DOI: 10.3724/SP.J.1095.2013.30073

Chinese Journal of Applied Chemistry (应用化学) 2013/30:12 PP.1443-1448

Oxidation of Cyclohexylamine to Cyclohexanone Oxime Catalyzed by NaY Zeolite Molecular Sieves

The liquid phase cyclohexyamine oxidation reaction to prepare cyclohexanone oxime on NaY zeolite catalyst was studied. The effects of oxidant and solvent on the reaction were investigated. The results show that NaY zeolite has the best catalytic performance when acetonitrile and hydrogen peroxide were used as solvent and oxidant respectively. An orthogonal experimental method to study the response of the optimum conditions was carried out. The results show that the effects of the amount of catalyst, the amount of solvent, reaction time, reaction temperature and amount of oxidant on the yield of cyclohexanone oxime decrease in turn. The optimal reaction conditions are as follows:0.3 g catalyst, V(cyclohexylamine):V(solvents):V(oxidants)=1:3:3, 65 ℃ and 2 h.

Key words:cyclohexylamine,oxidation,cyclohexanone oxime,hydrogen peroxide,NaY catalyst

ReleaseDate:2015-06-08 13:48:01

[1] Suzuki K,Nagahara H. Process for Preparation of Cyclohexanone Oxime:US 0176592 A1[P].2004-9.

[2] Ichihashi H,Sato H. The Development of New Heterogeneous Catalytic Processes for the Production of ε-Caprolactam[J]. Appl Catal,2001,221(1/2):359-366.

[3] Corma A,Serna P. Chemoselective Hydrogenation of Nitro Compounds with Supported Gold Catalysts[J]. Science,2006,313:332-334.

[4] MAO Liqiu,LV Xing,YIN Dulin,et al. Hydrogenation of Nitrocyclohexane to Cyclohexanone Oxime Catalyzed by Pd/C[J]. Chem Ind Eng Prog,2009,28(6):1024-1026(in Chinese).毛丽秋,吕兴,尹笃林,等。 Pd/C催化硝基环己烷氢化制备环己酮肟[J]. 化工进展,2009,28(6):1024-1026.

[5] WU Bohua,MAO Liqiu,YIN Dulin,et al. One-step Synthesis of Caprolactam by Liquid-phase Nitrosation Reaction of Cyclohexane[J]. Chinese J Appl Chem,2008,25(4):502-504(in Chinese).吴伯华,毛丽秋,尹笃林,等。 环己烷液相亚硝化一步合成己内酰胺反应的研究[J]. 应用化学,2008,25(4):502-504.

[6] Rakottyay K,Kaszonyi A. Oxidation of Cyclohexylamine over Modified Alumina by Molecular Oxygen[J]. Appl Catal A,2009,367(1/2):32-38.

[7] GAO Meixiang,LUO Dong,MAO Liqiu,et al. Oxidation of Cyclohexylamine to Cyclohexanone Oxime Catalyzed by Al2O3-SiO2[J]. Chinese J Appl Chem,2013,30(1):28-31(in Chinese).高美香,罗东,毛丽秋,等。 Al2O3-SiO2催化环己胺氧化制备环己酮肟[J]. 应用化学,2013,28(1):28-31.

[8] Gu F N,Wei F,Yang J Y. New Strategy to Synthesis of Hierarchical Mesoporous Zeolites[J]. Chem Mater,2010,22:2442-2450.

[9] Orthogonal Test Drafting Group. Orthogonal Test[M]. Beijing:Publishing House of Defense Industry, 1976:7-25(in Chinese).正交试验编写组。 正交试验法[M]. 北京:国防工业出版社,1976:7-25.

[10] XU Ruren,PANG Wenqin,YU Jihong,et al. Chemistry-Zeolites and Porous Materials[M]. Beijing:Science Press,2004:170-175(in Chinese).徐如人,庞文琴,于吉红,等。 分子筛与多孔材料化学[M]. 北京:科学出版社,2004:170-175.