Skip to main content
SpringerLink
Log in

Catalytic oxidative desulfurization of 4,6-dimethyl dibenzothiophene by phosphotungstic acid loaded on Al2O3, V2O5, and ZrO2 oxides

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

Abstract

This work reports the synthesis, characterization, and catalytic testing of ZrO2, V2O5, and Al2O3 that have been loaded with two amounts of phosphotungstic acid for the catalytic oxidative desulfurization of 4,6-dimethyl dibenzothiophene as a reaction test model to reduce the sulfur content in diesel. The catalysts were synthesized through the impregnation of individual oxides with a solution of the heteropolyacid to 3% and 3.5% mol with respect to the metal in each oxide. The materials were characterized by x-ray diffraction, infrared and Raman spectroscopy, nitrogen adsorption–desorption technique, scanning electron microscopy, and x-ray photoelectron spectroscopy. The acidity of the catalysts was determined by potentiometry by titration of the catalysts with pyridine. The reaction test is considered a viable alternative, because it is performed at ambient temperature and pressure. This reaction can be conducted in the liquid–liquid, liquid–solid, or triphasic phase using oxidants and catalysts. In this study, dimethyl dibenzothiophene was used as the sulfur species in diesel and as the molecule for evaluating catalyst activity. Acetonitrile was the solvent, and hydrogen peroxide was the oxidizing agent. Al2O3-based catalysts had the highest surface area and acidity among all catalysts. Catalytic activity was affected by the type of support and the heteropolyacid content. As the level of heteropolyacid increased, the catalytic activity rose. Other factors that influenced catalytic activity were the catalyst's surface area, acidity, and morphology. The catalytic activity improved when the acidity and surface area in the catalysts increased. For V2O5, empty spaces were observed, favoring adsorption of the reactants.

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
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  1. Babich IV, Moulijn JA (2003) Science and technology of novel processes for deep desulfurization of oil refinery streams: a review. Fuel 82:607–631

    Article  CAS  Google Scholar 

  2. Torres-García E, Galano A, Rodrıguez-Gattorno G (2011) Oxidative desulfurization (ODS) of organosulfur compounds catalyzed by peroxo-metallate complexes of WOx-ZrO2: thermochemical, structural and reactivity indexes analyses. J Catal 282:201–208

    Article  Google Scholar 

  3. Wachs I, Chen Y, Jehng J, Briand L, Tanaka T (2003) Molecular structure and reactivity of the group V metal oxides. Catal Today 78:13–24

    Article  CAS  Google Scholar 

  4. Ismagilov Z, Yashnik S, Kerzhentsev M, Parmon V, Bourane A, Al-Shahrani FM, Hajji AA, Koseoglu OR (2011) Oxidative desulfurization of hydrocarbon fuels. Catal Rev Sci Eng 53:199–255

    Article  CAS  Google Scholar 

  5. González-García O, Cedeño-Caero L (2009) V-Mo based catalysts for oxidative desulfurization of diesel fuel. Catal Today 148:42–48

    Article  Google Scholar 

  6. Bakar W, Ali R, Kadir A, Mokhtar W (2012) Effect of transition metal oxides catalysts on oxidative desulfurization of model diesel. Fuel Process Technol 101:78–84

    Article  CAS  Google Scholar 

  7. Rezvani MA, Shaterian M, Akbarzadeh F, Khandan S (2018) Deep oxidative desulfurization of gasoline induced by PMoCu@MgCu2O4- PVA composite as a high-performance heterogeneous nanocatalyst. Chem Eng J 333:537–544

    Article  CAS  Google Scholar 

  8. Chen LJ, Li FT (2015) Oxidative desulfurization of model gasoline over modified titanium silicalite. Pet Sci Technol 33:196–202

    Article  CAS  Google Scholar 

  9. Subhan S, Rahman AU, Yaseen M, Haroon HU, Ishaq M, Sahibzada M, Tong Z (2019) Ultra-fast and highly efficient catalytic oxidative desulfurization of dibenzothiophene at ambient temperature over low Mn loaded Co-Mo/Al2O3 and Ni-Mo/Al2O3 catalysts using NaClO as oxidant. Fuel 237:793–805

    Article  CAS  Google Scholar 

  10. Zhao H, Baker GA, Zhang Q (2017) Design rules of ionic liquids tasked for highly efficient fuel desulfurization by mild oxidative extraction. Fuel 189:334–339

    Article  CAS  Google Scholar 

  11. Rezvani MA, Shaterian M, Aghbolagh ZS, Babaei R (2018) Oxidative desulfurization of gasoline catalyzed by IMID@PMA@CS nanocomposite as a high-performance amphiphilic nano catalyst. Environ Prog Sustain Energy 37:1891–1900

