一步合成核壳结构ZSM-5/EU-1复合分子筛及其表征

doi:10.15541/jim20150511

无机材料学报 ›› 2016, Vol. 31 ›› Issue (5): 492-498.DOI: 10.15541/jim20150511 CSTR: 32189.14.10.15541/jim20150511

一步合成核壳结构ZSM-5/EU-1复合分子筛及其表征

李建华¹, 杨冬花¹, 吕爱凝¹, 马存存¹, 李晓峰¹, 窦涛^1,2

(1. 太原理工大学化学化工学院, 太原030024; 2. 中国石油大学(北京)化工学院 CNPC催化重点实验室, 北京 102249)

收稿日期:2015-10-20 修回日期:2015-12-06 出版日期:2016-05-20 网络出版日期:2016-04-25
作者简介:李建华(1991–), 女, 硕士研究生. E-mail：ljhwxb0904@163.com
基金资助:
国家重点基础研究发展计划(973 计划, 2012CB215002).国家自然科学基金(20973123).山西省自然科学基金

Synthesis and Characterization of ZSM-5/EU-1 Composite Zeolite with ore-shell Structure by One Step

LI Jian-Hua¹, YANG Dong-Hua¹, LV Ai-Ning¹, MA Cun-Cun¹, Li Xiao-Feng¹, DOU Tao^1,2

(1. College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China; 2. CNPC Key Laboratory of Catalysis, College of Chemical Engineering, China University of Petroleum-Beijing, Beijing 102249, China)

Received:2015-10-20 Revised:2015-12-06 Published:2016-05-20 Online:2016-04-25
About author:LI Jian-Hua. E-mail：ljhwxb0904@163.com
Supported by:
National Basic Research Program of China (2012CB215002).National Natural Science Foundation of China (20973123).Natural Sciece Foundation of Shanxi Province, China (2013011041-1)

摘要/Abstract

摘要：

在添加适量柠檬酸的条件下采用双模板剂一步法, 一次晶化合成ZSM-5/EU-1核壳共生复合分子筛, 对其物理化学性质进行表征, 结果显示: 核壳分子筛中存在ZSM-5和EU-1两种分子筛晶相, 且EU-1分子筛在ZSM-5分子筛表面缺陷处外延生长; 复合以后核壳分子筛为微孔-介孔多级孔道结构, 且其微孔孔径达到0.94 nm; 相比于单一分子筛, 核壳分子筛的强酸量相对提高, 酸性质有所改善。通过对柠檬酸加入量、晶化时间影响因素的分析, 得到合成核壳共生结构的最佳条件为: n(citrate)/n(Al₂O₃)=0.8~1.2, 晶化时间为72~96 h, 并推测核壳分子筛可能的生长过程。

关键词: 核壳分子筛, ZSM-5/EU-1, 多级孔道, 酸性

Abstract:

ZSM-5/EU-1 core-shell intergrowth composite zeolite was synthesized by one-step crystallization method based on dual-template and appropriate citric acid addition. The properties of core-shell zeolite were characterized by XRD, TEM, FT-IR, NH₃-TPD, etc. The results showed that there were ZSM-5 and EU-1 zeolite crystalline phases formed in the core-shell zeolite, as EU-1 overgrowing around ZSM-5 surface defects. The synthetic sample composed of microporous and mesoporous multiple porous composite zeolite, with micropore diameter of 0.94 nm. The core-shell structure increased strong acid content and improved its acidity as compared with the single zeolite. Based on the investigation of citric acid addition and crystallization time influence on the structure and Zeta potential of core-shell zeolite, the optimum condition of core-shell intergrowth was as follows, i.e. n(citrate)/n(Al₂O₃)=0.8-1.2 and crystallization time of 72-96 h. And the possible growth process of core-shell zeolite was proposed.

Key words: core-shell zeolite, ZSM-5/EU-1, multiple porous, acidity

中图分类号:

O643
TQ426

李建华, 杨冬花, 吕爱凝, 马存存, 李晓峰, 窦涛. 一步合成核壳结构ZSM-5/EU-1复合分子筛及其表征[J]. 无机材料学报, 2016, 31(5): 492-498.

LI Jian-Hua, YANG Dong-Hua, LV Ai-Ning, MA Cun-Cun, Li Xiao-Feng, DOU Tao. Synthesis and Characterization of ZSM-5/EU-1 Composite Zeolite with ore-shell Structure by One Step[J]. Journal of Inorganic Materials, 2016, 31(5): 492-498.

图/表 10

图1 分子筛样品的XRD谱图和FT-IR谱图

Fig. 1 XRD patterns and FT-IR spectra of different zeolites

图2 EU-1分子筛(a)、ZSM-5分子筛(b)的SEM照片和核壳结构复合分子筛的SEM照片(c)及其不同放大倍数下的TEM(d, e, f)照片

Fig. 2 SEM images of EU-1 zeolite (a), ZSM-5 zeolite (b), and SEM (c) and different magnifications TEM (d, e, f ) images of core-shell composite zeolite

图3 核壳分子筛N2吸附-脱附等温线及孔径分布图

Fig. 3 Nitrogen adsorption-desorption isotherms pore size distribution of core/shell zeolite

表1 分子筛的孔结构参数

Table 1 Pore structure parameters of different zeolites

Sample	A_BET/(m²·g^-1)	V_total/(cm³∙g^-1)	V_micro/(cm³∙g^-1)	D/nm
EU-1	271.0	0.1914	0.1152	0.6031
ZSM-5	332.0	0.1908	0.1406	0.5121
ZSM-5/EU-1	208.9	0.1313	0.0630	0.9400

图4 核壳ZSM-5/EU-1分子筛TG-DTG曲线

Fig. 4 TG-DTG curves of ZSM-5/EU-1 core-shell zeolite

图5 不同柠檬酸添加量合成ZSM-5/EU-1核壳分子筛的XRD图谱

Fig. 5 XRD patterns of core/shell ZSM-5/EU-1 zeolites synthesized with different citric acid additions n(Citrate)/n(Al2O3)=0.6 (a), 0.8 (b), 1.0 (c), 1.2 (d), 1.5 (e)

图6 不同柠檬酸加入量合成核壳分子筛的Zeta电位图及相对结晶度曲线

Fig. 6 Zeta potential and relativity crystallization curves for core/shell ZSM-5/EU-1 zeolites synthesized with different citric acid additions

图7 核壳分子筛的SEM(a)和不同放大倍数下的TEM(b~e)照片

Fig. 7 SEM(a) and different magnifications TEM(b-e) images of core-shell zeolite

图8 不同晶化时间下核壳分子筛ZSM-5/EU-1的XRD图谱

Fig. 8 XRD patterns of core-shell ZSM-5/EU-1 synthesized with different crystallization time a,b,c,d,e,f,g=8 h, 12 h, 24 h, 48 h, 72 h, 96 h, 108 h

图9 H-ZSM-5(a)、H-EU-1(b)、核壳分子筛H-ZSM-5/EU-1(c)的NH3-TPD图谱

Fig. 9 NH3-TPD patterns of H-ZSM-5 (a), H-EU-1 (b), and core/shell ZSM-5/EU-1 zeolite (c)

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一步合成核壳结构ZSM-5/EU-1复合分子筛及其表征

Synthesis and Characterization of ZSM-5/EU-1 Composite Zeolite with ore-shell Structure by One Step

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