Effect of Extra-Framework Titanium in TS-1 on the Ammoximation of Cyclohexanone

Abstract

Titanium silicalite (TS-1) without and with extra-framework titanium have been prepared and TiO₂ is also prepared under the same conditions. All the samples are characterized with XRD, FT-IR, and UV–Vis. The effects of extra-framework titanium in TS-1 on the ammoximation of cyclohexanone have been studied in a continuous slurry reactor. The characterization results reveal that the extra-framework titanium exists as anatase. The catalytic evaluation results show that the anatase has a positive effect on the ammoximation of cyclohexanone by extending the catalytic life because it also exhibits some activity, while the conversion of cyclohexanone and the selectivity to cyclohexanone oxime are not influenced. The anatase TiO₂ does not catalyze H₂O₂ decomposition appreciably compared with TS-1 without extra-framework titanium. The results are very useful in guiding the TS-1 production.

Keywords

TS-1 / Cyclohexanone / Ammoximation / Cyclohexanone oxime / TiO₂

References

[1] Taramasso M, Perego G, Notari B (1983) Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides. US, 4,410,501. 1983-10-18

[2] Tatsumi T, Jappar N. Ammoximation of cyclic ketones on TS-1 and amorphous SiO₂-TiO₂. J Catal, 1996, 161(2): 570-576.

[3] Zhang T, Wang Y, Wang S, et al. Effect of triethylamine treatment of titanium silicalite-1 on cyclohexanone ammoximation in a continuous system. React Kinet Mech Catal, 2015, 114(2): 735-752.

[4] Wu X, Wang Y, Zhang T, et al. Effect of TS-1 treatment by tetrapropyl ammonium hydroxide on cyclohexanone ammoximation. Catal Commun, 2014, 50: 59-62.

[5] Yao P, Wang Y, Teng Z, et al. Effect of sodium ions in synthesis of titanium silicalite-1 on its catalytic performance for cyclohexanone ammoximation. Front Chem Sci Eng, 2014, 8(2): 149-155.

[6] Xu J, Wang Y, Feng W, et al. Effect of triethylamine treatment of titanium silicalite-1 on propylene epoxidation. Front Chem Sci Eng, 2014, 8(4): 478-487.

[7] Feng W, Wang Yaquan Y, Wu G, et al. Liquid phase propylene epoxidation with H₂O₂ on TS-1/SiO₂ catalyst in a fixed-bed reactor: experiments and deactivation kinetics. J Chem Technol Biotechnol, 2015, 90: 1489-1496.

[8] Song W, Xiong G, Long H, et al. Effect of treatment with different bases on the catalytic properties of TS-1/SiO₂ extrudates in propylene epoxidation. Microporous Mesoporous Mater, 2015, 212: 48-55.

[9] Park S, Cho KM, Youn MH, et al. Direct epoxidation of propylene with hydrogen peroxide over TS-1 catalysts: effect of hydrophobicity of the catalysts. Catal Commun, 2008, 9(15): 2485-2488.

[10] Tanev PT, Chibwe M, Pinnavaia TJ. Titanium-containing mesoporous molecular sieves for catalytic oxidation of aromatic compounds. Nature, 1994, 368: 321-323.

[11] Zuo Y, Song W, Dai C, et al. Modification of small-crystal titanium silicalite-1 with organic bases: recrystallization and catalytic properties in the hydroxylation of phenol. Appl Catal A, 2013, 453: 272-279.

[12] Choi JS, Kim DJ, Chang SH, et al. Catalytic applications of MCM-41 with different pore sizes in selected liquid phase reactions. Appl Catal A, 2003, 254(2): 225-237.

[13] Yip ACK, Lam FLY, Hu X, et al. Study on the synthesis of clay-based titanium silicalite-1 catalytic composite. Ind Eng Chem Res, 2009, 48(11): 5266-5275.

[14] Zuo Y, Liu M, Zhang T, et al. Role of pentahedrally coordinated titanium in titanium silicalite-1 in propene epoxidation. RSC Adv, 2015, 5(23): 17897-17904.

[15] Borin MF, Silva TD, Felisbino RF, et al. Synthesis of TS-1 molecular sieves using a new Ti source. J Phys Chem B, 2006, 110(31): 15080-15084.

[16] Rajakovic VN, Mintova S, Senker J, et al. Synthesis and characterization of V- and Ti-substituted mesoporous materials. Mater Sci Eng, C, 2003, 23(6): 817-821.

[17] Bengoa JF, Gallegos NG, Marchetti SG, et al. Influence of TS-1 structural properties and operation conditions on benzene catalytic oxidation with H₂O₂. Microporous Mesoporous Mater, 1998, 24(4): 163-172.

[18] Khouw CB, Dartt CB, Labinger JA, et al. Studies on the catalytic oxidation of alkanes and alkenes by titanium silicates. J Catal, 1994, 149(1): 195-205.

[19] Liu C, Huang J, Sun D, et al. Anatase type extra-framework titanium in TS-1: A vital factor influencing the catalytic activity toward styrene epoxidation. Appl Catal A, 2013, 459: 1-7.