    Article  CAS  Google Scholar 

  12. Muhammad Y, Shoukat A, Rahman AU, Rashid HU, Ahmad W (2018) Oxidative desulfurization of dibenzothiophene over Fe promoted Co-Mo/Al2O3 and Ni-Mo/Al2O3 catalysts using hydrogen peroxide and formic acid as oxidants. Chin J Chem Eng 26:593–600

    Article  CAS  Google Scholar 

  13. Rezvani MA, Asli MA, Khandan S, Mousavi H, Aghbolagh ZS (2017) Synthesis and characterization of new nanocomposite CTAB-PTA@CS as an efficient heterogeneous catalyst for oxidative desulfurization of gasoline. Chem Eng J 312:243–251

    Article  CAS  Google Scholar 

  14. Jiang B, Yang H, Zhang L, Zhang R, Sun Y, Huang Y (2016) Efficient oxidative desulfurization of diesel fuel using amide-based ionic liquids. Chem Eng J 283:89–96

    Article  CAS  Google Scholar 

  15. Ito E, Rob van Veen JA (2006) On novel processes for removing sulphur from refinery streams. Catal Today 116:446–460

    Article  CAS  Google Scholar 

  16. Gazzoli D, Rossi S, Ferraris G, Mattei G, Spinicci R, Valigi M (2009) Bulk and surface structures of V2O5/ZrO2 catalysts for n-butane oxidative dehydrogenation. J Mol Catal A 310:17–23

    Article  CAS  Google Scholar 

  17. Zheng H, Sun Z, Chen X, Zhao Q, Wang X, Jiang Z (2013) A micro reaction-controlled phase-transfer catalyst for oxidative desulfurization based on polyoxometalate modified silica. Appl Catal A 467:26–32

    Article  CAS  Google Scholar 

  18. Yang P, Zhou S, Du Y, Li J, Lei J (2016) Synthesis of ordered meso/macroporous H3PW12O40/SiO2 and its catalytic performance in oxidative desulfurization. RSC Adv 6:53860–53866

    Article  CAS  Google Scholar 

  19. Parry DB, Samant MG, Seki H, Philpott MR, Ashley K (1993) In situ Fourier transform infrared spectroelectrochemical study of bisulfate and sulfate adsorption on gold, with and without the underpotential deposition of copper. Langmuir 9:1878–1887

    Article  CAS  Google Scholar 

  20. Otsuki S, Nonaka T, Takashima N, Qian W, Ishihara A, Imai T, Kabe T (2000) Oxidative desulfurization of light gas oil and vacuum gas oil by oxidation and solvent extraction. Energy Fuels 14:1232–1239

    Article  CAS  Google Scholar 

  21. Kurhade A, Zhu J, Hu Y, Dalai AK (2018) Surface investigation of tungstophosphoric acid supported on ordered mesoporous aluminosilicates for biodiesel synthesis. ACS Omega 3:14064–14075

    Article  CAS  Google Scholar 

  22. Li SW, Gao R, Zhang W, Zhang Y, Zhao J (2018) Heteropolyacids supported on macroporous materials POM@MOF-199@LZSM-5: highly catalytic performance in oxidative desulfurization of fuel oil with oxygen. Fuel 221:1–11

    Article  Google Scholar 

  23. Yang H, Liu M, Ouyang J (2010) Novel synthesis and characterization of nanosized γ-Al2O3 from kaolin. Appl Clay Sci 47:438–443

    Article  CAS  Google Scholar 

  24. Srilakshmi P, Maheswari AU, Sajeev V, Sivakumar M (2019) Tuning the optical bandgap of V2O5 nanoparticles by doping transition metal ions. Mater Today: Proc 18:1375–1379

    CAS  Google Scholar 

  25. Zhang M, Zhu WS, Xun SH, Li HM, Gu QQ, Zhao Z, Wang Q (2013) Deep oxidative desulfurization of dibenzothiophene with POM-based hybrid materials in ionic liquids. Chem Eng J 220:328–336

    Article  CAS  Google Scholar 

  26. Di Grégorio F, Keller V, Di Costanzo T, Vignes JL, Michel D, Maire G (2001) Cracking and skeletal isomerization of hexenes on acidic MoO3–WO3/α-Al2O3 oxide. Appl Catal A 218:13–24

    Article  Google Scholar 

  27. Ramana CV, Hussain OM, Srinivasulu Naidu B, Reddy PJ (1997) Spectroscopy characterization of electron- beam evaporated V2O5 thin films. Thin Solid Films 305:219–226

    Article  CAS  Google Scholar 

  28. Gannoun C, Delaigle R, Debecker DP, Eloy P, Ghorbel A, Gaigneaux EM (2012) Effect of support on V2O5 catalytic activity in chlorobenzene oxidation. Appl Catal A 7:1–6

