CN103058216A - Method for preparing mesoporous molecular sieve having crystal microporous wall - Google Patents
Method for preparing mesoporous molecular sieve having crystal microporous wall Download PDFInfo
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- CN103058216A CN103058216A CN2012104355028A CN201210435502A CN103058216A CN 103058216 A CN103058216 A CN 103058216A CN 2012104355028 A CN2012104355028 A CN 2012104355028A CN 201210435502 A CN201210435502 A CN 201210435502A CN 103058216 A CN103058216 A CN 103058216A
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Abstract
The invention discloses a method for preparing a mesoporous molecular sieve having a crystal microporous wall. The method comprises the following steps of: synthesizing two kinds of long-chain quaternary ammonium salts, sequentially, further synthesizing a long-chain polyquaternium surface active agent as a template guiding agent, by a hydro-thermal synthesis method, mixing appropriate amount of silicon source with aluminum source, under alkaline condition, preparing the mesoporous molecular sieve having the crystal microporous wall and a zeolite molecular sieve-like silicon/aluminum skeleton structure. The mesoporous molecular sieve prepared by the method of the invention has important application in the fields of chemical industry, information technology, biotechnology, environmental energy, and so on.
Description
Technical field
The present invention relates to a kind of molecular sieve catalyst or carrier preparation method, more specifically say a kind of preparation method with mesopore molecular sieve of micro-pore wall structure.
Background technology
Micro porous molecular sieve is as the carrier of a class an acidic catalyst or acid carrier, cationite and nanoparticle, have that specific surface area is large, silicon/aluminium modulation in very large range, acid strong, sour amount is easy to control, shows preferably heat, hydrothermal stability, chemical stability and physical strength (Chem. Rev., 2003,103:663; Appl. Catal. A Gen. 1999,189:163; Energy Environ. Sci. 2009,2:610), the second, the duct that the molecular sieve bore diameter homogeneous distributes also demonstrates its unique shape selective catalysis function.In addition, because acid can present different intensity because different heteroatomss replace on the framework of molecular sieve, most of solid acid be used for a series of catalyzed reactions such as petroleum catalytic cracking, hydrocracking, isomerization, disproportionation, alkylation industrial production (Energy Environ. Sci. 2009,2:610).Yet because its small aperture only has small molecules to adsorb or chemical reaction by its small duct, limited the reactive applications that the many macromole of its catalysis participate in.
From 20th century the nineties, about the many macromolecular reactions of mesopore molecular sieve catalysis, (Nature 1992,359:710 to have caused people's extensive concern; Chem. Mater. 1997,9:2491; Science 1998,279:548).1992, researchist's reported first of Mobil company the synthetic method of MCM-41 mesoporous material and its characteristic (J. Amer. Chem. Soc., 1992,114 (27): 10834).But the aperture of M41S series mesoporous material is about 2-4 nm, and hole wall is thinner, caves in easily, and poor heat stability causes the practical application in industry of mesopore molecular sieve still to be had difficulty in taking a step.Researcher is attempted the advantage in conjunction with micropore and mesopore molecular sieve, synthesize the matrix material that ducts at different levels characteristics are combined, the diffusion that has greatly improved reactant and product improves catalytic activity, again owing to be the crystal hole wall, hydrothermal stability also improves greatly simultaneously.Yet all aforesaid methods all are the two-step approachs from the assembly mesoporous structure of nano molecular sieve, although some investigators have synthesized Jie's poromerics (J. Phys. Chem. B 2000, the 104:2817 of ordered structure; J. Mater. Chem. 2001,11:1886; J. Am. Chem. Soc. 2006 128:10636), but in most of situation, can only obtain undesirable micropore and mesoporous two phase structure.
