Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

Experimental and theoretical study of microwave enhanced catalytic hydrodesulfurization of thiophene in a continuous-flow reactor

  • 110 Accesses

  • 1 Citations


Hydrodesulfurization (HDS) of thiophene, as a gasoline model oil, over an industrial Ni-Mo/Al2O3 catalyst was investigated in a continuous system under microwave irradiation. The HDS efficiency was much higher (5%–14%) under microwave irradiation than conventional heating. It was proved that the reaction was enhanced by both microwave thermal and non-thermal effects. Microwave selective heating caused hot spots inside the catalyst, thus improved the reaction rate. From the analysis of the non-thermal effect, the molecular collisions were significantly increased under microwave irradiation. However, instead of being reduced, the apparent activation energy increased. This may be due to the microwave treatment hindering the adsorption though upright S-bind (η1) and enhancing the parallel adsorption (η5), both adsorptions were considered to favor to the direct desulfurization route and the hydrogenation route respectively. Therefore, the HDS process was considered to proceed along the hydrogenation route under microwave irradiation.


  1. 1.

    Kaufmann T G, Kaldor A, Stuntz G F, Kerby M C, Ansell L L. Catalysis science and technology for cleaner transportation fuels. Catalysis Today, 2000, 62(1): 77–90

  2. 2.

    Song C. An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel. Catalysis Today, 2003, 86(1-4): 211–263

  3. 3.

    Liu N, Wang X, Xu W, Hu H, Liang J, Qiu J. Microwave-assisted synthesis of MoS2/graphene nanocomposites for efficient hydrodesulfurization. Fuel, 2014, 119: 163–169

  4. 4.

    Shang H, Du W, Liu Z, Zhang H. Development of microwave induced hydrodesulfurization of petroleum streams: A review. Journal of Industrial and Engineering Chemistry, 2013, 19(4): 1061–1068

  5. 5.

    Ghosh P, Andrews A T, Quann R J, Halbert T R. Detailed kinetic model for the hydro-desulfurization of FCC naphtha. Energy & Fuels, 2009, 23(12): 5743–5759

  6. 6.

    Wang H, Wu Y, Liu Z, He L, Yao Z, Zhao W. Deposition of WO3 on Al2O3 via a microwave hydrothermal method to prepare highly dispersed W/Al2O3 hydrodesulfurization catalyst. Fuel, 2014, 136: 185–193

  7. 7.

    Miadonye A, Snow S, Irwin D J G, Khan M R, Britten A J. Desulfurization of heavy crude oil by microwave irradiation. International Journal of Multiphase Flow, 2009, 63: 455–465

  8. 8.

    Mutyala S, Fairbridge C, Paré J R J, Bélanger J M R, Ng S, Hawkins R. Microwave applications to oil sands and petroleum: A review. Fuel Processing Technology, 2010, 91(2): 127–135

  9. 9.

    Leadbeater N E, Khan M R. Microwave-promoted desulfurization of heavy and sulfur-containing crude oil. Energy & Fuels, 2008, 22(3): 1836–1839

  10. 10.

    Rodriguez A M, Prieto P, de la Hoz A, Díaz-Ortiz Á, Martin D R, García J I. Influence of polarity and activation energy in microwave-assisted organic synthesis (MAOS). ChemistryOpen, 2015, 4(3): 308–317

  11. 11.

    Zhang X, Hayward D O, Mingos D M P. Effects of microwave dielectric heating on heterogeneous catalysis. Catalysis Letters, 2003, 88(1/2): 33–38

  12. 12.

    Perry W L, Katz J D, Rees D, Paffet M T, Datye A K. Kinetics of the microwave-heated CO oxidation reaction over alumina-supported Pd and Pt catalysts. Journal of Catalysis, 1997, 171(2): 431–438

  13. 13.

    Booske J H, Cooper R F, Freeman S A. Microwave enhanced reaction kinetics in ceramics. Materials Research Innovations, 1997, 1(2): 77–84

  14. 14.

