Transactions of Tianjin University

, Volume 23, Issue 3, pp 230–236 | Cite as

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

  • Yaquan Wang
  • Shuhai Wang
  • Teng Zhang
  • Jiaxin Ye
  • Xiao Wang
  • Dali Wang
Research article

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 

Notes

Acknowledgements

This study was supported by the National Basic Research Program of China (“973” Program, No. G2000048005) and the National Natural Science Foundation of China (No. 21276183).

References

  1. 1.
    Taramasso M, Perego G, Notari B (1983) Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides. US, 4,410,501. 1983-10-18Google Scholar
  2. 2.
    Tatsumi T, Jappar N (1996) Ammoximation of cyclic ketones on TS-1 and amorphous SiO2-TiO2. J Catal 161(2):570–576CrossRefGoogle Scholar
  3. 3.
    Zhang T, Wang Y, Wang S et al (2015) Effect of triethylamine treatment of titanium silicalite-1 on cyclohexanone ammoximation in a continuous system. React Kinet Mech Catal 114(2):735–752CrossRefGoogle Scholar
  4. 4.
    Wu X, Wang Y, Zhang T et al (2014) Effect of TS-1 treatment by tetrapropyl ammonium hydroxide on cyclohexanone ammoximation. Catal Commun 50:59–62CrossRefGoogle Scholar
  5. 5.
    Yao P, Wang Y, Teng Z et al (2014) Effect of sodium ions in synthesis of titanium silicalite-1 on its catalytic performance for cyclohexanone ammoximation. Front Chem Sci Eng 8(2):149–155CrossRefGoogle Scholar
  6. 6.
    Xu J, Wang Y, Feng W et al (2014) Effect of triethylamine treatment of titanium silicalite-1 on propylene epoxidation. Front Chem Sci Eng 8(4):478–487CrossRefGoogle Scholar
  7. 7.
    Feng W, Wang Yaquan Y, Wu G et al (2015) Liquid phase propylene epoxidation with H2O2 on TS-1/SiO2 catalyst in a fixed-bed reactor: experiments and deactivation kinetics. J Chem Technol Biotechnol 90:1489–1496CrossRefGoogle Scholar
  8. 8.
    Song W, Xiong G, Long H et al (2015) Effect of treatment with different bases on the catalytic properties of TS-1/SiO2 extrudates in propylene epoxidation. Microporous Mesoporous Mater 212:48–55CrossRefGoogle Scholar
  9. 9.
    Park S, Cho KM, Youn MH et al (2008) Direct epoxidation of propylene with hydrogen peroxide over TS-1 catalysts: effect of hydrophobicity of the catalysts. Catal Commun 9(15):2485–2488CrossRefGoogle Scholar
  10. 10.
    Tanev PT, Chibwe M, Pinnavaia TJ (1994) Titanium-containing mesoporous molecular sieves for catalytic oxidation of aromatic compounds. Nature 368:321–323CrossRefGoogle Scholar
  11. 11.
    Zuo Y, Song W, Dai C et al (2013) Modification of small-crystal titanium silicalite-1 with organic bases: recrystallization and catalytic properties in the hydroxylation of phenol. Appl Catal A 453:272–279CrossRefGoogle Scholar
  12. 12.
    Choi JS, Kim DJ, Chang SH et al (2003) Catalytic applications of MCM-41 with different pore sizes in selected liquid phase reactions. Appl Catal A 254(2):225–237CrossRefGoogle Scholar
  13. 13.
    Yip ACK, Lam FLY, Hu X et al (2009) Study on the synthesis of clay-based titanium silicalite-1 catalytic composite. Ind Eng Chem Res 48(11):5266–5275CrossRefGoogle Scholar
  14. 14.
    Zuo Y, Liu M, Zhang T et al (2015) Role of pentahedrally coordinated titanium in titanium silicalite-1 in propene epoxidation. RSC Adv 5(23):17897–17904CrossRefGoogle Scholar
  15. 15.
    Borin MF, Silva TD, Felisbino RF et al (2006) Synthesis of TS-1 molecular sieves using a new Ti source. J Phys Chem B 110(31):15080–15084CrossRefGoogle Scholar
  16. 16.
    Rajakovic VN, Mintova S, Senker J et al (2003) Synthesis and characterization of V- and Ti-substituted mesoporous materials. Mater Sci Eng, C 23(6):817–821CrossRefGoogle Scholar
  17. 17.
    Bengoa JF, Gallegos NG, Marchetti SG et al (1998) Influence of TS-1 structural properties and operation conditions on benzene catalytic oxidation with H2O2. Microporous Mesoporous Mater 24(4):163–172CrossRefGoogle Scholar
  18. 18.
    Khouw CB, Dartt CB, Labinger JA et al (1994) Studies on the catalytic oxidation of alkanes and alkenes by titanium silicates. J Catal 149(1):195–205CrossRefGoogle Scholar
  19. 19.
    Liu C, Huang J, Sun D et al (2013) Anatase type extra-framework titanium in TS-1: A vital factor influencing the catalytic activity toward styrene epoxidation. Appl Catal A 459:1–7CrossRefGoogle Scholar
  20. 20.
    Li G, Wang X, Guo X et al (2001) Titanium species in titanium silicalite TS-1 prepared by hydrothermal method. Mater Chem Phys 71(2):195–201CrossRefGoogle Scholar
  21. 21.
    Zhang Y, Guo X, Wang X et al (2000) Extra-framework titanium species (TiO2)x in TS-1 zeolite and its effect on epoxidation of propylene. Acta Petrolei Sinica Petrol Process Sect 16(5):41–46 (in Chinese) Google Scholar
  22. 22.
