Reaction Kinetics, Mechanisms and Catalysis

, Volume 125, Issue 2, pp 887–900 | Cite as

Oxidative regeneration study of spent V2O5 catalyst from sulfuric acid manufacture

  • Phuong N. X. Vo
  • Nguyen Le-Phuc
  • Tri V. Tran
  • Phuong T. Ngo
  • Thuy N. Luong


In this work, the efficiency of the regeneration process of spent V2O5 catalyst from sulfuric acid plant under different atmospheres (5%O2/N2 or air) was evaluated. Temperature-programmed results showed that the observed reduction profiles of the samples are attributed to the reduction of amorphous V+5 and low-valence V+5−x species at low temperatures followed by the reduction of their crystalline structures at high temperatures. Significantly low values of SO2 conversion of the spent samples can be explained by the significant drop in quantity of all vanadium species, coupled with their structural change to more thermally stable forms. It was found that the exposure of the spent catalyst to 5%O2/N2 stream at 550 °C for 1 h allowed at first the re-oxidation of amorphous low-valence V species and second the dissolution of crystalline low-valence V species, thus resulted in recovery of their catalytic activity for SO2 oxidation. However, the regeneration in air was less effective than in 5%O2/N2 stream. This is supposedly due to the differential behaviors of the spent sample in different oxidative streams toward re-oxidizing low-valence V species and re-dissolving V precipitates.


V2O5 Oxidative regeneration SO2 oxidation reaction Temperature-programmed reduction 



This work is supported by The Ministry of Industry and Trade of the Socialist Republic of Vietnam under Grant 06/HD-DT.06.14/CNMT.

Compliance with ethical standards

Conflict of interest

On behalf of all authors, the corresponding author states that there is no conflict of interest.


