己二腈 己二胺 己二酸 丙烯腈 尼龙66 

分 类 号：TQ226.61[化学工程—有机化工]