化工学报 ›› 2015, Vol. 66 ›› Issue (8): 3098-3105.DOI: 10.11949/j.issn.0438-1157.20150645

• 催化、动力学与反应器 • 上一篇    下一篇

后处理改性对HZSM-5沸石丁烯裂解性能的影响

张荣荣, 王正宝   

  1. 浙江大学化学工程与生物工程学院, 浙江 杭州 310027
  • 收稿日期:2015-05-21 修回日期:2015-05-30 出版日期:2015-08-05 发布日期:2015-08-05
  • 通讯作者: 王正宝
  • 基金资助:

    国家自然科学基金项目(U1162129)。

Effects of post treatment of HZSM-5 zeolites on catalytic cracking of butene

ZHANG Rongrong, WANG Zhengbao   

  1. College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China
  • Received:2015-05-21 Revised:2015-05-30 Online:2015-08-05 Published:2015-08-05
  • Supported by:

    supported by the National Natural Science Foundation of China (U1162129).

摘要:

采用不同后处理手段(碱处理、水汽处理以及碱处理-水汽处理)对HZSM-5沸石的孔结构和酸性质进行了调变,并对其丁烯裂解性能进行了研究。运用N2吸脱附、扫描电镜(SEM)、X射线衍射(XRD)以及吡啶吸附红外(Py-IR)对后处理改性前后的沸石样品的物理化学性质进行了表征。碱处理后HZSM-5的质子酸量增加,在5~20 nm处具有分布较宽的介孔,其反应活性升高,丙烯选择性下降,但失活速率没有加快。单独水汽处理在2~4 nm处产生介孔,但介孔体积较小。碱处理-水汽处理在2~4和5~20 nm处具有双分布介孔,前者分布较集中,后者分布较宽。单独水汽处理和碱处理-水汽处理的样品可以提高HZSM-5的丙烯选择性,主要归功于酸量的降低;反应2.5 h后具有较稳定的丙烯收率(高碱浓度处理-水汽处理的样品除外)。

关键词: 沸石, 催化剂, 反应, 碱处理, 多级孔

Abstract:

The structure and acidity of HZSM-5 zeolites were modified using different post treatment methods: alkaline treatment, steam treatment, and alkaline-steaming treatment. The catalytic performances of modified zeolites were tested in 1-butene catalytic cracking. Their physicochemical properties were characterized by N2 adsorption, scanning electron microscopy (SEM), X-ray diffraction (XRD), and infrared spectroscopy with pyridine adsorption (Py-IR). The acidities of zeolites increased after the alkaline treatment, and as a result, the activity of butene cracking increased and the selectivity of propylene decreased. However, the deactivation rate of alkaline-treated zeolites had no significant change. There was a pronounced development of mesopores (5—20 nm) with a broad pore-size distribution in alkaline-treated ZSM-5 zeolites. Mesopores (2—4 nm) with a narrow distribution is observed after steaming treatment, while the mesopore volume is low. Zeolites after alkaline-and steaming-treatment showed two kinds of mesopore distributions, 2—4 nm (narrow) and 5—20 nm (broad). Due to the decrease of Brønsted acidic sites, the selectivity of propylene increased over ZSM-5 zeolites with any of the post treatments; a relatively stable propylene yield was obtained after the reaction of 2.5 h (except for zeolites treated with high concentration of alkaline followed by steaming treatment).

Key words: zeolite, catalyst, reaction, alkaline treatment, hierarchical pores

中图分类号: