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

引用本文: 刘璞生, 张忠东, 贾明君, 高雄厚, 于吉红. 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[J]. 催化学报, 2015, 36(6): 806-812. doi: 10.1016/S1872-2067(14)60311-9 shu

Citation: Pusheng Liu, Zhongdong Zhang, Mingjun Jia, Xionghou Gao, Jihong Yu. ZSM-5 zeolites with different SiO₂/Al₂O₃ ratios as fluid catalytic cracking catalyst additives for residue cracking[J]. Chinese Journal of Catalysis, 2015, 36(6): 806-812. doi: 10.1016/S1872-2067(14)60311-9 shu

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,
,}

通讯作者: 高雄厚,电话/传真: (0431)85168608; 电子信箱: jihong@jlu.edu.cn;于吉红,电话/传真: (0931)7961603; 电子信箱: gaoxionghou@petrochina.com.cn; 高雄厚,电话/传真: (0431)85168608; 电子信箱: jihong@jlu.edu.cn;于吉红,电话/传真: (0931)7961603; 电子信箱: gaoxionghou@petrochina.com.cn

基金项目:
国家重点基础研究发展计划(973计划, 2011CB808703) (973计划, 2011CB808703)

国家自然科学基金(91122029, 21320102001). (91122029, 21320102001)

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:

English

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

1.
a State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012, Jilin, China;

Corresponding author: 高雄厚,电话/传真: (0431)85168608; 电子信箱: jihong@jlu.edu.cn;于吉红,电话/传真: (0931)7961603; 电子信箱: gaoxionghou@petrochina.com.cn; 高雄厚,电话/传真: (0431)85168608; 电子信箱: jihong@jlu.edu.cn;于吉红,电话/传真: (0931)7961603; 电子信箱: gaoxionghou@petrochina.com.cn

Received Date: 25 December 2014
Available Online: 20 June 2015
Fund Project:
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).

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:

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沈阳化工大学材料科学与工程学院沈阳 110142

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

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