    Li YG, Lee YM, Porter JF (2002) The synthesis and characterization of titanium silicalite-1. J Mater Sci 37(10):1959–1965CrossRefGoogle Scholar
  23. 23.
    Su J, Xiong G, Zhou J et al (2012) Amorphous Ti species in titanium silicalite-1: structural features, chemical properties, and inactivation with sulfosalt. J Catal 288:1–7CrossRefGoogle Scholar
  24. 24.
    Roffia P, Leofanti G, Cesana A et al (1990) Cyclohexanone ammoximation: a breakthrough in the 6-caprolactam production process. Stud Surf Sci Catal 55:43–52CrossRefGoogle Scholar
  25. 25.
    Roffia P, Leofanti G, Cesana A et al. (1988) Catalytic process for the manufacture of oximes. US 4,794,198. 1988-12-27Google Scholar
  26. 26.
    Lin M, Zhu B, Shu XT et al (2005) The development and application of hierarchical titanium silicalite-1. Petrochemical Technology 34:377–379Google Scholar
  27. 27.
    Wang Y, Meng F, Zhang Y et al (2009) A preparation method of granular titanium silicon molecular sieve. CN, 200910069663. 2009-12-09Google Scholar
  28. 28.
    Wang Y, Yang K, Zheng R et al (2009) A preparation method of large particle size titanium silicon molecular sieve. CN, 200910067853. 2009-07-15Google Scholar
  29. 29.
    Wu G, Wang Y, Wang L et al (2013) Epoxidation of propylene with H2O2 catalyzed by supported TS-1 catalyst in a fixed-bed reactor: experiments and kinetics. Chem Eng J 215:306–314CrossRefGoogle Scholar
  30. 30.
    Wang Y, Ye J, Wang S et al (2016) Synthesis of mesoporous titanium silicalite-1 with high stability in cyclohexanone ammoximation. Trans of Tianjin Univ 22:254–260CrossRefGoogle Scholar
  31. 31.
    Khomane RB, Kulkarni BD, Paraskar A et al (2002) Synthesis, characterization and catalytic performance of titanium silicalite-1 prepared in micellar media. Mater Chem Phys 76(1):99–103CrossRefGoogle Scholar
  32. 32.
    Xia QH, Gao Z (1997) Crystallization kinetics of pure TS-1 zeolite using quaternary ammonium halides as templates. Mater Chem Phys 47(2):225–230CrossRefGoogle Scholar
  33. 33.
    Perego C, Carati A, Ingallina P et al (2001) Production of titanium containing molecular sieves and their application in catalysis. Appl Catal A 221(1):63–72CrossRefGoogle Scholar
  34. 34.
    Blasco T, Camblor MA, Corma A et al (1993) The state of Ti in titanoaluminosilicates isomorphous with zeolite. beta. J Am Chem Soc 115(25):11806–11813CrossRefGoogle Scholar
  35. 35.
    Geobaldo F, Bordiga S, Zecchina A et al (1992) DRS UV-Vis and EPR spectroscopy of hydroperoxo and superoxo complexes in titanium silicalite. Catal Lett 16(1–2):109–115CrossRefGoogle Scholar
  36. 36.
    Astorino E, Peri JB, Willey RJ et al (1995) Spectroscopic characterization of silicalite-1 and titanium silicalite-1. J Catal 157(2):482–500CrossRefGoogle Scholar
  37. 37.
    Huybrechts DRC, Vaesen I, Li HX et al (1991) Factors influencing the catalytic activity of titanium silicalites in selective oxidations. Catal Lett 8(2–4):237–244CrossRefGoogle Scholar
  38. 38.
    Thangaraj A, Kumar R, Mirajkar SP et al (1991) Catalytic properties of crystalline titanium silicalites I, Synthesis and characterization of titanium-rich zeolites with MFI structure. J Catal 130(1):1–8CrossRefGoogle Scholar
  39. 39.
    Ricchiardi G, Damin A, Bordiga S et al (2001) Vibrational structure of titanium silicate catalysts. A spectroscopic and theoretical study. J Am Chem Soc 123(46):11409–11419CrossRefGoogle Scholar
  40. 40.
    Sun Z, Zhang Y, Deng X et al (2012) Fabrication and application of silicalite-1 and TS-1 hollow fibers with polyethylene imine (PEI) fibers as substrates. J Ind Eng Chem 18(1):92–97CrossRefGoogle Scholar
  41. 41.
    Yinqian L, Yongxiang L, Wei W et al (2002) Study on deactivation behavior of TS-1 molecular sieve in cyclohexanone ammoximation. Petrol Process Petrochem 33(5):41–45Google Scholar
  42. 42.
    Wu P, Komatsu T, Yashima T (1997) Ammoximation of ketones over titanium mordenite. J Catal 168(2):400–411CrossRefGoogle Scholar
  43. 43.
    Mantegazza MA, Petrini G, Spano G et al (1999) Selective oxidations with hydrogen peroxide and titanium silicalite catalyst. J Mol Catal A Chem 146(1):223–228CrossRefGoogle Scholar
  44. 44.
    Dal Pozzo L, Fornasari G, Monti T (2002) TS-1, catalytic mechanism in cyclohexanone oxime production. Catal Commun 3(8):369–375CrossRefGoogle Scholar

Copyright information

© Tianjin University and Springer-Verlag Berlin Heidelberg 2017

Authors and Affiliations

  • Yaquan Wang
    • 1
  • Shuhai Wang
    • 1
  • Teng Zhang
    • 1
  • Jiaxin Ye
    • 1
  • Xiao Wang
    • 1
  • Dali Wang
    • 2
  1. 1.Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and TechnologyTianjin UniversityTianjinChina
  2. 2.Tianjin Synthetic Fiber CompanyTianjinChina

Personalised recommendations