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NiMoW/P-Al2O3 four-component catalysts with different Mo:W molar ratios and P2O5 contents: the effect of the composition and active phase morphology on the catalytic activity

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Abstract

NiMoW/P-Al2O3 catalysts were synthesized with a different ratio of Mo:W (W-free sample, Mo:W = 2:1, Mo:W = 1:1, Mo:W = 1:2 and Mo-free sample) and various P2O5 contents in the carrier (up to 5 wt%). The surface of the sulfide phase of the samples was investigated by means of high-resolution transmission electron microscopy (HR TEM) and X-ray photoelectron spectroscopy (XPS). The catalytic activity of patterns was estimated in the reactions of hydrodesulfurization of dibenzothiophene (DBT) and hydrogenation of naphthalene. The results are presented in the form of three-dimensional diagrams “P2O5 content—ratio Mo/W—catalytic activity” or “P2O5 content—ratio Mo/W—property”. The influence of the phosphorus content on the maximum peak position of the binding energy S2p/1 of the S2− atomic group for the investigated systems is shown. Comparison of the shape of the curve of changes in the binding energy with the previously presented results on the catalytic activity of the samples in the HDS of a vacuum gas oil allows us to conclude that phosphorus is able to change the electronic state of the active phase of the catalysts, which leads to a change in their catalytic activity in the reactions of HDS.

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References

  1. Espinoza-Armenta Y, Cruz-Reyes F, Paraguay-Delgado M, Del Valle M, Alonso G, Fuentes S, Romero-Rivera R (2014) CoMoW sulfide nanocatalysts for the HDS of DBT from novel ammonium and alkyltrimethylammonium-thiomolybdate-thiotungstate-cobaltate(II) precursors. Appl Catal A 486:62–68. https://doi.org/10.1016/j.apcata.2014.08.017

    Article  CAS  Google Scholar 

  2. Wen XD, Zeng T, Teng BT, Zhang FQ, Li YW, Wang J, Jiao H (2006) Hydrogen adsorption on a Mo27S54 cluster: a density functional theory study. J Mol Catal A 249:191–200. https://doi.org/10.1016/j.molcata.2006.01.018

    Article  CAS  Google Scholar 

  3. Cervantes-Gaxiola ME, Arroyo-Albiter M, Perez-Larios A, Balbuena PB, Espino-Valencia J (2013) Experimental and theoretical study of NiMoW, NiMo, and NiW sulfide catalysts supported on an AlTiMg mixed oxide during the hydrodesulfurization of dibenzothiophene. Fuel 113:733–743. https://doi.org/10.1016/j.fuel.2013.06.041

    Article  CAS  Google Scholar 

  4. Zuo D, Vrinat M, Nie H, Mauge F, Shi Y, Lacroix M, Li D (2004) The formation of the active phases in sulfided NiW/Al2O3 catalysts and their evolution during post-reduction treatment. Catal Today 93–95:751–760. https://doi.org/10.1016/j.cattod.2004.06.078

    Article  CAS  Google Scholar 

  5. Liu C, Yu Y, Zhao H (2004) Hydrodenitrogenation of quinoline over Ni–Mo/Al2O3 catalyst modified with fluorine and phosphorus. Fuel Process. Technol. 86:449–460. https://doi.org/10.1016/j.fuproc.2004.05.002

    Article  CAS  Google Scholar 

  6. Usman U, Yamamoto T, Kubota T, Okamoto Y (2007) Effect of phosphorus addition on the active sites of a Co–Mo/Al2O3 catalyst for the hydrodesulfurization of thiophene. Appl Catal A 328:219–225. https://doi.org/10.1016/j.apcata.2007.06.020

    Article  CAS  Google Scholar 

  7. Sun M, Nicosia D, Prins R (2003) The effects of fluorine, phosphate and chelating agents on hydrotreating catalysts and catalysis. Catal Today 86:173–189. https://doi.org/10.1016/S0920-5861(03)00410-3

    Article  CAS  Google Scholar 

  8. Pleshakova NA, Tyshchenko VA, Tomina NN, Pimerzin AA (2008) Hydrofining of oil fractions of naphtheno-aromatic crude. Petrol Chem 48:346–354. https://doi.org/10.1134/S0965544108050034

