Exploring Organic Structure-directing Agents Used for SAPO-34 to Synthesize SSZ-13

doi:10.7503/cjcu20200855

Abstract

Abstract:

The aluminosilicate zeolite SSZ-13 and zeolitic silicoaluminophosphate molecular sieve（SAPO MS） SAPO-34 have been widely used in commercialized catalytic applications， such as the methanol-to-olefins（MTO） process and the selective catalytic reduction of NO_x with NH₃（NH₃-SCR）. Nowadays， a variety of commercialized organic structure-directing agents（OSDAs） have been utilized for preparing SAPO-34， while the OSDAs for synthesizing SSZ-13 still mainly relies on the classical N，N，N-trimethyladamantammonium hydroxide（TMAdaOH）. Therefore， it is of great significance to seek for the suitable OSDAs， which can direct the synthesis of SSZ-13 with higher cost performance and appliable high silicon-to-alumina ratio（SAR）. Herein， three OSDAs used for preparing SAPO-34［diisopropylamine（DIPA）， dipropylamine（DPA） and n-butylamine（nBA）］ were successfully employed for synthesizing SSZ-13 by partial replacing the expensive TMAdaOH with or without the assistance of seeds. Systemic investigation focused on SSZ-13 preparation was explored by powder X-ray diffraction（PXRD） and solid-state nuclear magnetic resonance（ss-NMR） analyses. As a result， the as-synthesized SSZ-13 zeolites possess a tunable range of SARs（11―22） and Cu-SSZ-13 catalysts show excellent NH₃-SCR performance compared with commercialized ones. The crystallization mechanism of SSZ-13 synthesized by DIPA and TMAdaOH were also studied and the addition of DIPA would accelerate the crystallization process， improve the yields， and prevent the formation of amorphous phase. The work presented here might provide new insights for identifying more efficient and commercialized OSDAs for preparing SSZ-13 with tailored properties.

Key words: Porous material, Zeolite, Organic structure-directing agent, SSZ-13, SAPO-34

CLC Number:

O611

TrendMD:

WANG Lei, SUN Tantan, YAN Nana, MA Chao, LIU Xiaona, TIAN Peng, GUO Peng, LIU Zhongmin. Exploring Organic Structure-directing Agents Used for SAPO-34 to Synthesize SSZ-13[J]. Chem. J. Chinese Universities, 2021, 42(6): 1716.

Figures/Tables 7

Table 1 Synthesis of SSZ-13 under different conditions*

Sample	OSDA/Si	TMAda⁺/Si	Si/Al	Seeds/SiO₂	Yield	Product
1	0	0.2	40	10%	74.3%	CHA
2	0.4	0	40	20%	—	No production
3	0.2	0	40	20%	—	No production
4	0.15	0.05	40	10%	73.5%	CHA + MOR + Cri
5	0.15	0.05	27	10%	74.4%	CHA+ MOR + Cri
6	0.15	0.05	20	10%	85.1%	CHA+ MOR + Cri
7	0.1	0.1	40	10%	69.4%	CHA
8	0.1	0.1	27	10%	76.6%	CHA
9	0.1	0.1	20	10%	80.2%	CHA
10	0.1	0.1	20	0	83.1%	CHA
11	0	0.1	20	0	67.4%	CHA + AP
12	0.1	0.1	40	10%	73.6%	CHA
13	0.1	0.1	40	10%	77.5%	CHA

Table 2 Chemical compositions and textural properties of Samples 7―13

Sample	Framework composition^a	SAR^b	Na/Al^c	S^d_micro/(m²·g^-1)	V^d_micro/(cm³·g^-1)
7	Si_34.4Al_1.6O₇₂	21.3	0.20	540.0	0.27
8	Si_33.8Al_2.2O₇₂	15.1	0.22	—	—
9	Si_33.6Al_2.4O₇₂	13.6	0.23	—	—
10	Si_33.0Al_3.0O₇₂	11.3	0.35	529.4	0.26
12	Si_34.1Al_1.9O₇₂	17.6	0.30	538.8	0.26
13	Si_34.0Al_2.0O₇₂	17.1	0.32	547.4	0.27

Fig.1 PXRD patterns of Sample 10(A) and Sample 11(B) during 0―96 hThe insert molecular structures are on behalf of the moment, at which the corresponding organic molecules firstly occurred. The colors of C atoms and N atoms are brown and pink, respectively. H atoms are ignored for clarity.

