http://www.hxtb.org 2005 68 w026-1 1,2,* 1 1 1 ( 1 () CNPC 102249; 2 030024) - - - 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 102249; 2 Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024) 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-41 27 *E-mail: doutao@bjpeu.edu.cn (20476060) 973 (2004CB217806) 2004-03-18 2004-08-05
http://www.hxtb.org 2005 68 w026 - Davis [3] - 1996 kloetstra [4] MCM-41 - - -(1) () (2) ( ) - - 1 1-1 ( ) (60 120 ) (120 180 ) [8,9] [7] Bein [10] 100 β 3d MCM-48 ( 1) 100 8 11d 110 140nm - 2
http://www.hxtb.org 2005 68 w026 1 - 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 60 150, 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/ 0.044 C 16 TMABr/ 120 H 2 O 103.0 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
http://www.hxtb.org 2005 68 w026 Kloetstra [12] PNA-1 PNA-2 MCM-41 TPAOH TPA + Na + MCM-41 120 24h MFI PNA-1 HMS PNA-2 PNA-1 PNA-2 XRD MFI MFI FT-IR 550 560cm -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-41 125pH 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
http://www.hxtb.org 2005 68 w026 - Pinnavaia [17,18] Faujasite ZSM-5 β CTAB MSU-S Faujasite 800 90% 75% Xiao [19~21] β L CTAB MAS-5 MAS-3 XRD MAS-5 800 2h 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-5 84-1.7 250 HMCM-41 80-65.8 250 HMCM-41 80 6h 1.0 250 HMCM-41 80 100% 600 2h 1.0 250 MAS-5 81-78.8 250 MAS-5 81 300h 79.1 250 MAS-5 81 100% 600 4h 78.9 250 MAS-5 80 100% 800 2h 77.5 250 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-1 0.55nm 2,3,6-0.55nm) 5
http://www.hxtb.org 2005 68 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) 13 22 42 90 nm ZSM-5 5 - Y β ZSM-5 MCM-41 SBA-15 - - Inagaki [37] - 6
http://www.hxtb.org 2005 68 w026 - [1] C Zhang, Q Liu, Z Xu et al. Micropor. Mesopor. Mater., 2003,62:157~163. [2] B Samantha, V Jeroen A, K Frank et al. Micropor. Mesopor. Mater., 2003, 66: 21~26. [3] M Davis. Nature, 2002, 417: 813 828. [4] K R Kloetstra, H W Zandbergen, J C Jansen. Micropor. Mater., 1996, 6: 287~293. [5],,., 2001, 29(): 28~29. [6],,., 2003, 11(1): 40~42. [7] A Karlsson, M Stocker, R Schmidt. Micropor. Mesopor. Mater., 1999, 27: 181~192. [8] R H P R Poladi, C L Christopher. J. Solid State Chem., 2002, 167: 363~369. [9] RH P R Poladi, C L Christopher. Micropor. Mesopor. Mater., 2002, 52: 11~18. [10] P Prokesova, S Mintova, J Cejka et al. Micropor. Mesopor. Mater., 2003, 64: 165~174. [11],,. : 1393404A, 2003. [12] K R Kloetdtra, H V Bekkum, C Jansen. Chem. Commun.,1997, 2281~2282. [13] D Trong On, S Kaliaguine. Angew. Chem. Int. Ed, 2001, 17: 40. [14] D Trong On, D Lutic, S Kaliaguine. Micropor. Mesopor. Mater., 2001, 44-45: 435~444. [15] L M Huang, W Guo, P Deng. J. Phys.Chem.B, 2000,104: 2817~2823. [16] L M Huang, H Y Chen, Q Z Li.. :,1998: 500~501. [17] Y Liu, W Zhang,T J Pinnavaia. J. Am. Chem. Soc., 2000, 122: 8791. [18] Y Liu, W Zhang, T J Pinnavaia. Angew. Chem. Int. Ed., 2001, 40: 1255. [19] Z Zhang, Y Han, L Zhu et al. Angew. Chem. Int. Ed. Eng., 2001, 40: 1258. [20] Z T Zhang, Y Han, F S Xiao et al. J. Am. Chem. Soc., 2001, 123: 5014~5021. [21] Y Di, Y Yu, Y Y Sun et al. Micropor. Mesopor. Mater., 2003, 62: 221~228. [22],,., 2002, 5: 759~763. [23] Y Han, S Wu, Y Sun et al. Chem. Mater., 2002, 14: 1144. [24] F S Xiao, Y Han, X J Meng et al. J. Am. Chem. Soc., 2002, 124: 888. [25] W Guo,L Huang, P Deng et al. Micropor. Mesopor. Mater., 2001,44-45: 427~434. [26] W Guo, C Xiong, L Huang et al. J. Mater. Chem, 2001, 11: 1886~1890. [27]Y Goto, Y Fukushima, P Ratu et al. J. Por. Mater., 2002, 9: 43 48. [28] T Sen, J T T Gordon, L John et al. Angew. Chem. Int. Ed., 2003, 42: 4649~4653. [29] V Valtchev, B Schoeman, J Hedlund et al. Zeolites, 1996, 17: 408~415. [30] A Dong, Y Wang, YTang et al. Adv. Mater., 2002, 14: 926~929. [31] R Daw. Nature, 2002, 418: 491. [32] L Tosheva, B Mihailova, V Valtchev et al. Micropor. Mesopor. Mater., 2001, 48: 31~37. [33] I Schmidt, A Boisen, E Gustavsson et al. Chem. Mater., 2001, 13: 4416~4418. [34] Y Tao, H Kanoh, K Kaneko. J. Phys. Chem. B, 2003, 107: 10974~10976. [35] YTao, H Kanoh, K Kaneko. J. Am. Chem. Soc., 2003, 125: 6044~6045. [36] S S Kim, J Shah,T J Pinnavaia. Chem. Mater., 2003, 15: 1664~1668. [37] S Inagaki, S Guan, T Ohsuna et al. Nature, 2002, 416: 304~307. 7