CN106809851A - A kind of three-dimensional order pore structure zeolite molecular sieve and preparation method thereof - Google Patents
A kind of three-dimensional order pore structure zeolite molecular sieve and preparation method thereof Download PDFInfo
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- CN106809851A CN106809851A CN201710030922.0A CN201710030922A CN106809851A CN 106809851 A CN106809851 A CN 106809851A CN 201710030922 A CN201710030922 A CN 201710030922A CN 106809851 A CN106809851 A CN 106809851A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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Abstract
The invention discloses a kind of three-dimensional order pore structure zeolite molecular sieve and preparation method thereof, belong to inorganic material synthesis and catalytic field.The zeolite molecular sieve has macroporous structure, and macropore duct arranges in three-dimensional order, and macropore size is 50~700nm.By ethanol, HNO3, tetraethyl orthosilicate uniformly mix, add polystyrene spheres, suction filtration, drying obtain SiO2PS ball composites；By SiO2PS ball composites are added in the TPAOH aqueous solution, after suction filtration, drying, add a certain amount of NaAlO2, drying；Gained dry glue steam auxiliary crystallization method is changed into molecular sieve, drying, roasting removal PS ball templates obtain the zeolite molecular sieve with three-dimensional order pore structure, and the method is applied to the types of ZSM 5 that prepare, β types, and Y types equimolecular sieve.The three-dimensional order pore structure zeolite molecular sieve of the method synthesis has big specific surface area, homogeneous macropore, crystallinity high, structural integrity, the functional material such as the characteristics of acid adjustable, can be used as being catalyzed, adsorb, separate.
Description
Technical field
The invention belongs to inorganic material synthesis and catalytic field, and in particular to a kind of three-dimensional order pore structure zeolite molecular sieve
And preparation method thereof.
Background technology
Zeolite molecular sieve is the porous compounds of alumino-silicate composition, by TO4Between tetrahedron by shared summit shape
Into three-dimensional four-coordination skeleton, skeleton T atom is usually Si, Al atom.According to the difference of its skeleton structure, ZSM-5, β can be divided into,
The species such as Y, X, SAPO.Molecular sieve is due to big specific surface area, highly acid, unique micropore canals and good hydro-thermal
And heat endurance, therefore effective capture in small molecule, shape selective catalysis, transition state molecule and product molecule such as efficiently separate at the side
Mask is widely used.But conventional zeolite molecular sieve is limited to the micropore canals of itself, is deposited in chemical reaction process is participated in
In huge resistance to mass tranfer, so as to cause carbon deposition phenomenon in micropore canals, limitation zeolite molecular sieve is used as heterogeneous catalyst
Using.
To solve the diffusion problem that traditional zeolite molecular screen material faces, scientists study goes out a series of order mesoporous knots
The molecular sieve of structure, wherein most representational is MCM-41 and SBA-15 silicon base ordered mesopore molecular sieves.But mesopore molecular sieve
Noncrystalline skeleton structure causes that its hydrothermal stability is poor, surface acidity is relatively low, it is impossible to meet the need for Industrial Catalysis reacts.
The diffusion problem of macromolecular can also be solved by by molecular sieve nanosizing, shortening diffusion admittance, but is faced with nano particle
Total shortcoming：Stability of material is poor, separation is difficult, yield is low.
Therefore, exploitation have concurrently zeolite molecular sieve strong acid catalyst activity and can reduce resistance to mass tranfer hierarchical porous structure it is new
Type molecular sieve for the complicated gas component absorption for the treatment of with separate, macromolecular transmission it is square with conveying and macromolecular reaction of high order etc.
Face has great importance.The design of hierarchical porous structure molecular sieve not only needs to introduce ducts at different levels, it is often more important that Ge Jikong
Fully connection is needed between road.Up to the present, the three-dimensional order pore structure with Rational structure and peracidity intensity is prepared
Zeolite molecular sieve is still a challenge.
The content of the invention
The present invention is for the deficiency in hierarchical porous structure zeolite molecular sieve prior art, there is provided a kind of three-dimensional order hole knot
Structure zeolite molecular sieve and preparation method thereof, it is characterised in that the zeolite molecular sieve has macroporous structure, macropore duct has in three-dimensional
Sequence is arranged, and macropore size is 50~700nm；The specific surface area of zeolite molecular sieve is 100~800m2/g。
The zeolite molecular sieve is one or more in type ZSM 5 molecular sieve, beta molecular sieve and Y type molecular sieve, its
In, the Si/Al mol ratios of the type ZSM 5 molecular sieve are 8:1~100:1；The Si/Al mol ratios of the beta molecular sieve are 10:
1~50:1；The Si/Al mol ratios of the Y type molecular sieve are 4:1~30:1.
