Skip to main content
SpringerLink
Log in

Synthesis of mesoporous titanium silicalite-1 with high stability in cyclohexanone ammoximation

  • Published:
Transactions of Tianjin University Aims and scope Submit manuscript

Abstract

Mesoporous titanium silicalite-1(TS-1)was hydrothermally synthesized with the addition of triethanolamine( TEA)in the conventional process, and used in the cyclohexanone ammoximation in a continuous slurry reactor. The as-prepared TS-1 was characterized with X-ray diffraction(XRD), scanning electron microcopy( SEM), N2 adsorption-desorption, Fourier transform infrared (FT-IR)spectroscopy, UV-Visible(UV-Vis) diffuse reflectance spectra and UV Raman spectroscopy. The results indicated that the addition of TEA resulted in the formation of mesopores and the slight increase of framework titanium in TS-1. TS-1 synthesized with the addition of TEA exhibited a higher stability in the cyclohexanone ammoximation than that without the addition of TEA, attributing to the increase of mesopore volumes and the slight increase of the framework titanium in TS-1. However, when the addition of TEA was up to TEA/SiO2 ratio of 0.24, the crystallinity and framework titanium of TS-1 decreased markedly, and the average crystal sizes of TS-1 increased, with the catalyst stability becoming poor.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Khouw C B, Dartt C B, Labinger J A et al. Studies on the catalytic-oxidation of alkanes and alkenes by titanium silicates [J]. Journal of Catalysis, 1994, 149(1): 195–205.

    Article  Google Scholar 

  2. Park S, Cho K M, Youn M H et al. Direct epoxidation of propylene with hydrogen peroxide over TS-1 catalysts: Effect of hydrophobicity of the catalysts [J]. Catalysis Communications, 2008, 9(15): 2485–2488.

    Article  Google Scholar 

  3. Wróblewska A, Rzepkowska M, Milchert E. Epoxidation of methallyl alcohol with hydrogen peroxide over TS-1 catalyst [J]. Applied Catalysis A: General, 2005, 294(2): 244–250.

    Article  Google Scholar 

  4. Tanev P T, Chibwe M, Pinnavaia T J. Titanium-containing mesoporous molecular sieves for catalytic oxidation of aromatic compounds [J]. Nature, 1994, 368(6469): 321–323.

    Article  Google Scholar 

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

    Article  Google Scholar 

  6. Taramasso M, Perego G, Notari B. Preparation of Porous Crystalline Synthetic Material Comprised of Silicon and Titanium Oxides: US, 4410501[P]. 1983-10-18.

    Google Scholar 

  7. Roffia P, Leofanti G, Cesana A et al. Cyclohexanone ammoximation: A break through in the 6-caprolactam production process [J]. Studies in Surface Science and Catalysis, 1990, 55: 43–52.

    Article  Google Scholar 

  8. Borin M F, Da Silva T, Felisbino R F et al. Synthesis of TS-1 molecular sieves using a new Ti source [J]. The Journal of Physical Chemistry B, 2006, 110(31): 15080–15084.

    Article  Google Scholar 

  9. Chandra D, Mal N K, Mukherjee M et al. Titanium-rich highly ordered mesoporous silica synthesized by using a mixed surfactant system [J]. Journal of Solid State Chemistry, 2006, 179(6): 1802–1807.

    Article  Google Scholar 

  10. Fan Weibin, Duan Renguan, Yokoi T et al. Synthesis, crystallization mechanism, and catalytic properties of titaniumrich TS-1 free of extraframework titanium species [J]. Journal of the American Chemical Society, 2008, 130(31): 10150–10164.

    Article  Google Scholar 

  11. Fang Yunming, Hu Haoquan. Mesoporous TS-1: Nanocasting synthesis with CMK-3 as template and its performance in catalytic oxidation of aromatic thiophene [J]. Catalysis Communications, 2007, 8(5): 817–820.

    Article  Google Scholar 

  12. Ok D, Jiang N, Prasetyanto E A et al. Epoxidation of cyclic-olefins over carbon template mesoporous TS-1 [J]. Microporous and Mesoporous Materials, 2011, 141(1): 2–7.