    Article  Google Scholar 

  9. Tomina NN, Antonov SA, Maksimov NM, Samsonov MV, Pimerzin AA (2015) Hydrogenolysis of dibenzothiophene on zinc-modified NiMoW/Al2O3 hydrotreating catalysts. Petrol Chem 55:578–584. https://doi.org/10.1134/S0965544115070129

    Article  CAS  Google Scholar 

  10. Solmanov PS, Maksimov NM, Timoshkina VV, Tomina NN, Pimerzin AA (2019) Effect of phosphorus content in the support of NiMoW/P–Al2O3 quaternary hydrotreating catalysts on their hydrodesulfurization and hydrogenation activity. Petrol Chem 59:201–205. https://doi.org/10.1134/S096554411902018X

    Article  CAS  Google Scholar 

  11. Solmanov PS, Maksimov NM, Tomina NN, Pimerzin AA, Verevkin SP (2018) Effect of the composition and morphology of the active phase of NiMoW/P-Al2O3 catalysts with different Mo/W ratios on their activity in the reactions of dibenzothiophene hydrogenolysis and naphthalene hydrogenation. Kinet Catal 59:644–652. https://doi.org/10.1134/S0023158418050142

    Article  CAS  Google Scholar 

  12. Hensen EJM, van der Meer Y, van Veen JAR, Niemantsverdriet JW (2007) Insight into the formation of the active phases in supported NiW hydrotreating catalysts. Appl Catal A 322:16–32. https://doi.org/10.1016/j.apcata.2007.01.003

    Article  CAS  Google Scholar 

  13. van der Meer Y, Hensen EJM, van Veen JAR, van der Kraan AM (2004) Characterization and thiophene hydrodesulfurization activity of amorphous-silica–alumina-supported NiW catalysts. J Catal 228:433–446. https://doi.org/10.1016/j.jcat.2004.09.019

    Article  CAS  Google Scholar 

  14. Mingfeng L, Huifeng L, Feng J, Chu Y, Nie H (2010) The relation between morphology of (Co)MoS2 phases and selective hydrodesulfurization for CoMo catalysts. Catal Today 149:35–39. https://doi.org/10.1016/j.cattod.2009.03.017

    Article  CAS  Google Scholar 

  15. Gandubert AD, Krebs E, Legens C, Costa D, Guillaume D, Raybaud P (2008) Optimal promoter edge decoration of CoMoS catalysts: a combined theoretical and experimental study. Catal Today 130:149–159. https://doi.org/10.1016/j.cattod.2007.06.041

    Article  CAS  Google Scholar 

  16. Lélias MA, Kooyman PJ, Mariey L, Oliviero L, Travert A, Gestel G, Veen JAR, Mauge F (2009) Effect of NTA addition on the structure and activity of the active phase of cobalt-molybdenum sulfide hydrotreating catalysts. J Catal 267:14–23. https://doi.org/10.1016/j.jcat.2009.07.006

    Article  CAS  Google Scholar 

  17. Tomina NN, Maksimov NM, Solmanov PS, ZanozinaII PAA (2016) Hydrotreating of vacuum gas oil on modified Ni–Mo/Al2O3 catalysts. Petrol Chem 56:753–760. https://doi.org/10.1134/S096554411608017X

    Article  CAS  Google Scholar 

  18. Nguyen MT, Tayakout-Fayolle M, Chainet F, Pringruber GD, Geantet C (2017) Use of kinetic modeling for investigating support acidity effects of NiMo sulfide catalysts on quinoline hydrodenitrogenation. Appl Catal A 530:132–144. https://doi.org/10.1016/j.apcata.2016.11.015

    Article  CAS  Google Scholar 

  19. Garcia-Cruz I, Valencia D, Klimova T, Oviedo-Roa R, Martinez-Magadan JM, Gomes-Balderas R, Illas F (2008) Proton affinity of S-containing aromatic compounds: implications for crude oil hydrodesulfurization. J Mol Catal A 281:79–84. https://doi.org/10.1016/j.molcata.2007.08.031

