钛硅分子筛催化环己酮氨肟化反应过程——工艺条件的考察  

AMMOXIMATION OF CYCLOHEXANONE TO CYCLOHEXANONE OXIME OVER TITANIUM SILICALITE MOLECULAR SIEVE——Study on the Effects of Process Parameters

作　　者：李永祥[1] 吴巍[1] 闵恩泽[1] 

机构地区：[1]石油化工科学研究院,北京100083

出　　处：《石油炼制与化工》2010年第10期1-6,共6页Petroleum Processing and Petrochemicals

基　　金：国家重点基础研究发展规划(973)项目(G2000048005);中国石油化工股份有限公司资助项目(200025)

摘　　要：在加压连续淤浆床反应器中,研究了以HTS新型钛硅分子筛催化环己酮、H_2O_2和氨反应一步合成环己酮肟的氨肟化新工艺,考察和分析了进料组成、反应温度、反应物料的平均停留时间和催化剂用量对环己酮氦肟化反应的影响规律。实验结果表明,适宜的反应条件为:进料中N(H_2O_2)/n(环己酮)=1.05～1.10、n(NH_3)/n(环己酮)=1.7～2.0,反应压力0.3 MPa,反应温度75～85℃,物料的平均停留时间65～75min,钛硅分子筛催化剂质量分数为2.5%左右,溶剂为叔丁醇与水的混合溶剂(体积比1.5～2.5)。在此条件下,环己酮转化率大于98%,环己酮肟选择性大于99.5%,H_2O_2,有效利用率不低于90%。The liquid-phase ammoximation of cyclohexanone, ammonia and hydrogen peroxide to cyclohexanone oxime over titanium silicalite molecular sieve was studied using a continuous tank slurry reactor under a reaction pressure of 0.3 MPa. The effects of process parameters such as feed composition, reaction temperature, average residence time and the amount of catalyst on the ammoximation performance were investigated. Results show that the optimum reaction conditions are as follows： the molar ratio of H2O2/ cyclohexanone in the range of 1.05-1.10, the molar ratio of NH3/cyclohexanone in the range of 1.7-2.0, a tert-butanol/cyclohexanone inlet mass ratio of 2.5, the reaction temperature in the range of 75-85℃, the average residence time in the range of 65-75 min, catalyst mass fraction of about 2.5% and using the mixtureof tert-butanol and water as system solvent with a tert-butanol/water volume ratio of 1.5-2.5. Under such reaction conditions, the conversion of cyclohexanone and the selectivity to cyclohexanone oxime reach more than 98% and 99.5%, respectively. Furthermore, the effective utilization rate of H2O2 is not less than 90%.

关 键 词：钛硅分子筛 氨肟化 环己酮 环己酮肟 过氧化氢 

分 类 号：TQ203.2[化学工程—有机化工]