摘要
亚氨基二乙腈在没有外加催化剂的近邻界水中可以顺利发生水解。实验测定了亚氨基二乙腈在近临界水中（压力10MPa，温度200-260℃，反应时间10～60min）的水解反应动力学数据并考察了时间、温度、压力和初始反应物／水比对反应物转化率和产物产率的影响。在最佳反应条件下，210℃、压力10MPa、反应时间20min，反应物几乎完全转化，此时亚氨基二乙酸的产率可达到92．3mol％。根据一级反应动力学，得到反应的表观活化能E和1nA（min^-1）分别为（45．77±5．26）kJ／mol和8．6±0．1。最终反应产物主要包括亚氨基二乙酸和氨以及少量的副产物，反应过程中除生成的氨气外其它气体的生成可以忽略。近临界水中亚氨基二乙腈的水解反应机理和普通碱催化条件的水解反应机理相似。
Near-critical water is a promising reaction medium for conducting the hydrolysis of nitriles without the addition of any additives. Iminodiacetonitrile （IDAN） was chosen as a heteroatom-containing model compound for the hydrolytic kinetic and mechanism investigations of dinitriles because IDAN is an important raw material for the preparation of iminodiacetic acid （IDA） which is an indispensable intermediate in herbicide manufacturing. Hydrolysis of IDAN in near-critical water, without added catalysts, has been successfully conducted. Hydrolysis kinetics data of the reaction were measured at 10MPa with temperature and residence time ranges of 200-260℃ and 10-60min, respectively. The effects of temperature, pressure, and initial reactant/water ratio on conversion and yield have been investigated. Final reaction products primarily included iminodiacetic acid （IDA） and ammonia associated with other byproducts; gas formation was negligible. The maximum yield of IDA was 92.3mol% at 210℃, 10MPa with a conversion almost of 100%. The apparent activation energy and 1nA（min^-1） of IDAN hydrolysis were evaluated as （45. 77±5.26）kJ/mol and 8.6 ± 0.1 based on the assumption of first-order reaction. Reaction mechanism and network are similar to that of base-catalyzed reactions of nitriles examined in less severe conditions.
出处
《功能材料》
EI
CAS
CSCD
北大核心
2007年第11期1845-1848,1852,共5页
Journal of Functional Materials
基金
教育部科学技术研究资助项目(重点105075)
关键词
近临界水
自催化
亚氨基二乙腈
亚氨基二乙酸
水解
near-critical water
self-catalysis
iminodiaeetonitrile
iminodiacetic acid
hydrolysis