    Article  Google Scholar 

  13. Wang Weihai, Li Gang, Liu Liping et al. Synthesis and catalytic performance of hierarchical TS-1 directly using agricultural products sucrose as meso/macropores template[ J]. Microporous and Mesoporous Materials, 2013, 179: 165–171.

    Article  Google Scholar 

  14. Cheneviere Y, Chieux F, Caps V et al. Synthesis and catalytic properties of TS-1 with mesoporous/microporous hierarchical structures obtained in the presence of amphiphilic organosilanes [J]. Journal of Catalysis, 2010, 269(1): 161–168.

    Article  Google Scholar 

  15. Schmidt I, Krogh A, Wienberg K et al. Catalytic epoxidation of alkenes with hydrogen peroxide over first mesoporous titanium-containing zeolite [J]. Chemical Communications, 2000(21): 2157–2158.

    Article  Google Scholar 

  16. Wang Yongrui, Lin Min, Tuel Alain. Hollow TS-1 crystals formed via a dissolution-recrystallization process [J]. Microporous and Mesoporous Materials, 2007, 102(1): 80–85.

    Article  Google Scholar 

  17. Zuo Yi, Song Wancang, Dai Chengyi et al. Modification of small-crystal titanium silicalite-1 with organic bases: Recrystallization and catalytic properties in the hydroxylation of phenol [J]. Applied Catalysis A: General, 2013, 453: 272–279.

    Article  Google Scholar 

  18. Xu Juan, Wang Yaquan, Feng Wenping et al. Effect of triethylamine treatment of titanium silicalite-1 on propylene epoxidation [J]. Frontiers of Chemical Science and Engineering, 2014, 8(4): 478–487.

    Article  Google Scholar 

  19. Wu Xiaoxue, Wang Yaquan, Zhang Teng et al. Effect of TS-1 treatment by tetrapropyl ammonium hydroxide on cyclohexanone ammoximation[J]. Catalysis Communications, 2014, 50: 59–62.

    Article  Google Scholar 

  20. Zhang Teng, Wang Yaquan, Wang Shuhai et al. Effect of triethylamine treatment of titanium silicalite-1 on cyclohexanone ammoximation in a continuous system [J]. Reaction Kinetics, Mechanisms and Catalysis, 2015, 114(2): 735–752.

    Article  Google Scholar 

  21. Yao Pengxu, Wang Yaquan, Zhang Teng et al. Effect of sodium ions in synthesis of titanium silicalite-1 on its catalytic performance for cyclohexanone ammoximation [J]. Frontiers of Chemical Science and Engineering, 2014, 8(2): 149–155.

    Article  Google Scholar 

  22. Khomane R B, Kulkarni B D, Paraskar A et al. Synthesis, characterization and catalytic performance of titanium silicalite-1 prepared in micellar media [J]. Materials Chemistry and Physics, 2002, 76(1): 99–103.

    Article  Google Scholar 

  23. Xia Q H, Gao Z. Crystallization kinetics of pure TS-1 zeolite using quaternary ammonium halides as templates [J]. Materials Chemistry and Physics, 1997, 47(2): 225–230.

    Article  Google Scholar 

  24. Ke Xuebin, Xu Li, Zeng Changfeng et al. Synthesis of mesoporous TS-1 by hydrothermal and steam-assisted dry gel conversion techniques with the aid of triethanolamine [J]. Microporous and Mesoporous Materials, 2007, 106(1): 68–75.

    Article  Google Scholar 

  25. Shan Z, Jansen J C, Marchese L et al. Synthesis, characterization and catalytic testing of a 3-D mesoporous titanosilica, Ti-TUD-1 [J]. Microporous and Mesoporous Materials, 2001, 48(1): 181–187.

    Article  Google Scholar 

  26. Shan Z, Gianotti E, Jansen J C et al. One-step synthesis of a highly active, mesoporous, titanium-containing silica by using bifunctional templating [J]. Chemistry-A European Journal, 2001, 7(7): 1437–1443.

