Wuhan University Journal of Natural Sciences

, Volume 24, Issue 1, pp 23–29 | Cite as

Influence of V/P Ratio on the Catalytic Performance of VPO/SiO2 Catalysts for Ammoxidation of Chloro-Substituted Toluenes

  • Yanling Dong
  • Longlong Xu
  • Zhenguo Zhang
  • Wenhui Liu
  • Xiongjian Li
  • Yalan ZhongEmail author
  • Chi Huang


A series of vanadium phosphate oxide (VPO) catalysts supported on silica (VPO/SiO2) with various mole ratios of V/P (nV:nP=1:0.8-1:3) were prepared through impregnation method. The catalytic activity was evaluated by ammoxidation reactions of several kinds of chloro-substituted toluenes (CT) in a fixed-bed reactor. The catalyst presented the best performance when nV:nP is 1:1.6. The prepared catalysts were characterized by N2 adsorption, hydrogen temperature programmed reduction (TPR) and ammonia temperature programmed desorption (TPD) and etc. The results reveal that P can decrease the bonding energy of V=O and increase the mobility of lattice oxygen which was beneficial for the improvement of the catalysts, while too much P can greatly decrease the average oxidation number of V which leads to deactivation of the catalysts. The surface acidity of the VPO/SiO2 catalysts is affected by nV:nP and the catalyst had the highest surface acidity when nV:nP is 1:1.6. The selectivity of catalysts is proportional to the surface acidity when nV:nP is lower than 1:3.0.

