CN106268928B - A kind of ordered big hole-is mesoporous-synthetic method of micropore multistage pore catalyst - Google Patents
A kind of ordered big hole-is mesoporous-synthetic method of micropore multistage pore catalyst Download PDFInfo
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Abstract
The invention discloses ordered big hole-made of a kind of nanocrystalline accumulation as Beta molecular sieve it is mesoporous-synthetic method of micropore hierarchical pore molecular sieve catalyst, in conjunction with template and chemical rotating crystal method, orderly foramen magnum-mesoporous-micropore hierarchical pore molecular sieve catalyst is prepared in the system using glycerol as medium.Present invention incorporates the important scientific research meanings constructed with macropore, the significant application value of mesoporous and microcellular structure multistage porous molecular sieve and multistage pore canal order, developed with ordered big hole-it is mesoporous-molecular sieve of micropore multi-stage artery structure is for conventional molecular sieve, with better catalytic activity, selective catalysis performance and higher structural stability, have a extensive future.
Description
Technical field
The present invention relates to Zeolite synthesis technical fields, and in particular to one kind is as made of the nanocrystalline accumulation of Beta molecular sieve
Ordered big hole-is mesoporous-synthetic method of micropore multistage pore catalyst.
Background technique
Beta zeolite molecular sieve has unique three-dimensional staggered twelve-ring cellular structure, has good structure choice
Property, acid catalysis characteristic and hydrothermal stability and good absorption, catalytic performance, are widely applied to be hydrocracked, isomerization, alkene
In the petrochemical process such as hydrocarbon hydration.However its micropore canals limits reactant molecule and product molecule in catalytic process
Circulation and diffusion, limit the application range of molecular sieve.
In order to overcome the diffusion restricted problem of zeolite molecular sieve, first method is the molecular sieve of synthesizing nano-particle.It receives
Rice molecular sieve is with biggish external surface area and shorter diffusion path, but its complicated removal process and lower raw material
Utilization rate makes directly nano molecular sieve to be used to have significant limitation as catalyst on a large scale.Second method is that synthesis is more
The molecular sieve in grade duct.This kind of material also contains biggish mesoporous or mesopore-macropore cellular structure other than with micropore canals,
Thus have the high diffusibility of mesoporous material can be with the high catalytic performance of zeolite molecular sieve simultaneously.Nanosizing advantage is introduced into more
In grade porous molecular sieve structure, the advantage that can give full play to the two simultaneously again can be to avoid the deficiency of the two.
Currently, the method for synthesizing multistage porous molecular sieve is introducing macropore/Jie in the synthetic system of conventional microporous molecular sieve
Pore structure is self-assembly of the aggregation with multi-stage artery structure using nano zeolite crystal.Wherein, molecular sieve is nanocrystalline
Aggregation has the problems such as advantage of nano zeolite can solve production separation again simultaneously.The thus synthesis of polycrystalline aggregation molecular sieve
Great attention is obtained.Molecular sieve polycrystal divides compared with having better mass transfer ability for conventional mesoporous single crystals material
The microcellular structure of son sieve is more complete, and good hydrothermal stability filters the advantages that simple.
The research of existing multi-stage pore zeolite molecular sieve is concentrated mainly on constructing for hierarchical porous structure, has for multistage pore canal
The regulation of sequence is rarely reported.However, in molecular screen material orderly cellular structure construct to design synthesizing new high-efficiency multi-stage
Pore zeolite catalyst has very important scientific theory directive significance.The concern of researchers is caused in recent years.
As Ryoo study group [Nat.Mater.2006,5,718-723.] prepares three using organosilan macromolecular as mesoporous template
The mesoporous zeolite molecular sieve that dimension is orderly and aperture is controllable.Andreas Stein study group [J.Am.Chem.Soc.1999,121,
4308-4309.] using monodispersed polystyrene microsphere as macropore template three-dimensional ordered macroporous molecular sieve is prepared for the first time.
At present have the controlledly synthesis of multi-stage pore zeolite molecular sieve multistage pore canal order is limited only to it is mesoporous or macropore orderly, together
When have ordered big hole and order mesoporous multi-stage pore zeolite molecular sieve not yet has been reported that.
