双模板剂B-EU-1/ZSM-5复合分子筛的快速合成及催化应用

doi:10.15541/jim20150363

无机材料学报 ›› 2016, Vol. 31 ›› Issue (3): 248-256.DOI: 10.15541/jim20150363 CSTR: 32189.14.10.15541/jim20150363

双模板剂B-EU-1/ZSM-5复合分子筛的快速合成及催化应用

杨冬花¹(), 李建华¹, 王新波¹, 郭超², 吕爱凝¹, 董梅³, 李晓峰¹, 窦涛^1,⁴

1.太原理工大学化学化工学院, 太原 030024
2.中国矿业大学(北京) 力建学院, 北京 100083
3.中国科学院山西煤炭化学研究所, 煤转化国家重点实验室, 太原 030001
4.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:2015-08-10 修回日期:2015-09-13 出版日期:2016-03-20 网络出版日期:2016-02-24
作者简介:
杨冬花(1963-), 女, 教授. E-mail: ydh1962@163.com
基金资助:
国家重点基础发展计划(973计划, 2012CB215002);国家自然科学基金(20973123);山西省自然科学基金(2013011041-1)

Rapid Synthesis and Catalytic Application of B-EU-1/ZSM-5 Composite Zeolite Based on Dual Template

YANG Dong-Hua¹(), LI Jian-Hua¹, WANG Xin-Bo¹, GUO Chao², LV Ai-Ning¹, DONG Mei³, Li Xiao-Feng¹, DOU Tao^1,⁴

1. College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China
2. School of Mechanics and Civil Engineering, China University of Mining and Technolog-Beijing, Beijing 100083, China
3. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry,Chinese Academy of Sciences,Taiyuan 030001, China
4. CNPC Key Laboratory of Catalysis, College of Chemical Engineering, China University of Petroleum-Beijing, Beijing 102249, China

Received:2015-08-10 Revised:2015-09-13 Published:2016-03-20 Online:2016-02-24
Supported by:
Natural National Key Basic Research Development Plan (973 Plan 2012CB215002);National Natural Science Foundation of China (20973123);Natural Science Foundation of Shanxi Province of China (2013011041-1)

摘要/Abstract

摘要：

以不同氢氧化物做碱源合成B-EU-1/ZSM-5复合分子筛, 并比较各平衡阳离子的结构导向作用及其形貌特征, 发现钠离子的导向作用最强, 且合成复合分子筛的表面较光滑、无明显晶面界限。对合成样品进行了TG-DTG、N₂吸附-脱附和NH₃-TPD分析。结果表明: 双模板剂一步法合成的复合分子筛模板剂脱除的失重率为5.67%, 小于机械复合分子筛的失重率7.31%, 复合分子筛的比表面积、孔容和微孔平均孔径均有所增大, 同时其酸强度、酸量都增大, 有利于二甲苯优先从复合分子筛的孔道结构中扩散出来。将分子筛应用于甲醇转化制二甲苯催化反应, 结果显示, 双模板剂一步法合成的复合分子筛催化产物油相中芳烃的选择性最高达到66.72%, 芳烃中二甲苯的含量为46.15%, 二甲苯中对二甲苯的含量达到30.75%。这是由于B-EU-1/ZSM-5催化剂的特殊孔道结构具备择形效应, 使得分子动力学直径较小的二甲苯分子优先从其孔道中扩散出来。

关键词: 双模板剂, 一步法, B-EU-1/ZSM-5复合分子筛, 酸性, 孔道结构

Abstract:

B-ZSM-5/EU-1 composite zeolite was synthesized with different hydroxides as alkaline materials. It was found that guiding role of sodium was the strongest by comparing structure-directing effect and appearance characteristics. The surface of B-ZSM-5/EU-1 composite zeolite was smooth without obvious crystal limits. The synthetic samples were investigated by TG-DTG, N₂ adsorption-desorption and NH₃-TPD. The results show that the template weight loss rate of dual-mode-one-step composite zeolite is 5.67% , which is lower than that of mechanical composite zeolite (7.31%). The specific surface area, pore volume and microporous average pore size have significantly enlarged, meanwhile the amount and strength of acid have also increased, which will be favorable for the aromatization trend of methanol and the priority diffusion of xylene from the composite zeolite. The performance of the composite zeolite catalyst was evaluated in conversion of methanol to xylene. The results show that the selectivity of aromatics in the oil phase reaches 66.72% by using a dual-mode composite zeolite as a catalyst, of xylene in the aromatics reaches 46.15%, and of p-xylene in the xylene reaches 30.75%. The above results can be attributed to special pore structure for the catalytic reaction, which benefits for the priority diffusion of xylene with a smaller particle size from the B-EU-1/ZSM-5 zeolite.