    Article  Google Scholar 

  27. Cundy C S, Forrest J O. Some observations on the preparation and properties of colloidal silicalites(Part ?): Preparation, characterisation and properties of colloidal silicalite-1, TS-1, silicalite-2 and TS-2 [J]. Microporous and Mesoporous Materials, 2004, 72(1): 67–80.

    Article  Google Scholar 

  28. Ricchiardi G, Damin A, Bordiga S et al. Vibrational structure of titanium silicate catalysts. A spectroscopic and theoretical study[J]. Journal of the American Chemical Society, 2001, 123(46): 11409–11419.

    Article  Google Scholar 

  29. Thangaraj A, Kumar R, Mirajkar S P et al. Catalytic properties of crystalline titanium silicalites I. Synthesis and characterization of titanium-rich zeolites with MFI structure [J]. Journal of Catalysis, 1991, 130(1): 1–8.

    Article  Google Scholar 

  30. On D T, Kaliaguine S, Bonneviot L. Titanium boralites with MFI structure characterized using XRD, XANES, IR, and UV-visible techniques: Effect of hydrogen peroxide on the preparation [J]. Journal of Catalysis, 1995, 157(1): 235–243.

    Article  Google Scholar 

  31. Ratnasamy P, Srinivas D, Knözinger H. Active sites and reactive intermediates in titanium silicate molecular sieves [J]. Advances in Catalysis, 2004, 48: 1–169.

    Google Scholar 

  32. Song Wancang, Xiong Guang, Long Huayun et al. Effect of treatment with different bases on the catalytic properties of TS-1/SiO2 extrudates in propylene epoxidation [J]. Microporous and Mesoporous Materials, 2015, 212: 48–55.

    Article  Google Scholar 

  33. Song Wancang, Zuo Yi, Xiong Guang et al. Transformation of SiO2 in titanium silicalite-1/SiO2 extrudates during tetrapropylammonium hydroxide treatment and improvement of catalytic properties for propylene epoxidation [J]. Chemical Engineering Journal, 2014, 253: 464–471.

    Article  Google Scholar 

  34. Su Ji, Xiong Guang, Zhou Juncheng et al. Amorphous Ti species in titanium silicalite-1: Structural features, chemical properties, and inactivation with sulfosalt [J]. Journal of Catalysis, 2012, 288: 1–7.

    Article  Google Scholar 

  35. Li Can, Xiong Guang, Liu Jianke et al. Identifying framework titanium in TS-1 zeolite by UV resonance Raman spectroscopy [J]. The Journal of Physical Chemistry B, 2001, 105(15): 2993–2997.

    Article  Google Scholar 

  36. Huang Denggao, Zhang Xian, Liu Tianwei et al. Synthesis of high-performanced titanium silicalite-1 zeolite at very low usage of tetrapropyl ammonium hydroxide[J]. Industrial & Engineering Chemistry Research, 2013, 52(10): 3762–3772.

    MathSciNet  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072, China

    Yaquan Wang  (王亚权), Jiaxin Ye  (叶家鑫), Shuhai Wang  (王书海), Yongjie Lin  (林永杰), Shougui Wang  (王守桂) & Wei Liu  (刘 伟)

Authors
  1. Yaquan Wang  (王亚权)
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jiaxin Ye  (叶家鑫)
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Shuhai Wang  (王书海)
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yongjie Lin  (林永杰)
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Shougui Wang  (王守桂)
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Wei Liu  (刘 伟)
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Yaquan Wang  (王亚权).

Additional information

Supported by the National Natural Science Foundation of China(No. 21276183).

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wang, Y., Ye, J., Wang, S. et al. Synthesis of mesoporous titanium silicalite-1 with high stability in cyclohexanone ammoximation. Trans. Tianjin Univ. 22, 254–260 (2016). https://doi.org/10.1007/s12209-016-2774-z

Download citation

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12209-016-2774-z

Keywords

Search

Navigation