[20] Li G, Wang X, Guo X, et al. Titanium species in titanium silicalite TS-1 prepared by hydrothermal method. Mater Chem Phys, 2001, 71(2): 195-201.

[21] Zhang Y, Guo X, Wang X, et al. Extra-framework titanium species (TiO₂)_x in TS-1 zeolite and its effect on epoxidation of propylene. Acta Petrolei Sinica Petrol Process Sect, 2000, 16(5): 41-46 (in Chinese)

[22] Li YG, Lee YM, Porter JF. The synthesis and characterization of titanium silicalite-1. J Mater Sci, 2002, 37(10): 1959-1965.

[23] Su J, Xiong G, Zhou J, et al. Amorphous Ti species in titanium silicalite-1: structural features, chemical properties, and inactivation with sulfosalt. J Catal, 2012, 288: 1-7.

[24] Roffia P, Leofanti G, Cesana A, et al. Cyclohexanone ammoximation: a breakthrough in the 6-caprolactam production process. Stud Surf Sci Catal, 1990, 55: 43-52.

[25] Roffia P, Leofanti G, Cesana A et al. (1988) Catalytic process for the manufacture of oximes. US 4,794,198. 1988-12-27

[26] Lin M, Zhu B, Shu XT, et al. The development and application of hierarchical titanium silicalite-1. Petrochemical Technology, 2005, 34: 377-379.

[27] Wang Y, Meng F, Zhang Y et al (2009) A preparation method of granular titanium silicon molecular sieve. CN, 200910069663. 2009-12-09

[28] Wang Y, Yang K, Zheng R et al (2009) A preparation method of large particle size titanium silicon molecular sieve. CN, 200910067853. 2009-07-15

[29] Wu G, Wang Y, Wang L, et al. Epoxidation of propylene with H₂O₂ catalyzed by supported TS-1 catalyst in a fixed-bed reactor: experiments and kinetics. Chem Eng J, 2013, 215: 306-314.

[30] Wang Y, Ye J, Wang S, et al. Synthesis of mesoporous titanium silicalite-1 with high stability in cyclohexanone ammoximation. Trans of Tianjin Univ, 2016, 22: 254-260.

[31] Khomane RB, Kulkarni BD, Paraskar A, et al. Synthesis, characterization and catalytic performance of titanium silicalite-1 prepared in micellar media. Mater Chem Phys, 2002, 76(1): 99-103.

[32] Xia QH, Gao Z. Crystallization kinetics of pure TS-1 zeolite using quaternary ammonium halides as templates. Mater Chem Phys, 1997, 47(2): 225-230.

[33] Perego C, Carati A, Ingallina P, et al. Production of titanium containing molecular sieves and their application in catalysis. Appl Catal A, 2001, 221(1): 63-72.

[34] Blasco T, Camblor MA, Corma A, et al. The state of Ti in titanoaluminosilicates isomorphous with zeolite. beta. J Am Chem Soc, 1993, 115(25): 11806-11813.

[35] Geobaldo F, Bordiga S, Zecchina A, et al. DRS UV-Vis and EPR spectroscopy of hydroperoxo and superoxo complexes in titanium silicalite. Catal Lett, 1992, 16(1–2): 109-115.

[36] Astorino E, Peri JB, Willey RJ, et al. Spectroscopic characterization of silicalite-1 and titanium silicalite-1. J Catal, 1995, 157(2): 482-500.

[37] Huybrechts DRC, Vaesen I, Li HX, et al. Factors influencing the catalytic activity of titanium silicalites in selective oxidations. Catal Lett, 1991, 8(2–4): 237-244.

[38] Thangaraj A, Kumar R, Mirajkar SP, et al. Catalytic properties of crystalline titanium silicalites I, Synthesis and characterization of titanium-rich zeolites with MFI structure. J Catal, 1991, 130(1): 1-8.

[39] Ricchiardi G, Damin A, Bordiga S, et al. Vibrational structure of titanium silicate catalysts. A spectroscopic and theoretical study. J Am Chem Soc, 2001, 123(46): 11409-11419.

[40] Sun Z, Zhang Y, Deng X, et al. Fabrication and application of silicalite-1 and TS-1 hollow fibers with polyethylene imine (PEI) fibers as substrates. J Ind Eng Chem, 2012, 18(1): 92-97.

[41] Yinqian L, Yongxiang L, Wei W, et al. Study on deactivation behavior of TS-1 molecular sieve in cyclohexanone ammoximation. Petrol Process Petrochem, 2002, 33(5): 41-45.

[42] Wu P, Komatsu T, Yashima T. Ammoximation of ketones over titanium mordenite. J Catal, 1997, 168(2): 400-411.

[43] Mantegazza MA, Petrini G, Spano G, et al. Selective oxidations with hydrogen peroxide and titanium silicalite catalyst. J Mol Catal A Chem, 1999, 146(1): 223-228.

[44] Dal Pozzo L, Fornasari G, Monti T. TS-1, catalytic mechanism in cyclohexanone oxime production. Catal Commun, 2002, 3(8): 369-375.