A kind of preparation method of three-dimensional order pore structure zeolite molecular sieve, the method is comprised the following steps：
(1) ethanol, 0.3molL-1HNO3With tetraethyl orthosilicate example in mass ratio (1~20)：(0.2~5)：(1~
30) mix, be stirred at room temperature to form colloidal sol, add polystyrene (PS) ball, fully infiltration, suction filtration, drying obtain SiO2- PS balls
A diameter of 50~700nm of composite, wherein PS balls；
(2) by SiO2- PS balls composite is added in TPAOH or the tetraethyl ammonium hydroxide aqueous solution, is taken out
After filter, drying, the NaAlO of 1mol/L is added2Solution so that Si/Al mol ratios (8~50):(0~1), drying；Or will
SiO2- PS balls composite adds NaOH, NaAlO2In the aqueous solution, stir, NaOH, NaAlO2With tetraethyl orthosilicate quality
Ratio (1~2)：(2~4)：(15~60), drying；
(3) placed in the water heating kettle of polytetrafluoroethyllining lining and water is added in a support, water heating kettle, the addition of water is only
Flood into support, above support place a small container, by step (2) gained sample be put into a small container, water not with powder
Last directly contact, the crystallization at 100~140 DEG C is cooled down after the completion of crystallization, dried, being calcined removal PS ball templates, is had
There is three-dimensional order pore structure zeolite molecular sieve.
The quality of step (1) the PS balls is 1~3 times of tetraethyl orthosilicate.
The concentration of step (2) the TPAOH solution is 25~50wt%, adds quality and SiO2Quality
Than being 1：(0.1~10)；The tetraethyl ammonium hydroxide solution concentration is 25~50wt%, adds quality and SiO2Mass ratio
It is 1：(0.1~10).
Step (3) described crystallization time is 48~120h.
The temperature of step (3) described roasting is 500~900 DEG C, and roasting time is 1~12h.
The PS balls can be synthesized using following methods：
(1) 8~140mL styrene, 600mL water, 0.12g dodecyl sodium sulfates are added sequentially to the there-necked flask of 1L
In, 60~90 DEG C of heating stirrings lead to N230min excludes air, and then, 0.33g potassium peroxydisulfate initiators are water-soluble using 10mL
Solution, is added in above-mentioned round-bottomed flask, 60 DEG C of heating stirring 18h after 60 DEG C of heating；
(2) the PS balls mineral wool that will be obtained is filtered to remove aggregate, and the PS ball suspensions that then will be filtrated to get exist
5000rpm is centrifuged 12h, and the drying precipitate that will be obtained both had obtained the PS balls of 50~700nm.
Compared with the prior art, the method for preparing orderly pore structure zeolite molecular sieve material in the present invention, its advantage exists
In：
(1) the steam auxiliary crystallization method that the present invention is used is simple, and wide adaptation range can prepare ZSM-5, β types
And the molecular sieve of Y types, than the method low cost 60~80% for preparing corresponding molecular sieve in aqueous at present；
(2) hierarchical porous structure for preparing is through the inside of material, the surface that not soft template technique is frequently encountered
Pore structure；
(3) preparation method is simple, mild condition, easy large-scale promotion application.
Brief description of the drawings
Fig. 1 is the SEM figures of PS balls used in embodiment 3；
Fig. 2 is unformed SiO prepared in embodiment 32SEM figure；
Fig. 3 is the SEM figures of three-dimensional order pore structure ZSM-5 molecular sieve prepared in embodiment 3；
Fig. 4 is the XRD of three-dimensional order pore structure ZSM-5 molecular sieve prepared in embodiment 3.
Embodiment 1
8mL styrene, 600mL water, 0.12g dodecyl sodium sulfates are added sequentially in the there-necked flask of 1L, and 60 DEG C add
Thermal agitation, leads to N230min excludes air, and then, 0.33g potassium peroxydisulfate initiators use 10mL water dissolves, add after 60 DEG C of heating
Enter in above-mentioned round-bottomed flask, 60 DEG C of heating stirring 18h.The PS balls mineral wool that will be obtained is filtered to remove aggregate, then
The PS balls suspension that will be filtrated to get is centrifuged 12h in 5000rpm, and the drying precipitate that will be obtained both obtained the~PS balls of 50nm.
By ethanol, HNO3(0.3mol·L-1) and tetraethyl orthosilicate with mass ratio 20：0.2：1 mixing, is stirred at room temperature shape
Into colloidal sol, addition~50nm PS balls, wherein PS balls are 1 with the mass ratio of tetraethyl orthosilicate, fully infiltration, and suction filtration, drying are obtained
To SiO2- PS ball composites；By SiO2- PS balls composite is added in the 25wt% TPAOH aqueous solution, SiO2Matter
Amount is 1 with the mass ratio of the TPAOH aqueous solution：1, after suction filtration, drying, add 0.1mol/L NaAlO2Solution,
SiO2With NaAlO2Mol ratio is 8：1, drying.
A support is placed in a water heating kettle with polytetrafluoroethyllining lining, and pours into a certain amount of water, control water
Addition only flood into support.Above support place a small container, sample is put into a small container, make water not with institute
Obtain powder directly contact.The crystallization 72h at 100 DEG C, cools down, dries, 2h removal PS ball templates are calcined at 600 DEG C, is had
The ZSM-5 zeolite molecular sieve of three-dimensional order pore structure.
