以胆碱为绿色无毒有机结构导向剂合成高硅Y型分子筛（英文）
|
摘要
分子筛作为一类重要的无机多孔晶体材料,由于其规整的孔道结构以及优异的酸性质等特点,在催化剂、吸附剂和离子交换床等许多领域有着重要而广泛的应用.而现代分子筛制备方法的发展主要得益于有机结构导向剂(OSDA)在分子筛合成中的广泛使用.但是,大部分OSDA都具有剧毒、价格昂贵、制备方法繁琐等缺点,因而限制了其大规模应用.高硅Y型分子筛的合成研究也面临同样的问题.Y型分子筛具有十二元环孔口和三维孔道结构,是目前催化裂化催化剂中的主要活性组分.目前,通过常规合成方法无法获得硅铝比大于6.0的Y型分子筛,无法满足石油化工对其酸性的要求.目前工业上主要通过后处理法得到高硅Y沸石,但该方法繁杂的后处理过程、不均匀的化学分布、大量损失的结晶度以及严重的环境污染促使人们开发直接合成高硅Y型分子筛的新方法以替代后处理过程.此外,使用OSDA一步法合成的高硅铝比Y型分子筛具有优异的热和水热稳定性.因此,使用OSDA一步直接合成高硅Y型分子筛在材料合成和催化领域一直备受关注.然而,目前尚未见关于绿色OSDA用于高硅Y型分子筛合成的报道.本研究首次将氢氧化胆碱或氯化胆碱作为一种新型、绿色、廉价的OSDA引入到高硅Y分子筛的合成凝胶体系,成功合成了高结晶度且硅铝比大于6.0的高硅Y型分子筛.实验详细考察了合成条件对硅铝比的影响,并采用XRD, XRF, NMR,TG以及N2物理吸附等表征手段研究了合成样品的物理化学性质.表征结果证明,胆碱阳离子作为一个稳定的OSDA存在于分子筛的孔结构中,并且取代了部分Na~+以平衡分子筛骨架的负电荷,因此胆碱的使用可使样品的硅铝比提高并具有更加优异的热稳定性和水热稳定性.实验确定了Na~+和OSDA~+在高硅Y分子筛合成中的竞争关系.大量的实验证据表明, Na~+进料比例对FAU骨架硅铝比有决定性的影响.首次提出采用氢氧根离子型OSDA是一种直接有效提高骨架硅铝比的方法.
Zeolite synthesis in contemporary chemical industries is predominantly conducted using organic structure-directing agents(OSDAs), which are chronically hazardous to humans and the environment.It is a growing trend to develop an eco-friendly and nuisanceless OSDA for zeolite synthesis.Herein, choline is employed as a non-toxic and green OSDA to synthesize high silica Y zeolite with SiO_2/Al_2 O_3 ratios of 6.5–6.8. The prepared Y zeolite samples exhibited outstanding(hydro)thermal stability at ultrahigh temperature owing to the higher SiO_2/Al_2 O_3 ratio. The XRF, SEM, 29 Si-NMR and13 Na~+ results suggested that choline plays a structure-directing role in the synthesis of Y zeolite,while the feed molar fraction of Na+ is a crucial determinant for the framework SiO_2/Al_2 O_3 ratio and the crystal morphology.
Zeolite synthesis in contemporary chemical industries is predominantly conducted using organic structure-directing agents(OSDAs), which are chronically hazardous to humans and the environment.It is a growing trend to develop an eco-friendly and nuisanceless OSDA for zeolite synthesis.Herein, choline is employed as a non-toxic and green OSDA to synthesize high silica Y zeolite with SiO_2/Al_2 O_3 ratios of 6.5–6.8. The prepared Y zeolite samples exhibited outstanding(hydro)thermal stability at ultrahigh temperature owing to the higher SiO_2/Al_2 O_3 ratio. The XRF, SEM, 29 Si-NMR and13 Na~+ results suggested that choline plays a structure-directing role in the synthesis of Y zeolite,while the feed molar fraction of Na+ is a crucial determinant for the framework SiO_2/Al_2 O_3 ratio and the crystal morphology.
引文
[1]R.M.Barrer,Zeolites,1981,1,130-140.
[2]M.E.Davis,R.F.Lobo,Chem.Mater.,1992,4,756-768.
[3]M.E.Davis,Nature,2002,417,813-821.
[4]A.Corma,J.Catal.,2003,216,298-312.
[5]W.Vermeiren,J.P.Gilson,Top.Catal.,2009,52,1131-1161.
[6]G.T.Kerr,G.T.Kokotailo,J.Am.Chem.Soc.,1961,83,4675.
[7]C.S.Cundy,P.A.Cox,Chem.Rev.,2003,103,663-702.
[8]L.A.Villaescusa,W.Zhou,R.E.Morris,P.A.Barrett,J.Mater.Chem.,2004,14,1982-1987.