Summary of the invention
The purpose of the present invention is to provide a kind of ordered big hole-it is mesoporous-synthetic method of micropore multistage pore catalyst, use
The product of this method synthesis can sieve the advantage of both nanocrystalline and multi-stage artery structures with binding molecule, expand effectively shortening to circulate
The transmittability of substance can be effectively improved while dissipating path again.
To achieve the above object, the technical solution adopted by the present invention are as follows: a kind of ordered big hole-is mesoporous-and micropore multi-stage porous urges
The synthetic method of agent, comprising the following steps:
1) it disperses macropore template and mesoporous template (being also silicon source) in the aqueous solution containing organic carbon source, ultrasonic disperse
Suspension solution is obtained, sulfuric acid is then added, through evaporation self assembly and carbonization curing process, obtains molecular sieve persursor material (titanium dioxide
Silicon nanosphere/carbon mixing material)；
2) mixed solution I is stirred evenly to obtain by silicon source and organic formwork agent are soluble in water；
3) molecular sieve precursor material made from step 1) is transferred in mixed solution I, stirs evenly to obtain mixed solution
II；
4) water in rotary evaporation removal mixed solution I I is carried out under vacuum systems, and glycerol is then added and is uniformly mixed,
It is packed into autoclave, carries out turning brilliant processing, there is unformed silica nanosphere in molecular sieve precursor material
Turn brilliant to be nano molecular sieve under the action of machine template, obtains the mixing material of the nanocrystalline molecular sieve/carbon of Beta；
5) mixing material of the nanocrystalline molecular sieve/carbon of the resulting Beta of step 4) is washed, is dried in vacuo, and is finally carried out
Roasting, obtain the ordered big hole-it is mesoporous-micropore multistage pore catalyst (ordered big hole-is mesoporous-micropore multi-stage porous Beta molecule
Sieve monocrystalline).
In above scheme, the macropore template be monodispersed polystyrene microsphere, poly (methyl methacrylate) micro-sphere or
Polymer microballoons, the partial sizes such as polystyrene-poly methyl methacrylate-polymethylacrylic acid propyl sulfonic acid sodium copolymer microsphere are
100~1000nm；Mesoporous template is monodispersed silica nanosphere, and partial size is 10~50nm；Organic carbon source be glucose,
One of sucrose, fructose, lactose, maltose；Organic formwork agent is tetraethyl ammonium hydroxide；Silicon source is sodium metaaluminate, isopropyl
One of aluminium alcoholates, hydrazine aluminum sulfate.
In above scheme, the mass ratio of mesoporous template, macropore template, organic carbon source and sulfuric acid in the step 1) is 1:
(6~8): (0.8~1.2): (0.08~0.24)；The molar ratio of mesoporous template and silicon source and organic formwork agent in step 2) is
1:(0.01~0.05): (0.6~1.5)；The solid-to-liquid ratio of glycerol is 1:(10~15 in mesoporous template and step 4)) g/ml.
In above scheme, temperature used in the evaporation self assembling process in the step 1) be 30~60 DEG C, the time be 6~
24h。
In above scheme, the carbonization solidification process includes first carbonization and two steps of secondary carbonization, is carbonized for the first time
Step are as follows: be heated to 90~1100 DEG C of 4~6h of heat preservation, be again heated to 160~180 DEG C of 4~6h of heat preservation；Secondary carburising step are as follows:
The resulting product that will tentatively be carbonized, which is placed in inert atmosphere, is heated to 600~700 DEG C of 2~4h of roasting.
In above scheme, in the step 2) whipping temp of mixed solution I I be 15~40 DEG C, mixing time be 0.5~
1h；The whipping temp of mixed solution I II is 15~40 DEG C in the step 3), and mixing time is 1~2h.
In above scheme, the volume of high temperature water heating kettle used is 50~150mL in the step 4), and described turns brilliant processing
Temperature is 150~200 DEG C, and turning the brilliant time is 6~12d.
In above scheme, in the step 5) vacuum drying temperature be 60~120 DEG C, the time be 2~for 24 hours.
In above scheme, the maturing temperature in the step 5) is 500~600 DEG C, and calcining time is 4~7h.