Embodiment 2
140mL styrene, 600mL water, 0.12g dodecyl sodium sulfates are added sequentially in the there-necked flask of 1L, 90 DEG C
Heating stirring, leads to N230min excludes air, and then, 0.33g potassium peroxydisulfate initiators use 10mL water dissolves, after 90 DEG C of heating
It is added in above-mentioned round-bottomed flask, 90 DEG C of heating stirring 18h.The PS balls mineral wool that will be obtained is filtered to remove aggregate, so
The PS balls suspension that will be filtrated to get afterwards is centrifuged 12h in 5000rpm, and the drying precipitate that will be obtained both obtained the~PS of 700nm
Ball.
By ethanol, HNO3(0.3mol·L-1) and tetraethyl orthosilicate with mass ratio 20：5：30 mixing, are stirred at room temperature to be formed
Colloidal sol, wherein addition~700nm PS balls, PS balls are 1 with the mass ratio of tetraethyl orthosilicate, fully infiltration, and suction filtration, drying are obtained
SiO2- PS ball composites；By SiO2- PS balls composite is added in the 40wt% TPAOH aqueous solution, SiO2Quality
It is 1 with the mass ratio of the TPAOH aqueous solution：1, after suction filtration, drying, add 0.1mol/L NaAlO2Solution, SiO2
With NaAlO2Mol ratio is 8：1, drying.
A support is placed in a water heating kettle with polytetrafluoroethyllining lining, and pours into a certain amount of water, control water
Addition only flood into support.Above support place a small container, sample is put into a small container, make water not with institute
Obtain powder directly contact.The crystallization 48h at 140 DEG C, cools down, dries, 1h removal PS ball templates are calcined at 900 DEG C, is had
The ZSM-5 zeolite molecular sieve of three-dimensional order pore structure.
Embodiment 3
36.6mL styrene, 600mL water, 0.12g dodecyl sodium sulfates are added sequentially in the there-necked flask of 1L, 60 DEG C
Heating stirring, leads to N230min excludes air.Then, 0.33g potassium peroxydisulfate initiators use 10mL water dissolves, after 60 DEG C of heating
It is added in above-mentioned round-bottomed flask, 60 DEG C of heating stirring 18h.The PS balls mineral wool that will be obtained is filtered to remove aggregate, so
The PS balls suspension that will be filtrated to get afterwards is centrifuged 12h in 5000rpm, and the drying precipitate that will be obtained both obtained the~PS of 200nm
Ball.
By ethanol, HNO3(0.3mol·L-1) and tetraethyl orthosilicate with mass ratio 1：5：1 mixing, is stirred at room temperature to form molten
Glue, wherein addition~200nm PS balls, PS balls are 1 with the mass ratio of tetraethyl orthosilicate, fully infiltration, and suction filtration, drying are obtained
SiO2- PS ball composites；By SiO2- PS balls composite is added in the 25wt% TPAOH aqueous solution, SiO2Quality
It is 1 with the mass ratio of the TPAOH aqueous solution：10, after suction filtration, drying, add 0.1mol/L NaAlO2Solution, SiO2
With NaAlO2Mol ratio is 8：1, drying.
A support is placed in a water heating kettle with polytetrafluoroethyllining lining, and pours into a certain amount of water, control water
Addition only flood into support, above support place a small container, sample is put into a small container, make water not with institute
Powder directly contact is obtained, the crystallization 96h at 110 DEG C is cooled down, dried, 5h removal PS ball templates are calcined at 600 DEG C, being had
The ZSM-5 zeolite molecular sieve of three-dimensional order pore structure.
Fig. 1 is the SEM photograph of PS balls used in the present embodiment, and Fig. 2 is three-dimensional order hole knot prepared in the present embodiment
The unformed SiO of structure2SEM photograph, Fig. 3 is the ZSM-5 zeolite molecule of prepared three-dimensional order pore structure in the present embodiment
The SEM photograph of sieve, Fig. 4 is the XRD of the ZSM-5 zeolite molecular sieve of three-dimensional order pore structure prepared in the present embodiment, can
To find out that the sample after crystallization has regular three-dimensional open-framework and crystallinity higher.
Embodiment 4
73.2mL styrene, 600mL water, 0.12g dodecyl sodium sulfates are added sequentially in the there-necked flask of 1L, 80 DEG C
Heating stirring, leads to N230min excludes air.Then, 0.33g potassium peroxydisulfate initiators use 10mL water dissolves, after 80 DEG C of heating
It is added in above-mentioned round-bottomed flask, 80 DEG C of heating stirring 18h.The PS balls mineral wool that will be obtained is filtered to remove aggregate.So
The PS balls suspension that will be filtrated to get afterwards is centrifuged 12h in 5000rpm, and the drying precipitate that will be obtained both obtained the~PS of 400nm
Ball.