For these reasons, still have a large amount of orderly micro porous molecular sieves of research structure that are operated in, (Science. 1998 such as Zhao etc., 279 (5350): 548) adopting segmented copolymer is mesoporous directed agents, having synthesized the aperture under acidic conditions can be adjustable in 10-30 nm scope, and having a mesoporous material SBA-15 of the thick hole wall of 3-5 nm, SBA-15 has larger mesoporous aperture and better hydrothermal stability.(the Angew. Chem. Int. Ed. such as Che, 2003,42 (33): 3930) by adding the method for second surface promoting agent, at room temperature synthesize the FDU-5 mesoporous material with three-dimensional cubic structure in the acid system, its aperture larger (about 8 nm).(the Angew. Chem. Int. Ed. such as Ryoo, 2004,43 (39): 5231) in the solution system of P123, add a certain amount of propyl carbinol, in weak acid system, synthesized the big-pore mesoporous material KIT-6 with three-dimensional cubic structure, and successfully resolved KIT-6.Recently, Ryoo (Science2011,
333: 328) seminar makes directed agents with the poly-quaternary ammonium salt tensio-active agent of binary hole trace, has synthesized a series of crystal micro-pore walls that have, the mesopore molecular sieve of silicon/aluminium skeleton structure as the zeolite molecular sieve.Thereby expanded the 2-50 nm of nano molecular sieve range of application to mesopore molecular sieve, with respect to traditional microsized zeolite and orderly unbodied mesoporous material, this have a crystal micro-pore wall, the mesopore molecular sieve of silicon as the zeolite molecular sieve/aluminium skeleton structure is a kind of highly active acid catalyst, can the many reactions that contain the macromolecular reaction thing of catalysis.
The present invention on the preparation method's of Ryoo seminar basis, with it 60
oThe C lower magnetic force stirs 6 h, is transferred in the stainless steel cauldron of Teflon liner, is heated to 140
oC, continue 4 days under the roll over condition of 60 rpm, make and thisly have as crystal micro-pore wall, the zeolite molecular sieve mesopore molecular sieve of silicon/aluminium skeleton structure and change into raw material certain temperature lower magnetic force in different containers is stirred, aging certain hour, in the hydrothermal synthesis reaction still, crystallization under the certain temperature has finally made the mesopore molecular sieve of the crystal hole wall of better effects if.
Purpose of the present invention namely provides a kind of method, participates in mesoporous molecular sieve catalyst or the carrier of reaction crystal hole wall for the preparation of the many macromole of energy catalysis.
Summary of the invention
Purpose of the present invention namely provides a kind of method, the method replaces the organic amine of general structure as directed agents with the polyquaternium tensio-active agent that is synthesized, under alkaline condition, synthesize and have the crystal micro-pore wall, the mesopore molecular sieve of silicon as the zeolite molecular sieve/aluminium skeleton structure is as catalyzer or the carrier of the many macromole participations of catalysis reaction.
Involved template is that Ryoo seminar has the crystal micro-pore wall in preparation among the present invention, the polyquaternium tensio-active agent of mentioning during the mesopore molecular sieve of silicon/aluminium skeleton structure as the zeolite molecular sieve.Involved in the present invention to silicon source and aluminium source be respectively in silicate, aluminate or the aluminium salt one or more.Reactor involved in the present invention is the hydrothermal synthesis reaction still.
Preparation method's following steps of the mesoporous molecular sieve catalyst of crystal hole wall of the present invention or carrier.
1. tensio-active agent is synthetic
According to the synthetic method in the document, synthesize respectively C
18H
37-N+ (CH
3)
2-C
6H
12Br (Br-), C
18H
37-N
+(CH
3)
2-C
6H
12-N (CH
3)
2(Br
-) and polyquaternium tensio-active agent C
18H
37-N
+(CH
3)
2-C
6H
12-N
+(CH
3)
2-C
6H
12-N
+(CH
3)
2-C
18H
37(Br
-)
3
2. the preparation of the mesopore molecular sieve of crystal hole wall
1) take the polyquaternium tensio-active agent as the template direction agent, and an amount of silicon source, aluminium source, water and other auxiliary agents mix;
2) behind 30-80 ℃ of aging 5-10 h, be warming up to 100-170 ℃, crystallization 4-6 days;
3) after the crystallization, product is filtered, use distilled water wash;
4) product is 120
oDry 10-16 h under the C, and under flowing air roasting 4-10 h under 550-600 ℃ of high temperature, to remove organic surface active agent.
