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Reaction Kinetics, Mechanisms and Catalysis

, Volume 126, Issue 1, pp 365–382 | Cite as

Assessment of a three step process using tungsten catalyzed hydrogen peroxide-based oxidative desulfurization for commercial diesel fuels

  • Abdennour Bourane
  • Omer Koseoglu
  • Adnan Al-Hajji
  • Frederick AdamEmail author
  • Hendrik Muller
Article
  • 35 Downloads

Abstract

A three-step oxidative desulfurization (ODS) process comprising of oxidation, liquid–liquid extraction, and adsorption was applied to two compositionally very different commercial diesel samples, namely a straight run middle distillate and a blend of primary and secondary refining streams, to assess the ODS process feasibility. The oxidation of sulfur compounds was achieved using hydrogen peroxide as an oxidant in the presence of tungstic acid catalyst. The diesel feedstocks, intermediate and final products were characterized in detail using standard analytical methods along with state-of-the-art speciation techniques. Under mild conditions (ambient pressure and 80 °C), ODS was found to target sulfur species that are refractory to low-severity hydrodesulfurization (HDS), specifically dibenzothiophenes. The ODS process removed 85.3% and 33.5% of the sulfur compounds in the blend and straight run diesel samples, respectively. A comprehensive material balance for the overall process and each process step was also established, revealing that approximately 80% of the initial diesel could be recovered after desulfurization, when accounting for the removed sulfur compounds. However, any extraction based desulfurization approach has an inherent limit for the achievable overall diesel recovery because of the potentially high mass fraction of organosulfur compounds that is removed in the process. Consequently, ODS should be preceded by an HDS process to target the main bulk of sulfur compounds while the ODS process then removes the remaining HDS refractory compounds. Removal of nitrogen species, which are also undesirable in the final product, was a positive side effect of the studied ODS process.

Keywords

Oxidative desulfurization Tungsten catalyzed Hydrogen peroxide Hydrodesulfurized diesel Straight run diesel Sulfur Speciation Two-dimensional gas chromatography (2D-GC) Mass balance 

Notes

Acknowledgements

Christophe Geantet and his team at IRCE Lyon are thanked for their technical support and fruitful discussions.

