Solvent-free rapid synthesis of ZSM-12 zeolite

doi:10.16085/j.issn.1000-6613.2022-1629

Abstract

Abstract:

A solvent-free rapid synthesis method of ZSM-12 zeolite was developed. The method consists of two steps. The first step was to prepare Si-Al precursor. Tetraethylorthosilicate, sodium aluminate, sodium fluoride, methanol and water were mixed and reacted for 3h under agitation at room temperature. After reaction, the liquid phase was evaporated, resulting in the Si-Al precursor. The second step involves the crystallization of Si-Al precursor. The Si-Al precursor was mixed with seeds and tetraethylammonium hydroxide, and subsequently transferred to autoclave for crystallization for 24h at 160℃ to obtain the ZSM-12 zeolite. The crystallization of ZSM-12 zeolite was faster in solvent-free synthesis system than in hydrothermal synthesis system. By using XRD, SEM, solid-state NMR, TG, and FTIR characterizations, the physicochemical properties of Si-Al precursor were analyzed, and the crystallization process of ZSM-12 zeolite was investigated. The results showed that the rapid crystallization was attributed to the addition of seeds and the formation of Si—O—Al in advance in Si-Al precursor. The seeds provided surface for the crystallization of ZSM-12 zeolite, thereby shortening the induction period. The formation of Si—O—Al bonds in the Si-Al precursor promoted structural rearrangement, and shortened the growth period.

Key words: solvent-free method, rapid synthesis, ZSM-12 zeolite, seeds, Si-Al precursor

摘要：

开发出一种无溶剂快速合成ZSM-12分子筛的方法。该方法分为两步。第一步是硅铝前体的制备：将正硅酸乙酯、铝酸钠、氟化钠、甲醇、水混合，在室温搅拌条件下反应3h后蒸干液体，得到硅铝前体。第二步是硅铝前体的晶化：将硅铝前体与晶种、四乙基氢氧化铵模板剂混合均匀后，移入反应釜中，在160℃条件下晶化24h得到ZSM-12分子筛产品。相比于已有的ZSM-12分子筛水热过程，无溶剂合成过程的晶化时间大大缩短。采用XRD、SEM、solid-state NMR、TG、FTIR等手段分析了硅铝前体的物化性质，跟踪了ZSM-12分子筛的晶化过程。结果表明，晶种的加入和硅铝前体中Si—O—Al键的提前构筑是ZSM-12分子筛快速晶化的原因。晶种为ZSM-12分子筛的生长提供表面，缩短诱导期；硅铝前体中Si—O—Al键的提前构筑促进结构重排，从而缩短生长期。

关键词: 无溶剂法, 快速合成, ZSM-12分子筛, 晶种, 硅铝前体

CLC Number:

O611.4

WANG Shuaiqi, WANG Congxin, WANG Xuelin, TIAN Zhijian. Solvent-free rapid synthesis of ZSM-12 zeolite[J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3561-3571.

王帅旗, 王从新, 王学林, 田志坚. 无溶剂快速合成ZSM-12分子筛[J]. 化工进展, 2023, 42(7): 3561-3571.