Sign of the present invention: mesopore molecular sieve can be identified by little angle x-ray diffractometer (SAXRD) order of molecular sieve type, purity and molecular sieve structure.
Catalyzer of the present invention is analyzed through little angle x-ray diffractometer, and very sharp-pointed intensity peak is arranged, and shows that prepared molecular sieve is the mesopore molecular sieve of silicon with crystal micro-pore wall/aluminium skeleton structure.
Mode below by example is carried out more specific description to the present invention, but the invention is not restricted to this.
Description of drawings
Fig. 1 is the XRD analysis result of mesopore molecular sieve of the silicon/aluminium skeleton structure of the crystal micro-pore wall for preparing of the present invention.
Fig. 2 is the XRD analysis result of mesopore molecular sieve of the silicon/aluminium skeleton structure of the crystal micro-pore wall of Ryoo seminar preparation.
Embodiment
Embodiment 1
(1) C
18H
37-N
+(CH
3)
2-C
6H
12-Br (Br
-) (quaternary ammonium salt 1) synthetic: with 10 g N, N '-dimethyl stearyl amine and 10 g 1,6-dibromo-hexane are dissolved in (1:1 V:V) in an amount of acetonitrile/toluene mixture liquid, 80 ℃ of lower heating 10 h.Behind the cool to room temperature, evaporating solvent, solid phase prod after filtration, ether washing, 40 ℃ of lower vacuum-drying 2 h, obtain quaternary ammonium salt 1; (2) C
18H
37-N
+(CH
3)
2-C
6H
12-N (CH
3)
2(Br
-) (quaternary ammonium salt 2) synthetic: with 8 g 1-bromo-octadecanes and 8 g N, N, N ', N '-tetramethyl--1, the own diamino hexane of 6-is dissolved in (1:1 V:V) in an amount of acetonitrile/toluene mixture liquid, 80 ℃ of lower heating 10 h.Behind the chilling, solid phase prod after filtration, ether washing, 40 ℃ of lower vacuum-drying 2 h, obtain quaternary ammonium salt 2; (3) C
18H
37-N
+(CH
3)
2-C
6H
12-N
+(CH
3)
2-C
6H
12-N
+(CH
3)
2-C
18H
37(Br
-)
3(abbreviation 18-N
3-18): the quaternary ammonium salt 1 of equimolar amount and quaternary ammonium salt 2 are in acetonitrile solution, and 10 h reflux.Evaporating solvent, the precipitation product is through filtration, washing, 40 ℃ of lower vacuum-dryings.Obtain at last pure final solid phase prod; (4) take the polyquaternium tensio-active agent that synthesized as template direction agent (1 g), 10 g water glass, 20 g Tai-Ace S 150,0.5 g NaOH and an amount of distilled water are mixed to get silica gel, magnetic agitation 6 h in 30 ℃ of uncovered beakers, be transferred in the stainless steel cauldron of Teflon liner, be heated to 100 ℃, in baking oven, kept 4 days, after the crystallization, zeolite product is filtered, use distilled water wash, 120 ℃ of lower dry 12 h, 550 ℃ of high-temperature roasting 4h under flowing air are to remove organic surface active agent.
(1) step of preparation quaternary ammonium salt 1, quaternary ammonium salt 2 and polyquaternium tensio-active agent is with embodiment 1; (2) take the polyquaternium tensio-active agent that synthesized as template direction agent (1 g), 5 g tetraethoxys, 15 g Tai-Ace S 150,0.3 g NaOH and an amount of distilled water are mixed to get silica gel, at 30 ℃, magnetic agitation 6 h in the uncovered beaker, be transferred to the stainless steel cauldron of Teflon liner, be heated to 100 ℃, in baking oven, kept 3 days, after the crystallization, zeolite product is filtered, use distilled water wash, 120 ℃ of lower dry 12 h, 600 ℃ of high-temperature roasting 6h under flowing air are to remove organic surface active agent.
