Performance of Surfactant-Type Polyoxometalate, [(C16H33)N(CH3)3]6 [PV3W9O40] in Oxidative Desulfurization of Gas Condensate and Straight Run Gasoil

Document Type : Research Paper


Catalyst Research Center, Department of Chemical Engineering, Faculty of Engineering, Razi University, Kermanshah, Iran


A novel hybrid surfactant-type polyoxometalate, [(C16H33)N(CH3)3]6 [PV3W9O40] was synthesized and characterized by FT-IR, SEM and EDX analyze. Oxidation of sulfur compounds in gas condensate with H2O2 as oxidant using surfactant-type polytangestovanado phosphoric catalyst and acetonitrile as solvent was studied. The total sulfur content of the samples was determined by UV Fluorescence. The catalyst were evaluated for the oxidative desulfurization of gas condensate from Ilam Refinery Company and straight-run diesel from Kermanshah Oil Refining. Results show that the catalysts keep the Keggin structure. The sulfur level of a gas condensate can be lowered from a few hundred 1800 µg/g to 83 µg/g only at 5 min and the sulfur removal 98.83% was obtained at 15 min. Also, the desulfurization rate of straight-run diesel can be up to 82% at 30 min. In addition, the reusability of catalyst after five times showed that the catalytic activity had a few decrease from 97.22 to 92.11 percent sulfur removal of gas condensate.


  1. A. Ganiyu, K. Alhooshani, K.O. Sulaiman, M. Qamaruddin, I.A. Bakare, A. Tanimu, T.A. Saleh, Influence of aluminium impregnation on activated carbon for enhanced desulfurization of DBT at ambient temperature: role of surface acidity and textural properties, Chem. Eng. J., 303 (2016) 489-500,
  2. R. Jalali, M.A. Sobati, Intensification of oxidative desulfurization of gas oil by ultrasound irradiation: Optimization using Box-Behnken design (BBD), Appl. Therm. Eng., 111(2017) 1158-1170,
  3. Middle East Fuel Quality – Overview, Hart Energy Consulting, Presented to UNEP Jordan, National post lead workshop, July 24, 2008, Amman, Jordan,
  4. Huang, Z. Zhou, J. Qin, Y. Li, G. Liu, W. Wu, A facile synthesis of mesoporous Mo–Al oxides for desulfurization of dibenzothiophene in the extractive catalytic oxidative desulfurization system. Reac Kinet Mech Cat (2020) 130:1–17,
  5. Safa, R. Bouresli, R. Majren, T. Shamary, X. Ma, Oxidative desulfurization kinetics of refractory sulfur compounds in hydrotreated middle distillates, Journal Pre-proof Fuel, 239 (2019) 24-31,
  6. S. Wang, L. Li, J. Liang, Y.B. Huang, R. Cao: Boosting Oxidative Desulfurization of Model and Real Gasoline over Phosphotungstic Acid Encapsulated in Metal–Organic Frameworks: The Window Size Matters, ChemCatChem 2017;9:971–9,
  7. Zeng, X. Xiao, Y. Li, J. Chen, H. Wang, Deep desulfurization of liquid fuels with molecular oxygen through graphene photocatalytic oxidation, Appl. Catal. BEnviron., 209 (2017) 98-109,
  8. C. Caero, E. Hernandez, F. Pedraza, F. Murrieta, Oxidative desulfurization of synthetic diesel using supported catalysts: part 1. Study of the operation conditions with a vanadium oxide based catalyst, Catalysis Today 107–108 (2005) 564-549,
  9. Gao , S. Zhu, Y. Dai ,C. Xiong, C. Li,, W. Yang, X. Jiang , Performance and mechanism for extractive desulfurization of fuel oil using modified polyethylene glycol, Fuel Volume 233, 1 December 2018, Pages 704-713,
