使用四乙基氢氧化铵作为有机模板剂和常规硅铝源直接合成SSZ-13沸石分子筛

doi:10.7503/cjcu20200197

高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (7): 1470.doi: 10.7503/cjcu20200197

• 庆祝《高等学校化学学报》复刊40周年专栏 • 上一篇下一篇

使用四乙基氢氧化铵作为有机模板剂和常规硅铝源直接合成SSZ-13沸石分子筛

栾慧敏¹,陈伟²,吴勤明^1,^*(),徐好¹,韩世超¹,孟祥举¹,郑安民²,肖丰收^1,^*()

1.浙江大学化学系, 浙江省应用化学重点实验室, 杭州 310028
2.中国科学院武汉物理与数学研究所, 波谱与原子分子国家重点实验室, 武汉磁共振中心, 武汉 430071

收稿日期:2020-04-11 出版日期:2020-07-10 发布日期:2020-05-11
通讯作者: 吴勤明,肖丰收 E-mail:qinmingwu@zju.edu.cn;fsxiao@zju.edu.cn
基金资助:
国家自然科学基金(21720102001);国家自然科学基金(91634201);国家自然科学基金(21703203)

Direct Synthesis of SSZ-13 Zeolite Using Tetraethylammonium Hydroxide as an Efficient Organic Template in the Presence of Conventional Aluminum and Silicon Sources^†

LUAN Huimin¹,CHEN Wei²,WU Qinming^1,^*(),XU Hao¹,HAN Shichao¹,MENG Xiangju¹,ZHENG Anmin²,XIAO Fengshou^1,^*()

1. Key Laboratory of Applied Chemistry of Zhejiang Province, Department of Chemistry, Zhejiang University, Hangzhou 310028, China
2. State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, National Center for Magnetic Resonance in Wuhan, Wuhan Institute of Physics and Mathematics, the Chinese Academy of Sciences, Wuhan 430071, China

Received:2020-04-11 Online:2020-07-10 Published:2020-05-11
Contact: Qinming WU,Fengshou XIAO E-mail:qinmingwu@zju.edu.cn;fsxiao@zju.edu.cn
Supported by:
† National Natural Science Foundation of China(21720102001);National Natural Science Foundation of China(91634201);National Natural Science Foundation of China(21703203)

1. ESM to 1470-1476.pdf(626KB)

摘要/Abstract

摘要：

使用四乙基氢氧化铵作为有机模板剂, 利用常规铝源和硅源而不需要高硅Y沸石作为起始原料, 同时加入适量的沸石晶种直接合成了SSZ-13沸石分子筛. 所合成的沸石产物结晶度好, 具有良好的水热稳定性, 并在氨选择性催化还原(NH₃-SCR)反应中显示出优异的催化性能, 为其在工业上广泛应用提供了可能.

关键词: SSZ-13沸石, 四乙基氢氧化铵, 常规原料, 直接合成, NH₃-SCR

Abstract:

High silica CHA zeolite(SSZ-13) has been commercially applied in selective catalytic reduction of NO_x with ammonia currently, but the use of costly organic templates of N,N,N-trimethyl-adamantammonium hydroxide(TMAdaOH) in the synthesis strongly limits its industrial application. To solve this problem, it is developed a synthetic route using relatively low-cost organic templates such as tetraethylammonium hydroxide(TEAOH), but in this case it is necessary to use costly high silica Y zeolite as a starting source. In this report, we for the first time show that SSZ-13 zeolite could be synthesized directly from conventional silicon and aluminum sources using TEAOH as an efficient organic template by carefully adjusting the starting gels in the presence of SSZ-13 seeds. The obtained aluminosilicate SSZ-13 product has good crystallinity, uniform crystals, and excellent hydrothermal stability. Furthermore, copper-exchanged SSZ-13 zeolite has excellent catalytic performance in NH₃-SCR reaction before and after hydrothermal treatment. The combination of good catalytic performance with low-cost synthesis offers a good opportunity for wide applications of this zeolite in the future.

Key words: SSZ-13 zeolite, TEAOH, Conventional source, Design synthesis, NH₃-SCR

中图分类号:

O643

TrendMD:

栾慧敏, 陈伟, 吴勤明, 徐好, 韩世超, 孟祥举, 郑安民, 肖丰收. 使用四乙基氢氧化铵作为有机模板剂和常规硅铝源直接合成SSZ-13沸石分子筛. 高等学校化学学报, 2020, 41(7): 1470.