Embodiment 3
(1) step of preparation quaternary ammonium salt 1, quaternary ammonium salt 2 and polyquaternium tensio-active agent is with embodiment 1; (2) take the polyquaternium tensio-active agent that synthesized as template direction agent (1 g), 6 g tetraethoxys, 0.1 g sodium metaaluminate, 0.3 g NaOH and an amount of distilled water are mixed to get silica gel, magnetic agitation 8 h in 40 ℃ of uncovered beakers, be transferred in the stainless steel cauldron of Teflon liner, be heated to 130 ℃, in baking oven, kept 6 days, after the crystallization, zeolite product is filtered, use distilled water wash, 120 ℃ of lower dry 12 h, 600 ℃ of high-temperature roasting 6h under flowing air are to remove organic surface active agent.
Embodiment 4
(1) step of preparation quaternary ammonium salt 1, quaternary ammonium salt 2 and polyquaternium tensio-active agent is with embodiment 1; (2) take the polyquaternium tensio-active agent that synthesized as template direction agent (1 g), 5 g water glass, 0.2 g sodium metaaluminate, 0.4 g NaOH and an amount of distilled water are mixed to get silica gel, in 70 ℃ of uncovered beakers, magnetic agitation 10 h, be transferred in the stainless steel cauldron of Teflon liner, be heated to 170 ℃, in baking oven, kept 6 days, after the crystallization, zeolite product is filtered, use distilled water wash, 120 ℃ of lower dry 16 h, 550 ℃ of high-temperature roasting 10 h under flowing air are to remove organic surface active agent.
Embodiment 5
(1) step of preparation quaternary ammonium salt 1, quaternary ammonium salt 2 and polyquaternium tensio-active agent is with embodiment 1; (2) take the polyquaternium tensio-active agent that synthesized as template direction agent (1 g), 10 g water glass, 0.2 g sodium metaaluminate, 0.4 g NaOH and an amount of distilled water are mixed to get silica gel, in 70 ℃ of there-necked flasks, reflux and magnetic agitation 10 h, be transferred in the stainless steel cauldron of Teflon liner, be heated to 150 ℃, in baking oven, kept 5 days, after the crystallization, zeolite product is filtered, use distilled water wash, 120 ℃ of lower dry 10 h, 600 ℃ of high-temperature roasting 6 h under flowing air are to remove organic surface active agent.
(1) step of preparation quaternary ammonium salt 1, quaternary ammonium salt 2 and polyquaternium tensio-active agent is with embodiment 1; (2) take the polyquaternium tensio-active agent that synthesized as template direction agent (1 g), 6 g tetraethoxys, 0.1 g sodium metaaluminate, 0.3 g NaOH and an amount of distilled water are mixed to get silica gel, magnetic agitation 5 h in 50 ℃ of uncovered beakers, be transferred in the stainless steel cauldron of Teflon liner, be heated to 110 ℃, in baking oven, kept 4 days, after the crystallization, zeolite product is filtered, use distilled water wash, 120 ℃ of lower dry 12 h, 600 ℃ of high-temperature roasting 6h under flowing air are to remove organic surface active agent.
Embodiment 7
(1) step of preparation quaternary ammonium salt 1, quaternary ammonium salt 2 and polyquaternium tensio-active agent is with embodiment 1; (2) take the polyquaternium tensio-active agent that synthesized as template direction agent (1 g), 6 g tetraethoxys, 0.1 g sodium metaaluminate, 0.3 g NaOH and an amount of distilled water are mixed to get silica gel, in 60 ℃ of there-necked flasks, reflux and magnetic agitation 5 h, be transferred in the stainless steel cauldron of Teflon liner, be heated to 120 ℃, in baking oven, kept 4 days, after the crystallization, zeolite product is filtered, use distilled water wash, 120 ℃ of lower dry 12 h, 550 ℃ of high-temperature roasting 4 h under flowing air are to remove organic surface active agent.
(1) step of preparation quaternary ammonium salt 1, quaternary ammonium salt 2 and polyquaternium tensio-active agent is with embodiment 1; (2) take the polyquaternium tensio-active agent that synthesized as template direction agent (1 g), 10 g water glass, 20 g Tai-Ace S 150,0.5 g NaOH and an amount of distilled water are mixed to get silica gel, in 80 ℃ of there-necked flasks, reflux and magnetic agitation 10 h, be transferred in the stainless steel cauldron of Teflon liner, be heated to 160 ℃, in baking oven, kept 4 days, after the crystallization, zeolite product is filtered, use distilled water wash, 120 ℃ of lower dry 12 h, 550 ℃ of high-temperature roasting 8 h under flowing air are to remove organic surface active agent.