Figures/Tables 13

References 53

1	DAVIS M E. Ordered porous materials for emerging applications[J]. Nature, 2002, 417(6891): 813-821.
2	王达锐, 孙洪敏, 杨为民. 分子筛催化剂清洁高效制备技术的进展[J]. 化工进展, 2021, 40(4): 1837-1848.
	WANG Darui, SUN Hongmin, YANG Weimin. Advances in the clean and efficient preparation of zeolite catalysts[J]. Chemical Industry and Engineering Progress, 2021, 40(4): 1837-1848.
3	刘佳奇, 尚华, 唐轩, 等. 分子筛基CH₄-N₂分离材料的研究进展[J]. 化工进展, 2019, 38(1): 449-456.
	LIU Jiaqi, SHANG Hua, TANG Xuan, et al. Zeolite based materials for CH₄-N₂ separation[J]. Chemical Industry and Engineering Progress, 2019, 38(1): 449-456.
4	REN Limin, WU Qinming, YANG Chengguang, et al. Solvent-free synthesis of zeolites from solid raw materials[J]. Journal of the American Chemical Society, 2012, 134(37): 15173-15176.
5	WU Qinming, LIU Xiaolong, ZHU Longfeng, et al. Solvent-free synthesis of zeolites from anhydrous starting raw solids[J]. Journal of the American Chemical Society, 2015, 137(3): 1052-1055.
6	JIN Yinying, SUN Qi, QI Guodong, et al. Solvent-free synthesis of silicoaluminophosphate zeolites[J]. Angewandte Chemie International Edition, 2013, 52(35): 9172-9175.
7	WU Qinming, WANG Xiong, QI Guodong, et al. Sustainable synthesis of zeolites without addition of both organotemplates and solvents[J]. Journal of the American Chemical Society, 2014, 136(10): 4019-4025.
8	NG E P, CHATEIGNER D, BEIN T, et al. Capturing ultrasmall EMT zeolite from template-free systems[J]. Science, 2012, 335(6064): 70-73.
9	WANG Yeqing, ZHANG Jian, MENG Xiangju, et al. Sustainable and efficient synthesis of nanosized EMT zeolites under solvent-free and organotemplate-free conditions[J]. Microporous and Mesoporous Materials, 2019, 286: 105-109.
10	LAPIERRE R B, ROHRMAN A C, SCHLENKER J L, et al. The framework topology of ZSM-12: A high-silica zeolite[J]. Zeolites, 1985, 5(6): 346-348.
11	GOPAL S, SMIRNIOTIS P G. Pt/H-ZSM-12 as a catalyst for the hydroisomerization of C₅-C₇ n-alkanes and simultaneous saturation of benzene[J]. Applied Catalysis A: General, 2003, 247(1): 113-123.
12	CHEN C Y, OUYANG X, ZONES S I, et al. Characterization of shape selective properties of zeolites via hydroisomerization of n-hexane[J]. Microporous and Mesoporous Materials, 2012, 164: 71-81.
13	MEHLA S, KRISHNAMURTHY K R, VISWANATHAN B, et al. N-hexadecane hydroisomerization over BTMACl/TEABr/MTEABr templated ZSM-12[J]. Microporous and Mesoporous Materials, 2013, 177: 120-126.
14	ZHANG Kai, LUO Shaojuan, LIU Zewei, et al. In situ fabrication of hierarchical MTW zeolite via nanoparticle assembly by a tailored simple organic molecule[J]. Chemistry: A European Journal, 2018, 24(32): 8133-8140.
15	MILLINI R, FRIGERIO F, BELLUSSI G, et al. A priori selection of shape-selective zeolite catalysts for the synthesis of 2,6-dimethylnaphthalene[J]. Journal of Catalysis, 2003, 217(2): 298-309.
16	WU Wei, WU Weiguo, KIKHTYANIN O V, et al. Methylation of naphthalene on MTW-type zeolites. Influence of template origin and substitution of Al by Ga[J]. Applied Catalysis A: General, 2010, 375(2): 279-288.
17	GOPAL S, YOO K, SMIRNIOTIS P G. Synthesis of Al-rich ZSM-12 using TEAOH as template[J]. Microporous and Mesoporous Materials, 2001, 49(1/2/3): 149-156.
18	DE BAERDEMAEKER T, MÜLLER U, YILMAZ B. Alkali-free synthesis of Al-MTW using 4-cyclohexyl-1,1-dimethylpiperazinium hydroxide as structure directing agent[J]. Microporous and Mesoporous Materials, 2011, 143(2/3): 477-481.
19	MASOUMIFARD N, KALIAGUINE S, KLEITZ F. Synergy between structure direction and alkalinity toward fast crystallization, controlled morphology and high phase purity of ZSM-12 zeolite[J]. Microporous and Mesoporous Materials, 2016, 227: 258-271.