Key words

ammoxidation VPO/SiO2 catalyst substituted toluenes substituted benzonitriles 

CLC number

O 625.67 


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  1. [1]
    Xu L L, Zhang Y F, Deng Y, et al. One-step hydrothermal synthesis and characterization of V-Cr-O nanospheres and their excellent performance in the ammoxidation of 3,4- and 2,6-DCT [J]. Materials Research Bulletin, 2013, 48(9): 3620–3624.Google Scholar
  2. [2]
    Kalevaru V N, Madaan N, Martin A. Synthesis, characterization and catalytic performance of titania supported VPO catalysts for the ammoxidation of 3-picoline [J]. Applied Catalysis A: General, 2011, 391(1-2): 52–62.Google Scholar
  3. [3]
    Brazdil J F. A critical perspective on the design and development of metal oxide catalysts for selective propylene ammoxidation and oxidation [J]. Applied Catalysis A: General, 2017, 543: 225–233.Google Scholar
  4. [4]
    Baek M, Lee J K, Kang H J, et al. Ammoxidation of propane to acrylonitrile over Mo-V-P-Oy/Al2O3 catalysts: Effect of phosphorus content [J]. Catalysis Communications, 2017, 92: 27–30.Google Scholar
  5. [5]
    Velankar H, Clarke K G, Preez R D, et al. Developments in nitrile and amide biotransformation processes [J]. Trends in Biotechnology, 2010, 28(11): 561–569.Google Scholar
  6. [6]
    Al-Shehri A, Katabathini N. Influence of polyoxometalate structure in ammoxidation of 2-methylpyrazine [J]. Catalysis Communications, 2018, 108: 17–22.Google Scholar
  7. [7]
    Goto Y, Shimizu K I, Murayama T, et al. Hydrothermal synthesis of microporous W-V-O as an efficient catalyst for ammoxidation of 3-picoline [J]. Applied Catalysis A: General, 2016, 509: 118–122.Google Scholar
  8. [8]
    Goto Y, Shimizu K I, Kon K, et al. NH3-efficient ammoxidation of toluene by hydrothermally synthesized layered tungsten-vanadium complex metal oxides [J]. Journal of Catalysis, 2016, 344: 346–353.Google Scholar
  9. [9]
    Dwivedi R, Sharma P, Sisodiya A, et al. A DFT-assisted mechanism for evolution of the ammoxidation of 2-chlorotoluene (2-CLT) to 2-chlorobenzonitrile (2-CLBN) over aluminasupported V2O5 catalyst prepared by a solution combustion method [J]. Journal of Catalysis, 2017, 345: 245–257.Google Scholar
  10. [10]
    Xie G Y, Huang C, Zheng Q, et al. Reasearch on preparation of p-chlorobenzonitrile by ammoxidation of p-chlorotoluene [J]. Journal of Wuhan University (Natural Science Edition), 2000, 46(6): 692–694(Ch).Google Scholar
  11. [11]
    Yang W L, Lan H L, Song F, et al. Synthesis of 3,4-difluorobenzonitrile by phses transfer catalysis [J]. Chemical World, 2015, 56(1): 47–50(Ch).Google Scholar
  12. [12]
    Zheng Q, Huang C, Han Q Y, et al. The research on a process for producing 2,6-dichlorobenzonitrile by ammoxidation [J]. Journal of Wuhan University (Natural Science Edition), 1998, 44(2): 167–170(Ch).Google Scholar
  13. [13]
    Huang C, Xiao D, Xu H X, et al. 3,4-dichlorotoluene ammoxidation to 3,4-dichlorobenzonitrile over VPO/SiO2 catalyst [J]. Wuhan University Journal of Natural Sciences, 2002, 7(3): 353–355.Google Scholar
  14. [14]
    Dropka N, Kalevaru V, Martin A, et al. The kinetics of vapour-phase ammoxidation of 2,6-dichlorotoluene over VPO catalyst [J]. Journal of Catalysis, 2006, 240(1): 8–17.Google Scholar
  15. [15]
    Kalevaru V N, Lücke B, Martin A. Synthesis of 2,6-dichlorobenzonitrile from 2,6-dichlorotoluene by gas phase ammoxidation over VPO catalysts [J]. Catalysis Today, 2009, 142(3-4): 158–164.Google Scholar
  16. [16]
    Huang C, Zheng Q, Xie G Y, et al. Ammoxidation of 2,6-dichlorotoluene on silica supported vanadium-phosphorus oxide catalyst [J]. Chinese Journal of Catalysis, 1999, 20(6): 679–680.Google Scholar
  17. [17]
    Xie G Y, Zheng Q, Huang C, et al. Ammoxidation of substituted toluenes on silica supported VPO catalysts [J]. Wuhan University Journal of Natural Sciences, 2002, 7(3): 356–360.Google Scholar
  18. [18]
    Bondareva V M, Andrushkevich T V, Lapina O B, et al. Methylpyrazine ammoxidation over binary oxide systems: V. Effect of phosphorus additives on the physicochemical and catalytic properties of a vanadium-yitanium catalyst in methylpyrazine ammoxidation [J]. Kinetics and Catalysis, 2004, 45(1): 104–113.Google Scholar
  19. [19]
    Zheng Q, Huang C, Xie G Y, et al. A direct synthesis of aromatic nitriles from methylaromatic compounds by ammoxidation on DC-108 catalyst [J]. Synthetic Communications, 1999, 29(13): 2349–2353.Google Scholar
  20. [20]
    Makowski W, Lojewska J, Dziembaj R. TPR and TPD studies of vanadia/silica catalysts for selective oxidation of methane to formaldehyde [J]. Reaction Kinetics and Catalysis Letters, 2004, 8(1): 121–128.Google Scholar
  21. [21]
    Ciambelli P, Lisi L, Patrono P, et al. VOPO4·2H2O and Fe(H2O)x(VO)1-xPO4·2H2O supported on TiO2 as catalysts for oxidative dehydrogenation of ethane [J]. Catalysis Letters, 2002, 82(3): 243–247.Google Scholar
  22. [22]
    Li X K, Ji W J, Zhao J, et al. n-Butane oxidation over VPO catalysts supported on SBA-15 [J]. Journal of Catalysis, 2006, 238(1): 232–241.Google Scholar
  23. [23]
    Rownaghi A A, Taufiq-Yap Y H, Jiunn T W. Influence of the ethylene glycol, water treatment and microwave irradiation on the characteristics and performance of VPO catalysts for n-butane oxidation to maleic anhydride [J]. Catalysis Letters, 2009, 130(3): 593–603.Google Scholar
  24. [24]
    Taufiq-Yap Y H, Goh C K, Hutchings G J, et al. Influence of milling media on the physicochemicals and catalytic properties of mechanochemical treated vanadium phosphate catalysts[J]. Catalysis Letters, 2011, 141(3): 400–407.Google Scholar
  25. [25]
    Martin A, Zhang Y, Zanthoff H W, et al. The role of ammonium ions during toluene ammoxidation on α-(NH4)2[(VO)3(P2O7)2] used as catalyst [J]. Applied Catalysis A: General, 1996, 139(1-2): L11–L16.Google Scholar
  26. [26]
    Martin A, Zhang Y, Meisel M. Effect of the surface vanadium valence state on activity and selectivity properties of (VO)2P2O7 used as catalyst in the ammoxidation of toluene [J]. Reaction Kinetics and Catalysis Letters, 1997, 60(1): 3–8.Google Scholar
  27. [27]
    Kamata H, Takahashi K, Odenbrand C U. Surface acid property and its relation to SCR activity of phosphorus added to commercial V2O5(WO3)/TiO2 catalyst [J]. Catalysis Letters, 1998, 53(1): 65–71.Google Scholar
  28. [28]
    Zhu J M, Rebenstorf B, Andersson S L T. Influence of phosphorus on the catalytic properties of V2O5/TiO2 catalysts for toluene oxidation [J]. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 1989, 85(11): 3645–3662.Google Scholar

Copyright information

© Wuhan University and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Yanling Dong
    • 1
  • Longlong Xu
    • 2
  • Zhenguo Zhang
    • 2
  • Wenhui Liu
    • 3
  • Xiongjian Li
    • 4
  • Yalan Zhong
    • 4
    Email author
  • Chi Huang
    • 4
  1. 1.State Key Laboratory of Advanced Technology for Materials Synthesis and ProcessingWuhan University of TechnologyHubeiChina
  2. 2.Tianhua Chemical Branch, Xi’an Sunward Aeromat Co., Ltd.ShaanxiChina
  3. 3.Sanjiang Chemical Factory of CSSGHubeiChina
  4. 4.College of Chemistry and Molecular SciencesWuhan UniversityHubeiChina

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