LUAN Huimin, CHEN Wei, WU Qinming, XU Hao, HAN Shichao, MENG Xiangju, ZHENG Anmin, XIAO Fengshou. Direct Synthesis of SSZ-13 Zeolite Using Tetraethylammonium Hydroxide as an Efficient Organic Template in the Presence of Conventional Aluminum and Silicon Sources^†. Chem. J. Chinese Universities, 2020, 41(7): 1470.

图/表 8

Scheme 1 Diagrammatic representation for synthesizing aluminosilicate SSZ-13 zeolite

Fig.1 XRD patterns (A), SEM image(B), N2 sorption isotherms(C), 13C MAS NMR spectra(D), 29Si MAS NMR spectra(E) and 27Al MAS NMR spectrum(F) of SSZ-13-TEA zeolite (D) a. 13C MAS NMR spectrum of as-made SSZ-13-TEA zeolite; b. the liquid 13C NMR spectrum of terraethyl-ammonium cation dissolved in the D2O solution.

Table 1 Synthesis of aluminosilicate SSZ-13 zeolite under diverse condition

Entry^a	Molar ratio			Seed/SiO₂ (mass fraction, %)	Temp./℃	Product^b
Entry^a	Si/Al	Na₂O/SiO₂	H₂O/SiO₂	Seed/SiO₂ (mass fraction, %)	Temp./℃	Product^b
1	10	0.12	20	10	160	Amorphous
2	10	0.16	20	10	160	MOR+CHA+GME
3	10	0.21	20	10	160	MOR+GME
4	20	0.22	20	10	160	MOR+CHA
5	20	0.25	20	10	160	CHA
6	20	0.28	20	10	160	ANA+CHA
7	20	0.25	20	0	160	MOR+CHA
8	40	0.24	20	10	160	MOR+CHA
9	40	0.31	20	10	160	CHA
10	40	0.37	20	10	160	CHA+ANA
11	40	0.31	5	10	160	MFI+CHA
12	40	0.31	35	10	160	CHA+Amorphous
13	60	0.33	20	10	160	CHA
14	∞	0.34	20	10	160	Beta
15	40	0.31	20	10	140	CHA+GME
16	40	0.31	20	10	180	CHA
17	40	0.31	20	10	200	CHA+MOR

Fig.2 XRD patterns of SSZ-13-TEA zeolite crystallized at 0(a), 2(b), 8(c), 16 (d), 24(e), 36(f), 48(g) and 72 h(h), respectively

Fig.3 SEM images of SSZ-13-TEA zeolite crystallized at 0(A), 2(B), 8(C), 6 (D), 24(E), 36(F), 148(G) and 72 h(H), respectively

Fig.4 Position of OSDA molecules within the SSZ-13 framework over TEAOH (tt.tt)(A), TEAOH(tg.tg)(B) and TMAdaOH(C)

Table 2 Stability energies between the organic templates and CHA zeolite framework

Organic template	TEAOH (tt.tt)	TEAOH (tg.tg)	TMAdaOH
Number	3	3	3
Stability energy/(kJ·mo $l Si - 1$ )	-1.33	-1.02	-1.55

Table 2 Stability energies between the organic templates and CHA zeolite framework

Organic template	TEAOH (tt.tt)	TEAOH (tg.tg)	TMAdaOH
Number	3	3	3
Stability energy/(kJ·mo $l Si - 1$ )	-1.33	-1.02	-1.55

Fig.5 NOx conversion vs. temperature over Cu-SSZ-13-TEA and Cu-SSZ-13-TMAda catalysts in NH3-SCR before and after hydrothermal treatment with GHSV of 80000 h-1

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使用四乙基氢氧化铵作为有机模板剂和常规硅铝源直接合成SSZ-13沸石分子筛

Direct Synthesis of SSZ-13 Zeolite Using Tetraethylammonium Hydroxide as an Efficient Organic Template in the Presence of Conventional Aluminum and Silicon Sources^†

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使用四乙基氢氧化铵作为有机模板剂和常规硅铝源直接合成SSZ-13沸石分子筛

Direct Synthesis of SSZ-13 Zeolite Using Tetraethylammonium Hydroxide as an Efficient Organic Template in the Presence of Conventional Aluminum and Silicon Sources†

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Direct Synthesis of SSZ-13 Zeolite Using Tetraethylammonium Hydroxide as an Efficient Organic Template in the Presence of Conventional Aluminum and Silicon Sources^†