Rapid Synthesis of Aluminophosphate Molecular Sieve AlPO4-5 Under Ambient Pressure and In situ Thermogravimetric-Mass Spectroscopy Investigation of the Crystallization†

doi:10.7503/cjcu20180013

Abstract

Abstract:

The crystallization behavior of the initial gels containing the structure-directing agents of triethylamine, cyclohexylamine or tetraethylammonium hydroxide under ambient pressure and autogenous pressure at elevated temperature was investigated. At 300 or 180 ℃ under ambient pressure, highly crystalline aluminophosphate molecular sieve AlPO₄-5 was rapidly crystallized from the initial gels containing triethylamine, cyclohexylamine or tetraethylammonium hydroxide. When the same initial gels were loaded into autoclaves and heated at 180 ℃ in an oven, three-dimensional open-framework aluminophosphate JDF-20, layered aluminophosphate UT-5, and a mixture containing aluminophosphate molecular sieve AlPO₄-5, were obtained, respectively. The crystallization process of the initial gel containing triethylamine under ambient pressure was investigated with in situ thermogravimetric-mass spectroscopy analysis. It was confirmed that the formation of aluminophosphate molecular sieve AlPO₄-5 under ambient pressure was mainly occurred in the stage of 150—300 ℃. We found that the pressure can significantly affect the structure-directing effect of amines. This finding greatly enhanced the understanding on the formation process and crystallization mechanism of zeolites and open-framework crystals.

Key words: Aluminophosphate, Molecular sieve, Ambient pressure, Autogenous pressure, Thermogravime-tric-mass spectroscopy

CLC Number:

O611.4

TrendMD:

GUO Junhui,YAN Wenfu,SHI Wei,XU Ruren. Rapid Synthesis of Aluminophosphate Molecular Sieve AlPO₄-5 Under Ambient Pressure and In situ Thermogravimetric-Mass Spectroscopy Investigation of the Crystallization^†[J]. Chem. J. Chinese Universities, 2018, 39(5): 841.

Figures/Tables 10

Table 1 Crystallization of Al2O3-P2O5-R-TEG system under ambient pressure and autogenous pressure

Structure-directing agent	Gel composition n(Al₂O₃)∶n(P₂O₅)∶n(R)^*∶n(TEG)	Product
Structure-directing agent	Gel composition n(Al₂O₃)∶n(P₂O₅)∶n(R)^*∶n(TEG)	300 ℃, ambient pressure	180 ℃, ambient pressure	180 ℃, autogenous pressure
TEA	1∶1.8∶4.7∶18	AlPO₄-5	AlPO₄-5	JDF-20^[10]
CHA	1∶2∶4∶30	AlPO₄-5	AlPO₄-5	UT-5^[11]
TEAOH	1∶2∶1∶30	AlPO₄-5	AlPO₄-5	AlPO₄-5+Unknown phase

Fig.1 Simulated XRD patterns of AlPO4-5, JDF-20 and UT-5 and the experimental XRD patterns of the products crystallized from the initial gels containing triethylamine(A, D), cyclohexylamine(B, E) and tetraethylammonium hydroxide(C, F) heated at 300 and 180 ℃ under ambient pressure(A—C) and heated at 180℃ under autogenous pressure(D—F) (A)—(C) a. Simulated AlPO4-5; b. under ambient pressure at 180 ℃; c. under ambient pressure at 300 ℃. (D)—(F) a. under autogenous pressure at 180 ℃; b1. simulated JDF-20; b2. simulated UT-5; b3. simulated AlPO4-5.

Fig.2 XRD patterns of the products crystallized from the initial gels containing triethylamine(a), cyclohexylamine(b) and tetraethylammonium hydroxide(c) heated at 180 ℃(B) in a U-tube device(A)

Fig.3 Simulated XRD pattern of AlPO4-5(a) and the experimental XRD pattern of the product(b) crystallized from the initial gels containing triethylamine heated at 300 ℃ for 1 h under ambient pressure with a heating rate of 10 ℃/min

Fig.4 TG curves of the initial gel containing triethylamine(A), cyclohexylamine(B) and tetraethylammonium hydroxide(C)

Fig.5 XRD patterns of the products crystallized from the initial gels containing triethylamine(A), cyclohexylamine(B) and tetraethylammonium hydroxide(C) heated from room temperature(RT) to different temperatures with a heating rate of 10 ℃/min

Fig.6 Mass spectrum of the volatiles from the initial gel containing triethylamine when the temperature reached 100 ℃ The signals at m/z of 14, 16, 28 and 32 are from N, O, N2 and O2, respectively.