Key words: dual-template, one-step-method, B-EU-1/ZSM-5, composite zeolite, acidity, porous structure

中图分类号:

O643
TQ426

杨冬花, 李建华, 王新波, 郭超, 吕爱凝, 董梅, 李晓峰, 窦涛. 双模板剂B-EU-1/ZSM-5复合分子筛的快速合成及催化应用[J]. 无机材料学报, 2016, 31(3): 248-256.

YANG Dong-Hua, LI Jian-Hua, WANG Xin-Bo, GUO Chao, LV Ai-Ning, DONG Mei, Li Xiao-Feng, DOU Tao. Rapid Synthesis and Catalytic Application of B-EU-1/ZSM-5 Composite Zeolite Based on Dual Template[J]. Journal of Inorganic Materials, 2016, 31(3): 248-256.

图/表 9

图1 平衡阳离子为Li+(A)、Na+(B)、K+(C), 合成产物的XRD图谱

Fig. 1 XRD patterns of the samples synthesized in presence of Li+(A), Na+(B) and K+(C)(n(MOH)/n(SiO2): (a) 0.25; (b) 0.3; (c) 0.5; (d) 1)

图2 不同碱源(MOH=LiOH(a)、NaOH(b)、KOH(c))合成 B- EU-1/ZSM-5分子筛SEM照片

Fig. 2 SEM images of B-EU-1/ZSM-5 zeolites samples synthesized by different alkali sources of MOH (LiOH (a), NaOH (b) and KOH (c))

图3 B-EU-1/ZSM-5分子筛的SEM (a)及TEM (b~d)照片

Fig. 3 SEM (a) and TEM (b-d) images of as-synthesized samples B-EU-1/ZSM-5

图4 复合分子筛样品的N2吸附-脱附曲线(a)和孔径分布图(b)

Fig. 4 N2 adsorption/desorption curves (a) and pore size distributions (b) of composite zeolite samples

表1 复合分子筛样品的孔结构参数

Table 1 Pore structure parameters of composite zeolite samples

Zeolite	A_BET/(m²∙g^-1)	V_total/(cm³∙g^-1)	V_micro/(cm³∙g^-1)	D/nm
EU-1	271	0.1914	0.1152	0.6031
ZSM-5	332	0.1908	0.1406	0.5121
B-ZSM-5/EU-1	304	0.1497	0.1029	0.8698

图5 EU-1/ZSM-5复合分子筛的氨程序升温脱附谱图

Fig. 5 NH3-TPD profiles of EU-1/ZSM-5 composite zeolite a: Mechanical mixture; b: Dual-template

图6 EU-1/ZSM-5机械混合(a)和双模板剂法(b)样品的TG-DTG曲线

Fig. 6 TG-DTG curves of EU-1/ZSM-5 mechanical mixture (a) and (b) dual-template

图7 机械EU-1/ZSM-5复合分子筛(a)和B-EU-1/ZSM-5复合分子筛(b)催化产物中芳香烃的分布图

Fig. 7 Distribution of aromatic hydrocarbons in mechanical mixture EU-1/ZSM-5 (a) and B-EU-1/ZSM-5 composite (b)

图8 机械复合EU-1/ZSM-5(a)和B-EU-1/ZSM-5(b)催化产物芳烃中二甲苯的分布图

Fig. 8 Xylene distribution among aromatic hydrocarbon products in mechanical mixture EU-1/ZSM-5 (a) and B-EU-1/ZSM-5 composite (b) zeolite catalysis

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双模板剂B-EU-1/ZSM-5复合分子筛的快速合成及催化应用

Rapid Synthesis and Catalytic Application of B-EU-1/ZSM-5 Composite Zeolite Based on Dual Template

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