Embodiment 9
(1) step of preparation quaternary ammonium salt 1, quaternary ammonium salt 2 and polyquaternium tensio-active agent is with embodiment 1; (2) take the polyquaternium tensio-active agent that synthesized as template direction agent (1 g), 10 g water glass, 20 g Tai-Ace S 150,0.5 g NaOH and an amount of distilled water are mixed to get silica gel, in 40 ℃ of stainless steel cauldrons that are transferred to the Teflon liner, sealed reactor, magnetic agitation 6 h are heated to 120 ℃, keep 5 days in baking oven, after the crystallization, zeolite product is filtered, use distilled water wash, 120 ℃ of lower dry 12 h, 600 ℃ of high-temperature roasting 4 h under flowing air are to remove organic surface active agent.
(1) step of preparation quaternary ammonium salt 1, quaternary ammonium salt 2 and polyquaternium tensio-active agent is with embodiment 1; (2) take the polyquaternium tensio-active agent that synthesized as template direction agent (1 g), 10 g water glass, 0.2 g sodium metaaluminate, 0.4 g NaOH and an amount of distilled water are mixed to get silica gel, in 50 ℃ of stainless steel cauldrons that are transferred to the Teflon liner, sealed reactor, magnetic agitation 10 h are heated to 110 ℃, keep 4 days in baking oven, after the crystallization, zeolite product is filtered, use distilled water wash, 120 ℃ of lower dry 16 h, 550 ℃ of high-temperature roasting 10 h under flowing air are to remove organic surface active agent.
(2) step of preparation quaternary ammonium salt 1, quaternary ammonium salt 2 and polyquaternium tensio-active agent is with embodiment 1; (2) take the polyquaternium tensio-active agent that synthesized as template direction agent (1 g), 5 g water glass, 0.2 g Tai-Ace S 150,0.5 g NaOH and an amount of distilled water are mixed to get silica gel, in 40 ℃ of stainless steel cauldrons that are transferred to the Teflon liner, sealed reactor, magnetic agitation 10 h are heated to 150 ℃, keep 5 days in baking oven, after the crystallization, zeolite product is filtered, use distilled water wash, 120 ℃ of lower dry 10 h, 550 ℃ of high-temperature roasting 8 h under flowing air are to remove organic surface active agent.
Embodiment 12
(3) step of preparation quaternary ammonium salt 1, quaternary ammonium salt 2 and polyquaternium tensio-active agent is with embodiment 1; (2) take the polyquaternium tensio-active agent that synthesized as template direction agent (1 g), 6 g tetraethoxys, 0.1 g sodium metaaluminate, 0.3 g NaOH and an amount of distilled water are mixed to get silica gel, in 30 ℃ of stainless steel cauldrons that are transferred to the Teflon liner, sealed reactor, magnetic agitation 6 h are heated to 150 ℃, keep 5 days in baking oven, after the crystallization, zeolite product is filtered, use distilled water wash, 120 ℃ of lower dry 10 h, 550 ℃ of high-temperature roasting 6 h under flowing air are to remove organic surface active agent.XRD sees Fig. 1.
Claims (7)
1. preparation method with mesopore molecular sieve of crystal micro-pore wall, the preparation method is as follows for its feature: (1) tensio-active agent synthetic: synthetic C respectively
18H
37-N+ (CH
3)
2-C
6H
12Br (Br-), C
18H
37-N
+(CH
3)
2-C
6H
12-N (CH
3)
2(Br
-) and polyquaternium tensio-active agent C
18H
37-N
+(CH
3)
2-C
6H
12-N
+(CH
3)
2-C
6H
12-N
+(CH
3)
2-C
18H
37(Br
-)
3(2) preparation of the mesopore molecular sieve of crystal hole wall: 1. take the polyquaternium tensio-active agent as the template direction agent, and an amount of silicon source, aluminium source, water and other auxiliary agents mix; 2. behind 30-80 ℃ of aging 5-10 h, be warming up to 100-170 ℃, crystallization 4-6 days; 3. after the crystallization, product is filtered, be washed with distilled water to neutrality; 4. product is 120
oDry 10-16 h under the C, and in flowing air 550-600 ℃ of roasting temperature 4-10 h, to remove the organic surface active agent as template, make a kind of mesopore molecular sieve with crystal micro-pore wall.
