高效ZSM-5-L二元复合分子筛的合成及正戊烷芳构化性能

doi:10.7503/cjcu20140274

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (10): 2220.doi: 10.7503/cjcu20140274

高效ZSM-5-L二元复合分子筛的合成及正戊烷芳构化性能

万海^1,^2,³(), 张小雨², 张若杰², 张晓彤², 宋丽娟^1,²()

1. 中国石油大学(华东)化学工程学院, 青岛 266555
2. 辽宁石油化工大学辽宁省石油化工催化科学与技术重点实验室, 抚顺 113001
3. 中国石油抚顺石化公司石油三厂, 抚顺113001

收稿日期:2014-03-28 出版日期:2014-10-10 发布日期:2014-09-18
作者简介:联系人简介: 万海, 男, 高级工程师, 主要从事催化材料制备及应用研究. E-mail: sea3215@126.com 。宋丽娟, 女, 博士, 教授, 博士生导师, 主要从事工业催化及吸附化学研究. E-mail: lsong56@263.net。
基金资助:
国家自然科学基金(批准号: 21076100)资助

Synthesis of High Performance ZSM-5-L Composite Zeolite and Its Catalytic Properities for n-Pentane Aromatization^†

WAN Hai^1,^2,^3,^*(), ZHANG Xiaoyu², ZHANG Ruojie², ZHANG Xiaotong², SONG Lijuan^1,^2,^*()

1. College of Chemistry & Chemical Engineering, China University of Petroleum, Qingdao 266555, China
2. Liaoning Key Laboratory of Petrochemical Catalytic Science and Technology,Liaoning Shihua University, Fushun 113001, China
3. No.3 Refinery of Petro China Fushun Petrochemical Company, Fushun 113001, China

Received:2014-03-28 Online:2014-10-10 Published:2014-09-18
Contact: WAN Hai,SONG Lijuan E-mail:sea3215@126.com;lsong56@263.net
Supported by:
Supported by the National Natural Science Foundation of China(No.21076100)

摘要/Abstract

摘要：

通过优化水热陈化条件制备纳米L沸石, 再采用水热合成结合原位二次晶化法, 合成具有微-介复合孔结构的高效ZSM-5-L二元复合分子筛. 考察了体系pH、二次晶化温度等因素对ZSM-5-L复合分子筛合成的影响, 采用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和傅里叶变换红外光谱(FTIR)等技术对复合分子筛进行表征, 确定了最佳复合条件: pH=10.5~11.5, 晶化温度170 ℃, 晶化时间24 h. ZSM-5-L复合分子筛具有不同于ZSM-5沸石、 L沸石及两者机械混合物的物性特征, 且具有微-介复合孔结构. 以正戊烷催化转化为探针反应, 评价了ZSM-5-L复合分子筛轻烃芳构化反应性能. 在相同反应条件下, ZSM-5-L复合分子筛具有优于2种单分子筛及二者机械混合物的正戊烷芳构化催化性能.

关键词: 水热晶化法, L沸石, ZSM-5沸石, 复合分子筛, 芳构化

Abstract:

Nano-sized L zeolite was synthesized via an improved hydrothermal synthesis method. On this basis, efficiently ZSM-5-L molecular sieves with micro-mesoporous hierarchically structure were obtained through the way of hydrothermal treatment incorporated with in situ recrystallization. X-Ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), Fourier transform infrared spectroscopy(FTIR) were applied to characterize the effect of pH value and recrystallize temperature on the manufacture of the composite ZSM-5-L molecular sieves, and optimum synthesis conditions(pH=10.5—11.5, crystallization temperature 170 ℃, crystallization time 24 h) were confirmed. The structure of the as-synthesized composite ZSM-5-L molecular sieves was micro-mesoporous hierarchically, which was different from that of pure L zeolite, ZSM-5 zeolite and their mechanical mixture zeolite. The light hydrocarbon aromatization properties of the composite ZSM-5-L molecular sieves were evaluated via a n-pentane probe reaction. Compared with the properties of L zeolite, ZSM-5 zeolite and their mechanical mixture zeolite catalyst, the composite ZSM-5-L molecular sieves show superior catalytic performances in aromatization, and exhibit potentially applications as a catalyst in light hydrocarbon aromatization field.