By ethanol, HNO3(0.3mol·L-1) and tetraethyl orthosilicate with mass ratio 20：0.2：30 mixing, are stirred at room temperature shape
Into colloidal sol, addition~400nm PS balls, wherein PS balls are 2 with the mass ratio of tetraethyl orthosilicate, fully infiltration, and suction filtration, drying are obtained
To SiO2- PS ball composites；By SiO2- PS balls composite is added in the 50wt% TPAOH aqueous solution, SiO2Matter
Amount is 1 with the mass ratio of the TPAOH aqueous solution：5, after suction filtration, drying, add 0.1mol/L NaAlO2Solution,
SiO2With NaAlO2Mol ratio is 8：1, drying.
A support is placed in a water heating kettle with polytetrafluoroethyllining lining, and pours into a certain amount of water, control water
Addition only flood into support.Above support place a small container, sample is put into a small container, make water not with institute
Obtain powder directly contact.The crystallization 72h at 120 DEG C, cools down, dries, 1h removal PS ball templates are calcined at 900 DEG C, is had
The ZSM-5 zeolite molecular sieve of three-dimensional order pore structure.
Embodiment 5
8mL styrene, 600mL water, 0.12g dodecyl sodium sulfates are added sequentially in the there-necked flask of 1L, and 60 DEG C add
Thermal agitation, leads to N230min excludes air.Then, 0.33g potassium peroxydisulfate initiators use 10mL water dissolves, add after 60 DEG C of heating
Enter in above-mentioned round-bottomed flask, 60 DEG C of heating stirring 18h.The PS balls mineral wool that will be obtained is filtered to remove aggregate.Then
The PS balls suspension that will be filtrated to get is centrifuged 12h in 5000rpm, and the drying precipitate that will be obtained both obtained the~PS balls of 50nm.
By ethanol, HNO3(0.3mol·L-1) and tetraethyl orthosilicate with mass ratio 1：0.2：1 mixing, is stirred at room temperature to be formed
Colloidal sol, wherein addition~50nm PS balls, PS balls are 2 with the mass ratio of tetraethyl orthosilicate, fully infiltration, and suction filtration, drying are obtained
SiO2- PS ball composites；By SiO2- PS balls composite is added in the TEAOH aqueous solution of 25wt%, SiO2Quality and TEAOH
The mass ratio of the aqueous solution is 1：1, after suction filtration, drying, add 0.1mol/L NaAlO2Solution, SiO2With NaAlO2Mol ratio is
10：1, drying.
A support is placed in a water heating kettle with polytetrafluoroethyllining lining, and pours into a certain amount of water, control water
Addition only flood into support.Above support place a small container, sample is put into a small container, make water not with institute
Obtain powder directly contact.The crystallization 120h at 100 DEG C, cools down, dries, 5h removal PS ball templates are calcined at 550 DEG C, is had
The zeolite beta molecular sieve of three-dimensional order pore structure.
Embodiment 6
140mL styrene, 600mL water, 0.12g dodecyl sodium sulfates are added sequentially in the there-necked flask of 1L, 90 DEG C
Heating stirring, leads to N230min excludes air.Then, 0.33g potassium peroxydisulfate initiators use 10mL water dissolves, after 90 DEG C of heating
It is added in above-mentioned round-bottomed flask, 90 DEG C of heating stirring 18h.The PS balls mineral wool that will be obtained is filtered to remove aggregate.So
The PS balls suspension that will be filtrated to get afterwards is centrifuged 12h in 5000rpm, and the drying precipitate that will be obtained both obtained the~PS of 700nm
Ball.
By ethanol, HNO3(0.3mol·L-1) and tetraethyl orthosilicate with mass ratio 20：5：30 mixing, are stirred at room temperature to be formed
Colloidal sol, wherein addition~700nm PS balls, PS balls are 3 with the mass ratio of tetraethyl orthosilicate, fully infiltration, and suction filtration, drying are obtained
SiO2- PS ball composites；By SiO2- PS balls composite is added in the 35wt%TEAOH aqueous solution, SiO2Quality and TEAOH water
The mass ratio of solution is 1：5, after suction filtration, drying, add 0.1mol/L NaAlO2Solution, SiO2With NaAlO2Mol ratio is 30：
1, drying.
A support is placed in a water heating kettle with polytetrafluoroethyllining lining, and pours into a certain amount of water, control water
Addition only flood into support.Above support place a small container, sample is put into a small container, make water not with institute
Obtain powder directly contact.The crystallization 48h at 140 DEG C, cools down, dries, 1h removal PS ball templates are calcined at 900 DEG C, is had
The zeolite beta molecular sieve of three-dimensional order pore structure.