In above scheme, the inert atmosphere is nitrogen or argon gas etc..
According to above scheme synthesize ordered big hole-it is mesoporous-micropore multistage pore catalyst (foramen magnum-mesoporous-micropore multi-stage porous
Beta zeolite single crystal), it is assembled by Beta molecular sieve is nanocrystalline, there is three-dimensional ordered macroporous-mesoporous cellular structure,
Macropore diameter is 100~1000nm, and mesoporous pore size is 10~50nm.
The principle of the present invention are as follows: the present invention uses macropore template (polymer microballoon) and mesoporous template (silica nanometer
Ball) it is self-assembly of three-dimensional order matrix arrangement, it then carries out carbonization curing process and obtains silica nanosphere/carbon point
Son sieve persursor material.Molecular sieve precursor material is sufficiently mixed with silicon source and organic formwork agent, is removed by rotary evaporation
The water in mixed system is removed, enters silicon source and organic formwork agent molecule uniformly penetrating in presoma system, it is anti-to transfer to high pressure
It answers in kettle, using glycerol as reaction medium, crystallizes amorphous silica gradually under the action of organic formwork agent molecule
It is nanocrystalline for molecular sieve.Finally remove polymer microballoon and carbon material obtain the ordered big hole-it is mesoporous-catalysis of micropore multi-stage porous
Agent (ordered big hole-mesoporous-micropore multi-stage porous Beta zeolite single crystal).
The invention has the benefit that
1) products obtained therefrom of the present invention combines the nanocrystalline advantage with both multi-stage artery structures of Beta molecular sieve, effective
The transmittability that substance can be effectively improved while shortening circulation diffusion path again, has than conventional mesoporous single crystals molecular screen material
There is better mass transfer ability.
2) glycerol system is used in the present invention during turning brilliant.On the one hand, the property of glycerol is similar with water section, sweet
Zeolite molecular sieve can be limited under oil systems turns brilliant speed, but can allow the crystallization of molecular sieve；On the other hand, glycerol viscosity
Greatly, poor fluidity has functioned simultaneously as the proppant of big hole on framework during turning brilliant, has been conducive to the guarantor of big hole on framework in product
It holds.
3) present invention obtained in product have ordered big hole-it is mesoporous-microcellular structure, macropore diameter and mesoporous pore size can
Individually regulated and controled by selecting various sizes of macropore template and mesoporous template, thus to realize the type multistage porous molecular sieve knot
The optimization of structure provides theoretical model.
Detailed description of the invention
Fig. 1 be ordered big hole-made from the embodiment of the present invention 1 it is mesoporous-XRD diagram of micropore multistage pore catalyst.
Fig. 2 be ordered big hole-made from the embodiment of the present invention 1 it is mesoporous-(a, b) scanning electron microscope of micropore multistage pore catalyst
Figure and (c, d) transmission electron microscope picture.
Fig. 3 be ordered big hole-made from the embodiment of the present invention 1 it is mesoporous-(a) of micropore multistage pore catalyst29Si NMR and
(b)27Al NMR figure.
Fig. 4 be ordered big hole-made from the embodiment of the present invention 1 it is mesoporous-(a) nitrogen adsorption of micropore multistage pore catalyst is bent
Line, (b) micropore size distribution map and (c) mesoporous pore size distribution map.
Fig. 5 be the embodiment of the present invention 2 (a), embodiment 3 (b), ordered big hole-made from embodiment 4 (c) it is mesoporous-micropore is more
The scanning electron microscope (SEM) photograph of grade pore catalyst.
Fig. 6 be the embodiment of the present invention 2 (a), embodiment 3 (b), ordered big hole-made from embodiment 4 (c) it is mesoporous-micropore is more
The mesoporous pore size distribution map of grade pore catalyst.
Specific embodiment
Further the present invention will be described with reference to the accompanying drawings and examples, but the contents of the present invention are not limited solely to
The following examples.
In following embodiment, unless specific instructions, the reagent is commercially available chemical reagent.