    Article  Google Scholar 

  29. Zeleke MA, Kuo DH (2019) Synthesis and application of V2O5-CeO2 nanocomposite catalyst for enhanced degradation of methylene blue under visible light illumination. Chemosphere 235:935–944

    Article  CAS  Google Scholar 

  30. Brenier R, Mugnier J, Mirica E (1999) XPS study of amorphous zirconium oxide films prepared by sol-gel. Appl Surf Sci 143:85–91

    Article  CAS  Google Scholar 

  31. Bielanski A, Lubansk A, Pozniczek J, Micek-Ilnicka A (2003) Oxide supports for 12-tungstosilicic acid catalysts in gas phase synthesis of MTBE. App Catal A 238:239–250

    Article  CAS  Google Scholar 

  32. Aida T, Yamamoto D, Iwata M, Sakata K (2000) Development of oxidative desulfurization process for diesel fuel. Rev Heteroat Chem 22:241–256

    CAS  Google Scholar 

  33. González J, Wang JA, Chen LF, Manríquez ME, Dominguez JM (2017) Structural defects, Lewis acidity, and catalysis properties of mesostructured WO3/SBA-15 nanocatalysts. J Phys Chem C 121:23988–23999

    Article  Google Scholar 

  34. Moreau P, Hulea V, Gomez S, Brunel D, Di Renzo F (1997) Oxidation of sulfoxides to sulfones by hydrogen peroxide over Ti-containing zeolites. Appl Catal A 155:253–263

    Article  CAS  Google Scholar 

  35. Tago T, Kataoka N, Tanaka H, Kinoshita K, Kishid S (2017) XPS study from a clean surface of Al2O3 single crystals. Procedia Eng 216:175–181

    Article  Google Scholar 

  36. Wang R, Zhang GF, Zhao HX (2010) Polyoxometalate as effective catalyst for the deep desulfurization of diesel oil. Catal Today 149:117–121

    Article  CAS  Google Scholar 

  37. Chakrabarti A, Hermann K, Druzinic R, Witko WF, Petersen M (1999) Geometric and electronic structure of vanadium pentoxide: a density functional bulk and surface study. Phys Rev B 59:10583–10590

    Article  CAS  Google Scholar 

  38. Arias M, Laurenti D, Bellière V, Geantet C, Vrinat M, Yoshimura Y (2008) Preparation of supported H3PW12O40·6H2O for thiophenic compounds alkylation in FCC gasoline. Appl Catal A 348:142–147

    Article  CAS  Google Scholar 

  39. Wang P, Gan M, Deng P, Xu Y, Hou Yu (2021) Phosphotungstic acid-supported zirconia mesoporous material for deep and fast oxidative desulfurization. Inorg Chem Commun 133:1–7

    Google Scholar 

  40. González J, Chena LF, Wanga JA, Manríquez M, Limas R, Schachat P, Navarrete J, Contreras JL (2016) Surface chemistry and catalytic properties of VOX/Ti-MCM-41 catalysts for dibenzothiophene oxidation in a biphasic system. Appl Surf Sci 379:367–376

    Article  Google Scholar 

Download references

Acknowledgements

The authors thank to the Instituto Politécnico Nacional for Project Number 20210813 funded.

Author information

Authors and Affiliations

  1. Escuela Superior de Ingeniería Química e Industrias Extractivas (ESIQIE)-Instituto Politécnico Nacional, Col. Zacatenco, 07738, Mexico City, Mexico

    Ma Elena Manríquez, Ana Laura Ortiz, Martín Trejo-Valdez & Laura V. Castro

  2. Laboratorio de Nanotecnología, Instituto Nacional de Neurología y Neurocirugía, Col. La Fama, 14269, Mexico City, Mexico

    Emma Ortiz-Islas

Authors
  1. Ma Elena Manríquez
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ana Laura Ortiz
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Martín Trejo-Valdez
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Laura V. Castro
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Emma Ortiz-Islas
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Conceptualization: MEM, EO-I; methodology: MEM, ALO, MT-V, LVC, EO-I; formal analysis and investigation: MEM, ALO, MT-V, LVC, EO-I; writing—original draft preparation: MEM, EO-I; writing—review and editing: EO-I; resources: MEM; supervision: MEM, EO-I.

Corresponding author

Correspondence to Emma Ortiz-Islas.

Ethics declarations

Conflict of interest

The authors declare not conflict of interest.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 2112 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Manríquez, M.E., Ortiz, A.L., Trejo-Valdez, M. et al. Catalytic oxidative desulfurization of 4,6-dimethyl dibenzothiophene by phosphotungstic acid loaded on Al2O3, V2O5, and ZrO2 oxides. Reac Kinet Mech Cat 135, 1523–1539 (2022). https://doi.org/10.1007/s11144-022-02201-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11144-022-02201-1

Keywords

Search

Navigation