[9]X.Meng,F.S.Xiao,Chem.Rev.,2014,114,1521-1543.
[10]L.Ren,L.Zhu,C.Yang,Y.Chen,Q.Sun,H.Zhang,C.Li,F.Nawaz,X.Meng,F.S.Xiao,Chem.Commun.,2011,47,9789-9791.
[11]S.I.Zones,S.J.Hwang,Chem.Mater.,2002,14,313-320.
[12]S.Liu,L.Li,C.Li,X.Xiong,F.S.Xiao,J.Porous Mater.,2008,15,295-301.
[13]D.W.Breck,US Patent,3130007A,1964.
[14]P.K.Maher,E.W.Albers,C.V.McDaniel,US Patent,3639099A,1972.
[15]J.P.Arhancet,M.E.Davis,Chem.Mater.,1991,3,567-569.
[16]S.M.Babitz,B.A.Williams,J.T.Miller,R.Q.Snurr,W.Q.Haag,H.H.Kung,Appl.Catal.,A,1999,179,71-86.
[17]M.A.Camblor,A.Corma,A.Martínez,F.A.Mocholí,J.P.Pariente,Appl.Catal.,1989,55,65-74.
[18]E.F.S.Aguiar,M.L.M.Valle,M.P.Silva,D.F.Silva,Zeolites,1995,15,620-623.
[19]R.A.Beyerlein,G.B.McVicker,L.N.Yacullo,J.J.Ziemiak,J.Phys.Chem.,1988,92,1967-1970.
[20]B.Xu,S.Bordiga,R.Prins,J.A.van Bokhoven,Appl.Catal.A,2007,333,245-253.
[21]M.D.Oleksiak,K.Muraoka,M.F.Hsieh,M.T.Conato,A.Shimojima,T.Okubo,W.Chaikittisilp,J.D.Rimer,Angew.Chem.Int.Ed.,2017,56,13366-13371.
[22]L.Kubelková,S.Beran,A.Malecka,V.M.Mastikhin,Zeolites,1989,9,12-17.
[23]G.Garralon,V.Fornes,A.Corma,Zeolites,1988,8,268-272.
[24]J.Datka,W.Kolidziejski,J.Klinowski,B.Sulikowski,Catal.Lett.,1993,19,159-165.
[25]E.F.T.Lee,L.V.C.Rees,J.Chem.Soc.,Faraday Trans.1,1987,83,1531-1537.
[26]X.H.Du,X.L.Li,H.T.Zhang,X.H.Gao,Chin.J.Catal.,2016,37,316-323.
[27]F.Delprato,L.Delmotte,J.L.Guth,L.Huve,Zeolites,1990,10,546-552.
[28]F.Dougnier,J.Patarin,J.L.Guth,D.Anglerot,Zeolites,1993,13,122-127.
[29]L.Zhu,L.Ren,S.Zeng,C.Yang,H.Zhang,X.Meng,M.Rigutto,A.van der Made,F.S.Xiao,Chem.Commun.,2013,49,10495-10497.
[30]D.Yuan,D.He,S.Xu,Z.Song,M.Zhang,Y.Wei,Y.He,S.Xu,Z.Liu,Y.Xu,Microporous Mesoporous Mater.,2015,204,1-7.
[31]D.He,D.Yuan,Z.Song,Y.Tong,Y.Wu,S.Xu,Y.Xu,Z.Liu,Chem.Commun.,2016,52,12765-12768.
[32]S.H.Zeisel,Ann.Nutr.Metab.,2012,61,254-258.
[33]F.Liu,M.Audemar,K.De Oliveira Vigier,D.Cartigny,J.M.Clacens,M.F.C.Gomes,A.A.H.Padua,F.De Campo,F.Jerome,Green Chem.,2013,15,3205-3213.
[34]A.J.Perrotta,C.Kibby,B.R.Mitchell,E.R.Tucci,J.Catal.,1978,55,240-249.
[35]B.Chen,R.Xu,R.Zhang,N.Liu,Environ.Sci.Technol.,2014,48,13909-13916.
[36]X.Zhao,H.Wang,C.Kang,Z.Sun,G.Li,X.Wang,Microporous Mesoporous Mater.,2012,151,501-505.
[37]A.I.Lupulescu,J.D.Rimer,Angew.Chem.Int.Ed.,2012,51,3345-3349.
[38]A.I.Lupulescu,M.Kumar,J.D.Rimer,J.Am.Chem.Soc.,2013,135,6608-6617.
[39]A.Burton,Catal.Rev.-Sci.Eng.,2018,60,132-175.
[2]M.E.Davis,R.F.Lobo,Chem.Mater.,1992,4,756-768.
[3]M.E.Davis,Nature,2002,417,813-821.
[4]A.Corma,J.Catal.,2003,216,298-312.
[5]W.Vermeiren,J.P.Gilson,Top.Catal.,2009,52,1131-1161.