Embodiment 1
A kind of ordered big hole-is mesoporous-micropore multistage pore catalyst, preparation method includes the following steps:
By 20g polystyrene microsphere (macropore template, 500nm) and 3g silica nanosphere, (mesoporous template is also silicon
Source, 30nm) it sequentially adds ultrasonic disperse in 100g aqueous sucrose solution (organic carbon source, mass concentration 3%) and obtains suspension, then
Be added the sulfuric acid solution that 3g mass fraction is 10%, intermediary hole template, macropore template, organic carbon source and sulfuric acid mass ratio be
1:6.6:1:0.1, through evaporation self assembly (being kept the temperature for 24 hours at 40 DEG C) and carbonization solidification (including be tentatively carbonized and secondary carbonisation,
Preliminary carbonisation is that 6h is heated at 100 DEG C, then heats 6h at 160 DEG C, secondary carbonisation be in nitrogen atmosphere and
High-temperature roasting 4h at 700 DEG C) obtain silica nanosphere/carbon mixing material (molecular sieve precursor material)；0.082g is inclined
Sodium aluminate (silicon source) is dissolved in 18g tetraethyl ammonium hydroxide aqueous solution (organic formwork agent, mass concentration 25%), at room temperature
1h is sufficiently stirred and obtains mixed solution I, wherein the molar ratio of silicon source, silicon source and organic formwork agent is 1:0.02:0.6, molten to mixing
Molecular sieve precursor material is added in liquid I, 1h is sufficiently stirred at room temperature and obtains mixed solution I I.Rotary evaporation removes under vacuum systems
The water in mixed solution I I is removed, 30ml glycerol is then added and is uniformly mixed in the autoclave for being packed into 50ml, is heated to 150 DEG C
Turn crystalline substance 12d, by resulting Beta molecular sieve it is nanocrystalline/mixture of carbon is repeatedly washed with deionized water and vacuum is done at 60 DEG C
It is dry for 24 hours, finally roasted at 550 DEG C 6h remove support carbon material obtain the ordered big hole-it is mesoporous-micropore multistage pore catalyst
(ordered big hole-mesoporous-micropore multi-stage porous Beta molecular sieve).
Fig. 1 is the XRD diagram that product is made in this example, occurs the characteristic diffraction peak of Beta molecular sieve in figure, and peak intensity is high,
Illustrate that the crystallinity of gained Beta molecular sieve is very high.(a, b) scanning electron microscope (SEM) photograph and (c, d) that Fig. 2 is the obtained product of this example are thoroughly
Electron microscope is penetrated, gained Beta molecular sieve maintains complete three-dimensional ordered macroporous-mesoporous cellular structure, and macropore diameter is
500nm, macropore hole wall nanocrystalline are accumulated by the Beta molecular sieve of 30nm or so.Fig. 3 is (a) that product is made in this example
29Si NMR and (b) 27Al NMR schemes.There is no Q2 species (two terminal hydroxy groups of connection in product after turning brilliant known to Fig. 3 (a)
Silicon species, chemical shift is mainly made of Q4 species (silicon species for being not connected to terminal hydroxy group being condensed completely) in -92ppm),
There are a small amount of Q3 species (silicon species of one terminal hydroxy group of connection).Illustrate that product crystallinity is very high.The product known to Fig. 3 (b)
Substantially exist with the aluminium species (chemical shift 52ppm) of four-coordination and there is no hexa-coordinate aluminium (chemical shift 0ppm), explanations
There are in the skeleton of Beta zeolite molecular sieve substantially in a manner of four-coordination for the aluminium in product after turning brilliant.Fig. 4 is respectively this
Nitrogen adsorption curve 4 (a), micropore size distribution map 4 (b) and the mesoporous pore size distribution map 4 (c) of product is made in example.By Fig. 4
(a) adsorption isothermal curve of products obtained therefrom illustrates to deposit in product when relative pressure is less than 0.02 in the presence of very big absorption known to
In a large amount of micropore canals structure；Products obtained therefrom, there are hysteresis loop, illustrates exist in the range of relative pressure is 0.7~1.0
Mesopore orbit structure.The micropore size of product is concentrated mainly on 0.56nm or so, while material in conjunction with known to Fig. 4 (b) and Fig. 4 (c)
There are apertures in material in the meso-hole structure of 2.8nm or so, and illustrating products obtained therefrom, there are mesopore orbit structures, and pore-size distribution is opposite
It is relatively narrow.The micropore specific area of product is 129m2/ g, mesopore surface area 93m2/g。
Embodiment 2
A kind of ordered big hole-is mesoporous-micropore multistage pore catalyst, preparation method includes the following steps:
