Acta Phys. -Chim. Sin. ›› 2014, Vol. 30 ›› Issue (3): 544-550.doi: 10.3866/PKU.WHXB201401021

• CATALYSIS AND SURFACE SCIENCE • Previous Articles     Next Articles

Effects on Adsorption Desulfurization of CeY Zeolites:Acid Catalysis and Competitive Adsorption

QIN Yu-Cai1,2, GAO Xiong-Hou3, DUAN Lin-Hai2, FAN Yue-Chao2, YU Wen-Guang2, ZHANG Hai-Tao3, SONG Li-Juan1,2   

  1. 1 College of Chemistry & Chemical Engineering, China University of Petroleum (East China), Qingdao 266426, Shandong Province, P. R. China;
    2 Key Laboratory of Petrochemical Catalytic Science and Technology, Liaoning Province, Liaoning Shihua University, Fushun 113001, Liaoning Province, P. R. China;
    3 Petrochemical Research Institute, PetroChina Company Limited, Beijing 100007, P. R. China
  • Received:2013-10-06 Revised:2013-12-31 Published:2014-02-27
  • Contact: SONG Li-Juan E-mail:lsong56@263.net
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (20976077, 21076100), National Key Basic Research Program of China (973) (2007CB216403), China National Petroleum Corporation (10-01A-01-01-01), and Innovation Team of Liaoning Province Colleges, China.

Abstract:

The effects of olefin and aromatic hydrocarbons, as well as the acidic catalytic reactions on the adsorption desulfurization performance of CeY zeolites prepared by liquid phase ion exchange (LPIE) technique were systemically investigated. The capacities of sulfur removal were measured by fixed-bed breakthrough experiments. It is shown that the desulfurization performance of the adsorbents is reduced by olefin and aromatic hydrocarbons in model gasoline with olefin having a more significant effect. In-situ Fourier transform infrared (FTIR) spectroscopy was used to study the adsorption of thiophene, cyclohexene, and benzene on the zeolites. The effects of the olefin and aromatic hydrocarbons differed. For the olefins, the desulfurization capacity of the CeY adsorbents depends on the surface acidity of the zeolites, particularly on the Brönsted acidity. Protonation of olefin and thiophene compounds can be found at Brönsted acidic sites. It is the oligomerization of the protonated species that decrease the adsorption of other thiophenes. It is, therefore, the acidic catalytic reactions caused by the strong Brönsted acidity on the adsorbent surface that could be the dominant factor for olefin hydrocarbons. While for the aromatic hydrocarbons, the decreased desulfurization capacity can be ascribed to the competitive adsorption on the active sites by π-complexation between the organic sulfur compounds and arenes.

Key words: Adsorption desulfurization, Brö, nsted acidity, π-complexation, Protonization, Oligomerization

MSC2000: 

  • O643