Fig.7 In situ mass spectra of the volatiles from the initial gel containing triethylamine heated at

Fig.8 Evolution of the intensity of the main m/z signals in the temperature range of 40—600 ℃ a. m/z=29; b. m/z=27; c. m/z=18; d. m/z=1; e. m/z=40; f. m/z=2.

Table 2 Possible formula of the fragments with m/z of 1, 2, 18, 27, 29 and 40 containing C, H, O and N

m/z	Fragment
1	H
2	H₂
18	H₂O
27	C₂H₃
29	C₂H₅ , CHO
40	C₂H₂N, C₃H₄

References 40

[1]	Wilson S.T., Lok B. M., Messina C. A., Cannan T. R., Flanigen E. M.,. Am. Chem. Soc., 1982, 104(4), 1146—1147
[2]	Yan W.F., Yu J. H., Shi Z., Miao P., Wang K. X., Wang Y., Xu R. R., Micropor. Mesopor. Mater., 2001, 50, 151—158
[3]	Yan W.F., Yu J. H., Xu R. R., Zhu G. S., Xiao F. S., Han Y., Sugiyama K., Terasaki O., Chem.Mater., 2000, 12(9), 2517—2519
[4]	Bennett J.M., Richardson J. W., Pluth J. J., Smith J. V., Zeolites, 1987, 7(2), 160—162
[5]	Yu J.H., Xu R. R., Acc. Chem. Res., 2003, 36(7), 481—490
[6]	Yu J.H., Xu R. R., Chem. Soc. Rev., 2006, 35(7), 593—604
[7]	Davis M.E., Saldarriaga C., Montes C., Garces J., Crowdert C., Nature, 1988, 331(6158), 698—699
[8]	Huo Q.S., Xu R. R.,. Chem. Soc. Chem. Commun., 1992, (2), 168—169
[9]	Leech M.A., Cowley A. R., Prout K., Chippindale A. M., Chem. Mater., 1998, 10(1), 451—456
[10]	Huo Q.S., Xu R. R., Li S. G., Ma Z. G., Thomas J. M., Jones R. H., Chippindalec A. M., J. Chem. Soc., Chem. Commun., 1992, (12), 875—876
[11]	Oliver S., Kuperman A., Lough A., Ozin G.A., Chem. Commun., 1996, (15), 1761—1762
[12]	Sun Y.Y., Xu J., Wang Q., Wang C., Deng F., Xu R. R.,Yan W. F., Micropor. Mesopor. Mater., 2017, 240, 178—188
[13]	Wang A.T., Xu J., Wang C., Deng F., Xu R. R.,Yan W. F., Chem. Res. Chinese Universities, 2017, 33(4), 513—519
[14]	Hu C.Y., Yan W. F., Xu R. R., Acta Chim. Sinica, 2017, 75(7), 679—685
	胡成玉, 闫文付, 徐如人. 化学学报, 2017, 75(7), 679—685
[15]	Jegatheeswaran S., Cheng C., Cheng C., Micropor. Mesopor. Mater., 2015, 201, 24—34
[16]	Huang P., Xu J., Qi G.D., Deng F., Xu R. R., Yan W. F., Sci. Rep., 2016, 6, 22019
[17]	Wang A.T., Sun Y. Y., Xu R. R.,Yan W. F., Chem.. Chinese Universities, 2017, 38(5), 701—705
	王爱天, 孙洋洋, 徐如人, 闫文付. 高等学校化学学报, 2017, 38(5), 701—705
[18]	Ren X., Komarneni S., Roy D.M., Zeolites, 1991, 11(2), 142—148
[19]	Tian Y., Xu J., Wang Z., Deng F., Xu R.R., Yan W. F., Chem. Res. Chinese Universities, 2017, 33(6), 853—859
[20]	Wang Z., Yan W.F., Xu R. R., Chinese [J]. Inorg. Chem., 2017, 33(9), 1595—1620
	王子, 闫文付, 徐如人. 无机化学学报, 2017, 33(9), 1595—1620