    Kappe C O. Microwave dielectric heating in synthetic organic chemistry. Chemical Society Reviews, 2008, 37(6): 1127–1139

  15. 15.

    Gao X, Li X G, Zhang J S, Sun J Y, Li H. Influence of a microwave irradiation field on vapor-liquid equilibrium. Chemical Engineering Science, 2013, 90: 213–220

  16. 16.

    Meredith R. Engineers Handbook of Industrial Microwave Heating. London: Institute of Electrical Engineers, 1998, 19–20

  17. 17.

    Raner K D, Strauss C R, Vyskoc F, Mokbel L. A comparison of reaction kinetics observed under microwave irradiation and conventional heating. Journal of Organic Chemistry, 1993, 58(4): 950–953

  18. 18.

    Borges I Jr, Silva A M, Aguiar A P, Borges L E P, Santos J C A, Dias M H C. Density functional theory molecular simulation of thiophene adsorption on MoS2 including microwave effects. Journal of Molecular Structure THEOCHEM, 2007, 822(1-3): 80–88

  19. 19.

    Mills P, Korlann S, Bussell M E, Reynolds M A, Ovchinnikov M V, Angelici R J, Stinner C, Weber T, Prins R. Vibrational study of organometallic complexes with thiophene ligands: Models for adsorbed thiophene on hydrodesulfurization catalysts. Journal of Physical Chemistry A, 2001, 105(18): 4418–4429

  20. 20.

    Moses P, Hinnemann B, Topsoe H, Norskov J. The hydrogenation and direct desulfurization reaction pathway in thiophene hydrodesulfurization over MoS2 catalysts at realistic conditions: A density functional study. Journal of Catalysis, 2007, 248(2): 188–203

  21. 21.

    Wang H, Iglesia E. Thiophene hydrodesulfurization catalysis on supported Ru clusters: Mechanism and site requirements for hydrogenation and desulfurization pathways. Journal of Catalysis, 2010, 273(2): 245–256

  22. 22.

    Zheng P, Duan A, Chi K, Zhao L, Zhang C, Xu C, Zhao Z, Song W, Wang X, Fan J. Influence of sulfur vacancy on thiophene hydrodesulfurization mechanism at different MoS2 edges: A DFT study. Chemical Engineering Science, 2017, 164: 292–306

  23. 23.

    Ma X, Schobert H H. Molecular simulation on hydrodesulfurization of thiophenic compounds over MoS2 using ZINDO. Journal of Molecular Catalysis A Chemical, 2000, 160(2): 409–427

  24. 24.

    Wiegand B C, Friend C M. Model studies of the desulfurization reactions on metal surfaces and in organometallic complexes. Chem Inform, 1992, 23: 491–504

  25. 25.

    Cristol S, Paul J F, Schovsbo C, Veilly E, Payen E. DFT study of thiophene adsorption on molybdenum sulfide. Journal of Catalysis, 2006, 239(1): 145–153

  26. 26.

    Raybaud P, Hafner J, Kresse G, Toulhoat H. Adsorption of thiophene on the catalytically active surface of MoS2: An ab initio, local-density-functional study. Physical Review Letters, 1998, 80(7): 1481–1484

  27. 27.

    Shang H, Zhao J M, liu Z C, Bai B, Zhang H C. China Patent, 201210160627.4, 2015-04-01

  28. 28.

    Shang H, Zhao J M. China Patent, 201210160686.1, 2015-01-07

  29. 29.

    Shang H, Zhao J M, liu Z C, Zhang H C. China Patent, 201210320334.8, 2014-09-03

  30. 30.

    Shang H, Zhao J M, Liu Z C. China Patent, 201210454604.4, 2015-06-03

  31. 31.

    Shang H, Zhao J M, Zhang W H. China Patent, 201410156106.0, 2017-05-03

  32. 32.

    Shang H, Zhang H, Li W, Liu Z, Bai B, Liu Z. Study on the hydrodesulfurization of thiophene model compound under micro-wave irradiation. Journal of Kunming University Technology: Nature Science Edition, 2012, 37: 294–299 (in Chinese)

  33. 33.

