Preparation, Characterization and Catalytic Performance of Supported Titanium Silicalite-1 Zeolite Membrane Catalyst

doi:10.15541/jim20160460

Abstract

Abstract:

Titanium silicalite-1(TS-1) zeolite membranes were successfully prepared on porous α-Al₂O₃ tubes using hydrothermal synthesis method for epoxidation of propylene to propylene oxide (PO). SEM, XRD, FT-IR, and UV-vis spectroscopy were used to investigate the effects of Ti/Si molar ratio on surface morphology and structure of the TS-1 zeolite membrane. When the Ti/Si molar ratio was set between 0.01 and 0.04, continuous and compact TS-1 zeolite membranes were deposited on the porous support. The obtained TS-1 membranes displayed typical characteristics diffraction peaks of MFI structure. With the increase of the Ti/Si molar ratio, the deposition amounts of the TS-1 zeolites decreased. As a result, some intercrystalline defects were formed and the propylene permeance increased. For the TS-1 membranes prepared with the Ti/Si molar ratio of 0.03-0.04, poor PO selectivity and low PO formation rate were observed in the epoxidation reaction of propylene. This was attributed to the formation of extra-framework TiO₂ in the TS-1 membranes that could catalyze the decomposition of hydrogen peroxide. In contrast, the TS-1 membrane prepared with the Ti/Si ratio of 0.02 exhibited the best catalytic performance. The conversion of hydrogen peroxide, PO selectivity and PO formation rate were 12.43%, 95.80% and 15.78 mmol/(h·g), respectively. Moreover, the regeneration tests revealed that the catalytic ability of the TS-1 membrane was relatively stable after regeneration for 8 times. And the TS-1 membrane was easier to be separated and recovered after reaction.

Key words: titanium silicalite-1 zeolite, zeolite membrane, hydrothermal synthesis, propylene oxide

CLC Number:

TQ174

GUO Yu, LI Dong-Xin, WU Hong-Mei, JIN Yu-Jia, ZHOU Li-Dai, CHEN Qiang-Qiang. Preparation, Characterization and Catalytic Performance of Supported Titanium Silicalite-1 Zeolite Membrane Catalyst[J]. Journal of Inorganic Materials, 2017, 32(6): 631-636.

Figures/Tables 9

Table 1 Preparation conditions of the TS-1 membranes

Sample	Ti/Si ratio	Time/h	Synthesis solution
Sample	Ti/Si ratio	Time/h	TEOS	TPAOH	TBOT	H₂O
T_0.01	0.01	48	1	0.36	0.01	250
T_0.02	0.02	48	1	0.36	0.02	250
T_0.03	0.03	48	1	0.36	0.03	250
T_0.04	0.04	48	1	0.36	0.04	250

Fig. 1 SEM images of porous α-Al2O3 support (a), seeded support (b) and TS-1 membranes with different Ti/Si molar ratios ((c) 0.01, (d) 0.02, (e) 0.03, (f) 0.04)

Fig. 2 SEM images of the TS-1 zeolites collected from bottom of autoclave(a) T0.01; (b) T0.02; (c) T0.03; (d) T0.04

Fig. 3 Particle size of the TS-1 zeolites collected from bottom of autoclave

Fig. 4 Deposition amounts and C3H6 permeances of TS-1 membranes

Fig. 5 XRD patterns (a), FT-IR spectra (b) and UV-Vis spectra (c) of the resulting TS-1 membranes

Fig. 6 Catalytic properties of the TS-1 zeolite membranes in terms of H2O2 conversion, PO yield, PO selectivity (a) and PO formation rate (b) in the epoxidation of propylene

Fig. 7 Ratio of I960/I800 in the FT-IR spectra of the TS-1 membranes

Fig. 8 Catalytic properties of the TS-1 membranes for repeated employment in epoxidation of propylene