[21]	Tekin R., Bac N., Warzywoda J., Sacco A., J. Cryst. Growth, 2015, 411, 45—48
[22]	Newalkar B.L., Kamath B. V., Jasra R. V., Bhat S. G. T., Zeolites, 1997, 18(4), 286—290
[23]	Wang D.H., Tian P., Fan D., Yang M., Gao B. B., Qiao Y. Y., Wang C., Liu Z. M., [J]. Colloid Interface Sci., 2015, 445, 119—126
[24]	Wang P.C., Zhao Y., Zhang H. B., Yu T., Zhang Y. H., Tang Y., RSC Adv., 2017, 7(38), 23272—23278
[25]	Moliner M., Rey F., Corma A., Angew. Chem. Int.Ed., 2013, 52(52), 13880—13889
[26]	Wang L., Xu Y.P., Wei Y., Duan J. C., Chen A. B., Wang B. C., Ma H. J., Tian Z. J., Lin L. W., [J]. Am. Chem. Soc., 2006, 128(23), 7432—7433
[27]	Camblor M.A., Mifsud A., Pérez P. J., Zeolites, 1991, 11(8), 792—797
[28]	Chen C.M., Jehng J. M., Catal. Lett., 2003, 85(1), 73—80
[29]	Lok B.M., Cannan T. R., Messina C. A., Zeolites, 1983, 3(4), 282—291
[30]	Xin L., Sun H., Xu R.R., Yan W. F., Sci. Rep., 2015, 5, 14940
[31]	Keoh S.H., Chaikittisilp W., Muraoka K., Mukti R. R., Shimojima A., Kumar P., Tsapatsis M., Okubo T., Chem. Mater., 2016, 28(24), 8997—9007
[32]	Lu H.Y., Xu J., Gao P., Yan W. F., Deng F., Xu R. R., Micropor. Mesopor. Mater., 2015, 208, 105—112
[33]	Wagner P., Nakagawa Y., Lee G.S., Davis M. E., Elomari S., Medrud R. C., Zones S. I., [J]. Am. Chem. Soc., 2000, 122(2), 263—273
[34]	Lu T.T., Gao P., Xu J., Wang Y. R., Yan W. F., Yu J. H., Deng F., Mu X. H., Xu R. R., Chinese [J]. Catal., 2015, 36(6), 889—896
[35]	Tian Y., Wang S.R., Yan W. F., Xu R. R., Wang Y. R., Mu X. H., Chem. [J]. Chinese Universities, 2015, 36(3), 428—435
	田野, 王淑荣, 闫文付, 徐如人, 王永睿, 慕旭宏. 高等学校化学学报, 2015, 36(3), 428—435
[36]	van Tendeloo L., Gobechiya E., Breynaert E., Martens J. A., Kirschhock C. E. A., Chem. Commun., 2013, 49(100), 11737—11739
[37]	Lu H.Y., Liu S., Xu J., Yan W. F., Liu Z. Q., Deng F., Xu R. R., Chinese [J]. Inorg. Chem., 2015, 31(9), 1885—1893
	卢慧英, 刘舒, 徐君, 闫文付, 刘志强, 邓风, 徐如人. 无机化学学报, 2015, 31(9), 1885—1893
[38]	Beatriz B.M., Fernando L. A., Joaquín P. P., Luis G. H., Micropor. Mesopor. Mater., 2017, 254, 211—224
[39]	Tong X.Q., Xu J., Li X., Li Y., Yan W. F., Yu J. H., Deng F., Sun H., Xu R. R., Micropor. Mesopor. Mater., 2013, 176, 112—122
[40]	Park M.B., Ahn N. H., Broach R. W., Nicholas C. P., Lewis G. J., Hong S. B., Chem. Mater., 2015, 27(5), 1574—1582

Rapid Synthesis of Aluminophosphate Molecular Sieve AlPO₄-5 Under Ambient Pressure and In situ Thermogravimetric-Mass Spectroscopy Investigation of the Crystallization^†

