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Catalyst particle shapes and pore structure engineering for hydrodesulfurization and hydrodenitrogenation reactions

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Abstract

Catalyst particle shapes and pore structure engineering are crucial for alleviating internal diffusion limitations in the hydrodesulfurization (HDS)/hydrodenitrogenation (HDN) of gas oil. The effects of catalyst particle shapes (sphere, cylinder, trilobe, and tetralobe) and pore structures (pore diameter and porosity) on HDS/HDN performance at the particle scale are investigated via mathematical modeling. The relationship between particle shape and effectiveness factor is first established, and the specific surface areas of different catalyst particles show a positive correlation with the average HDS/HDN reaction rates. The catalyst particle shapes primarily alter the average HDS/HDN reaction rate to adjust the HDS/HDN effectiveness factor. An optimal average HDS/HDN reaction rate exists as the catalyst pore diameter and porosity increase, and this optimum value indicates a tradeoff between diffusion and reaction. In contrast to catalyst particle shapes, the catalyst pore diameter and the porosity of catalyst particles primarily alter the surface HDS/HDN reaction rate to adjust the HDS/HDN effectiveness factor. This study provides insights into the engineering of catalyst particle shapes and pore structures for improving HDS/HDN catalyst particle efficiency.

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References

  1. Ancheyta-Juárez J, Aguilar-Rodríguez E, Salazar-Sotelo D, Betancourt-Rivera G, Leiva-Nuncio M. Hydrotreating of straight run gas oil light cycle oil blends. Applied Catalysis A, General, 1999, 180(1–2): 195–205

    Article  Google Scholar 

  2. Marroquín-Sánchez G, Ancheyta-Juárez J. Catalytic hydrotreating of middle distillates blends in a fixed-bed pilot reactor. Applied Catalysis A, General, 2001, 207(1–2): 407–420

    Article  Google Scholar 

  3. Schmitz C, Datsevitch L, Jess A. Deep desulfurization of diesel oil: kinetic studies and process-improvement by the use of a two-phase reactor with pre-saturator. Chemical Engineering Science, 2004, 59(14): 2821–2829

    Article  CAS  Google Scholar 

  4. Novaes L da R, de Resende N S, Salim V M M, Secchi A R. Modeling, simulation and kinetic parameter estimation for diesel hydrotreatin. Fuel, 2017, 209: 184–193

    Article  CAS  Google Scholar 

  5. Stanislaus A, Marafi A, Rana M S. Recent advances in the science and technology of ultra low sulfur diesel (ULSD) production. Catalysis Today, 2010, 153(1–2): 1–68

    Article  CAS  Google Scholar 

  6. Mjalli F S, Ahmed O U, Al-Wahaibi T, Al-Wahaibi Y, Al Nashef I M. Deep oxidative desulfurization of liquid fuels. Reviews in Chemical Engineering, 2014, 30(4): 337–378

    Article  CAS  Google Scholar 

  7. Breysse M, Djega-Mariadassou G, Pessayre S, Geantet C, Vrinat M, Pérot G, Lemaire M. Deep desulfurization: reactions, catalysts and technological challenges. Catalysis Today, 2003, 84(3–4): 129–138

    Article  CAS  Google Scholar 

  8. Babich I V, Moulijn J A. Science and technology of novel processes for deep desulfurization of oil refinery streams: a review. Fuel and Energy Abstracts, 2003, 82(6): 607–631

    CAS  Google Scholar 

  9. Bej S K. Performance evaluation of hydroprocessing catalysts—a review of experimental techniques. Energy & Fuels, 2002, 16(3): 774–784

    Article  CAS  Google Scholar 

  10. De Bruljn A, Naka I, Sonnemans J W M. Effect of the noncylindrical shape of extrudates on the hydrodesulfurization of oil fractions. Industrial & Engineering Chemistry Process Design and Development, 1981, 20(1): 40–45

    Article  Google Scholar 

  11. Jarullah A T, Mujtaba I M, Wood A S. Kinetic parameter estimation and simulation of trickle-bed reactor for hydrodesulfurization of crude oil. Chemical Engineering Science, 2011, 66(5): 859–871

    Article  CAS  Google Scholar 

  12. Mann P, Diez F V, Ordonez S. Fixed bed membrane reactors for WGSR-based hydrogen production: optimization of modelling approaches and reactor performance. International Journal of Hydrogen Energy, 2012, 37(6): 4997–5010

    Article  Google Scholar 

  13. Farahani H F, Shahhosseini S. Simulation of hydrodesulfurization trickle bed reactor. Chemical Product and Process Modeling, 2011, 6(1): 1–19

    Article  Google Scholar 

  14. Ancheyta J, Muñoz J A D, Macías M J. Experimental and theoretical determination of the particle size of hydrotreating catalysts of different shapes. Catalysis Today, 2005, 109(1–4): 120–127

    Article  CAS  Google Scholar 

  15. Macías M J, Ancheyta J. Simulation of an isothermal hydrodesulfurization small reactor with different catalyst particle shapes. Catalysis Today, 2004, 98(1–2): 243–252

    Article  Google Scholar 

  16. Macías Hernández M J, Morales R D, Ramírez-Lopez A. Simulation of the effectiveness factor for a tri-lobular catalyst on the hydrodesulfurization of diesel. International Journal of Chemical Reactor Engineering, 2009, 7(1): 91–97

