一步法合成多级孔结构ZSM-5分子筛

YU Dao-ke; FU Mei-li; YUAN Ya-hui; SONG Yi-bing; CHEN Jia-yang; FANG Yi-wen

一步法合成多级孔结构ZSM-5分子筛

汕头大学化学系, 广东汕头 515063

基金项目:

the National Fund Cultivation Project NFC 15001

the Science and Technology Plan Project of Guangdong Province 2013B030600001

the Subject and Specialty Construction Special Fund of Guangdong Provincial Higher Education Institution 2012CXZD0024

the Subject and Specialty Construction Special Fund of Guangdong Provincial Higher Education Institution 2013KJCX0081

详细信息

中图分类号: O643.36
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出版历程
- 收稿日期: 2016-04-15
- 修回日期: 2016-07-09
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-11-10

One-step synthesis of hierarchical-structured ZSM-5 zeolite

Department of Chemistry, Shantou University, Shantou 515063, China

Funds:

the National Fund Cultivation Project NFC 15001

the Science and Technology Plan Project of Guangdong Province 2013B030600001

the Subject and Specialty Construction Special Fund of Guangdong Provincial Higher Education Institution 2012CXZD0024

the Subject and Specialty Construction Special Fund of Guangdong Provincial Higher Education Institution 2013KJCX0081

More Information

Corresponding author: FANG Yi-wen, Tel:+86-13502753026, E-mail:ywfang@stu.edu.cn

摘要

摘要: 多级孔结构ZSM-5分子筛的合成过程复杂。利用双模板剂, 通过优化晶化条件(如晶化时间与晶化温度) 和Si/Al物质的量比等一步水热晶化合成了具有多级孔结构的ZSM-5分子筛, 并采用XRD、N₂吸附-脱附、吡啶红外吸脱附、SEM和TEM等方法对样品的晶体结构、孔道结构、表面酸性和形貌等进行了表征。结果表明, 一步法合成多级孔结构ZSM-5分子筛的适宜条件是:晶化温度160-180℃, 晶化时间24-96 h, 反应物组成为SiO₂/Al₂O₃/Na₂O/CTAB/TPABr/H₂O=1/x/0.4/0.05/0.12/280, (x:50-240)。其中, 晶化温度160℃、晶化时间48 h和以Si/Al物质的量比50的凝胶合成的样品具有有序的介孔(平均尺寸3.60 nm) 结构、较高的结晶度和较强的酸性。
- 一步法 /
- 双模板剂 /
- 多级孔结构 /
- ZSM-5分子筛 /
- 合成条件
Abstract: Generally, the process for synthesis of hierarchical-structured ZSM-5 zeolite is complex. Here, the polygonal three-dimensional ZSM-5 zeolite with hierarchical structure was hydrothermally synthesized by one-step synthesis method with dual templates. The effects of crystallization conditions and synthesis gel compositions, including crystallization temperature, crystallization time, Si/Al molar ratio, on the products were investigated for optimizing synthesis conditions. The X-ray diffraction (XRD), N₂ adsorption-desorption experiment, Pyridine adsorption FT-IR (Py-FTIR), scanning electron microscopy (SEM) and transmission electron microscope (TEM) were used to characterize the crystalline structure, pore structure, surface acidity and crystal morphology of products. It was shown that the hierarchical-structured ZSM-5 zeolite can be synthesized under the following conditions: crystallization temperature of 160-180℃, crystallization time of 24-96 h, the SiO₂/Al₂O₃/Na₂O/CTAB/TPABr/H₂O ratio of 1/x/0.4/0.05/0.12/280, (x: 50-240). The sample crystallized at 160℃ for 48 h with a synthesis gel having a Si/Al molar ratio of 50 had uniform cylindrical crystal morphology, high crystallinity and ordered mesoporous structure with a pore diameter of 3.60 nm. It contains both strong Brønsted and Lewis acid sites at 300℃, which contribute to its catalytic properties.
- one-step synthesis method /
- dual templates /
- hierarchical structured /
- ZSM-5 /
- synthesis

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Figure 1 XRD patterns of Z1, Z2, Z3 and Z4

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Figure 2 XRD patterns of samples synthesized at different crystallization temperature

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Figure 3 XRD patterns of samples synthesized with synthesis gels having different Si/Al molar ratios

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Figure 4 XRD patterns of samples synthesized at different crystallization times

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Figure 5 XRD patterns of samples synthesized with the synthesis gels having different Si/Al molar ratios at the crystallization time of 48 h

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Figure 6 N₂ adsorption-desorption isotherms and pore size distributions (insert) of Z9 and Z13

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Figure 7 Py-FTIR spectra of Z9, Z14 and Z13

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Figure 8 SEM (a) and TEM (b, c and e) images of Z9

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Table 1 Conditions for synthesis of different ZSM-5 samples

Sample	Crystallization temperature t/℃	Crystallization time t/h	Molar ratio
Sample	Crystallization temperature t/℃	Crystallization time t/h	Si/Al	CTAB/Si	TPABr/Si
Z1	160	24	50	0.00	0.00
Z2	160	24	50	0.00	0.15
Z3	160	24	50	0.12	0.00
Z4	160	24	50	0.12	0.15
Z5	140	24	50	0.12	0.15
Z6	180	24	50	0.12	0.15
Z7	160	24	25	0.12	0.15
Z8	160	24	120	0.12	0.15
Z9	160	48	50	0.12	0.15
Z10	160	72	50	0.12	0.15
Z11	160	108	50	0.12	0.15
Z12	160	48	25	0.12	0.15
Z13	160	48	40	0.12	0.15
Z14	160	48	80	0.12	0.15
Z15	160	96	50	0.12	0.15

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Table 2 Surface areas and pore parameters of Z9 and Z13

Sample	A_BET^a /(m²·g^-1)	A_micro^b /(m²·g^-1)	v _total^c /(cm³·g^-1)	v _meso^d /(cm³·g^-1)	Pore size^ed/nm
Sample	A_BET^a /(m²·g^-1)	A_micro^b /(m²·g^-1)	v _total^c /(cm³·g^-1)	v _meso^d /(cm³·g^-1)	micropore	mesopore
Z13	479.27	91.31	0.31	0.22	0.66	3.51
Z9	522.16	72.13	0.37	0.23	0.70	3.60
^a: BET model; ^b: t-plot model; ^c: DFT model; ^d: BJH model; ^e: from adsorption branch of N₂ adsorption isotherms

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