    Shang H, Shi J C, Li J, Liu Y, Zhang W H. Reactor design of microwave assisted demetallization of heavy crude oil. Chemical Engineering Transactions, 2014, 39: 511–516

  34. 34.

    Zhang X, Hayward D O, Mingos D M P. Effects of microwave dielectric heating on heterogeneous catalysis. Catalysis Letters, 2003, 88(1/2): 33–38

  35. 35.

    Chemat F, Esveld D C, Poux M, Di-Martino J L. Role of selective heating in the microwave activation of heterogeneous catalysis reactions using a continuous microwave reactor. Journal of Microwave Power and Electromagnetic Energy, 1998, 33(2): 88–94

  36. 36.

    Zhang X, Hayward D O, Lee C, Mingos D M P. Microwave assisted catalytic reduction of sulfur dioxide with methane over MoS2 catalysts. Applied Catalysis B: Environmental, 2001, 33(2): 137–148

  37. 37.

    Zhang X, Hayward D O, Mingos D M P. Dielectric properties of MoS2 and Pt catalysts: Effects of temperature and microwave frequency. Catalysis Letters, 2002, 84(3/4): 225–233

  38. 38.

    Topsøe H, Clausen B S, Massoth F E. Hydrotreating Catalysis. Berlin: Springer-Verlag, 1996, 116–118

  39. 39.

    Borgna A, Hensen E J M, Coulier L, de Croon M H J M, Schouten J C, van Veen J A R, Niemantsverdriet J W. Intrinsic thiophene hydrodesulfurization kinetics of a sulfided NiMo/SiO2 model catalyst: Volcano-type behavior. Catalysis Letters, 2003, 90(3/4): 117–122

  40. 40.

    Xu C M, Yang C H. Petroleum Refinery Engineering. 4th ed. Beijing: Petroleum Industry Press, 2009, 373–376 (in Chinese)

  41. 41.

    Clark D E, Folz D C, West J K. Processing materials with microwave energy. Materials Science and Engineering A, 2000, 287(2): 153–158

  42. 42.

    Perreux L, Loupy A. A tentative rationalization of microwave effects in organic synthesis according to the reaction medium and mechanistic considerations. Tetrahedron, 2001, 57(45): 9199–9223

  43. 43.

    Tarbuck T L, Mccrea K R, Logan J W, Heiser J L, Bussell M E. Identification of the adsorption mode of thiophene on sulfided Mo catalysts. Journal of Physical Chemistry B, 1998, 102(40): 7845–7857

  44. 44.

    Mitchell P C H, Green D A, Grimblot J, Payen E, Tomkinson J. Interaction of thiophene with a molybdenum disulfide catalyst: An inelastic neutron scattering study. Physical Chemistry Chemical Physics, 1995, 104: 325–329

  45. 45.

    Zhao L, Chen Y, Gao J, Chen Y. Desulfurization mechanism of FCC gasoline: A review. Frontiers of Chemical Science and Engineering, 2010, 4(3): 314–321

  46. 46.

    Ruette F, Valencia N, Sanchez-delgado R. Molecular analogs of surface species. 2. A theoretical study of molybdenum carbonyl thiophene complexes: Organometallic models for the chemisorption of thiophene. Journal of the American Chemical Society, 1989, 111(1): 40–46

Download references


This work was supported by the National Natural Science Foundation of China (Grant No. 21476258).

Author information

Correspondence to Hui Shang or Jiawei Wang.

Rights and permissions

Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Shang, H., Ye, P., Yue, Y. et al. Experimental and theoretical study of microwave enhanced catalytic hydrodesulfurization of thiophene in a continuous-flow reactor. Front. Chem. Sci. Eng. 13, 744–758 (2019). https://doi.org/10.1007/s11705-019-1839-7

Download citation


  • thiophene
  • microwave irradiation
  • hydrode-sulfurization
  • non-thermal microwave effect