Embodiment 7
36.6mL styrene, 600mL water, 0.12g dodecyl sodium sulfates are added sequentially in the there-necked flask of 1L, 60 DEG C
Heating stirring, leads to N230min excludes air.Then, 0.33g potassium peroxydisulfate initiators use 10mL water dissolves, after 60 DEG C of heating
It is added in above-mentioned round-bottomed flask, 60 DEG C of heating stirring 18h.The PS balls mineral wool that will be obtained is filtered to remove aggregate.So
The PS balls suspension that will be filtrated to get afterwards is centrifuged 12h in 5000rpm, and the drying precipitate that will be obtained both obtained the~PS of 200nm
Ball.
By ethanol, HNO3(0.3mol·L-1) and tetraethyl orthosilicate with mass ratio 1：5：1 mixing, is stirred at room temperature to form molten
Glue, wherein addition~200nm PS balls, PS balls are 1 with the mass ratio of tetraethyl orthosilicate, fully infiltration, and suction filtration, drying are obtained
SiO2- PS ball composites；By SiO2- PS balls composite is added in the 50wt%TEAOH aqueous solution, SiO2Quality and TEAOH water
The mass ratio of solution is 1：10, after suction filtration, drying, add 0.1mol/L NaAlO2Solution, SiO2With NaAlO2Mol ratio is
50：1, drying.
A support is placed in a water heating kettle with polytetrafluoroethyllining lining, and pours into a certain amount of water, control water
Addition only flood into support.Above support place a small container, sample is put into a small container, make water not with institute
Obtain powder directly contact.The crystallization 96h at 110 DEG C, cools down, dries, 10h removal PS ball templates are calcined at 550 DEG C, is had
The zeolite beta molecular sieve of three-dimensional order pore structure.
Embodiment 8
73.2mL styrene, 600mL water, 0.12g dodecyl sodium sulfates are added sequentially in the there-necked flask of 1L, 80 DEG C
Heating stirring, leads to N230min excludes air.Then, 0.33g potassium peroxydisulfate initiators use 10mL water dissolves, after 80 DEG C of heating
It is added in above-mentioned round-bottomed flask, 80 DEG C of heating stirring 18h.The PS balls mineral wool that will be obtained is filtered to remove aggregate.So
The PS balls suspension that will be filtrated to get afterwards is centrifuged 12h in 5000rpm, and the drying precipitate that will be obtained both obtained the~PS of 400nm
Ball.
By ethanol, HNO3(0.3mol·L-1) and tetraethyl orthosilicate with mass ratio 20：0.2：30 mixing, are stirred at room temperature shape
Into colloidal sol, addition~400nm PS balls, wherein PS balls are 1 with the mass ratio of tetraethyl orthosilicate, fully infiltration, and suction filtration, drying are obtained
To SiO2- PS ball composites；By SiO2- PS balls composite is added in the 25wt%TEAOH aqueous solution, SiO2Quality and TEAOH
The mass ratio of the aqueous solution is 1：0.1, after suction filtration, drying, add 0.1mol/L NaAlO2Solution, SiO2With NaAlO2Mol ratio
It is 20：1, drying.
A support is placed in a water heating kettle with polytetrafluoroethyllining lining, and pours into a certain amount of water, control water
Addition only flood into support.Above support place a small container, sample is put into a small container, make water not with institute
Obtain powder directly contact.The crystallization 72h at 120 DEG C, cools down, dries, 2h removal PS ball templates are calcined at 750 DEG C, is had
The zeolite beta molecular sieve of three-dimensional order pore structure.
Embodiment 9
8mL styrene, 600mL water, 0.12g dodecyl sodium sulfates are added sequentially in the there-necked flask of 1L, and 60 DEG C add
Thermal agitation, leads to N230min excludes air.Then, 0.33g potassium peroxydisulfate initiators use 10mL water dissolves, add after 60 DEG C of heating
Enter in above-mentioned round-bottomed flask, 60 DEG C of heating stirring 18h.The PS balls mineral wool that will be obtained is filtered to remove aggregate.Then
The PS balls suspension that will be filtrated to get is centrifuged 12h in 5000rpm, and the drying precipitate that will be obtained both obtained the~PS balls of 50nm.
By ethanol, HNO3(0.3mol·L-1) and tetraethyl orthosilicate with mass ratio 1：0.2：1 mixing, is stirred at room temperature to be formed
Colloidal sol, wherein addition~50nm PS balls, PS balls are 1 with the mass ratio of tetraethyl orthosilicate, fully infiltration, and suction filtration, drying are obtained
SiO2- PS ball composites；By SiO2- PS balls composite adds NaOH, NaAlO2In the aqueous solution, stir, NaOH,
NaAlO2With tetraethyl orthosilicate mass ratio 1：2：15, drying.
A support is placed in a water heating kettle with polytetrafluoroethyllining lining, and pours into a certain amount of water, control water
Addition only flood into support.Above support place a small container, sample is put into a small container, make water not with institute
Obtain powder directly contact.The crystallization 96h at 100 DEG C, cools down, dries, 10h removal PS ball templates are calcined at 500 DEG C, is had
The Y-type zeolite molecular sieve of three-dimensional order pore structure.