By 16g polystyrene microsphere (macropore template, 300nm) and 2g silica nanosphere, (mesoporous template is also silicon
Source, 40nm) it sequentially adds ultrasonic disperse in 80g aqueous sucrose solution (organic carbon source, mass concentration 2%) and obtains suspension, then
Be added 1.6g mass fraction be 10% sulfuric acid solution, intermediary hole template, macropore template, organic carbon source and sulfuric acid mass ratio
For 1:8:0.8:0.08, (including tentatively it is carbonized and was carbonized with secondary through evaporation self assembly (keeping the temperature 12h at 60 DEG C) and carbonization solidification
Journey, preliminary carbonisation are that 4h is heated at 1100 DEG C, and 4h is then heated at 180 DEG C, and secondary carbonisation is in nitrogen gas
High-temperature roasting 4h at atmosphere and 700 DEG C) silica nanosphere/carbon mixing material (molecular sieve precursor material)；By 0.34g
Aluminium isopropoxide (silicon source) is dissolved in 15.7g tetraethyl ammonium hydroxide aqueous solution (organic formwork agent, mass concentration 25%), room
1h is sufficiently stirred under temperature and obtains mixed solution I, wherein the molar ratio of silicon source, silicon source and organic formwork agent is 1:0.05:0.8, to mixed
It closes and molecular sieve precursor material is added in solution I, 1h is sufficiently stirred at room temperature and obtains mixed solution I I.It rotates and steams under vacuum systems
Hair removes the water in mixed solution I I, and 30ml glycerol is then added and is uniformly mixed in the autoclave for being packed into 50ml, is heated to
200 DEG C turn crystalline substance 9d, by resulting Beta molecular sieve it is nanocrystalline/mixture of carbon repeatedly washed with deionized water and at 60 DEG C very
Sky is dry for 24 hours, finally roasted at 550 DEG C 6h remove support carbon material obtain the ordered big hole-it is mesoporous-micropore multi-stage porous urges
Agent (ordered big hole-mesoporous-micropore multi-stage porous Beta molecular sieve).
Fig. 5 (a) is the scanning electron microscope (SEM) photograph that product is made in this example.Gained Beta molecular sieve maintains complete three-dimensional order
Foramen magnum-mesoporous cellular structure, macropore diameter 300nm, macropore hole wall are the nanocrystalline heaps of Beta molecular sieve by 40nm or so
Product forms.Fig. 6 (a) is the mesoporous pore size distribution map that product is made in this example, and there are apertures in 3.5nm or so for product as seen from the figure
Meso-hole structure, and pore-size distribution relative narrower.
Embodiment 3
A kind of ordered big hole-is mesoporous-micropore multistage pore catalyst, preparation method includes the following steps:
By 21g polystyrene microsphere (macropore template, 400nm) and 3g silica nanosphere, (mesoporous template is also silicon
Source, 50nm) it sequentially adds ultrasonic disperse in 90g aqueous sucrose solution (organic carbon source, mass concentration 4%) and obtains suspension, then
Be added 3.6g mass fraction be 10% sulfuric acid solution, intermediary hole template, macropore template, organic carbon source and sulfuric acid mass ratio
For 1:7:1.2:0.12, (including tentatively it is carbonized and was carbonized with secondary through evaporation self assembly (keeping the temperature 12h at 60 DEG C) and carbonization solidification
Journey, preliminary carbonisation are that 6h is heated at 100 DEG C, and 6h is then heated at 160 DEG C, and secondary carbonisation is in nitrogen atmosphere
High-temperature roasting 4h at 700 DEG C) silica nanosphere/carbon mixing material (molecular sieve precursor material)；By 0.164g
Sodium metaaluminate (silicon source) is dissolved in 22g tetraethyl ammonium hydroxide aqueous solution (organic formwork agent, mass concentration 25%), room temperature
Under 1h be sufficiently stirred obtain mixed solution I, wherein the molar ratio of silicon source, silicon source and organic formwork agent is 1:0.04:0.76, to mixing
Molecular sieve precursor material is added in solution I, 1h is sufficiently stirred at room temperature and obtains mixed solution I I.The rotary evaporation under vacuum systems
The water in mixed solution I I is removed, 30ml glycerol is then added and is uniformly mixed in the autoclave for being packed into 50ml, is heated to 180
DEG C turn crystalline substance 12d, by resulting Beta molecular sieve it is nanocrystalline/mixture of carbon is repeatedly washed with deionized water and the vacuum at 60 DEG C
It is dry for 24 hours, finally roasted at 550 DEG C 6h remove support carbon material obtain the ordered big hole-it is mesoporous-catalysis of micropore multi-stage porous
Agent (ordered big hole-mesoporous-micropore multi-stage porous Beta molecular sieve).
