物理化学学报 >> 2014, Vol. 30 >> Issue (3): 544-550.doi: 10.3866/PKU.WHXB201401021

催化和表面科学 上一篇    下一篇

酸催化及竞争吸附对CeY分子筛吸附脱硫性能的影响

秦玉才1,2, 高雄厚3, 段林海2, 范跃超2, 于文广2, 张海涛3, 宋丽娟1,2   

  1. 1 中国石油大学(华东)化学化工学院, 山东青岛266426;
    2 辽宁石油化工大学, 辽宁省石油化工催化科学与技术重点实验室, 辽宁抚顺113001;
    3 中国石油天然气股份有限公司, 石油化工研究院, 北京100007
  • 收稿日期:2013-10-06 修回日期:2013-12-31 发布日期:2014-02-27
  • 通讯作者: 宋丽娟 E-mail:lsong56@263.net
  • 基金资助:

    国家自然科学基金(20976077,21076100),国家重点基础研究发展规划项目(973) (2007CB216403),中国石油天然气股份有限公司(10-01A-01-01-01)及辽宁省高校创新团队资助

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.

摘要:

采用液相离子交换(LPIE)法制备了CeY分子筛,并研究烯烃和芳烃对其吸附脱硫性能的影响. 利用固定床穿透曲线技术研究吸附剂的脱硫性能,结果表明:烯烃和芳烃的存在均导致吸附剂吸附硫容量减少,然而,烯烃的影响明显强于芳烃. 采用原位傅里叶变换红外(FTIR)光谱技术研究噻吩、环己烯和苯的吸附行为,结果发现:烯烃和芳烃降低吸附剂脱硫性能的实质分别为吸附剂表面酸性导致的酸催化反应和π-络合吸附的芳烃分子与硫化物分子的竞争吸附. 另外,烯烃的影响取决于吸附剂的表面酸性,尤其是强B酸(Brönsted 酸)中心.这是由于B酸中心会导致烯烃和噻吩发生质子化反应,且质子化物种易于进一步发生低聚反应. 生成的低聚物覆盖吸附活性中心导致吸附剂对其它噻吩分子的吸附能力降低.

关键词: 吸附脱硫, B酸中心, π-络合, 质子化, 低聚反应

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