Embodiment 10
140mL styrene, 600mL water, 0.12g dodecyl sodium sulfates are added sequentially in the there-necked flask of 1L, 90 DEG C
Heating stirring, leads to N230min excludes air.Then, 0.33g potassium peroxydisulfate initiators use 10mL water dissolves, after 90 DEG C of heating
It is added in above-mentioned round-bottomed flask, 90 DEG C of heating stirring 18h.The PS balls mineral wool that will be obtained is filtered to remove aggregate.So
The PS balls suspension that will be filtrated to get afterwards is centrifuged 12h in 5000rpm, and the drying precipitate that will be obtained both obtained the~PS of 700nm
Ball.
By ethanol, HNO3(0.3mol·L-1) and tetraethyl orthosilicate with mass ratio 20：5：30 mixing, are stirred at room temperature to be formed
Colloidal sol, wherein addition~700nm PS balls, PS balls are 1 with the mass ratio of tetraethyl orthosilicate, fully infiltration, and suction filtration, drying are obtained
SiO2- PS ball composites；By SiO2- PS balls composite adds NaOH, NaAlO2In the aqueous solution, stir, NaOH,
NaAlO2With tetraethyl orthosilicate mass ratio 2：4：60, drying.
A support is placed in a water heating kettle with polytetrafluoroethyllining lining, and pours into a certain amount of water, control water
Addition only flood into support.Above support place a small container, sample is put into a small container, make water not with institute
Obtain powder directly contact.The crystallization 48h at 140 DEG C, cools down, dries, 5h removal PS ball templates are calcined at 550 DEG C, is had
The Y-type zeolite molecular sieve of three-dimensional order pore structure.
Embodiment 11
36.6mL styrene, 600mL water, 0.12g dodecyl sodium sulfates are added sequentially in the there-necked flask of 1L, 60 DEG C
Heating stirring, leads to N230min excludes air.Then, 0.33g potassium peroxydisulfate initiators use 10mL water dissolves, after 60 DEG C of heating
It is added in above-mentioned round-bottomed flask, 60 DEG C of heating stirring 18h.The PS balls mineral wool that will be obtained is filtered to remove aggregate.So
The PS balls suspension that will be filtrated to get afterwards is centrifuged 12h in 5000rpm, and the drying precipitate that will be obtained both obtained the~PS of 200nm
Ball.
By ethanol, HNO3(0.3mol·L-1) and tetraethyl orthosilicate with mass ratio 1：5：1 mixing, is stirred at room temperature to form molten
Glue, wherein addition~200nm PS balls, PS balls are 1 with the mass ratio of tetraethyl orthosilicate, fully infiltration, and suction filtration, drying are obtained
SiO2- PS ball composites；By SiO2- PS balls composite adds NaOH, NaAlO2In the aqueous solution, stir, NaOH,
NaAlO2With tetraethyl orthosilicate mass ratio 1：4：15, drying.
A support is placed in a water heating kettle with polytetrafluoroethyllining lining, and pours into a certain amount of water, control water
Addition only flood into support.Above support place a small container, sample is put into a small container, make water not with institute
Obtain powder directly contact.The crystallization 72h at 110 DEG C, cools down, dries, 2h removal PS ball templates are calcined at 550 DEG C, is had
The Y-type zeolite molecular sieve of three-dimensional order pore structure.
Embodiment 12
73.2mL styrene, 600mL water, 0.12g dodecyl sodium sulfates are added sequentially in the there-necked flask of 1L, 80 DEG C
Heating stirring, leads to N230min excludes air.Then, 0.33g potassium peroxydisulfate initiators use 10mL water dissolves, after 80 DEG C of heating
It is added in above-mentioned round-bottomed flask, 80 DEG C of heating stirring 18h.The PS balls mineral wool that will be obtained is filtered to remove aggregate.So
The PS balls suspension that will be filtrated to get afterwards is centrifuged 12h in 5000rpm, and the drying precipitate that will be obtained both obtained the~PS of 400nm
Ball.
By ethanol, HNO3(0.3mol·L-1) and tetraethyl orthosilicate with mass ratio 20：0.2：30 mixing, are stirred at room temperature shape
Into colloidal sol, addition~400nm PS balls, wherein PS balls are 3 with the mass ratio of tetraethyl orthosilicate, fully infiltration, and suction filtration, drying are obtained
To SiO2- PS ball composites；By SiO2- PS balls composite adds NaOH, NaAlO2In the aqueous solution, stir, NaOH,
NaAlO2With tetraethyl orthosilicate mass ratio 2：2：60, drying.
A support is placed in a water heating kettle with polytetrafluoroethyllining lining, and pours into a certain amount of water, control water
Addition only flood into support.Above support place a small container, sample is put into a small container, make water not with institute
Obtain powder directly contact.The crystallization 72h at 120 DEG C, cools down, dries, 5h removal PS ball templates are calcined at 550 DEG C, is had
The Y-type zeolite molecular sieve of three-dimensional order pore structure.
