软模板法合成多级孔沸石分子筛及其催化性能研究进展

doi:10.3969/j.issn.0438-1157.2013.02.002

摘要/Abstract

摘要： 详细介绍了软模板法合成多级孔沸石分子筛及其催化性能。合成多级孔沸石分子筛的软模板主要包括两种类型,一种是含多季铵基团的烷基季铵盐;另一种是双亲有机硅表面活性剂。对采用这两种表面活性剂合成多级孔沸石分子筛的方法以及得到的材料结构特性进行了综述。进一步讨论了这两种方法得到的分子筛的催化性能。关于这些材料的催化性能研究主要有三方面内容:有机大分子化合物合成的活性和选择性,生物质催化热解特性和大分子化合物合成中抗积炭失活性能。

关键词: 多级孔, 沸石分子筛, 软模板, 催化

Abstract: Hierarchical porous zeolites synthesis procedures with soft templates and their catalytic performance are described in detail.The soft templates used for this purpose mainly include two types.One type is the gemini-type, polyquaternary ammonium surfactant, and the other type is the amphiphilic organosilane surfactant.The synthesis techniques with the two types of surfactants and the structural properties of the synthesized zeolites are reviewed.The catalytic performance of synthesized zeolites is discussed.The research on catalytic behavior focuses on three aspects:the activity and selectivity of synthesis of organic macromolecular compounds, the properties of catalytic pyrolysis of biomass, and the slow deposition of coke against deactivation in the synthesis of organic macromolecular compounds.

Key words: hierarchical porous material, zeolite, soft template, catalytic application

中图分类号:

TQ032.4

田野, 李永丹. 软模板法合成多级孔沸石分子筛及其催化性能研究进展[J]. 化工学报, 2013, 64(2): 393-406.

TIAN Ye, LI Yongdan. Hierarchical porous zeolites synthesized with soft templates and their catalytic performance[J]. CIESC Journal, 2013, 64(2): 393-406.