Fig.2 13C MAS NMR spectra of Sample 10 at different timeThe molecular structures show the chemical shifts affiliations of OSDAs.

Fig.3 Results of NH3?SCR tests for fresh or HTA Sample 10 and seeds with the same SARThe reactant feed gas contains 0.05% NO, 0.05% NH3, 4.5% H2O, and 14% O2 balanced with N2. GHSV=300000 h-1 with 300 mg of catalysts.

Fig.4 13C MAS NMR spectra of SSZ?13 with different SARThe molecular structures show the chemical shifts affiliations of OSDAs.

Fig.5 13C MAS NMR spectra of SSZ?13 prepared with different OSDAsThe molecular structures show the chemical shifts affiliations of OSDAs.

References 29

1	Dusselier M.， Davis M. E.， Chem. Rev.， 2018， 118（11）， 5265―5329
2	Beale A. M.， Gao F.， Lezcano⁃Gonzalez I.， Peden C. H. F.， Szanyi J.， Chem. Soc. Rev.， 2015， 44（20）， 7371―7405
3	Mohan S.， Dinesha P.， Kumar S.， Chem. Eng. J.， 2020， 384， 123253
4	Tian P.， Wei Y.， Ye M.， Liu Z.， ACS Catal.， 2015， 5（3）， 1922―1938
5	Yang M.， Fan D.， Wei Y.， Tian P.， Liu Z.， Adv. Mater.， 2019， 31（50）， 1902181
6	Marchese L.， Frache A.， Gianotti E.， Martra G.， Causà M.， Coluccia S.， Microporous Mesoporous Mater.， 1999， 30（1）， 145―153
7	Qiao Y. Y.， Wu P. F.， Xiang X.， Yang M.， Wang Q. Y.， Tian P.， Liu Z. M.， Chin. J. Catal.， 2017， 38（3）， 574―582（乔昱焱，吴鹏飞，向骁，杨淼，王全义，田鹏，刘中民. 催化学报， 2017， 38（3）， 574―582）
8	Fan D.， Tian P.， Xu S.， Wang D.， Yang Y.， Li J.， Wang Q.， Yang M.， Liu Z.， New J. Chem.， 2016， 40（5）， 4236―4244
9	Aghamohammadi S.， Haghighi M.， Adv. Powder Technol.， 2016， 27（4）， 1738―1749
10	Sadeghpour P.， Haghighi M.， Particuology， 2015， 19， 69―81
11	Zones S. I.， Zeolite SSZ⁃13 and Its Method of Preparation， US Patent 4544538， 1985-10-01
12	Wang Y.， Wang C.， Wang J.， Wang J.， Wang L.， Xu C.， Shen M.， Materials， 2020， 13（8）， 1829
13	Tang L.， Haw K. G.， Zhang Y.， Fang Q.， Qiu S.， Valtchev V.， Microporous Mesoporous Mater.， 2019， 280， 306―314
14	Al Jabri H.， Miyake K.， Ono K.， Nakai M.， Hirota Y.， Uchida Y.， Miyamoto M.， Nishiyama N.， Microporous Mesoporous Mater.， 2019， 278， 322―326