    Article  Google Scholar 

  17. Kolitcheff S, Jolimate E, Hugon A, Verstraete J, Rivallan M, Carrette P L, Couenne F, Tayakout-Fayolle M. Tortuosity and mass transfer limitations in industrial hydrotreating catalysts: effect of particle shape and size distribution. Catalysis Science & Technology, 2018, 8(10): 4537–4549

    Article  CAS  Google Scholar 

  18. Shi Y, Yang C F, Zhao X Q, Cao Y Q, Qian G, Lu M K, Ye G H, Peng C, Sui B K, Lv Z H, et al. Engineering the hierarchical pore structures and geometries of hydrodemetallization catalyst pellets. Industrial & Engineering Chemistry Research, 2019, 58(23): 9829–9837

    Article  CAS  Google Scholar 

  19. Yang L, Lu J F, Chen H Y, Ruckenstein E, Qin Y H, Wang T L, Sun W, Wang C W. Screening and improving porous materials for ultradeep desulfurization of gasoline. Industrial & Engineering Chemistry Research, 2020, 60(1): 604–613

    Article  Google Scholar 

  20. Klimova T, Peña L, Lizama L, Salcedo C, Gutiérrez O Y. Modification of activity and selectivity of NiMo/SBA-15 HDS catalysts by grafting of different metal oxides on the support surface. Industrial & Engineering Chemistry Research, 2009, 48(3): 1126–1133

    Article  CAS  Google Scholar 

  21. Salmas C E, Androutsopoulos G P. A novel pore structure tortuosity concept based on nitrogen sorption hysteresis data. Industrial & Engineering Chemistry Research, 2011, 40(2): 721–730

    Article  Google Scholar 

  22. Zhou Z, Chen S L, Hua D, Zhang J H. Preparation and evaluation of a well-ordered mesoporous nickel-molybdenum/silica opal hydrodesulfurization model catalyst. Transition Metal Chemistry, 2011, 37(1): 25–30

    Article  Google Scholar 

  23. Lv Y P, Wang X L, Gao D W, Ma X L, Li S N, Wang Y, Song G L, Duan A J, Chen G Z. Hierarchically porous ZSM-5/SBA-15 zeolite: tuning pore structure and acidity for enhanced hydro-upgrading of FCC gasoline. Industrial & Engineering Chemistry Research, 2018, 57(42): 14031–14043

    Article  CAS  Google Scholar 

  24. Mederos F S, Ancheyta J, Elizalde I. Dynamic modeling and simulation of hydrotreating of gas oil obtained from heavy crude oil. Applied Catalysis A, General, 2012, 425–426: 13–27

    Article  Google Scholar 

  25. Macé O, Wei J. Diffusion in random particle models for hydrodemetalation catalysts. Industrial & Engineering Chemistry Research, 1991, 30(5): 909–918

    Article  Google Scholar 

  26. Rao S M, Coppens M O. Increasing robustness against deactivation of nanoporous catalysts by introducing an optimized hierarchical pore network—application to hydrodemetalation. Chemical Engineering Science, 2012, 83: 66–76

    Article  CAS  Google Scholar 

  27. Topalian P J, Liyanage D R, Danforth S J, Aquino A I, Brock S L, Bussell M E. Effect of particle size on the deep HDS properties of Ni2P catalysts. Journal of Physical Chemistry C, 2019, 123(42): 25701–25711

    Article  CAS  Google Scholar 

  28. Boahene P E, Soni K, Dalai A K, Adjaye J. Application of different pore diameter SBA-15 supports for heavy gas oil hydrotreatment using FeW catalyst. Applied Catalysis A, General, 2011, 402(1–2): 31–40

    Article  CAS  Google Scholar 

  29. Mouli K C, Soni K K, Dalai A K, Adjaye J. Effect of pore diameter of Ni-Mo/Al-SBA-15 catalysts on the hydrotreating of heavy gas oil. Applied Catalysis A, General, 2011, 404(1–2): 21–29

    Article  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Grant Nos. 22038003, 21922803, 22178100 and 21776077), the Innovation Program of Shanghai Municipal Education Commission, the Program of Shanghai Academic/Technology Research Leader (Grant No. 21XD1421000).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai, 200237, China

    Yao Shi, Zhao Li, Changfeng Yang, Weikang Yuan, Xinggui Zhou & Xuezhi Duan

  2. Dalian Research Institute of Petroleum and Petrochemicals, SINOPEC, Dalian, 116045, China

    Zhanlin Yang, Zhenhui Lv & Chong Peng

  3. Laboratory of Inorganic Materials Chemistry, University of Namur, B-5000, Namur, Belgium

    Bao-Lian Su

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  1. Yao Shi
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  2. Zhao Li
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  10. Xuezhi Duan
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Correspondence to Xuezhi Duan.

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Shi, Y., Li, Z., Yang, C. et al. Catalyst particle shapes and pore structure engineering for hydrodesulfurization and hydrodenitrogenation reactions. Front. Chem. Sci. Eng. 16, 897–908 (2022). https://doi.org/10.1007/s11705-021-2127-x

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  • DOI: https://doi.org/10.1007/s11705-021-2127-x

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