公开(公告)号：US06413902B1

公开(公告)日：2002-07-02

申请号：US09661023

申请日：2000-09-13

申请人： Thomas J. Pinnavaia ,  Peter T. Tanev ,  Ying Liang

发明人： Thomas J. Pinnavaia ,  Peter T. Tanev ,  Ying Liang

IPC分类号： C01B3338

CPC分类号： B01J21/04 ,  B01J21/066 ,  B01J23/14 ,  B01J29/0308 ,  B01J29/041 ,  B01J29/046 ,  B01J29/049 ,  B01J29/89 ,  B01J35/1061 ,  B01J37/03 ,  B01J37/036 ,  C01B33/20 ,  C01B37/00 ,  C01B37/005 ,  C01B37/02 ,  C07C46/06 ,  C07C46/08

摘要： A neutral templating route to mesoporous molecular sieves based on H-bonding and self-assembly between neutral primary amine or diamine surfactants (S°) and neutral inorganic precursors (I°) has been used to prepare hexagonal and lamellar mesoporous silicas with site isolated transition metal centers. The templating of neutral metallosilicate precursors (I°) with neutral diamine surfactants (S°—S°) affords thermally stable pillared lamellar metallosilicates exhibiting complementary framework-confined microporosity and textural mesoporosity while at the same time also providing for template recovery by solvent extraction. These new mesoporous metallosilicate molecular sieves exhibit exceptional catalytic activity for peroxide hydroxylation of benzene and oxidation of substituted aromatics with kinetic diameters that are too large (larger than 6 Å) to access the pore structure of the conventional microporous transition metal-substituted molecular sieves such as titano- and vanadosilicates.

摘要翻译： 已经使用了基于中性伯胺或二胺表面活性剂（S°）和中性无机前体（I°）之间的H键和自组装的介孔分子筛的中性模板化途径来制备具有位置分离转移的六方晶系和层状介孔二氧化硅 金属中心。 中性金属硅酸盐前体（I°）与中性二胺表面活性剂（S°-S°）的模板提供了表现出互补的框架限制的微孔性和结构中等孔隙度的热稳定的柱状金属硅酸盐，同时也提供了通过溶剂萃取的模板回收。 这些新的介孔金属硅酸盐分子筛对于苯的过氧化羟基化和对具有太大（大于6埃）的动力学直径的取代芳族化合物的氧化具有优异的催化活性，以进入常规的微孔过渡金属取代的分子筛的孔结构，例如 钛和钒硅酸盐。

公开(公告)号：US06410473B1

公开(公告)日：2002-06-25

申请号：US09541728

申请日：2000-04-03

申请人： Thomas J. Pinnavaia ,  Wenzhong Zhang ,  Thomas R. Pauly ,  Peter T. Tanev

发明人： Thomas J. Pinnavaia ,  Wenzhong Zhang ,  Thomas R. Pauly ,  Peter T. Tanev

IPC分类号： C01B3338

CPC分类号： B01J29/041 ,  B01J29/0308 ,  B01J29/89 ,  B01J37/036 ,  C01B37/00 ,  C01B37/005 ,  C01B37/02 ,  C07C46/06

摘要： Crystalline inorganic oxide compositions having regular wormhole-like channels are described. The formation of the mesoporous composition is accomplished by hydrogen bonding between a neutral amine template in water and a water miscible organic solvent and a neutral inorganic oxide precursor, wherein there is an excess of an alkanol or water used to dissolve the template. The template can be removed and recycled.

摘要翻译： 描述了具有规则虫洞状通道的结晶无机氧化物组合物。 中孔组合物的形成通过在水中的中性胺模板与水混溶性有机溶剂和中性无机氧化物前体之间的氢键结合来实现，其中存在用于溶解模板的过量的链烷醇或水。 模板可以被删除和回收。

公开(公告)号：US06193943B1

公开(公告)日：2001-02-27

申请号：US08797718

申请日：1997-02-11

申请人： Thomas J. Pinnavaia ,  Peter T. Tanev ,  Wenzhong Zhang ,  Jialiang Wang ,  Malama Chibwe

发明人： Thomas J. Pinnavaia ,  Peter T. Tanev ,  Wenzhong Zhang ,  Jialiang Wang ,  Malama Chibwe

IPC分类号： C01B3338

CPC分类号： B01J21/04 ,  B01J21/066 ,  B01J23/14 ,  B01J29/0308 ,  B01J29/041 ,  B01J29/046 ,  B01J29/049 ,  B01J29/89 ,  B01J35/1061 ,  B01J37/03 ,  B01J37/036 ,  C01B33/20 ,  C01B37/00 ,  C01B37/005 ,  C01B37/02 ,  C07C46/06 ,  C07C46/08

摘要： A neutral templating route to mesoporous molecular sieves based on H-bonding and self-assembly between neutral primary amine or diamine surfactants (S°) and neutral inorganic precursors (I°) has been used to prepare hexagonal and lamellar mesoporous silicas with site isolated transition metal centers. This templating approach allows for the preparation of hexagonal or hexagonal-like mesoporous oxidation catalysts with large framework wall thickness of at least about 17 Å, small elementary particle size (≦400 Å), and unique combinations of framework-confined mesopores and textural mesopores while at the same time providing for facile recovery of the neutral template by simple solvent extraction. The templating of neutral metallosilicate precursors (I°) with neutral diamine surfactants (S°—S°) affords thermally stable pillared lamellar metallosilicates exhibiting complementary framework-confined microporosity and textural mesoporosity while at the same time also providing for template recovery by solvent extraction. In addition, a hexagonal transition metal-substituted catalysts, analogous to MCM-41, have been prepared using the mediated S+X·I+ templating pathway (Pathway 3) and mild reaction conditions. These new mesoporous metallosilicate molecular sieves exhibit exceptional catalytic activity for peroxide hydroxylation of benzene and oxidation of substituted aromatics with kinetic diameters that are too large (larger than 6 Å) to access the pore structure of the conventional microporous transition metal-substituted molecular sieves such as titano- and vanadosilicates.

摘要翻译： 已经使用了基于中性伯胺或二胺表面活性剂（S°）和中性无机前体（I°）之间的H键和自组装的介孔分子筛的中性模板化途径来制备具有位置分离转移的六方晶系和层状介孔二氧化硅 金属中心。 该模板方法允许制备具有至少约17埃的大框架壁厚度，小的基本粒度（<= 400）的六边形或六边形样介孔氧化催化剂，以及框架约束的中孔和结构中孔的独特组合 同时通过简单的溶剂萃取提供中性模板的简便回收。 中性金属硅酸盐前体（I°）与中性二胺表面活性剂（S°-S°）的模板提供了表现出互补的框架限制的微孔性和结构中等孔隙度的热稳定的柱状金属硅酸盐，同时也提供了通过溶剂萃取的模板回收。 此外，已经使用介导的S + X.I +模板途径（途径3）和温和的反应条件制备了类似于MCM-41的六方晶过渡金属取代的催化剂。这些新的介孔金属硅酸盐分子筛显示出极好的催化活性 苯的过氧化羟基化和具有太大（大于6）的动力学直径的取代芳族化合物的氧化，以进入常规的微孔过渡金属取代的分子筛如钛和钒硅酸盐的孔结构。