  10. M. Moreira, H.L. Brandão, F.V. Hackbarth, D. Maass, A.A. Ulson de Souza, S.M.A. Guelli Souza, Adsorptive desulfurization of heavy naphthenic oil: Equilibrium and kinetic studies , Chemical Engineering Science Volume 172, 23 November 2017, Pages 23-31,
  11. Dehghan, M. Anbia , Zeolites for adsorptive desulfurization from fuels: A review, Fuel Processing Technology Volume 167, ( 2017) 99-116,
  12. Saha, S. Vedachalam,A.K. Dalai: Review on recent advances in adsorptive desulfurization, Fuel Processing Technology ,Volume 214 (2021) 106685,
  13. F. Palomeque-Santiago, R. López-Medina, R. Oviedo-Roa, J. Navarrete-Bolaños, R. Mora-Vallejo, J.A. Montoya-de la Fuente, J.M. Martínez-Magadán, Deep oxidative desulfurization with simultaneous oxidative denitrogenation of diesel fuel and straight run gas oil: Applied Catalysis B: Environmental Volume 236 (2018) 326-337,
  14. Mirante, L. Dias, M. Silva, S.O.Ribeiro, M.C.Corvo, B.Castro, C.M.Granadeiro, S.S.Balula, Efficient heterogeneous polyoxometalate-hybrid catalysts for the oxidative desulfurization of fuels, Catalysis Communications Volume 104( 2018) 1-8,
  15. Calzada, A. Alcon, V.E. Santos, F. Garcia-Ochoa, Extended kinetic  model  for  DBT  desulfurization  using  Pseudomonas  Putida CECT5279 in resting cells, Biochemical Engineering Journal 66 (2012) 52–60,
  16. G. Speight, N. Shafik, El-Gendy, Chapter 6 - Biocatalytic Desulfurization, Introduction to Petroleum Biotechnology 2018, Pages 165-227.
  17. A. Alvarez-Amparán, L. Cedeño-Caero, MoOx-VOx based catalysts for the oxidative desulfurization of refractory compounds: Influence of MoOx-VOx interaction on the catalytic performance, Catal. Today, 282 (2017)133-139,
  18. M. Dooley, D.Liu, A. M. Madrid, F. CarlKnopf, Oxidative desulfurization of diesel with oxygen: Reaction pathways on supported metal and metal oxide catalysts, Applied Catalysis A: General ,Volume 468, 5 November 2013, Pages 143-149,
  19. Jianga, J. Wanga, S. Wanga, H.Y. Guana, X. Wanga, M. Huob, Oxidative desulfurization of dibenzothiophene with dioxygen and reverse micellar peroxotitanium under mild conditions, Applied Catalysis B: Environmental 106 (2011) 343–349,
  20. M. Dehkordi, M.A. Sobati, M.A. Nazem, Oxidative Desulfurization of Non-hydrotreated Kerosene Using Hydrogen Peroxide and Acetic Acid, Chinese Journal of Chemical Engineering, 17(5) 869-874 (2009),
  21. Taghiyar, B. Yadollahi, Keggin polyoxometalates encapsulated in molybdenum-iron-type Keplerate nanoball as efficient and cost-effective catalysts in the oxidative desulfurization of sulfides, Science of The Total Environment Volume 708, 15 March 2020, 134860,
  22. Hao,L.Suna,T.Su,D.Haoa,W.Liaoa,C.Denga,W.Rena,Y.Zhangb,H.Lüa,Polyoxometalate-based ionic liquid catalyst with unprecedented activity and selectivity for oxidative desulfurization of diesel in [Omim]BF4, Chemical Engineering Journal Volume 358, 15 February 2019, Pages 419-426,
  23. Shakirullah,W.Ahmad,I.Ahmad, M.Ishaq, Oxidative desulphurization study of gasoline and kerosene Role of some organic and inorganic oxidants, Fuel Processing Technology 91(2010)1736–1741,
  24. Song, G.Li, X.Wang, Y.Chen, Characterization and catalytic performance of Au/Ti-HMS for direct generation of H2O2 and in situ-H2O2-ODS from H2 and O2: An in situ reduction synthesis and a recycle study of catalyst, Microporous and Mesoporous Materials 139 (2011) 104–109,
