Catalytic mechanism and reaction pathway of acetone ammoximation to acetone oxime over TS-1

Zhaohui Li; Rizhi Chen; Wanqin Jin; Weihong Xing

Korean Journal of Chemical Engineering, Vol.27, No.5, 1423-1427, September, 2010

DOI10.1007/s11814-010-0236-1 Export Citation

Catalytic mechanism and reaction pathway of acetone ammoximation to acetone oxime over TS-1

Zhaohui Li^{1, 2}, Rizhi Chen¹, Wanqin Jin¹, and Weihong Xing^{1, †}

¹State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and Chemical Engineering, Nanjing University of Technology, Nanjing 210009, China
²College of Chemistry and Biological Engineering, Changsha University of Science and Technology, Changsha 410076, China

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A series of two-step reactions and several special experiments were designed and carried out to discover the reaction pathway of acetone ammoximation to acetone oxime over titanium silicalites-1 (TS-1) employing 25 wt% ammonia and 30 wt% hydrogen peroxide as the ammoximation agents. The experimental results show that the acetone oxime can form even if there is no direct contact between acetone and TS-1 catalysts, indicating the hydroxylamine route may be the most important catalytic mechanism for the reaction. HPLC, GC/MS and ion chromatography characterization results show that hydrogen peroxide can oxidize acetone oxime to acetone, nitrite and nitrate in the presence of TS-1. In addition, nitrite and nitrate can form in the reaction of H2O2 and NH3 over TS-1. Based on these results, a possible overall reaction pathway of acetone ammoximation over TS-1 has been proposed.

Keywords:Acetone;Acetone Oxime;Ammoximation;TS-1;Hydrogen Peroxide

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[1] Liang XH, Mi ZT, Wang YQ, Wang L, Zhang XW, React. Kinet. Catal. Lett., 82(2), 333 (2004)

[2] Roffia P, Padovan M, Leofanti G, Mantegazza MA, Alberti GD, Tamazik GR, US Patent 4, 794,198 (1998)

[3] Liang XH, Mi ZT, Wang YQ, Wang L, Zhang XW, Liu TF, Chem. Eng. Technol., 27(2), 176 (2004)

[4] Zhang YJ, Wang YQ, Bu YF, Wang L, Mi ZT, Wu W, Min EZ, Fu SB, Zhu ZH, React. Kinet. Catal. Lett., 87, 25 (2006)

[5] Li ZH, Bu Z, Chen RZ, Zhong ZX, Xing XH, Xu NP, J. Chem. Eng. Chinese Univ., 23, 423 (2009)

[6] Thangaraj A, Sivasanker S, Ratnasamy P, J. Catal., 131, 394 (1991)

[7] Reddy JS, Kuma R, J. Catal., 130, 440 (1991)

[8] Reddy JS, Sivasanker S, Ratnasamy P, J. Mol. Catal., 69, 383 (1991)

[9] Tvaruzkova Z, Habersberger K, Zilkova N, Jiru P, Appl. Catal.A., 79, 105 (1991)

[10] Pieri E, Pinelli D, TifiroF, Chem. Eng. Sci., 47, 2641 (1992)

[11] Zecchina A, Bordiga S, Lamberti C, Ricchiardi G, Lamberti C, Ricchiardi G, Scarano D, Petrini G, Leofanti G, Mantegazza M, Catal. Today, 32(1-4), 97 (1996)

[12] Gao HX, Shu ZB, Cao J, Zhang YX, Lu WK, Chen QL, Chinese J. Catal., 19, 329 (1998)

[13] Mantegazza MA, Petrini G, Fornasari G, Rinaldo A, Trifiro F, Catal. Today, 32(1-4), 297 (1996)

[14] Perego C, Carati A, Ingallina P, Mantegazza MA, Bellussi G, Appl. Catal. A: Gen., 221(1-2), 63 (2001)

[15] Dal Pozzo L, Fornasari G, Monti T, Catal. Commun., 3, 369 (2002)

[16] Zhong ZX, Liu X, Chen RZ, Xing WH, Xu NP, Ind. Eng. Chem. Res., 48(10), 4933 (2009)

[17] Kim EH, Kwon SW, Lee EH, Yoo JH, Korean J. Chem. Eng., 19(2), 305 (2002)

[18] de Luis A, Lombrana JI, Varona F, Menendez A, Korean J. Chem. Eng., 26(1), 48 (2009)