Claims (10)
1. a kind of three-dimensional order pore structure zeolite molecular sieve, it is characterised in that the zeolite molecular sieve has macroporous structure, macropore hole
Road is arranged in three-dimensional order, and macropore size is 50~700nm；The specific surface area of zeolite molecular sieve is 100~800m2/g。
2. a kind of three-dimensional order pore structure zeolite molecular sieve according to claim 1, it is characterised in that the zeolite molecules
It is one or more in type ZSM 5 molecular sieve, beta molecular sieve and Y type molecular sieve to sieve, wherein, the type ZSM 5 molecular sieve
Si/Al mol ratios are 8:1~100:1；The Si/Al mol ratios of the beta molecular sieve are 10:1~50:1；The Y type molecular sieve
Si/Al mol ratios be 4:1~30:1.
3. a kind of preparation method of the three-dimensional order pore structure zeolite molecular sieve described in claim 1, it is characterised in that the method
Comprise the following steps：
(1) ethanol, 0.3molL-1HNO3With tetraethyl orthosilicate example in mass ratio (1~20)：(0.2~5)：(1~30) mix
Close, be stirred at room temperature to form colloidal sol, add polystyrene (PS) ball, fully infiltration, suction filtration, drying obtain SiO2- PS ball composite woods
Material, wherein a diameter of 50~700nm of PS balls；
(2) by SiO2- PS balls composite is added in TPAOH or the tetraethyl ammonium hydroxide aqueous solution, suction filtration, drying
Afterwards, the NaAlO of 1mol/L is added2Solution so that Si/Al mol ratios (8~50):(0~1), drying；Or by SiO2- PS balls are answered
Condensation material adds NaOH, NaAlO2In the aqueous solution, stir, NaOH, NaAlO2With tetraethyl orthosilicate mass ratio (1~2)：
(2~4)：(15~60), drying；
(3) support is placed in the water heating kettle of polytetrafluoroethyllining lining, water is added in water heating kettle, the addition of water only flood into
Support, places a small container above support, and step (2) gained sample is put into a small container, and water is not straight with powder
Contact, the crystallization at 100~140 DEG C is cooled down after the completion of crystallization, dried, being calcined removal PS ball templates, obtains having three
Tie up orderly pore structure zeolite molecular sieve.
4. a kind of preparation method of three-dimensional order pore structure zeolite molecular sieve according to claim 3, it is characterised in that step
Suddenly the quality of (1) described PS balls is 1~3 times of tetraethyl orthosilicate.
5. a kind of preparation method of three-dimensional order pore structure zeolite molecular sieve according to claim 3, it is characterised in that step
Suddenly the concentration of (2) described TPAOH solution is 25~50wt%, adds quality and SiO2Mass ratio be 1：(0.1
~10)；The tetraethyl ammonium hydroxide solution concentration is 25~50wt%, adds quality and SiO2Mass ratio be 1：(0.1~
10)。
6. a kind of preparation method of three-dimensional order pore structure zeolite molecular sieve according to claim 3, it is characterised in that step
Suddenly (3) described crystallization time is 48~120h.
7. a kind of preparation method of three-dimensional order pore structure zeolite molecular sieve according to claim 3, it is characterised in that step
Suddenly the temperature of (3) described roasting is 500~900 DEG C, and roasting time is 1~12h.
8. a kind of preparation method of three-dimensional order pore structure zeolite molecular sieve, it is characterised in that three-dimensional order pore structure ZSM-5 types
The preparation of molecular sieve is comprised the following steps：
(1) PS balls are synthesized：36.6mL styrene, 600mL water, 0.12g dodecyl sodium sulfates are added sequentially to three mouthfuls of burnings of 1L
In bottle, 60 DEG C of heating stirrings lead to N2Gas 30min excludes air, and 0.33g potassium peroxydisulfate initiators use 10mL water dissolves, 60 DEG C
Be added to after heating in above-mentioned round-bottomed flask, the heating stirring 18h under the conditions of 60 DEG C, the filtering of the PS balls mineral wool that will obtain with
Aggregate is removed, the PS balls suspension being filtrated to get is centrifuged 12h in 5000rpm, and the drying precipitate for obtaining both had obtained PS balls；
(2) prepared by xerogel：By ethanol, 0.3molL-1HNO3With tetraethyl orthosilicate with mass ratio 1：5：1 mixing, room temperature
Stirring forms colloidal sol, adds the PS balls of step (1) synthesis, and wherein PS balls and the mass ratio of tetraethyl orthosilicate is 1, fully infiltration,
Suction filtration, drying, obtain SiO2- PS ball composites；By SiO2- PS balls composite adds 25wt% TPAOH water
In solution, SiO2It is 1 with the mass ratio of the TPAOH aqueous solution：10, after suction filtration, drying, add 0.1mol/L
NaAlO2Solution, SiO2With NaAlO2Mol ratio is 8：1, drying；
(3) crystallization：A support is placed in a water heating kettle with polytetrafluoroethyllining lining, and pours into a certain amount of water, controlled
The addition of water processed is only flooded into support, and a small container is placed above support, and step (2) gained sample is put into a little Rong
In device, make water not with gained powder directly contact, the crystallization 96h at 110 DEG C, cooling, drying, 600 DEG C be calcined 5h removal PS
Ball template, obtains the ZSM-5 zeolite molecular sieve with three-dimensional order pore structure.