  25. Napanang, T. Sooknoi, Oxidative extraction of thiophene from n-dodecane over TS-1 in continuous process: A model for non-severe sulfur removal from liquid fuels, Catalysis Communications 11 (2009) 1–6,
  26. Te, C. Fairbridge, Z. Ring, Oxidation reactivities of dibenzothiophenes in polyoxometalate/H2O2 and formic acid/H2O2 systems, Applied Catalysis A: General 219 (2001) 267–280,
  27. Trakarnpruk, K. Rujiraworawut, Oxidative desulfurization of Gas oil by polyoxometalates catalysts, Fuel Processing Technology 90 (2009) 411–414,
  28. L. Hill, C.M. Prosser-McCarthe, Homogeneous catalysis by transition metal oxygen anion clusters, Coord. Chem. Rev. 143 (1995) 407–455,
  29. Jiang, H. Li , W. Zhu , L. He , H. Shu , J. Lu, Deep desulfurization of fuels catalyzed by surfactant-type decatungstates using H2O2 as oxidant, Fuel 88 (2009) 431–436,
  30. Li C, Jiang Z, Gao J, Yang Y, Wang S, Tian F, Ultra-deep desulfurization of diesel: oxidation with a recoverable catalyst assembled in emulsion. Chem EurJ 10(2004) 2277–80,
  31. Qiu, G. Wang, D. Zeng ,Y. Tang , M. Wang , Y. Li, Oxidative desulfurization of diesel fuel using amphiphilic quaternary ammonium phosphomolybdate catalysts, Fuel Processing Technology 90 (2009) 1538–1542,
  32. P. Ginsberg. Inorganic synthesis.Vol.27. A Wiley-Interscience Publication,1990, Library of Congress Catalog Number: 39-23015 ,ISBN 0-471-50976-0
  33. J. Domaille. 1-and 2-Dimensional Tungsten-183 and Vanadium-51 NMR Characterization of Isopolymetalates and Heteropolymetalates. J. Am. Chem. SOC.  1984, 106, 7677-7687,
  34. P. Das, J.J. Boruah, N. Sharma, N.S. Islam, New polymer-immobilized peroxotungsten compound as an efficient catalyst for selective and mild oxidation of sulfides by hydrogen peroxide,Journal of  Molecular  Catalysis  A:  Chemical  356 (2012) 36–   45,
  35. J. Wei, C.L. Zhang, C.L. Sun, A. Li, X.H. Wang, Fabrication of nano reactors based on polyoxoperoxometalates and enhancement of their catalytic activit, Chinese Chemical Letters 22(2011)875–878,
  36. Zhanga, H. Lüb, L. Wanga, Y. Zhanga, P. Liua,H. Hana,Z. Jianga ,C. Li, The oxidation of benzothiophene using the Keggin-type lacunary Polytungstophosphate as catalysts in emulsion, Journal of Molecular Catalysis A: Chemical 332 (2010) 59–64,
  37. Zongxuan, L. Hongying, Z. Yongna, L. Can, Oxidative Desulfurization of Fuel Oils, CHINESE JOURNAL OF CATALYSIS , 32( 5)( 2011)10-16,
  38. Ghorbani N, Moradi G (2019) Oxidative desulfurization of model and real oil samples using Mo supported on hierarchical alumina–silica: process optimization by Box Behnken experimental design. Chin J Chem Eng 27(11):2759–2770,
  39. Zhu , G. Zhu , H. Li, Y. Chao , M. Zhang , D. Du ,Q. Wang , Z. Zhao, Catalytic kinetics of oxidative desulfurization with surfactant-type polyoxometalate-based ionic liquids, Fuel Processing Technology 106 (2013) 70–76,
  40. L.G. Gutierrez , G.A. Fuentes, M.E. Hernandez-Tera ,F. Murrieta, J. Navarrete , F. Jimenez-Cruz, Ultra-deep oxidative desulfurization of diesel fuel with H2O2 catalyzed under mild conditions by polymolybdates supported on Al2O3, Applied Catalysis A: General 305 (2006) 15–20,