Fig. 5 (b) is the scanning electron microscope (SEM) photograph that product is made in this example.Gained Beta molecular sieve maintains complete three-dimensional order
Foramen magnum-mesoporous cellular structure, macropore diameter 400nm, macropore hole wall are the nanocrystalline heaps of Beta molecular sieve by 50nm or so
Product forms.Fig. 6 (b) is the mesoporous pore size distribution map that product is made in this example, and there are apertures in 4.0nm or so for product as seen from the figure
Meso-hole structure, and pore-size distribution relative narrower.
Embodiment 4
A kind of ordered big hole-is mesoporous-micropore multistage pore catalyst, preparation method includes the following steps:
By 10g polystyrene microsphere (macropore template, 600nm) and 1.25g silica nanosphere (mesoporous template, also for
Silicon source, 10nm) it sequentially adds ultrasonic disperse in 25g aqueous sucrose solution (organic carbon source, mass concentration 5%) and obtains suspension, so
Afterwards be added 3g mass fraction be 10% sulfuric acid solution, intermediary hole template, macropore template, organic carbon source and sulfuric acid mass ratio
For 1:8:1:0.24, (including tentatively it is carbonized and was carbonized with secondary through evaporation self assembly (being kept the temperature for 24 hours at 40 DEG C) and carbonization solidification
Journey, preliminary carbonisation are that 6h is heated at 100 DEG C, and 6h is then heated at 160 DEG C, and secondary carbonisation is in nitrogen atmosphere
High-temperature roasting 4h at 700 DEG C) silica nanosphere/carbon mixing material (molecular sieve precursor material)；By 0.082g
Aluminium isopropoxide (silicon source) is dissolved in 18g tetraethyl ammonium hydroxide aqueous solution (organic formwork agent, mass concentration 25%), room temperature
Under 1h be sufficiently stirred obtain mixed solution I, wherein the molar ratio of silicon source, silicon source and organic formwork agent is 1:0.019:1.47, to mixed
It closes and molecular sieve precursor material is added in solution I, 1h is sufficiently stirred at room temperature and obtains mixed solution I I.It rotates and steams under vacuum systems
Hair removes the water in mixed solution I I, and 20ml glycerol is then added and is uniformly mixed in the autoclave for being packed into 50ml, is heated to
150 DEG C turn crystalline substance 12d, by resulting Beta molecular sieve it is nanocrystalline/mixture of carbon repeatedly washs with deionized water and at 60 DEG C
Vacuum drying roasted at 550 DEG C for 24 hours, finally 6h remove support carbon material obtain the ordered big hole-it is mesoporous-micropore multi-stage porous
Catalyst (ordered big hole-mesoporous-micropore multi-stage porous Beta molecular sieve).
Fig. 5 (c) is the scanning electron microscope (SEM) photograph that product is made in this example.Gained Beta molecular sieve maintains complete three-dimensional order
Foramen magnum-mesoporous cellular structure, macropore diameter 600nm, macropore hole wall are the nanocrystalline heaps of Beta molecular sieve by 10nm or so
Product forms.Fig. 6 (c) is the mesoporous pore size distribution map that product is made in this example, and there are apertures in 2.1nm or so for product as seen from the figure
Meso-hole structure, and pore-size distribution relative narrower.