  1. 1.
    Louie DK (2005) Handbook of sulphuric acid manufacturing. DKL Engineering, ThornhillGoogle Scholar
  2. 2.
    Ognyanova A, Ozturk AT, de Michelis I, Ferella F, Taglieri G, Akcil A, Vegliò F (2009) Metal extraction from spent sulfuric acid catalyst through alkaline and acidic leaching. Hydrometallurgy 100:20–28CrossRefGoogle Scholar
  3. 3.
    MECS Standard Sulfuric Acid Catalysts MSDS, Monsanto Enviro-Chem Systems Inc. (2011)Google Scholar
  4. 4.
    King M, Moats M, Davenport WGI (2013) Sulfuric acid manufacture: analysis, control and optimization, 2nd edn. Elsevier, New YorkGoogle Scholar
  5. 5.
    Grobela M, Grzesiak P (2007) The influence of iron compounds in the sulfuric acid catalyst on the SO2 oxidation process. Pol J Chem Technol 9:2–6CrossRefGoogle Scholar
  6. 6.
    Hansen NH, Fehrmann R, Bjerrum NJ (1982) Complex formation in pyrosulfate melts. 1. Potentiometric, cryoscopic, and spectrophotometric investigations of the systems potassium disulfate-potassium sulfate and potassium disulfate-potassium sulfate-vanadium pentoxide in the temperature range 410–450 °C. Inorg Chem 21:744–752CrossRefGoogle Scholar
  7. 7.
    Karydis DA, Eriksen KM, Fehrmann R, Boghosian S (1994) High-temperature spectrophotometric and electron spin resonance spectroscopic investigations of vanadium complexes in the molten salt-gas system V2O5-K2S2O7/SO2-SO3-N2. J Chem Soc Dalton Trans 14:2151–2157CrossRefGoogle Scholar
  8. 8.
    Rasmussen SB, Eriksen KM, Fehrmann R (1999) Sulfato complex formation of V(V) and V(IV) in pyrosulfate melts investigated by potentiometry and spectroscopic methods. J Phys Chem B 103:11282–11289CrossRefGoogle Scholar
  9. 9.
    Boghosian S, Borup F, Chryssanthopoulos A (1997) Vanadium (V) complexes in molten salts of interest for the catalytic oxidation of sulphur dioxide. Catal Lett 48:145–150CrossRefGoogle Scholar
  10. 10.
    Eriksen KM, Karydis DA, Boghosian S, Fehrmann R (1995) Deactivation and compound formation in sulphuric-acid catalysts and model systems. J Catal 155:32–42CrossRefGoogle Scholar
  11. 11.
    Boghosian S, Fehrmann R, Bjerrum NJ, Papatheodorou GN (1989) Formation of crystalline compounds and catalyst deactivation during SO2 oxidation in V2O5/M2S2O7 (M = Na, K, Cs) melts. J Catal 119:121–134CrossRefGoogle Scholar
  12. 12.
    Wachs IE (2011) The generality of surface vanadium oxide phases in mixed oxide catalysts. Appl Catal A 391:36–42CrossRefGoogle Scholar
  13. 13.
    Olthof B, Khodakov J, Bell AT, Oglesia E (2000) Effects of support composition and pretreatment conditions on the structure of vanadia dispersed on SiO2, Al2O3, TiO2, ZrO2, and HfO2. J Phys Chem B 104:1516–1528CrossRefGoogle Scholar
  14. 14.
    Burcham LJ, Deo G, Gao X, Wachs IE (2000) In situ IR, Raman, and UV-Vis DRS spectroscopy of supported vanadium oxide catalysts during methanol oxidation. Top Catal 11:85–100CrossRefGoogle Scholar
  15. 15.
    Wang CB, Deo G, Wachs IE (1998) Characterization of vanadia sites in V-silicalite, vanadia-silica cogel, and silica-supported vanadia catalysts: X-ray powder diffraction, Raman spectroscopy, Solid-state51V NMR, Temperature-programmed reduction, and methanol oxidation studies. J Catal 178:640–648CrossRefGoogle Scholar
  16. 16.
    Eriksen KM, Nielsen K, Fehrmann R (1996) Crystal structure and spectroscopic characterization of K6(VO)4(SO4)8 containing mixed-valent vanadium (IV)-vanadium (V). Inorg Chem 35:480–484CrossRefGoogle Scholar
  17. 17.
    Bronkema JL, Bell AT (2007) Mechanistic studies of methanol oxidation to formaldehyde on isolated vanadate sites supported on MCM-48. J Phys Chem C 111:420–430CrossRefGoogle Scholar
  18. 18.
    Wachs IE, Weckhuysen BM (1997) Structure and reactivity of surface vanadium oxide species on oxide supports. Appl Catal A 157:67–90CrossRefGoogle Scholar
  19. 19.
    Bronkema JL, Bell AT (2008) An investigation of the reduction and reoxidation of isolated vanadate sites supported on MCM-48. Catal Lett 122:1–8CrossRefGoogle Scholar
  20. 20.
    Christodoulakis A, Boghosian S (2003) Molecular structure of supported molten salt catalysts for SO2 oxidation. J Catal 215:139–150CrossRefGoogle Scholar
  21. 21.
    Oehlers C, Fehrmann R, Masters SG, Eriksen KM, Sheinin DE, Bal’zhimaev BS, Elokhin VI (1996) In-situ spectroscopic studies and modelling of crystallization processes of sulphuric acid catalysts. Appl Catal A 147:127–144CrossRefGoogle Scholar
  22. 22.
    United States Environmental Protection Agency (1994) Waste analysis at facilities that generate, treat, store and dispose of hazard waste. A guidance manual US-EPA.
  23. 23.
    Mazurek K (2013) Recovery of vanadium, potassium and iron from a spent vanadium catalyst by oxalic acid solution leaching, precipitation and ion exchange processes. Hydrometallurgy 134–135:26–31CrossRefGoogle Scholar
  24. 24.
    Ceren E, Ata A, Zyuldyz B, Kuanysh A, Aliya B, Aysenur T (2016) Recovery of vanadium from spent catalysts of sulfuric acid plant by using inorganic and organic acids: Laboratory and semi-pilot tests. Waste Manag 49:455–461CrossRefGoogle Scholar
  25. 25.
    Gladyshev SV, Akcil A, Abdulvaliyev RA, Tastanov EA, Beisembekova KO, Temirova SS, Deveci H (2015) Recovery of vanadium and gallium from solid waste by-products of Bayer process. Miner Eng 74:91–98CrossRefGoogle Scholar
  26. 26.
    CIE S014-4/E:2007 (ISO11664-4 :2008) Colorimetry—part 4: CIE 1976 L*a*b* color spaces. Standard by Commission Internationale de l’EclairageGoogle Scholar
  27. 27.
    CIE S014-2/E:2006/ISO11664-2 :2007(E) CIE Standard Illuminants for Colorimetry. Standard by Commission Internationale de l’EclairageGoogle Scholar
  28. 28.
    CIE S014-6/E:2013 Colorimetry—part 6: CIEDE 2000 color—difference formula. Standard by Commission Internationale de l’EclairageGoogle Scholar
  29. 29.
    ASTM D7085-04 (2010)e1 Standard Guide for Determination of Chemical Elements in Fluid Catalytic Cracking Catalysts by X-ray Fluorescence Spectrometry (XRF)Google Scholar
  30. 30.
    Vahl JM, Converse JE (1980) Ripper procedure for determining sulfur dioxide in wine: collaborative study. J Assoc Off Anal Chem 63:194–199PubMedGoogle Scholar
  31. 31.
    Messi C, Carniti P, Gervasini A (2008) Kinetics of reduction of supported nanoparticles of iron oxide. J Therm Anal Calorim 91:93–100CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2018

Authors and Affiliations

  • Phuong N. X. Vo
    • 1
  • Nguyen Le-Phuc
    • 1
  • Tri V. Tran
    • 1
  • Phuong T. Ngo
    • 1
  • Thuy N. Luong
    • 1
  1. 1.Catalysis Research Department, PetroVietnam Research and Development Center for Petroleum Processing, Vietnam Petroleum InstituteVietnam Oil and Gas GroupHo Chi Minh CityVietnam

Personalised recommendations