参考文献 53

[1]	Kresge C T, Leonowicz M E, Roth W J, Vartuli J C, Beck J S.Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism[J].Nature, 1992, 359:710-712
[2]	Dessau R M, Valyocsik E W, Goeke N H.Aluminum zoning in ZSM-5 as revealed by selective silica removal[J].Zeolites, 1992, 12(7):776-779
[3]	Corma A, Fornes V, Pergher S B, Maesen T L M, Buglass J G.Delaminated zeolite precursors as selective acidic catalysts[J].Nature, 1998, 396:353-356
[4]	Janssen A H, Koster A J, Jong K P.On the shape of the mesopores in zeolite Y:a three-dimensional transmission electron microscopy study combined with texture analysis[J].J.Phys.Chem.B, 2002, 106(46):11905-11909
[5]	Groen J C, Moulijn J A, Pérez-Ramírez J.Desilication:on the controlled generation of mesoporosity in MFI zeolites[J].J.Mater.Chem., 2006, 16:2121-2131
[6]	Cheng K, Kang J C, Huang S W, You Z Y, Zhang Q H, Ding J S, Hua W Q, Lou Y C, Deng W P, Wang Y. Mesoporous beta zeolite-supported ruthenium nanoparticles for selective conversion of synthesis gas to C5—C11 isoparaffins[J].ACS Catal., 2012, 2(3):441-449
[7]	Verboekend D, Vilé G, Pérez-Ramírez J.Hierarchical Y and USY zeolites designed by post-synthetic strategies[J].Adv.Funct.Mater.,2012, 22(5):916-928
[8]	Jin F, Tian Y, Li Y D.Effect of alkaline treatment on the catalytic performance of ZSM-5 catalyst in pyridine and picolines synthesis[J].Ind.Eng.Chem.Res., 2009, 48(4):1873-1879
[9]	Jin F, Cui Y G, Li Y D.Effect of alkaline and atom-planting treatment on the catalytic performance of ZSM-5 catalyst in pyridine and picolines synthesis[J].Appl.Catal., A, 2008, 350(1):71-78
[10]	Wang J, Groen J C, Yue W B, Zhou W X, Coppens M O.Single-template synthesis of zeolite ZSM-5 composites with tunable mesoporosity[J].Chem.Commun., 2007:4653-4655
[11]	Zhou J, Hua Z L, Shi J L, He Q J, Guo L M, Ruan M L.Synthesis of a hierarchical micro/mesoporous structure by steam-assisted post-crystallization[J].Chem.Eur.J., 2009, 15:12949-12954
[12]	Zhou J, Hua Z L, Liu Z C, Wu W, Zhu Y, Shi J L.Direct synthetic strategy of mesoporous ZSM-5 zeolites by using conventional block copolymer templates and the improved catalytic properties[J].ACS Catal., 2011, 1(4):287-291
[13]	Mller K, Yilmaz B, Jacubinas R M, Müller U, Bein T.One-step synthesis of hierarchical zeolite beta via network formation of uniform nanocrystals[J].J. Am. Chem.Soc., 2011, 133(14):5284-5295
[14]	Neumann G T, Hicks J C.Novel hierarchical cerium-incorporated MFI zeolite catalysts for the catalytic fast pyrolysis of lignocellulosic biomass[J].ACS Catal., 2012, 2(4):642-646
[15]	Chen L H, Xu S T, Li X Y, Tian G, Li Y, Rooke J C, Zhu G S, Qiu S L, Wei Y X, Yang X Y, Liu Z M, Su B L. Multimodal Zr-silicalite-1 zeolite nanocrystal aggregates with interconnected hierarchically micro-meso-macroporous architecture and enhanced mass transport property[J].J.Colloid Interface Sci., 2012, 377:368-374
[16]	Jacobsen C J H, Madsen C, Houzvicka J, Schmidt I, Carlsson A.Mesoporous zeolite single crystals[J].J. Am. Chem.Soc., 2000, 122(29):7116-7117
[17]	Yang Z X, Xia Y D, Mokaya R.Zeolite ZSM-5 with unique supermicropores synthesized using mesoporous carbon as a template[J].Adv.Mater., 2004, 16(8):727-732
[18]	Xin H C, Zhao J, Xu S T, Li J P, Zhang W P, Guo X W, Hensen E J M, Yang Q H, Li C.Enhanced catalytic oxidation by hierarchically structured TS-1 zeolite[J].J.Phys.Chem.C, 2010, 114(14):6553-6559
[19]	Cho H S, Ryoo R.Synthesis of ordered mesoporous MFI zeolite using CMK carbon templates[J].Microporous Mesoporous Mater., 2012, 151:107-112
[20]	Lee J, Hong U G, Hwang S, Youn M H, Song I K.Production of light olefins through catalytic cracking of C5 raffinate over carbon-templated ZSM-5[J].Fuel Process Technol., 2012, doi:10.1016/j.fuproc. 2012. 03. 005
[21]	Choi M, Cho H S, Srivastava R, Venkatesan C, Choi D H, Ryoo R.Amphiphilic organosilane-directed synthesis of crystalline zeolite with tunable mesoporosity[J].Nature Materials, 2006, 5:718-723
[22]	Choi M, Na K, Kim J, Sakamoto Y, Terasaki O, Ryoo R.Stable single-unit-cell nanosheets of zeolite MFI as active and long-lived catalysts[J].Nature, 2009, 461:246-249
[23]	Na K, Jo C, Kim J, Cho K, Jung J, Seo Y, Messinger R J, Chmelka B F, Ryoo R.Directing zeolite structures into hierarchically nanoporous architectures[J].Science, 2011, 333:328-332
[24]	Xiao F S, Wang L F, Yin C Y, Lin K F, Di Y, Li J X, Xu R R, Su D S, Schlgl R, Yokoi T, Tatsumi T.Catalytic properties of hierarchical mesoporous zeolites templated with a mixture of small organic ammonium salts and mesoscale cationic polymers[J].Angew.Chem.Int.Ed., 2006, 45(19):3090-3093
[25]	Song J W, Ren L M, Yin C Y, Ji Y Y, Wu Z F, Li J X, Xiao F S.Stable, porous, and bulky particles with high external surface and large pore volume from self-assembly of zeolite nanocrystals with cationic polymer[J].J. Phys. Chem.C, 2008, 112(23):8609-8613
[26]	Wang L F, Zhang Z, Yin C Y, Shan Z C, Xiao F S. Hierarchical mesoporous zeolites with controllable mesoporosity templated from cationic polymers[J].Microporous Mesoporous Mater., 2010, 131(1/2/3):58-67
