Skip to main content
SpringerLink
Log in

Vapor-phase Beckmann rearrangement of cyclohexanone oxime over phosphorus modified Si-MCM-41

  • Published:
Reaction Kinetics, Mechanisms and Catalysis Aims and scope Submit manuscript

Abstract

A series of phosphorus modified Si-MCM-41 catalysts prepared via the impregnation method were used for the vapor-phase Beckmann rearrangement of cyclohexanone oxime to caprolactam. The catalysts were characterized by XRD, N2 adsorption, FT-IR, and NH3-TPD. The results indicated that weak acid sites increased with P content, leading to enhanced catalytic activity. The catalyst with Si/P mol ratio of 25 showed best performance at 633 K. The conversion of cyclohexanone oxime and the selectivity for caprolactam were 92.7 and 64.2%, respectively. The P–OH groups are main active sites for the Beckmann rearrangement. Grafting acid hydroxyl groups to cover the Si–OH groups may be a good way to improve the selectivity for this reaction.

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

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Hölderich WF, Röseler J, Heitmann G, Liebens AT (1997) Catal Today 37:353–366

    Article  Google Scholar 

  2. Curtin T, McMonagle JB, Hodnett BK (1992) Appl Catal A 93:91–101

    Article  CAS  Google Scholar 

  3. Xu B-Q, Cheng S-B, Jiang S, Zhu Q-M (1999) Appl Catal A 188:361–368

    Article  CAS  Google Scholar 

  4. Mao D, Lu G, Chen Q, Xie Z, Zhang Y (2001) Catal Lett 77:119–124

    Article  CAS  Google Scholar 

  5. Pillai SK, Gheevarghese O, Sugunan S (2009) Appl Catal A 353:130–136

    Article  CAS  Google Scholar 

  6. Yashima T, Oka N, Komatsu T (1997) Catal Today 38:249–253

    Article  CAS  Google Scholar 

  7. Dai L-X, Koyama K, Miyamoto M, Tatsumi T (1999) Appl Catal A 189:237–242

    Article  CAS  Google Scholar 

  8. Palkovits R, Schmidt W, Ilhan Y, Erdem-Şenatalar A, Schüth F (2009) Microporous Mesoporous Mater 117:228–232

    Article  CAS  Google Scholar 

  9. Heitmann GP, Dahlhoff G, Hölderich WF (1999) Appl Catal A 185:99–108

    Article  CAS  Google Scholar 

  10. Röseler J, Heitmann G, Hölderich WF (1996) Appl Catal A 144:319–333

    Article  Google Scholar 

  11. Dai L-X, Koyama K, Tatsumi T (1998) Catal Lett 53:211–214

    Article  CAS  Google Scholar 

  12. Takahashi T, Kai T, Nakao E (2004) Appl Catal A 262:137–142

    Article  CAS  Google Scholar 

  13. Kresge CT, Leonowicz ME, Roth WJ, Vartuli JC, Beck JS (1992) Nature 359:710–712

    Article  CAS  Google Scholar 

  14. Chaudhari K, Bal R, Chandwadkar AJ, Sivasanker S (2002) J Mol Catal A Chem 177:247–253

    Article  CAS  Google Scholar 

  15. O’Sullivan P, Forni L, Hodnett BK (2001) Ind Eng Chem Res 40:1471–1475

    Article  Google Scholar 

  16. Kawi S, Shen SC, Chew PL (2002) J Mater Chem 12:1582–1586

    Article  CAS  Google Scholar 

  17. Li D, Zheng Y, Wang X (2008) Appl Catal A 340:33–41

    Article  CAS  Google Scholar 

  18. Ko YS, Ahn WS (1999) Microporous Mesoporous Mater 30:283–291

    Article  CAS  Google Scholar 

  19. Anilkumar M, Hölderich WF (2008) J Catal 260:17–29

    Article  CAS  Google Scholar 

  20. Caponetti E, Minoja A, Saladino ML, Spinella A (2008) Microporous Mesoporous Mater 113:490–498

    Article  CAS  Google Scholar 

  21. Vicente-Rodríguez MA, Suarez M, Bañares-Muñoz MA, Lopez-Gonzalez JD (1996) Spectrochim Acta A 52:1685–1694

    Article  Google Scholar 

  22. Kovalchuk TV, Sfihi H, Korchev AS, Kovalenko AS, II’in VG, Zaitsev VN, Fraissard J (2005) J Phys Chem B 109:13948–13956

    Article  CAS  Google Scholar 

  23. Mao D, Chen Q, Lu G (2003) Appl Catal A 244:273–282

    Article  CAS  Google Scholar 

  24. Maheswari R, Shanthi K, Sivakumar T, Narayanan S (2003) Appl Catal A 248:291–301

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072, People’s Republic of China

    Dongshun Zhang, Rijie Wang & Xiaoxia Yang

  2. College of Chemistry and Chemical Engineering, Bohai University, Jinzhou, 121000, People’s Republic of China

    Wensheng Yao

Authors
  1. Dongshun Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Rijie Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Xiaoxia Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Wensheng Yao
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Xiaoxia Yang.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Zhang, D., Wang, R., Yang, X. et al. Vapor-phase Beckmann rearrangement of cyclohexanone oxime over phosphorus modified Si-MCM-41. Reac Kinet Mech Cat 101, 455–463 (2010). https://doi.org/10.1007/s11144-010-0226-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11144-010-0226-7

Keywords

Search

Navigation