References

  1. 1.
    Fox DL, Jeffries HE (1981) Air pollution. Anal Chem 53:1–13CrossRefGoogle Scholar
  2. 2.
    Larive J-F (2008) In EU refineries challenges to cope with supply/demand scenarios at the 2015 Horizon. In: 19th World Petroleum Congress, Madrid, SpainGoogle Scholar
  3. 3.
    Yanowitz J, McCormick RL, Graboski MS (2000) Environ Sci Technol 34:729–740CrossRefGoogle Scholar
  4. 4.
    EU (2012) Automotive fuels—unleaded petrol—requirements and test methods, EN 228Google Scholar
  5. 5.
    EU (2013) Automotive fuels—diesel—requirements and test methods, EN 590Google Scholar
  6. 6.
    Corbett J, Winebrake J, Gren E, Pasibhatla P, Eyring V, Lauer A (2007) Mortality from ship emissions: a global assessment. Environ Sci Technol 41:8512–8518CrossRefGoogle Scholar
  7. 7.
    Adam F, Muller H, Al-Hajji A, Bourane A, Koseoglu O (2015) Oxidative desulfurization process monitoring using comprehensive two-dimensional gas chromatography and fourier transform ion cyclotron resonance mass spectrometry, energy and fuels. Energy Fuels 29:2312–2318CrossRefGoogle Scholar
  8. 8.
    Kilanowski DR, Teeuwen H, Beer VHJD, Gates BC, Schuit GCA, Kwart H (1978) Hydrodesulfurization of thiophene, benzothiophene, dibenzothiophene, and related compounds catalyzed by sulfided CoOMo3O3Al2O3: CoO-MoO3γ-Al2O3: low-pressure reactivity studies. J Catal 55:129–137CrossRefGoogle Scholar
  9. 9.
    Whitehurst DD, Isoda T, Mochinda I (1998) Present state of the art and future challenges in the hydrodesulfurization of polyaromatic sulfur compounds. Adv Catal 42:345–471Google Scholar
  10. 10.
    Nejad DM, Rahemi N, Allahyari S (2017) Effect of tungsten loading on the physiochemical properties of nanocatalysts of Ni–Mo–W/carbon nanotubes for the hydrodesulfurization of thiophene. React Kinet Mech Catal 120:279–294CrossRefGoogle Scholar
  11. 11.
    Iriarte V, Cruz-Reyes J, Del Valle M, Alonso G, Fuentes S, Paraguay-Delgado F, Romero-Rivera R (2017) Trimetallic NiMoW sulfide catalysts by the thermal decomposition of thiosalt blends for the hydrodesulfurization of dibenzothiophene. React Kinet Mech Catal 121:593–605CrossRefGoogle Scholar
  12. 12.
    Varga Z, Szarvas T, Tétényi P, Hancsók J, Ollár T (2017) The particular characteristics of the active sites of MoS2, WS2 catalysts in thiophene hydrodesulfurization. React Kinet Mech Catal 124:61–74CrossRefGoogle Scholar
  13. 13.
    Song C (2003) An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel. Catal Today 86:211–263CrossRefGoogle Scholar
  14. 14.
    Ismagilov Z, Yashnik S, Kerzhentsev M, Parmon V, Bourane A, Shahrani F, Hajji A, Koseoglu O (2011) Oxidative desulfurization of hydrocarbon fuels. Catal Rev 53:199–255CrossRefGoogle Scholar
  15. 15.
    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 14:1232–1239CrossRefGoogle Scholar
  16. 16.
    Ogunlaja A, Chidawanyika W, Antunes E, Fernandes M, Nyokong T, Torto N, Tshentu Z (2012) Oxovanadium(IV)-catalysed oxidation of dibenzothiophene and 4,6-dimethyldibenzothiophene. Dalton Trans 41:13908–13918CrossRefGoogle Scholar
  17. 17.
    Toteva V, Georgiev A, Topalova L (2012) Investigation of the oxidative desulfurization of LCO model mixture by GC-MS and FTIR spectroscopy. Fuel Process Technol 101:4CrossRefGoogle Scholar
  18. 18.
    Ban L, Liu P, Ma C, Dai B (2013) Deep desulfurization of diesel fuels with plasma/air as oxidizing medium, diperiodatocuprate (III) as catalyzer and ionic liquid as extraction solvent. Plasma Sci Technol 15:1226–1231CrossRefGoogle Scholar
  19. 19.
    Zhang J, Wang A, Wang Y, Wang H, Gui J (2014) Heterogeneous oxidative desulfurization of diesel oil by hydrogen peroxide: catalysis of an amphipathic hybrid material supported on SiO2. Chem Eng J 245:65–70CrossRefGoogle Scholar
  20. 20.
    Li H, Zhu W, Lu J, Jiang X, Gong L, Zhu G, Yan Y (2009) Deep oxidative desulfurization of fuels catalyzed by pristine simple tungstic acid. React Kinet Catal Lett 96:165–173CrossRefGoogle Scholar
  21. 21.
    Rakhmanov EV, Jinyuan D, Fedorova OA, Tarakanova AV, Anisimov AV (2012) Oxidative desulfurization of diesel fuels in the presence of crown ethers and transition metal peroxo complexes. Theor Found Chem Eng 46:552–555CrossRefGoogle Scholar
  22. 22.
    Yu F, Wang R (2013) Deep oxidative desulfurization of dibenzothiophene in simulated oil and real diesel using heteropolyanion-substituted hydrotalcite-like compounds as catalysts. Molecules 18:13691–13704CrossRefGoogle Scholar
  23. 23.
    Etemadi O, Yen TF (2007) Selective adsorption in ultrasound-assisted oxidative desulfurization process for fuel cell reformer applications. Energy Fuels 21:2250–2257CrossRefGoogle Scholar
  24. 24.
    Wang L, Li C, Hou Y (2009) Phosphotungstic acid/semi-coke catalysts for oxidative desulfurization of diesel fuel. Adv Mater Res 79–82:1683–1696CrossRefGoogle Scholar
  25. 25.
    Liu G, Cao Y, Jiang R, Wang L, Zhang X, Mi Z (2009) Oxidative desulfurization of jet fuels and its impact on thermal-oxidative stability. Energy Fuels 23:5978–5985CrossRefGoogle Scholar
  26. 26.
    Schultz HS, Freyermuth HB, Buc SR (1963) New catalysts for the oxidation of sulfides to sulfones with hydrogen peroxide. J Org Chem 28:1140–1142CrossRefGoogle Scholar
  27. 27.
    Heimlich BN, Wallace TJ (1966) Kinetics and mechanism of the oxidation of dibenzothiophene in hydrocarbon solution: oxidation by aqueous hydrogen peroxide-acetic acid mixtures. Tetrahedron 22:3571–3579CrossRefGoogle Scholar
  28. 28.
    Rangarajan B, Havey A, Grulke EA, Culnan PD (1995) Kinetic parameters of a two-phase model for in situ epoxidation of soybean oil. J Am Oil Chem Soc 72:1161–1169CrossRefGoogle Scholar
  29. 29.
    Liu D, Gui J, Ding J, Ma J, Lee J, Sun Z (2011) Oxidation of dibenzothiophene catalyzed by Na2WO4 in halogen-free ionic liquid. React Kinet Mech Catal 104:111–123CrossRefGoogle Scholar
  30. 30.
    Caero C, Jorge F, Navarro A, Gutiérrez-Alejandre A (2006) Oxidative desulfurization of synthetic diesel using supported catalysts: part II. Effect of oxidant and nitrogen-compounds on extraction-oxidation process. Catal Today 116:562–568CrossRefGoogle Scholar
  31. 31.
    Bourane A, Koseoglu O, Kressmann S (2017) Process for oxidative desulfurization and sulfone management by gasification, US 20120055849Google Scholar
  32. 32.
    Bourane A, Koseoglu O, Kressmann S (2017) Process for oxidative desulfurization and denitrogenation using a fluid catalytic cracking (FCC) unit, US 20120055844Google Scholar
  33. 33.
    Bourane A, Koseoglu O, Kressmann S (2017) Desulfurization and sulfone removal using a coker, US 20120055845Google Scholar
  34. 34.
    Bourane A, Koseoglu O, Kressmann S (2017) Process for oxidative desulfurization and sulfone disposal using solvent deasphalting, US 20120055843Google Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2018

Authors and Affiliations

  • Abdennour Bourane
    • 1
  • Omer Koseoglu
    • 1
  • Adnan Al-Hajji
    • 1
  • Frederick Adam
    • 1
    Email author
  • Hendrik Muller
    • 1
  1. 1.Saudi Aramco Research & Development CenterDhahranSaudi Arabia

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