    Article  CAS  Google Scholar 

  20. Kharchenko YuV, Nasirov RK (1997) Prediction of activity of catalysis for hydrotreating petroleum fractions, on the basis of the electronic theory of catalysis. Chem Technol Fuels Oils 33:132–144. https://doi.org/10.1007/BF02767004

    Article  Google Scholar 

  21. Baeza P, Villarroel M, Ávila P, López Agudo A, Delmon B, Gil-Llambías FJ (2006) Spillover hydrogen mobility during Co–Mo catalyzed HDS in industrial-like conditions. Appl Catal A 304:109–115. https://doi.org/10.1016/j.apcata.2006.02.029

    Article  CAS  Google Scholar 

  22. Villarroel M, Baeza P, Gracia F, Escalona N, Avila P, Gil-Llambías FJ (2009) Phosphorus effect on Co//Mo and Ni//Mo synergism in hydrodesulphurization catalysts. Appl Catal A 364:75–79. https://doi.org/10.1016/j.apcata.2009.05.026

    Article  CAS  Google Scholar 

  23. Klimov OV, Nadeina KA, Vatutina YuV, Stolyarova EA, Danilova IG, Gerasimov EYu, Prosvirin IP, Noskov AS (2018) CoMo/Al2O3 hydrotreating catalysts of diesel fuel with improved hydrodenitrogenation activity. Catal Today 307:73–83. https://doi.org/10.1016/j.cattod.2017.02.032

    Article  CAS  Google Scholar 

  24. Gutiérrez OY, Hrabar A, Hein J, Yu Y, Han J, Lercher JA (2012) Ring opening of 1,2,3,4-tetrahydroquinoline and decahydroquinoline on MoS2/γ-Al2O3 and Ni–MoS2/γ-Al2O3. J Catal 295:155–168. https://doi.org/10.1016/j.jcat.2012.08.003

    Article  CAS  Google Scholar 

  25. Kaluza L, Gulková D, Vít Z, Zdrazil M (2015) High-activity MgO-supported CoMo hydrodesulfurization catalysts prepared by non-aqueous impregnation. Appl Catal B 162:430–436. https://doi.org/10.1016/j.apcatb.2014.07.016

    Article  CAS  Google Scholar 

  26. Afanasiev P (2017) Calculation of MoS2 slabs morphology descriptors from transmission electron microscopy data revisited. Case study of the influence of citric acid and treatment conditions on the properties of MoS2/Al2O3. Appl Catal A 529:10–19. https://doi.org/10.1016/j.apcata.2016.10.008

    Article  CAS  Google Scholar 

  27. Han W, Nie H, Long X, Li M, Yang Q, Li D (2017) Effects of the support Brønsted acidity on the hydrodesulfurizationand hydrodenitrogention activity of sulfided NiMo/Al2O3 catalysts. Catal Today 292:58–66. https://doi.org/10.1016/j.cattod.2016.11.049

    Article  CAS  Google Scholar 

  28. Arrouvel C, Breysse M, Toulhoat H, Raybaud P (2005) A density functional theory comparison of anatase (TiO2)- and γ-Al2O3-supported MoS2 catalysts. J Catal 232:161–178. https://doi.org/10.1016/j.jcat.2005.02.018

    Article  CAS  Google Scholar 

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Acknowledgements

The work was supported by the Government of the Russian Federation. Decision no. 220 of April 9, 2010. Grant 14.Z50.31.0038 of February 20, 2017. The authors thank Dr. A.V. Mozhaev (Samara State Technical University) for sulfiding the samples, Dr. K.I. Maslakov (Moscow State University) and Dr. P.A. Nikul’shin (Samara State Technical University) for recording and processing of the XPS spectra.

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Solmanov, P.S., Maximov, N.M., Tomina, N.N. et al. NiMoW/P-Al2O3 four-component catalysts with different Mo:W molar ratios and P2O5 contents: the effect of the composition and active phase morphology on the catalytic activity. Reac Kinet Mech Cat 129, 253–264 (2020). https://doi.org/10.1007/s11144-019-01702-w

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