20	吴伟, 黄娟, 吴维果. ZSM-12分子筛研究进展[J]. 化工进展, 2007, 26(7): 921-926.
	WU Wei, HUANG Juan, WU Weiguo. Research progress of ZSM-12 molecular sieve[J]. Chemical Industry and Engineering Progress, 2007, 26(7): 921-926.
21	CHEN Kuizhi, GAN Zhehong, HORSTMEIER S, et al. Distribution of aluminum species in zeolite catalysts: ²⁷Al NMR of framework, partially-coordinated framework, and non-framework moieties[J]. Journal of the American Chemical Society, 2021, 143(17): 6669-6680.
22	LIU Rongsheng, FAN Benhan, ZHI Yuchun, et al. Dynamic evolution of aluminum coordination environments in mordenite zeolite and their role in the dimethyl ether (DME) carbonylation reaction[J]. Angewandte Chemie International Edition, 2022, 61(42): e202210658.
23	IKUNO T, CHAIKITTISILP W, LIU Zhendong, et al. Structure-directing behaviors of tetraethylammonium cations toward zeolite beta revealed by the evolution of aluminosilicate species formed during the crystallization process[J]. Journal of the American Chemical Society, 2015, 137(45): 14533-14544.
24	SEL O, KUANG Daibin, THOMMES M, et al. Principles of hierarchical meso- and macropore architectures by liquid crystalline and polymer colloid templating[J]. Langmuir: the ACS Journal of Surfaces and Colloids, 2006, 22(5): 2311-2322.
25	WANG Shuaiqi, WANG Congxin, LIU Hao, et al. Acceleration effect of sodium halide on zeolite crystallization: ZSM-12 as a case study[J]. Microporous and Mesoporous Materials, 2022, 331: 111652.
26	ZHAO Yang, ZHANG Hongbin, WANG Peicheng, et al. Tailoring the morphology of MTW zeolite mesocrystals: intertwined classical/nonclassical crystallization[J]. Chemistry of Materials, 2017, 29(8): 3387-3396.
27	ŚRODA M, OLEJNICZAK Z. ¹⁹F MAS-NMR studies of strontium oxyfluoride aluminosilicate glass[J]. Journal of Molecular Structure, 2011, 1001(1/2/3): 78-82.
28	GRAHAM T, DEMBOWSKI M, MARTINEZ-BAEZ E, et al. In situ ²⁷Al NMR spectroscopy of aluminate in sodium hydroxide solutions above and below saturation with respect to gibbsite[J]. Inorganic Chemistry, 2018, 57(19): 11864-11873.
29	DEC Steven F, MACIEL Gary E, FITZGERALD John J. Solid-state ²³Na and ²⁷Al MAS NMR study of the dehydration of Na₂O·Al₂O₃·3H₂O[J]. Journal of the American Chemical Society, 1990, 112(25): 9069-9077.
30	BREW D M, MACKENZIE K D. Geopolymer synthesis using silica fume and sodium aluminate[J]. Journal of Materials Science, 2007, 42(11): 3990-3993.
31	POPE E J A, MACKENZIE J D. Sol-gel processing of silica II. The role of the catalyst[J]. Journal of Non-Crystalline Solids, 1986, 87(1/2): 185-198.
32	WU Qinming, MENG Xiangju, GAO Xionghou, et al. Solvent-free synthesis of zeolites: mechanism and utility[J]. Accounts of Chemical Research, 2018, 51(6): 1396-1403.
33	KOLLER H, WÖLKER A, VILLAESCUSA L A, et al. Five-coordinate silicon in high-silica zeolites[J]. Journal of the American Chemical Society, 1999, 121(14): 3368-3376.
34	CAMBLOR M A, CORMA A, VALENCIA S. Characterization of nanocrystalline zeolite beta[J]. Microporous and Mesoporous Materials, 1998, 25(1/2/3): 59-74.
35	REN Nan, SUBOTIĆ B, BRONIĆ J, et al. Unusual pathway of crystallization of zeolite ZSM-5 in a heterogeneous system: Phenomenology and starting considerations[J]. Chemistry of Materials, 2012, 24(10): 1726-1737.
36	MATSUKATA M, OSAKI T, OGURA M, et al. Crystallization behavior of zeolite beta during steam-assisted crystallization of dry gel[J]. Microporous and Mesoporous Materials, 2002, 56(1): 1-10.
