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第 36 卷第 5 期 精 细 化 工 Vol.36, No.5
201 9 年 5 月 FINE CHEMICALS May 2019

催化与分离提纯技术
多级孔 HZSM-5 分子筛的制备及其

催化丙烷脱氢反应性能

1
徐国皓 ，徐华胜 1,2,3,4 ，余金鹏 1,2,3,4 ，张春秀 1,2,3,4 ，
陈雅莹 1,2,3,4 ，王鹏飞 1,2,3,4*

（1. 上海化工研究院有限公司，上海 200062；2. 上海绿强新材料有限公司，上海 201608；3. 聚烯烃催化
技术与高性能材料国家重点实验室，上海 200062；4. 上海市聚烯烃催化技术重点实验室，上海 200062）

摘要：以十八水合硫酸铝、硅溶胶、四丙基氢氧化铵（TPAOH）、硝酸铵（NH 4 NO 3 ）为原料，合成硅铝物质的
量比为 100 的 HZSM-5 分子筛。采用乙酸钠溶液处理 HZSM-5 分子筛后加入 TPAOH 溶液进行二次晶化，通过
对处理前、后的 HZSM-5 分子筛负载 Pt，制得 Pt/HZSM-5 催化剂用于丙烷脱氢反应。利用 XRD、SEM、XRF、
BET、NH 3 -TPD 和 H 2 化学吸附对处理前、后的 HZSM-5 分子筛进行了表征，考察了不同浓度的 TPAOH 溶液对
HZSM-5 分子筛的晶体结构、表面形貌、孔结构、表面酸性及丙烷脱氢性能的影响。结果表明，采用乙酸钠溶
液处理后的 HZSM-5 分子筛在 TPAOH 溶液中发生了二次晶化，不仅形成了微孔-介孔多级孔结构，还能调变分
子筛的表面酸性；当 TPAOH 溶液浓度为 0.3 mol/L、晶化温度为 170 ℃、晶化时间为 24 h 时，得到的 Pt/HZSM-5
催化丙烷的初始转化率和丙烯选择性均达到最高值，分别为 34.2%和 99.0%。
关键词：二次晶化；丙烷脱氢；HZSM-5；多级孔；催化技术
中图分类号：O643.36 文献标识码：A 文章编号：1003-5214 (2019) 05-0892-07

Preparation of Hierarchical HZSM-5 Zeolites and Their
Catalytic Performance in Propane Dehydrogenation

1
XU Guo-hao , XU Hua-sheng 1,2,3,4 , YU Jin-peng 1,2,3,4 , ZHANG Chun-xiu 1,2,3,4 ,
CHEN Ya-ying 1,2,3,4 , WANG Peng-fei 1,2,3,4*
(1. Shanghai Research Institute of Chemical Industry Co., Ltd., Shanghai 200062, China; 2. Shanghai Luqiang New
Materials Co., Ltd., Shanghai 201608, China; 3. State Key Laboratory of Polyolefins and Catalysis, Shanghai 200062,
China; 4. Shanghai Key Laboratory of Catalysis Technology for Polyolefins, Shanghai 200062, China)

Abstract: Aluminium sulphate 〔Al 2(SO 4) 318H 2O〕, silica sol, tetrapropylammonium hydroxide (TPAOH)
and ammonium nitrate (NH 4NO 3) were used as raw materials to synthesize HZSM-5 zeolites with a SiO 2/
Al 2O 3 molar ratio of 100. The HZSM-5 zeolites were treated by adding TPAOH solution for secondary
crystallization after pre-treating with sodium acetate solution. Pt/HZSM-5 catalysts were prepared for
propane dehydrogenation by loading Pt onto HZSM-5 zeolites before and after treatment. The samples were
characterized by XRD, SEM, XRF, BET, NH 3-TPD and H 2 chemisorption. The effects of different TPAOH
crystallization concentrations on the crystal structure, surface morphology, pore structure, surface acidity
and propane dehydrogenation of HZSM-5 zeolites were investigated. The results showed that HZSM-5
zeolite treated with CH 3COONa solution was recrystallized in TPAOH solution, which not only formed
microporous-mesoporous hierarchical structure, but also modulated the surface acidity of the zeolite. When
the concentration of TPAOH solution was 0.3 mol/L, the crystallization temperature was 170 ℃, the
crystallization time was 24 h, the prepared Pt/HZSM-5 showed excellent catalytic performance for propane
dehydrogenation, and the propane conversion and propylene selectivity reached 34.2% and 99.0%,

收稿日期：2018-10-18; 定用日期：2019-01-15; DOI: 10.13550/j.jxhg.20180770
基金项目：上海市科技人才计划项目（15XD1522300）
作者简介：徐国皓（1993—），男，硕士生，E-mail：1447667520@qq.com。联系人：王鹏飞(1969—)，男，教授级高工，E-mail：
wpf@sh-lq.com。