催化学报

催化学报 ›› 2015, Vol. 36 ›› Issue (6): 806-812.DOI: 10.1016/S1872-2067(14)60311-9

• 论文 • 上一篇    下一篇

不同硅铝比ZSM-5分子筛作为助催化剂在渣油裂化中的应用

刘璞生a,b, 张忠东b, 贾明君a, 高雄厚b, 于吉红a   

  1. a 吉林大学无机合成与制备国家重点实验室, 吉林长春130012;
    b 中国石油兰州化工研究中心, 甘肃兰州730060
  • 收稿日期:2014-12-25 修回日期:2015-02-07 出版日期:2015-05-21 发布日期:2015-05-21
  • 通讯作者: 高雄厚,电话/传真: (0431)85168608; 电子信箱: gaoxionghou@petrochina.com.cn;于吉红,电话/传真: (0931)7961603; 电子信箱: jihong@jlu.edu.cn
  • 基金资助:

    国家重点基础研究发展计划(973计划, 2011CB808703); 国家自然科学基金(91122029, 21320102001).

ZSM-5 zeolites with different SiO2/Al2O3 ratios as fluid catalytic cracking catalyst additives for residue cracking

Pusheng Liua,b, Zhongdong Zhangb, Mingjun Jiaa, Xionghou Gaob, Jihong Yua   

  1. a State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012, Jilin, China;
    b Lanzhou Petrochemical Research Center, PetroChina, Lanzhou 730060, Gansu, China
  • Received:2014-12-25 Revised:2015-02-07 Online:2015-05-21 Published:2015-05-21
  • Supported by:

    This work was supported by the National Basic Research Program of China (973 Program, 2011CB808703) and the National Natural Science Foundation of China (91122029, 21320102001).

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1273

被引次数

18

摘要：

采用不同方法表征了硅铝比(SiO2/Al2O3)为33、266和487的质子型ZSM-5分子筛, 并研究了ZSM-5分子筛作为助催化剂在渣油裂解中的应用. 与USY分子筛基催化剂混合后, 在固定流化床上, 评价了ZSM-5分子筛助催化剂的催化裂化性能. 研究发现, 提高ZSM-5分子筛硅铝比, 可以有效抑制混合催化剂对汽油烯烃的裂解, 从而避免了汽油烷烃的大量损失. 加入ZSM-5助催化剂后, 伴随着液化气(LPG)产率的增加, 异丁烷和异戊烷产率增加, 这可能是由USY基催化剂和ZSM-5助催化剂的综合效应引起的. 汽油烷烃和芳烃含量的变化, 引起了汽油辛烷值的增加. 高硅铝比ZSM-5分子筛(硅铝比为266和487)不仅可以显著改善汽油的辛烷值, 而且有效避免了汽油的大量损失. 催化汽油辛烷值的改善主要是由于高硅铝比ZSM-5分子筛具有适宜的芳构化和异构化活性, 这些变化主要源于高硅铝比ZSM-5分子筛小的孔道直径和适宜的酸性.

关键词: 催化裂化, ZSM-5分子筛, 渣油, 辛烷值

Abstract:

Three proton-type ZSM-5 zeolites with different SiO2/Al2O3 ratios (SARs) of 33, 266, and 487 were characterized and examined as fluid catalytic cracking catalyst additives for residue oil cracking. The catalytic performance of the ZSM-5 additives was evaluated using an ultra-stable Y-zeolite (USY)-based fluid catalytic cracking catalyst in a fixed fluid bed unit. As observed, the cracking of primary olefins over the hybrid catalysts consisting of USY-based catalyst and ZSM-5 additive was considerably inhibited by increasing the SAR of the ZSM-5 zeolite, thus avoiding substantial loss of gasoline paraffins. The introduction of ZSM-5 additives led to higher liquid petroleum gas yields as well as higher isobutane and isopentane yields. The improved yields were attributed to the combined effects of the ZSM-5 additives and USY-based catalyst. The variations of gasoline paraffins and aromatics both accounted for the enhancement in the octane number values. The use of ZSM-5 with higher SARs (266 and 487) led to an enhancement in the octane number with minimal loss of gasoline. This enhancement was mainly attributed to the moderate aromatization and isomerization reactivity of the ZSM-5 additives that mainly originated from their relatively small pores and suitable acidic properties with higher SARs.

Key words: Catalytic cracking, ZSM-5 zeolite, Residue oil, Octane number