2. molecular sieve preparation method as claimed in claim 1 is characterized in that used silicon source is water glass crystal, water glass and tetraethoxy, and used aluminium source is Tai-Ace S 150 and sodium metaaluminate.
3. molecular sieve preparation method as claimed in claim 1 is characterized in that other auxiliary agents are sodium hydroxide.
4. molecular sieve preparation method as claimed in claim 1 is characterized in that the molecular sieve aging techniques is at 30-80 ℃, magnetic agitation 5-10 h in the beaker.
5. molecular sieve preparation method as claimed in claim 1 is characterized in that the molecular sieve aging techniques is at 30-80 ℃, refluxes magnetic agitation 5-10 h in the there-necked flask.
6. molecular sieve preparation method as claimed in claim 1 is characterized in that the molecular sieve aging techniques is at 30-80 ℃, directly raw material is added hydrothermal synthesis reaction still, sealed reactor, magnetic agitation 5-10 h.
7. molecular sieve preparation method as claimed in claim 1 is characterized in that the Crystallization of Zeolite mode is at 100-170 ℃, leaves standstill the hydrothermal synthesis reaction still 4-6 days.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2015024379A1 (en) * | 2013-08-20 | 2015-02-26 | 中国科学院大连化学物理研究所 | Method for preparing beta molecular sieve having mesoporous/microporous combined channel |
| CN107497480A (en) * | 2017-08-30 | 2017-12-22 | 天津大学 | A kind of synthetic method of Jie's mesoporous-microporous composite molecular sieve catalyst |
| CN107572547A (en) * | 2017-08-30 | 2018-01-12 | 天津大学 | A kind of synthetic method of multilevel ordered mesoporous Si-Al molecular sieve |
| CN107651693A (en) * | 2017-08-30 | 2018-02-02 | 天津大学 | A kind of direct synthesis method of multi-stage ordered mesoporous molecular sieve |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015024379A1 (en) * | 2013-08-20 | 2015-02-26 | 中国科学院大连化学物理研究所 | Method for preparing beta molecular sieve having mesoporous/microporous combined channel |
| CN104418348A (en) * | 2013-08-20 | 2015-03-18 | 中国科学院大连化学物理研究所 | Beta molecular sieve with multistage pore structure and preparation method thereof |
| CN104418348B (en) * | 2013-08-20 | 2018-11-02 | 中国科学院大连化学物理研究所 | A kind of Beta molecular sieves and preparation method thereof with multi-stage artery structure |
| CN107497480A (en) * | 2017-08-30 | 2017-12-22 | 天津大学 | A kind of synthetic method of Jie's mesoporous-microporous composite molecular sieve catalyst |
| CN107572547A (en) * | 2017-08-30 | 2018-01-12 | 天津大学 | A kind of synthetic method of multilevel ordered mesoporous Si-Al molecular sieve |
| CN107651693A (en) * | 2017-08-30 | 2018-02-02 | 天津大学 | A kind of direct synthesis method of multi-stage ordered mesoporous molecular sieve |
| CN107651693B (en) * | 2017-08-30 | 2019-09-17 | 天津大学 | A kind of direct synthesis method of multi-stage ordered mesoporous molecular sieve |
| CN107497480B (en) * | 2017-08-30 | 2019-09-17 | 天津大学 | A kind of synthetic method of Jie's mesoporous-microporous composite molecular sieve catalyst |
| CN107572547B (en) * | 2017-08-30 | 2019-09-17 | 天津大学 | A kind of synthetic method of multilevel ordered mesoporous Si-Al molecular sieve |
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Application publication date: 20130424 |