Synthesis of Micro/Mesopore Composite Molecular Sieves

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1 w ,2,* ( 1 () CNPC ; ) Synthesis of Micro/Mesopore Composite Molecular Sieves Zhang Ying 1, Dou Tao 1, 2 *, Kang Shanjiao 1, Zheng Yanying 1, Bao Xiaojun 1 ( 1 The Key Laboratory of Catalysis, China National Petroleum Corporation, Department of Chemical Engineering, University of Petroleum, Beijing ; 2 Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan ) Abstract Much attention has been paid to micro/mesopore composite molecular sieves due to the combination of the advantages of both mesoporous molecular sieves and zeolites, possessing bimodel pore systems, and the adjustability of pore size and acidity. In this paper advances in the synthesis of micro/mesopore composite molecular sieves are reviewed and various methods of preparing these composite materials are introduced, such as in-situ crystallization, ex-situ crystallization, crystallization of mesopore walls and nanoclusters self-assembly. Furthermore. The prospect of micro/mesopore composite molecular sieves and the problems during their preparation are also presented. Key words Molecular sieve, Zeolite, Mesoporous materials, Composite, Synthesis methods (<1.0nm) ( EDTA ( ) [1,2] 5 20nm ) MCM * doutao@bjpeu.edu.cn ( ) 973 (2004CB217806)

2 w026 - Davis [3] kloetstra [4] MCM (1) () (2) ( ) ( ) ( ) ( ) [8,9] [7] Bein [10] 100 β 3d MCM-48 ( 1) d nm - 2

3 w Tab.1 In-situ synthesis methods of micro/mesoporous composites C 16 TMACl,, C 16 TMABr, Na 2 SiO 3 9H 2 O, Al 2 (SO 4 ) 3, ZSM-5 C 16 TMABr,, C 6 H 13 Me 3 NBr, C 14 H 29 Me 3 NBr, C 16 TMABr, TPABr, TEOS TEAOH, C 16 TMABr, TEOS, 15SiO 2 /Al 2 O 3 /9Na 2 O/ 5.7C 16 TMACl/720H 2 O 1.0SiO 2 /0.01Al 2 O 3 /0.4C 2 H 5 OH/ 0.2NH 3 /0.75 C 16 TMABr/40H 2 O Na 2 SiO 3 /0.01Al 2 (SO 4 ) 3 / 0.2 C 16 TMABr: 30~50H 2 O 120, 12h FAU/MCM-41 [4] 160, 30h , 24h / MCM-41 D / MCM-41 C 6 /C 14 3/1 175,5d; 100,5d MFI/MCM-41 [7] 10 SiO 2 /0.68 Na 2 O/ 0.054TPABr/ C 16 TMABr/ 120 H 2 O SiO 2 / 1Al 2 O 3 / 36TEAOH/ 0.8 C 16 TMABr 8,20min; 170, 12 48h 100, 3d; 100, 8 11d MFI/MCM-41 (MMM-1) [5] [6] [8,9] β/mcm-48 [10] 2 ( ) Kloetstra [4] NaY NaX MCM-41 FAU/MCM-41 X S + I ZSM-5 F F ZSM-5 ZSM-5 MCM-41 MCM-41 ZSM-5 [11] 3 TPAOH TEAOH TPABr [12] [13,14] [15,16] 3

[13] TPAOH UL-ZSM-5 (EO 20 PO 70 EO 20 ) SiCl 4 -AlCl 4 -CH 3 CH 2 OH 10% TPAOH ( ) 130 Trong On [14] UL-TS-1 EO 20 PO 70 EO 20 TPAOH, UL-ZSM-5 PNA-1 PNA-2 UL-ZSM-5

4 w026 Kloetstra [12] PNA-1 PNA-2 MCM-41 TPAOH TPA + Na + MCM h MFI PNA-1 HMS PNA-2 PNA-1 PNA-2 XRD MFI MFI FT-IR cm -1 MFI ( 1) MFI Trong On [13] TPAOH UL-ZSM-5 (EO 20 PO 70 EO 20 ) SiCl 4 -AlCl 4 -CH 3 CH 2 OH 10% TPAOH ( ) 130 Trong On [14] UL-TS-1 EO 20 PO 70 EO 20 TPAOH, UL-ZSM-5 PNA-1 PNA-2 UL-ZSM-5 UL-TS-1 ( 2) 1 MCM-41(a) PNA-1(b) HMS(c) PNA-2(d) FT-IR [12] Fig.1 FTIR absorption spectra of MCM-41(a), PNA-1(b),HMS(c) and PNA-2(d) [12] 2 UL-TS-1 TEM [13] Fig.2 TEM image of the calcined sample UL-TS-1 [13] [15,16] 100pH 11 2d MCM pH 9.5 ZSM-5 (TPABr) (CTAB) 0.32Na 2 O/1.0SiO 2 /0.03A1 2 O 3 / 0.16CTAB/0.2TPABr/55H 2 O 4 4

5 w026 - Pinnavaia [17,18] Faujasite ZSM-5 β CTAB MSU-S Faujasite % 75% Xiao [19~21] β L CTAB MAS-5 MAS-3 XRD MAS h 300h 1,3,5- MCM-41 ( 2) [22] β CTAB HMB 120 HMB41(25) 2,4-10h2,4-(19.2%) 2,4,6- (42.8%) H-Al-MCM-41 ( 14.5% 33.9%) 2 1,3,5- Tab.2 Catalytic activities in cracking of 1,3,5-triisopropylbenzene on various catalysts n(sio 2 )/n(al 2 O 3 ) / % / HZSM HMCM HMCM h HMCM % 600 2h MAS MAS h MAS % 600 4h MAS % 800 2h Xiao [21,23] ZSM-5 β L P123 MAS-9 MAS-8 MAS-7 MAS-7 MAS-8 MAS-9 Xiao [24] TS-1 P123 MTS-9(1) (2) TiO 2 2,3,6-MTS-9 (18.8%) Ti-MCM-41 TS-1 Ti (TS nm 2,3,6-0.55nm) 5

6 w026 [25,26] β β CTAB β β Goto [27] -- ()- - - I - II 3 - Fig.3 Synthesis route for the synthesis of micro/mesoporous composites [28] [29] ( ) [30,31] [32] - Jacobsen [33] Tao [34,35] Y ZSM-5 Y ( 23nm) ZSM-5( 11nm)Pinnavaia [36] (colloid-imprinted carbons) nm ZSM Y β ZSM-5 MCM-41 SBA Inagaki [37] - 6

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