[6]G.T.Kerr,G.T.Kokotailo,J.Am.Chem.Soc.,1961,83,4675.
[7]C.S.Cundy,P.A.Cox,Chem.Rev.,2003,103,663-702.
[8]L.A.Villaescusa,W.Zhou,R.E.Morris,P.A.Barrett,J.Mater.Chem.,2004,14,1982-1987.
[9]X.Meng,F.S.Xiao,Chem.Rev.,2014,114,1521-1543.
[10]L.Ren,L.Zhu,C.Yang,Y.Chen,Q.Sun,H.Zhang,C.Li,F.Nawaz,X.Meng,F.S.Xiao,Chem.Commun.,2011,47,9789-9791.
[11]S.I.Zones,S.J.Hwang,Chem.Mater.,2002,14,313-320.
[12]S.Liu,L.Li,C.Li,X.Xiong,F.S.Xiao,J.Porous Mater.,2008,15,295-301.
[13]D.W.Breck,US Patent,3130007A,1964.
[14]P.K.Maher,E.W.Albers,C.V.McDaniel,US Patent,3639099A,1972.
[15]J.P.Arhancet,M.E.Davis,Chem.Mater.,1991,3,567-569.
[16]S.M.Babitz,B.A.Williams,J.T.Miller,R.Q.Snurr,W.Q.Haag,H.H.Kung,Appl.Catal.,A,1999,179,71-86.
[17]M.A.Camblor,A.Corma,A.Martínez,F.A.Mocholí,J.P.Pariente,Appl.Catal.,1989,55,65-74.
[18]E.F.S.Aguiar,M.L.M.Valle,M.P.Silva,D.F.Silva,Zeolites,1995,15,620-623.
[19]R.A.Beyerlein,G.B.McVicker,L.N.Yacullo,J.J.Ziemiak,J.Phys.Chem.,1988,92,1967-1970.
[20]B.Xu,S.Bordiga,R.Prins,J.A.van Bokhoven,Appl.Catal.A,2007,333,245-253.
[21]M.D.Oleksiak,K.Muraoka,M.F.Hsieh,M.T.Conato,A.Shimojima,T.Okubo,W.Chaikittisilp,J.D.Rimer,Angew.Chem.Int.Ed.,2017,56,13366-13371.
[22]L.Kubelková,S.Beran,A.Malecka,V.M.Mastikhin,Zeolites,1989,9,12-17.
[23]G.Garralon,V.Fornes,A.Corma,Zeolites,1988,8,268-272.
[24]J.Datka,W.Kolidziejski,J.Klinowski,B.Sulikowski,Catal.Lett.,1993,19,159-165.
[25]E.F.T.Lee,L.V.C.Rees,J.Chem.Soc.,Faraday Trans.1,1987,83,1531-1537.
[26]X.H.Du,X.L.Li,H.T.Zhang,X.H.Gao,Chin.J.Catal.,2016,37,316-323.
[27]F.Delprato,L.Delmotte,J.L.Guth,L.Huve,Zeolites,1990,10,546-552.
[28]F.Dougnier,J.Patarin,J.L.Guth,D.Anglerot,Zeolites,1993,13,122-127.
[29]L.Zhu,L.Ren,S.Zeng,C.Yang,H.Zhang,X.Meng,M.Rigutto,A.van der Made,F.S.Xiao,Chem.Commun.,2013,49,10495-10497.
[30]D.Yuan,D.He,S.Xu,Z.Song,M.Zhang,Y.Wei,Y.He,S.Xu,Z.Liu,Y.Xu,Microporous Mesoporous Mater.,2015,204,1-7.
[31]D.He,D.Yuan,Z.Song,Y.Tong,Y.Wu,S.Xu,Y.Xu,Z.Liu,Chem.Commun.,2016,52,12765-12768.
[32]S.H.Zeisel,Ann.Nutr.Metab.,2012,61,254-258.
[33]F.Liu,M.Audemar,K.De Oliveira Vigier,D.Cartigny,J.M.Clacens,M.F.C.Gomes,A.A.H.Padua,F.De Campo,F.Jerome,Green Chem.,2013,15,3205-3213.
[34]A.J.Perrotta,C.Kibby,B.R.Mitchell,E.R.Tucci,J.Catal.,1978,55,240-249.
[35]B.Chen,R.Xu,R.Zhang,N.Liu,Environ.Sci.Technol.,2014,48,13909-13916.
[36]X.Zhao,H.Wang,C.Kang,Z.Sun,G.Li,X.Wang,Microporous Mesoporous Mater.,2012,151,501-505.
[37]A.I.Lupulescu,J.D.Rimer,Angew.Chem.Int.Ed.,2012,51,3345-3349.
[38]A.I.Lupulescu,M.Kumar,J.D.Rimer,J.Am.Chem.Soc.,2013,135,6608-6617.
[39]A.Burton,Catal.Rev.-Sci.Eng.,2018,60,132-175.