The foregoing is merely the preferred embodiment of the present invention, it is noted that comes for those of ordinary skill in the art
It says, without departing from the concept of the premise of the invention, make several modifications and variations, these belong to protection model of the invention
It encloses.
Claims (8)
1. a kind of ordered big hole-is mesoporous-synthetic method of micropore multistage pore catalyst, which comprises the following steps:
1) it disperses macropore template and mesoporous template in the aqueous solution containing organic carbon source, ultrasonic disperse obtains suspension solution, so
After sulfuric acid is added, through evaporation self assembly and carbonization curing process, obtain molecular sieve persursor material；
2) mixed solution I is stirred evenly to obtain by silicon source and organic formwork agent are soluble in water；
3) molecular sieve precursor material made from step 1) is transferred in mixed solution I, stirs evenly to obtain mixed solution I I；
4) water in rotary evaporation removal mixed solution I I is carried out under vacuum systems, and glycerol is then added and is uniformly mixed, is packed into
In autoclave, carries out turning brilliant processing, obtain the mixing material of the nanocrystalline molecular sieve/carbon of Beta；
5) mixing material of the nanocrystalline molecular sieve/carbon of Beta obtained by step 4) washed, be dried in vacuo, finally roasted
Burn, obtain the ordered big hole-it is mesoporous-micropore multistage pore catalyst；
The macropore template is monodispersed polystyrene microsphere, poly (methyl methacrylate) micro-sphere or polystyrene-poly methyl
Methyl acrylate-polymethylacrylic acid propyl sulfonic acid sodium copolymer microsphere, partial size are 100~1000nm；Mesoporous template is single point
Scattered monox nanometer ball, partial size are 10~50nm；Organic carbon source is glucose, sucrose, fructose, lactose, one in maltose
Kind；Organic formwork agent is tetraethyl ammonium hydroxide；Silicon source is one of sodium metaaluminate, aluminium isopropoxide, hydrazine aluminum sulfate.
2. synthetic method according to claim 1, which is characterized in that mesoporous template, macropore template in the step 1),
The mass ratio of organic carbon source and sulfuric acid is 1:(6~8): (0.8~1.2): (0.08~0.24)；In mesoporous template and step 2)
Silicon source and the molar ratio of organic formwork agent are 1:(0.01~0.05): (0.6~1.5)；Glycerol in mesoporous template and step 4)
Solid-to-liquid ratio is 1:(10~15) g/ml.
3. synthetic method according to claim 1, which is characterized in that the evaporation self assembly temperature is 30~60 DEG C, when
Between for 6~for 24 hours.
4. synthetic method according to claim 1, which is characterized in that the carbonization solidification process includes preliminary carbonization and two
Two steps of secondary carbonization, first carburising step are as follows: be heated to 90~110 DEG C of 4~6h of heat preservation, be again heated to 160~180 DEG C of heat preservations
4~6h；Secondary carburising step are as follows: the resulting product that will tentatively be carbonized, which is placed in inert atmosphere, is heated to 600~700 DEG C of roastings 2
~4h.
5. synthetic method according to claim 1, which is characterized in that step 4) the transfer crystalline substance treatment temperature be 150~
200 DEG C, turning the brilliant time is 6~12d.
6. synthetic method according to claim 1, which is characterized in that in the step 5) vacuum drying temperature be 60~
120 DEG C, vacuum drying time be 2~for 24 hours.
7. synthetic method according to claim 1, which is characterized in that maturing temperature is 500~600 in the step 5)
DEG C, calcining time is 4~7h.
8. foramen magnum-mesoporous-micropore multistage pore catalyst made from any one of claim 1~7 synthetic method, it is by Beta
Molecular sieve is nanocrystalline to be assembled, the foramen magnum-mesoporous cellular structure with three-dimensional order, and macropore diameter is 100~1000nm, is situated between
Hole aperture is 2~5nm.
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| CN106986735B (en) * | 2017-04-18 | 2019-11-15 | 罗帮亮 | A method of the methanol based on porous structure Zeolite molecular sieve catalysis prepares aromatic hydrocarbons |
| CN107032369B (en) * | 2017-05-10 | 2019-07-02 | 武汉凯迪工程技术研究总院有限公司 | Mesoporous Beta zeolite and preparation method thereof |
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