[27]	Corma A.Catalysts made thinner[J].Nature, 2009, 461:182-183
[28]	Na K, Choi M, Park W, Sakamoto Y, Terasaki O, Ryoo R. Pillared MFI zeolite nanosheets of a single-unit-cell thickness[J].J.Am.Chem.Soc., 2010, 132(12):4169-4177
[29]	Na K, Park W, Seo Y, Ryoo R.Disordered assembly of MFI zeolite nanosheets with a large volume of intersheet mesopores[J].Chem.Mater., 2011, 23(5):1273-1279
[30]	Mller K, Bein T.Pores within pores—How to craft ordered hierarchical zeolites[J].Science, 2011, 333:297-298
[31]	Na K, Jo C, Kim J, Ahn W S, Ryoo R.MFI titanosilicate nanosheets with single-unit-cell thickness as an oxidation catalyst using peroxides[J].ACS Catal., 2011, 1(8):901-907
[32]	Wang J G, Xu L, Zhang K, Peng H, Wu H H, Jiang J G, Liu Y M, Wu P.Multilayer structured MFI-type titanosilicate:synthesis and catalytic properties in selective epoxidation of bulky molecules[J].J.Catal., 2012, 288:16-23
[33]	Serrano D P, Aguado J, Escola J M, Rodriguez J M, Peral A.Hierarchical zeolites with enhanced textural and catalytic properties synthesized from organofunctionalized seeds[J].Chem.Mater., 2006,18(10):2462-2464
[34]	Serrano D P, Aguado J, Escola J M, Rodriguez J M, Peral A.Effect of the organic moiety nature on the synthesis of hierarchical ZSM-5 from silanized protozeolitic units[J].J.Mater.Chem., 2008, 18(35):4210-4218
[35]	Aguado J, Serrano D P, Rodriguez J M.Zeolite Beta with hierarchical porosity prepared from organofunctionalized seeds[J].Microporous Mesoporous Mater., 2008, 115(3):504-513
[36]	Chmelka B F.Large molecules welcome[J].Nature, 2006, 5:681-682
[37]	Wang H, Pinnavaia T J.MFI zeolite with small and uniform intracrystal mesopores[J].Angew.Chem.Int.Ed., 2006, 45(45):7603-7606
[38]	Xue Z T, Zhang T, Ma J H, Miao H X, Fan W M, Zhang Y Y, Li R F.Accessibility and catalysis of acidic sites in hierarchical ZSM-5 prepared by silanization[J].Microporous Mesoporous Mater., 2012, 151:271-276
[39]	Koekkoek A J J, Tempelman C H L, Degirmenci V, Guo M L, Feng Z C, Li C, Hensen E J M.Hierarchical zeolites prepared by organosilane templating:a study of the synthesis mechanism and catalytic activity[J].Catal.Today, 2011, 168(1):96-111
[40]	Choi M, Srivastava R, Ryoo R.Organosilane surfactant-directed synthesis of mesoporous aluminophosphates constructed with crystalline microporous frameworks[J].Chem.Commun., 2006(42):4380-4382
[41]	Danilina N, Castelanelli S A, Troussard E, Bokhoven J A.Influence of synthesis parameters on the catalytic activity of hierarchical SAPO-5 in space-demanding alkylation reactions[J].Cataly.Today, 2011, 168(1):80-85
[42]	Kim J, Bhattacharjee S, Jeong K E, Jeong S Y, Choi M, Ryoo R, Ahn W S.CrAPO-5 catalysts having a hierarchical pore structure for the selective oxidation of tetralin to 1-tetralone[J].New J.Chem., 2010, 34(12):2971-2978
[43]	Sanz R, Serrano D P, Pizarro P, Moreno I.Hierarchical TS-1 zeolite synthesized from SiO2 TiO2 xerogels imprinted with silanized protozeolitic units[J].Chem.Eng.J., 2011, 171(3):1428-1438
[44]	Shetti V N, Kim J, Srivastava R, Choi M, Ryoo R. Assessment of the mesopore wall catalytic activities of MFI zeolite with mesoporous/microporous hierarchical structures[J].J.Catal., 2008, 254(2):296-303
[45]	Choi M, Lee D H, Na K, Yu B W, Ryoo R.High catalytic activity of Pd2+-exchanged mesoporous sodalite and NaA zeolite for bulky aryls coupling:reusability under aerobic condition[J].Angew.Chem.Int.Ed., 2009, 48(20):3673-3676
[46]	Shanbhag G V, Choi M, Kim J, Ryoo R.Mesoporous sodalite:a novel, stable solid catalyst for base-catalyzed organic transformations[J].J.Catal., 2009, 264(1):88-92
[47]	Park H J, Heo H S, Jeon J K, Kim J, Ryoo R, Jeong K E, Park Y K.Highly valuable chemicals production from catalytic upgrading of radiata pine sawdust-derived pyrolytic vapors over mesoporous MFI zeolites[J].Appl.Catal.B, 2010, 95(3/4):365-373
[48]	Park K H, Park H J, Kim J, Ryoo R, Jeon J K, Park J, Park Y K.Application of hierarchical MFI zeolite for the catalytic pyrolysis of Japanese larch[J].J. Nanosci. Nanotechno., 2010, 10(1):355-359
[49]	Kim S S, Heo H S, Kim S G, Ryoo R, Kim J, Jeon J K, Park S H, Park Y K.Catalytic pyrolysis of oil fractions separated from food waste leachate over nanoporous acid catalysts[J].J.Nanosci.Nanotechno., 2011, 11(7):6167-6171
[50]	Foster A J, Jae J, Cheng Y T, Huber G W, Lobo R F. Optimizing the aromatic yield and distribution from catalytic fast pyrolysis of biomass over ZSM-5[J].Appl.Catal.A, 2012, 423:154-161
[51]	Kim J, Choi M, Ryoo R.Effect of mesoporosity against the deactivation of MFI zeolite catalyst during the methanol-to-hydrocarbon conversion process[J].J.Catal., 2010, 269(1):219-228
[52]	Srivastava R, Choi M, Ryoo R.Mesoporous materials with zeolite framework:remarkable effect of the hierarchical structure for retardation of catalyst deactivation[J].Chem.Commun., 2006(43):4489-4491
[53]	Kim J, Park W, Ryoo R.Surfactant-directed zeolite nanosheets:a high-performance catalyst for gas-phase Beckmann rearrangement[J].ACS Catal., 2011, 1(4):337-341