15	Zeng L.， Yu Z.， Sun Z.， Han Y.， Xu Y.， Wu J.， Liang Z.， Wang Z.， Microporous Mesoporous Mater.， 2020， 293， 109789
16	Itakura M.， Inoue T.， Takahashi A.， Fujitani T.， Oumi Y.， Sano T.， Chem. Lett.， 2008， 37（9）， 908―909
17	Cao G.， Mertens M. M.， Guram A. S.， Li H.， Yoder J. C.， Synthesis of Chabazite⁃containing Molecular Sieves and Their Use in the Conversion of Oxygenates to Olefins， US 7754187 B2， 2010-07-13
18	Xiong X.， Yuan D.， Wu Q.， Chen F.， Meng X.， Lv R.， Dai D.， Maurer S.， McGuire R.， Feyen M.， Müller U.， Zhang W.， Yokoi T.， Bao X.， Gies H.， Marler B.， Vos D. E. D.， Kolb U.， Moini A.， Xiao F.， J. Mater. Chem. A， 2017， 5（19）， 9076―9080
19	Chen B.， Xu R.， Zhang R.， Liu N.， Environ. Sci. Technol.， 2014， 48（23）， 13909―13916
20	Xu R.， Zhang R.， Liu N.， Chen B.， Qiao S. Z.， ChemCatChem， 2015， 7（23）， 3842―3847
21	Ren L.， Zhu L.， Yang C.， Chen Y.， Sun Q.， Zhang H.， Li C.， Nawaz F.， Meng X.， Xiao F. S.， Chem. Commun.， 2011， 47（35）， 9789―9791
22	Imai H.， Hayashida N.， Yokoi T.， Tatsumi T.， Microporous Mesoporous Mater.， 2014， 196， 341―348
23	Nasser G. A.， Muraza O.， Nishitoba T.， Malaibari Z.， Al⁃Shammari T. K.， Yokoi T.， Microporous Mesoporous Mater.， 2019， 274， 277―285
24	Martínez⁃Franco R.， Moliner M.， Thogersen J. R.， Corma A.， ChemCatChem， 2013， 5（11）， 3316―3323
25	Guo Y.， Sun T.， Liu X.， Ke Q.， Wei X.， Gu Y.， Wang S.， Chem. Eng. J.， 2019， 358， 331―339
26	Luan H. M.， Chen W.， Wu Q. M.， Xu H.， Han S. C.， Meng X. J.， Zheng A. M.， Xiao F. S.， Chem. J. Chinese Universities， 2020， 41（7）， 1470―1476（栾慧敏，陈伟，吴勤明，徐好，韩世超，孟祥举，郑安民，肖丰收. 高等学校化学学报， 2020， 41（7）， 1470―1476）
27	Wang L.， Sun T. T.， Yan N.N.， Liu X. N.， Ma C.， Xu S. T.， Guo P.， Tian P.， Liu Z. M.， Acta Phys.⁃Chem. Sin.， doi：10.3866/PKU.WHXB202003046（王磊，孙毯毯，闫娜娜，刘晓娜，马超，徐舒涛，郭鹏，田鹏，刘中民. 物理化学学报， doi：10.3866/PKU.WHXB202003046）
28	Song J.， Wang Y.， Walter E. D.， Washton N. M.， Mei D.， Kovarik L.， Engelhard M. H.， Prodinger S.， Wang Y.， Peden C. H. F.， Gao F.， ACS Catal.， 2017， 7（12）， 8214―8227
29	Yan N.， Xu H.， Zhang W.， Sun T.， Guo P.， Tian P.， Liu Z.， Microporous Mesoporous Mater.， 2018， 264， 55―59