Key words: Hydrothermal crystallization, L zeolite, ZSM-5 zeolite, Composite zeolite, Aromatization

TrendMD:

万海, 张小雨, 张若杰, 张晓彤, 宋丽娟. 高效ZSM-5-L二元复合分子筛的合成及正戊烷芳构化性能. 高等学校化学学报, 2014, 35(10): 2220.

WAN Hai, ZHANG Xiaoyu, ZHANG Ruojie, ZHANG Xiaotong, SONG Lijuan. Synthesis of High Performance ZSM-5-L Composite Zeolite and Its Catalytic Properities for n-Pentane Aromatization^†. Chem. J. Chinese Universities, 2014, 35(10): 2220.

图/表 11

Fig.1 XRD patterns of zeolite L products for different aging time Aging time/h: a.0; b.1; c.2; d.6; e.12.

Fig.2 SEM image of zeolite L

Fig.3 XRD patterns of ZSM-5-L composite zeolite under different pH pH: a. 9; b. 10.5; c. 11.5; d. 12.5.

Fig.4 XRD patterns of the samples with different crystal temperatures Crystal temperature/℃: a. 90; b.130; c.150; d.170; e.190.

Fig.5 FTIR spectra of ZSM-5(a), L(b),ZSM-5+L(c) and ZSM-5-L(d)

Fig.6 SEM images of ZSM-5(A) and ZSM-5-L(B) composite zeolite

Fig.7 TEM images of grain boundary(A) and texture(B) of ZSM-5-L composite zeolite

Fig.8 NH3-TPD profiles of ZSM-5(a), ZSM-5+L(b), ZSM-5-L(c) and L zeolite(d)

Fig.9 N2 adsorption-desorption isotherms and pore size distributions(inset) of ZSM-5-L(a) and ZSM-5+L(b)

Table 1 Structural parameters of ZSM-5-L composite zeolite and mechanical mixture of L and ZSM-5 zeolites

Sample	Specific surface area/(m²·g^-1)			Pore diameter/nm	Pore volume/(cm³·g^-1)
Sample	S_BET		S_micro	S_ext	V_total	V_micro	V_meso
ZSM-5+L	289	240	49	1.63	0.17	0.12	0.05
ZSM-5-L	292	248	44	1.71	0.22	0.13	0.09

Table 2 Reaction results of n-pentane over different catalysts

Catalyst	Conversion(%)	YLP^a(%)	Distribution of aromatics(mass fraction, %)
Catalyst	Conversion(%)	YLP^a(%)	B^b	T^c	EBZ^d	PX^e	MX^f	OX^g	$C 9 +$
ZSM-5	93.4	62.7	12.3	39.6	3.1	7.0	15.9	7.2	14.9
L zeolite	89.5	68.8	12.5	41.9	4.3	6.9	16.6	7.9	9.9
ZSM-5+L	92.7	65.6	11.8	40.5	4.1	7.3	15.6	7.4	13.3
ZSM-5-L	95.7	70.9	13.9	38.5	2.8	9.2	14.7	8.3	12.6

Table 2 Reaction results of n-pentane over different catalysts

Catalyst	Conversion(%)	YLP^a(%)	Distribution of aromatics(mass fraction, %)
Catalyst	Conversion(%)	YLP^a(%)	B^b	T^c	EBZ^d	PX^e	MX^f	OX^g	$C 9 +$
ZSM-5	93.4	62.7	12.3	39.6	3.1	7.0	15.9	7.2	14.9
L zeolite	89.5	68.8	12.5	41.9	4.3	6.9	16.6	7.9	9.9
ZSM-5+L	92.7	65.6	11.8	40.5	4.1	7.3	15.6	7.4	13.3
ZSM-5-L	95.7	70.9	13.9	38.5	2.8	9.2	14.7	8.3	12.6

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高效ZSM-5-L二元复合分子筛的合成及正戊烷芳构化性能

Synthesis of High Performance ZSM-5-L Composite Zeolite and Its Catalytic Properities for n-Pentane Aromatization^†

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高效ZSM-5-L二元复合分子筛的合成及正戊烷芳构化性能

Synthesis of High Performance ZSM-5-L Composite Zeolite and Its Catalytic Properities for n-Pentane Aromatization†

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Synthesis of High Performance ZSM-5-L Composite Zeolite and Its Catalytic Properities for n-Pentane Aromatization^†