9. a kind of preparation method of three-dimensional order pore structure zeolite molecular sieve, it is characterised in that three-dimensional order pore structure β type molecules
The preparation of sieve is comprised the following steps：
(1) PS balls are synthesized：140mL styrene, 600mL water, 0.12g dodecyl sodium sulfates are added sequentially to the there-necked flask of 1L
In, 90 DEG C of heating stirrings lead to N2Gas 30min excludes air, and 0.33g potassium peroxydisulfate initiators use 10mL water dissolves, and 90 DEG C add
It is added to after heat in above-mentioned round-bottomed flask, 90 DEG C of heating stirring 18h, the PS balls mineral wool that will be obtained is filtered to remove reunion
Thing, the PS balls suspension being filtrated to get is centrifuged 12h in 5000rpm, and the drying precipitate that will be obtained both had obtained PS balls；
(2) prepared by xerogel：By ethanol, 0.3molL-1HNO3With tetraethyl orthosilicate with mass ratio 20：5：30 mixing, room
Temperature stirring forms colloidal sol, adds the PS balls of step (1) synthesis, and wherein PS balls and the mass ratio of tetraethyl orthosilicate is 3, fully leaching
Profit, suction filtration, drying obtain SiO2- PS ball composites；By SiO2- PS balls composite adds 35wt% tetraethyl ammonium hydroxides
In the aqueous solution, SiO2Quality is 1 with the mass ratio of the tetraethyl ammonium hydroxide aqueous solution：5, after suction filtration, drying, add 0.1mol/L
NaAlO2Solution, SiO2With NaAlO2Mol ratio is 30：1, drying；
(3) crystallization：A support is placed in a water heating kettle with polytetrafluoroethyllining lining, and pours into a certain amount of water, controlled
The addition of water processed is only flooded into support, and a small container is placed above support, and step (2) gained sample is put into a little Rong
In device, make water not with gained powder directly contact, the crystallization 48h at 140 DEG C, cooling, drying, 900 DEG C be calcined 1h removal PS
Ball template, obtains the zeolite beta molecular sieve with three-dimensional order pore structure.
10. a kind of preparation method of three-dimensional order pore structure zeolite molecular sieve, it is characterised in that three-dimensional order pore structure Y types point
The preparation of son sieve is comprised the following steps：
(1) PS balls are synthesized：8mL styrene, 600mL water, 0.12g dodecyl sodium sulfates are added sequentially to the there-necked flask of 1L
In, 60 DEG C of heating stirrings lead to N2Gas 30min excludes air, and 0.33g potassium peroxydisulfate initiators use 10mL water dissolves, and 60 DEG C add
It is added to after heat in above-mentioned round-bottomed flask, 60 DEG C of heating stirring 18h, the PS balls mineral wool that will be obtained is filtered to remove reunion
Thing, the PS balls suspension that will be filtrated to get is centrifuged 12h in 5000rpm, and the drying precipitate that will be obtained both had obtained PS balls；
(2) prepared by xerogel：By ethanol, 0.3molL-1HNO3With tetraethyl orthosilicate with mass ratio 1：0.2：1 mixing, room
Temperature stirring forms colloidal sol, adds the PS balls of step (1) synthesis, and wherein PS balls and the mass ratio of tetraethyl orthosilicate is 1, fully leaching
Profit, suction filtration, drying obtain SiO2- PS ball composites；By SiO2- PS balls composite adds NaOH, NaAlO2In the aqueous solution,
Stir, NaOH, NaAlO2With tetraethyl orthosilicate mass ratio 1：2：15, drying；
(3) crystallization：A support is placed in a water heating kettle with polytetrafluoroethyllining lining, and pours into a certain amount of water, controlled
The addition of water processed is only flooded into support, and a small container is placed above support, and step (2) gained sample is put into a little Rong
In device, make water not with gained powder directly contact, the crystallization 96h at 100 DEG C, cooling, drying, 500 DEG C be calcined 10h removal PS
Ball template, obtains the Y-type zeolite molecular sieve with three-dimensional order pore structure.
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| CN107737603A (en) * | 2017-09-05 | 2018-02-27 | 天津大学 | A kind of counter opal molecular sieve catalyst and preparation method |
| CN114682234A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | Preparation method of pressure swing adsorption molecular sieve adsorbent |
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| CN114682234B (en) * | 2020-12-31 | 2023-07-28 | 中国石油化工股份有限公司 | Preparation method of pressure swing adsorption molecular sieve adsorbent |
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