References 27

[1]	TARAMASSO M, PEREGO G, NOTARI B. Preparation of Porous Crystalline Synthetic Material Comprised of Silicon and Titanium Oxides. US. Patent, 4410501, 1983.
[2]	CHENG W G, WANG X S, LI G, et al.Highly efficient epoxidation of propylene to propylene oxide over TS-1 using urea + hydrogen peroxide as oxidizing agent.Journal of Catalysis, 2008, 255(2): 343-346.
[3]	NERI C, ANFOSSI B, ESPOSITO A, et al. Process for the Epoxidation of Olefinic Compounds. US. Patent, 4833260, 1989.
[4]	B. NOTARI.Titanium silicalites.Catalysis Today, 1993, 18(2): 163-172.
[5]	LI H, LEI Q, ZHANG X M, et al.Nitrogen-incorporated TS-1 zeolite: synthesis, characterization and application in the epoxidation of propylene.Microporous and Mesoporous Materials, 2012, 147(1): 110-116.
[6]	WRÓBLEWSKA A, MAKUCH E, MIĄDLICKI P. The studies on the limonene oxidation over the microporous TS-1 catalyst.Catalysis Today, 2016, 268: 121-129.
[7]	WANG R P, GUO X W, WANG X S, et al.Effects of preparation conditions and reaction conditions on the epoxidation of propylene with molecular oxygen over Ag/TS-1 in the presence of hydrogen.Applied Catalysis A: General, 2004, 261: 7-13.
[8]	WANG B R, LIN M, ZHU B, et al.The synthesis, characterization and catalytic activity of the hierarchical TS-1 with the intracrystalline voids and grooves.Catalysis Communications, 2016, 75: 69-73.
[9]	MANTEGAZZA M A, LEOFANTI G, PETRINI G, et al.Selective oxidation of ammonia to hydroxylamine with hydrogen peroxide on titanium based catalysts.Studies in Surface Science and Catalysis, 1994, 82: 541-550.
[10]	LIU M, CHANG Z H, WEI H J, et al.Low-cost synthesis of size-controlled TS-1 by using suspended seeds: from screening to scale-up.Applied Catalysis A: General, 2015, 525: 59-67.
[11]	JUNG K T, SHUL Y G.A new method for the synthesis of TS-1 monolithic zeolite.Microporous and Mesoporous Materials, 1998, 21(4/5/6): 281-288.
[12]	LIU X G, LIU Y, XU L, et al.Spreading-wetting method for highly reproducible tertiary growth of perfective bilayer TS-1 membranes.Applied Surface Science, 2015, 343: 77-87.
[13]	MENG L, JIANG H, CHEN R Z, et al.Template-free synthesis of TS-1 zeolite film on tubular mullite support.Applied Surface Science, 2011, 257(6): 1928-1931.
[14]	SHEN C, WANG Y J, DONG C, et al.In situ growth of TS-1 on porous glass beads for ammoximation of cyclohexanone.Chemical Engineering Journal, 2014, 235: 75-82.
[15]	SASIDHARAN M, PATRA A K, KIYOZUMI Y, et al.Fabrication, characterization and catalytic oxidation of propylene over TS-1/Au membranes.Chemical Engineering Science, 2012, 75: 250-255.
[16]	QIU F R, WANG X B, ZHANG X F, et al.Preparation and properties of TS-1 zeolite and film using Sil-1 nanoparticles as seeds.Chemical Engineering Journal, 2009, 147(2/3): 316-322.
[17]	WANG X B, ZHANG X F, LIU H O, et al.Preparation of titanium silicalite-1 catalytic films and application as catalytic membrane reactors.Chemical Engineering Journal, 2010, 156(3): 562-570.
[18]	OYAMA S T, ZHANG X M, LU J Q, et al.Epoxidation of propylene with H2 and O2 in the explosive regime in a packed-bed catalytic membrane reactor.Journal of Catalysis, 2008, 257: 1-4.
[19]	AU L T Y, CHAU J L H, ARISO C T, et al. Preparation of supported sil-1, TS-1 and VS-l membranes effects of Ti and V metal ions on the membrane synthesis and permeation properties.Journal of Membrane Science, 2001, 183(2): 269-291.
[20]	SEBASTIAN V, MOTUZAS J, DIRRIX R W J, et al. Synthesis of capillary titanosilicalite TS-1 ceramic membranes by MW-assisted hydrothermal heating for pervaporation application.Separation and Purification Technology, 2010, 75(3): 249-256.
[21]	MOTUZAS J, MIKUTAVICIUTE R, GERARDIN E, et al.Controlled growth of thin and uniform TS-1 membranes by MW-assisted heating.Microporous and Mesoporous Materials, 2010, 128(1/2/3): 136-143.
[22]	CHEN X S, CHEN P, KITA H.Pervaporation through TS-1 membrane.Microporous and Mesoporous Materials, 2008, 115(1/2): 164-169.
[23]	ZHANG X F, LIU H O, YEUNG K L.Influence of seed size on the formation and microstructure of zeolite silicalite-1 membranes by seeded growth.Materials Chemistry and Physics, 2006, 96(1): 42-50.
[24]	HANSON R M, SHARPLESS K B.Procedure for the catalytic asymmetric epoxidation of allylic alcohols in the presence of molecular sieves.The Journal of Organic Chemistry, 1986, 51(10): 1922-1925.
[25]	TARAMASSO M, PEREGO G, NOTARI B. Preparation of Porous Crystalline Synthetic Material Comprised of Silicon and Titanium Oxides. U.S. Patent, 4410501, 1983.
[26]	MUNUERA G, GONZLEZ-ELIPE R A, FERNNDER A, et al. Spectroscopic characterisation and photochemical behaviour of a titanium hydroxyperoxo compound.Journal of the Chemical Society, Faraday Transactions I, 1989, 85(6): 1279-1290.
[27]	SERRANO D P, UGUINA M A, OVEJERO G, et al.Synthesis of TS-1 by wetness impregnation of amorphous SiO2-TiO2 solids prepared by the Sol-Gel method.Microporous Materials, 1995, 4: 273-282.