[1]	YAO Yiting, LYU Jiamin, YU Shen, LIU Zhan, LI Yu, LI Xiaoyun, SU Baolian, CHEN Lihua. Preparation of Hierarchical Microporous-mesoporous Fe₂O₃/ZSM-5 Hollow Molecular Sieve Catalytic Materials and Their Catalytic Properties for Benzylation [J]. Chem. J. Chinese Universities, 2022, 43(8): 20220090.
[2]	GUO Cheng, ZHANG Wei, TANG Yun. Ordered Mesoporous Materials： History， Progress and Perspective [J]. Chem. J. Chinese Universities, 2022, 43(8): 20220167.
[3]	CHEN Weiqin, LYU Jiamin, YU Shen, LIU Zhan, LI Xiaoyun, CHEN Lihua, SU Baolian. Preparation of Organic Hybrid Mesoporous Beta Zeolite for Alkylation of Mesitylene with Benzyl Alcohol [J]. Chem. J. Chinese Universities, 2022, 43(6): 20220086.
[4]	LI Zhiguang, QI Guodong, XU Jun, DENG Feng. Role of Catalyst Acidity in Glucose Conversion over Sn-Al-β Zeolite as Studied by Solid-state NMR [J]. Chem. J. Chinese Universities, 2022, 43(6): 20220138.
[5]	LI Jiafu, ZHANG Kai, WANG Ning, SUN Qiming. Research Progress of Zeolite-encaged Single-atom Metal Catalysts [J]. Chem. J. Chinese Universities, 2022, 43(5): 20220032.
[6]	MENG Xianglong, YANG Ge, GUO Hailing, LIU Chenguang, CHAI Yongming, WANG Chunzheng, GUO Yongmei. Synthesis of Nano-zeolite and Its Adsorption Performance for Hydrogen Sulfide [J]. Chem. J. Chinese Universities, 2022, 43(3): 20210687.
[7]	WEI Lina, PENG Li, ZHU Feng, GU Pengfei, GU Xuehong. Preparation of Au-CeZr/FAU Catalytic Membranes for Preferential Oxidation of CO in H₂-rich Stream [J]. Chem. J. Chinese Universities, 2022, 43(10): 20220175.
[8]	WANG Kaixuan, LI Ziping, CHEN Xianyang, CUI Yong. Synthesis， Structure and Characterization of a Dihydrophenazine Based 3D Covalent Organic Framework [J]. Chem. J. Chinese Universities, 2022, 43(10): 20220210.
[9]	LUO Qiangqiang, JIN Shaoqing, SUN Hongmin, YANG Weimin. Post-synthesis of Ti-MWW Zeolite via Titanium Incorporation in Liquid Acid Solution [J]. Chem. J. Chinese Universities, 2021, 42(9): 2742.
[10]	LI Yichuan, ZHU Guofu, WANG Yu, CHAI Yongming, LIU Chenguang, HE Shengbao. Effects of Substrate Surface Properties and Precursor Chemical Environment on In⁃situ Oriented Construction of Titanium Silicalite Zeolite Membranes [J]. Chem. J. Chinese Universities, 2021, 42(9): 2934.
[11]	ZHANG Xu, QUE Jiaqian, HOU Yuexin, LYU Jiamin, LIU Zhan, LEI Kunhao, YU Shen, LI Xiaoyun, CHEN Lihua, SU Baolian. Hierarchical Mesoporous-microporous TS-1 Single Crystal Catalysts for Epoxidation of Allyl Chloride [J]. Chem. J. Chinese Universities, 2021, 42(8): 2529.
[12]	LI Jian, YU Mingming, SUN Yuan, FENG Wenhua, FENG Zhaochi, WU Jianfeng. Effect of Aqueous Solution pH on the Oxidation of Methane to Methanol at Low Temperature [J]. Chem. J. Chinese Universities, 2021, 42(3): 776.
[13]	LIU Pengchang, LAI Hua, CHENG Zhongjun, LIU Yuyan. Fabrication of Superwetting Porous Shape Memory Sponge and Its Application in Oil-water Separation [J]. Chem. J. Chinese Universities, 2021, 42(3): 894.
[14]	SHE Peihong, XU Wenzhou, GUAN Buyuan. Synthesis and Application of Silica/carbon-based Large-pore Mesoporous Nanomaterials [J]. Chem. J. Chinese Universities, 2021, 42(3): 671.
[15]	WU Shuaini, ZHU Pengfei, SHI Huaiqi, LI Na, HU Zhaoxia, CHEN Shouwen. Preparation of CoCr_x/SAPO-34 Catalyst and Its Catalytic Combustion Performance for 1，2-Dichloroethane [J]. Chem. J. Chinese Universities, 2021, 42(12): 3731.