Reaction Kinetics of MoCo/Al2O3-Meso-ZSM-5 Catalyst for Ultra-Deep Hydrodesulfurization of Diesel Fuel

Document Type: Research Paper


Dalian Research Institute of Petroleum and Petrochemicals, SINOPEC, Dalian, China



Series of Mo-Co type catalysts were supported on Al2O3, Al2O3-meso-ZSM-5-Al2O3-typical-ZSM-5 and tested in the hydrodesulfurization (HDS) of straight-run diesel feedstocks. The materials were characterized by N2 physisorption, X-ray diffraction, scanning electron microscopy, NH3 adsorption and temperature-programmed desorption, and Py-adsorbed IR spectra. The dynamics of the main steps in the HDS reaction were calculated, and seven lumped kinetic equations were established containing reaction pathways of hydrogenation (HYD), direct desulfurization (DDS) and alkyl transfer on the catalyst. The Levenberg-Marquardt (LM) algorithm method was used then to solve the resulting differential equations. The results showed that the HDS activity of C12-ZSM5 was highest because it had large VP and DP, and moderate acid content, which could improve the alkyl transfer activity and the macromolecular sulfide diffusion. By increasing the operating temperatures, the sulfur removal through the alkyl transfer route on C12-ZSM5 catalyst significantly increased, and the removal of sulfur content through alkyl transfer at 400 °C and 4.0 MPa or 6.0 MPa was 86 or 88%, respectively. Furthermore, the increase of sulfur removal confirmed that the alkyl transfer route was dominant at a deep HDS level at a high operating temperature.


  1. Kagami N, Vogelaar B M, Langeveld A D (2005)Reaction pathways on NiMo/Al2O3 catalysts for hydrodesulfurization of diesel fuel, Applied Catalysis A, 93:11-23.##
  2. Bouwens A M, Vanzon F B M, Vandijk M P (1994) On the structural differences between alumina-supported comos type I and alumina-, silica-, and carbon-supported comos type II phases studied by XAFS, MES, and XPS, Journal of Catalysis, 146: 375-393. ##
  3. Hensen E J M, Kooyman P J, Meer Y (2001) The relation between morphology and hydrotreating activity for supported MoS2 particles original research article, Journal of Catalysis,199:224-235. ##
  4. Narinobu K, Bas M V, Langeveld A D (2005) Reaction pathways on NiMo/Al2O3 catalysts for hydrodesulfurization of diesel fuel, Applied Catalysis A, 293:11-23. ##
  5. Laurtsen J V, Besenbacher F (2015) Atom-resolved scanning tunneling microscopy investigations of molecular adsorption on MoS2 and CoMoS hydrodesulfurization Catalysts, J. Catal., 328:49-58. ##
  6. Zepeda T A (2008) Comparison and performance of different sulphided Ti-loaded mesostructured silica-supported CoMo catalysts in deep HDS, Applied Catalysis A, 347:148-161. ##
  7. Pawelec B, Fierro J L G, Montesinos A (2008) Influence of the acidity of nanostructured CoMo/P/Ti-HMS catalysts on the HDS of 4,6-DMDBT reaction pathways, Journal of Applied Catalysis B: Environmental, 80(1-2):1-14. ##
  8. Walton A S, Lauritsen J V, Topsoe H (2013) MoS2 nanoparticle morphologies in hydrodesulfurization catalysis studied by scanning tunneling microscopy, Journal of Catalysis, 308:306-318. ##
  9. Macaud M, Milenkovic A, Schulz E, et al. (2000) Hydrodesulfurization of Alkyldibenzothiophenes: Evidence of Highly Unreactive Aromatic Sulfur Compounds, Journal of Catalysis, 193: 255–263. ##
  10. Meille V, Schulz E, Lemaire M, et al. (1997) Hydrodesulfurization of Alkyldibenzothiophenes over a NiMo/Al2O3 Catalyst: Kinetics and Mechanism, Journal of Catalysis, 170: 29–36. ##
  11. Houalla M, Broderick D, Sapre A V, et al. (1994) “Hydrodesulfurization of methyl-substituted dibenzothiophenes catalyzed by sulfided Co-Moγ-Al2O3, Journal of Catalysis, 61(2): 523-527. ##
  12. Meille V, Schulz E, Lemaire M, et al. (1997) Hydrodesulfurization of Alkyldibenzothiophenes over a NiMo/Al2O3 Catalyst: Kinetics and Mechanism,” Journal of Catalysis, 170, 29-36. ##
  13. Ramirez J, Fuentes S, Díaz G, et al. (1989) Hydrodesulphurization activity and characterization of sulphided molybdenum and cobalt-molybdenum catalysts: Comparison of Alumina-, Silica-Alumina- and Titania-Supported Catalysts, Applied Catalysis, 52: 221-224. ##
  14. Fang X C, Guo R, Yang C M (2013) the development and application of catalysts for ultra-deep hydrodesulfurization of diesel, Chinese Journal of Catalysis, 34: 130-139. ##
  15. Peng C, Guo R, Feng X (2019) Tailoring the structure of Co-Mo/mesoporous γ-Al2O3 catalysts by adding multihydroxyl compound: A 3000 kt/a industrial-scale diesel ultra-deep hydrodesulfurization study,” Chemical Engineering Journal, 377: 119706-119733. ##
  16. Krivtcova N I, Tataurshikov A A, Ivanchina E D, Krivtsov E B (2015) Mathematical Modelling of Diesel Fuel Hydrodesulfurization Kinetics, Procedia Chem.,  15: 180–186. ##
  17. Ganguly S K (2013) Kinetics of Hydrodesulfurization of Diesel: Internal Mass Transfer Aspects, Journal of Petroleum Science and Technology, 31: 672–679. ##
  18. Wu G, Yin Y, Chen W, et al. (2020) Catalytic kinetics for ultra-deep hydrodesulfurization of diesel, Journal of Chemical Engineering Science, 214, 115446. ##
  19. Ding L H, Zheng Y, Zhang Z H, Lu Y, Qin K, Zhang L, Song Y and Li M (2006) Hydrotreating of light cycled oil using WNi/Al2O3 catalysts containingzeolite beta and/or chemically treated zeolite Y,” Journal of Catalysis, 241:435–445. ##
  20. Jiang J, Yang C, Lu Z, Ding J, Li T, Lu Y, Cao F, (2015)Characterization and application of a Pt/ZSM-5/SSMF catalyst for hydrocracking of paraffin wax, Catalysis Communications, 60: 1-4. ##
  21. Yu Q Y, Zhang L, Guo R (2017) Catalytic performance of CoMo catalysts supported on mesoporous ZSM-5 zeolite-alumina composites in the hydrodesulfurizationof 4, 6-dimethyldibenzothiophene, Journal of Fuel Processing Technology, 159: 76-87. ##
  22. Kwak C, Lee J J, Bae J S, Moon S H (2001) Poisoning effect of nitrogen compounds on the performance of CoMoS/Al2O3 catalyst in the hydrodesulfurization of dibenzothiophene, 4-methyldibenzothiophene, and 4, 6-dimethyldibenzothiophene,” Journal of Applied Catalysis B: Environmental, 35: 59-68. ##