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 10

References 40

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	LI Haibo, XIAO Changfa, JIANG Long, HUANG Yun, DAN Yi. Copolymerization of Methyl Acrylate and 1-Octene Catalyzed by the Loaded Aluminum Chloride on MCM-41 Molecular Sieve [J]. Chem. J. Chinese Universities, 2021, 42(9): 2974.
[2]	WANG Ye, ZHANG Xiaosi, SUN Lijing, LI Bing, LIU Lin, YANG Miao, TIAN Peng, LIU Zhongyi, LIU Zhongmin. Morphology Control of SAPO Molecular Sieves under the Assistance of Organosilane [J]. Chem. J. Chinese Universities, 2021, 42(3): 683.
[3]	WANG Yong, DONG Biao, SUN Jiao, DONG Delu, SUN Liankun. Synthesis and Spectral Properties of Ag/SiO₂-Al₂O₃ Composite Nanomaterial Based on Molecular Sieve Template [J]. Chem. J. Chinese Universities, 2021, 42(10): 3233.
[4]	SONG Hongling, PENG Yuan, YANG Weishen. Two-dimensional Nanosheets for Ultra-permeable Membrane-Based Gas Separation with High Efficiency [J]. Chem. J. Chinese Universities, 2021, 42(1): 248.
[5]	WANG Binyu, LI Li, LI Jing, JIN Keyan, ZHANG Shaoqing, ZHANG Jianan, YAN Wenfu. Recent Progresses on the Synthesis of Zeolites from the Industrial Solid Wastes [J]. Chem. J. Chinese Universities, 2021, 42(1): 40.
[6]	CHEN Xiao, SHEN Boyuan, XIONG Hao, WEI Fei. Atomic Scale Structure of Beam Sensitive Materials [J]. Chem. J. Chinese Universities, 2021, 42(1): 133.
[7]	HE Zhechao, XIA Kun, WANG Jing, ZHOU Dan, LU Xinhuan, XIA Qinghua. Controllable Synthesis of SAPO-5 Molecular Sieves and Exploration of the Crystallization Process ^† [J]. Chem. J. Chinese Universities, 2020, 41(6): 1224.
[8]	YE Xiaodong, QI Guodong, XU Jun, DENG Feng. Glucose Oxidation on Au-supported SBA-15 Molecular Sieve ^† [J]. Chem. J. Chinese Universities, 2020, 41(5): 960.
[9]	PENG Li, WU Zhengqi, WANG Xing, WANG Boxuan, GU Xuehong. Preparation of Sn-doped MFI Molecular Sieve Membrane by CVD Method and Its Separation Performance for Ethanol/water System [J]. Chem. J. Chinese Universities, 2020, 41(12): 2710.
[10]	LUO Dongxia, LI Bing, WANG Quanyi, TIAN Peng, LIU Zhongyi, LIU Zhongmin. Study on Crystallization Process of SAPO-5 Molecular Sieve [J]. Chem. J. Chinese Universities, 2020, 41(11): 2442.
[11]	ZHAO Yun, WEI Jinjing, ZHOU Yu, ZHU Jixiu, WANG Houyong, CHEN Aimin. Ti-MCM-41 Catalysts for the Ring Opening Reaction of Epoxy Compounds with Amines ^† [J]. Chem. J. Chinese Universities, 2019, 40(9): 1937.
[12]	SHAO Guoquan,ZHU Hui,MA Wei,YAN Pan,MA Jilong. Synthesis of High-performance AlPO₄-14 Zeolite Membranes for Gas Separation ^† [J]. Chem. J. Chinese Universities, 2019, 40(11): 2265.
[13]	WANG Shuang,YU Yue,BAI Pu,LIU Jiancong,LI Lin,SONG Xiaowei. Synthesis of Aluminophosphate Molecular Sieves by Ball Milling and Recrystallization^† [J]. Chem. J. Chinese Universities, 2018, 39(9): 1859.
[14]	LI Chuansong, DU Yanyan, XUE Xuzhi, XIANG Xianzheng, LI Jiusheng, REN Tianhui. Preparation and Performance of Pt/IZM-2 Catalyst on the Hydroisomerization of n-Dodecane^† [J]. Chem. J. Chinese Universities, 2018, 39(4): 729.
[15]	CHANG Xiaowen, YAN Wenfu, SHI Wei, XU Ruren. Influence of Environment Change Around N-atom on the Structure-directing Effect of Methylamine in the Synthesis of Open-framework Aluminophosphates^† [J]. Chem. J. Chinese Universities, 2018, 39(1): 12.