37	XU Zhenhua, HUANG Yining, BUTLER I S. The effect of high external pressures on the infrared and Raman spectra of crystalline tetra-n-propylammonium bromide[J]. Vibrational Spectroscopy, 2009, 51(2): 251-254.
38	JACOBS P A, BEYER H K, VALYON J. Properties of the end members in the Pentasil-family of zeolites: Characterization as adsorbents[J]. Zeolites, 1981, 1(3): 161-168.
39	JANSEN J C, VAN DER GAAG F J, VAN BEKKUM H. Identification of ZSM-type and other 5-ring containing zeolites by i.r. spectroscopy[J]. Zeolites, 1984, 4(4): 369-372.
40	SCARANO D, ZECCHINA A, BORDIGA S, et al. Fourier-transform infrared and Raman spectra of pure and Al-, B-, Ti- and Fe-substituted silicalites: Stretching-mode region[J]. Journal of the Chemical Society, Faraday Transactions, 1993, 89(22): 4123-4130.
41	KARBOWIAK T, SAADA M A, RIGOLET S, et al. New insights in the formation of silanol defects in silicalite-1 by water intrusion under high pressure[J]. Physical Chemistry Chemical Physics, 2010, 12(37): 11454-11466.
42	INAGAKI S, OGURA M, INAMI T, et al. Synthesis of MCM-41-type mesoporous materials using filtrate of alkaline dissolution of ZSM-5 zeolite[J]. Microporous and Mesoporous Materials, 2004, 74(1/2/3): 163-170.
43	WANG Yeqing, WANG Xiong, WU Qinming, et al. Seed-directed and organotemplate-free synthesis of TON zeolite[J]. Catalysis Today, 2014, 226: 103-108.
44	ZHANG Haiyan, GUO Qiang, REN Limin, et al. Organotemplate-free synthesis of high-silica ferrierite zeolite induced by CDO-structure zeolite building units[J]. Journal of Materials Chemistry, 2011, 21(26): 9494-9497.
45	OLEKSIAK M D, RIMER J D. Synthesis of zeolites in the absence of organic structure-directing agents: Factors governing crystal selection and polymorphism[J]. Reviews in Chemical Engineering, 2014, 30(1): 1-49.
46	JAIN R, RIMER J D. Seed-Assisted zeolite synthesis: the impact of seeding conditions and interzeolite transformations on crystal structure and morphology[J]. Microporous and Mesoporous Materials, 2020, 300: 110174.
47	ERNST S, JACOBS P A, MARTENS J A, et al. Synthesis of zeolite ZSM-12 in the system (MTEA)₂O-Na₂O-SiO₂-Al₂O₃-H₂O[J]. Zeolites, 1987, 7(5): 458-462.
48	ROMANNIKOV V N, MASTIKHIN V M, HOČEVAR S, et al. Laws observed in the synthesis of zeolites having the structure of ZSM-5 and varying chemical composition[J]. Zeolites, 1983, 3(4): 311-320.
49	LINDNER T, LECHERT H. The influence of fluoride on the crystallization kinetics of zeolite NaY[J]. Zeolites, 1994, 14(7): 582-587.
50	MULLINS W W, SEKERKA R F. Morphological stability of a particle growing by diffusion or heat flow[J]. Journal of Applied Physics, 1963, 34(2): 323-329.
51	MULLINS W W, SEKERKA R F. Stability of a planar interface during solidification of a dilute binary alloy[J]. Journal of Applied Physics, 1964, 35(2): 444-451.
52	LANGER J S. Instabilities and pattern formation in crystal growth[J]. Reviews of Modern Physics, 1980, 52(1): 1-28.
53	LIBBRECHT K G. The physics of snow crystals[J]. Reports on Progress in Physics, 2005, 68(4): 855-895.

晶化时间/h	TEA⁺质量分数/%
0	5.33
12	10.80
18	10.85
24	10.85

晶化时间/h	TEA⁺质量分数/%
0	5.33
12	10.80
18	10.85
24	10.85

[1]	SHAO Guanying, HE Gaohong, JIANG Xiaobin. On-line monitoring and process control of membrane-assisted seeding for ammonium persulfate cooling crystallization [J]. Chemical Industry and Engineering Progress, 2022, 41(12): 6226-6234.
[2]	DU Shaolong，ZHOU Chunshan，LI Zhengfeng，CHEN Hongjing. Degumming of coix lachrymal-jobi seeds miscella by ceramic ultrafiltration membrane [J]. Chemical Industry and Engineering Progree, 2006, 25(9): 1074-.