CN109748291A - A kind of preparation method with super large mesoporous hierarchical porous structure zeolite molecular sieve - Google Patents
A kind of preparation method with super large mesoporous hierarchical porous structure zeolite molecular sieve Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods with super large mesoporous hierarchical porous structure zeolite molecular sieve, comprising the following steps: has partial size for the solid SiO of 30~80nm for evenly dispersed2The aqueous solution of spheric granules and structure directing agent carries out Crystallizing treatment 10~48 hours at 110~150 DEG C in steam condition;Calcined material after Crystallizing treatment is removed into structure directing agent, obtains the hierarchical porous structure zeolite for having super large mesoporous.This preparation method process is simple, template is at low cost, has high industrial applications prospect.
Description
Technical field
The invention belongs to inorganic material synthesis and catalytic fields.It is different from the mesoporous zeolite prepared in the past, the present invention is with ball
Shape SiO2Simultaneously as silicon source and super large mesoporous template, the cost of template is greatly reduced, and by the mesoporous of mesoporous zeolite
Aperture is expanded to the super large mesoporous range of 30-50nm, higher for reaction system viscosity or have larger reaction molecular to participate in
Reaction process is remarkably improved the diffusion mass transfer performance of mesopore orbit.This preparation method process is simple, template is at low cost, tool
There is high industrial applications prospect.
Background technique
Multilevel structure zeolite (HSZs) can be considered the zeolite micropore duct as microreactor and provide Jie of transmission channel
The assembly system that hole is constituted.According to the difference of cellular structure, HSZs can be divided into micro--mesoporous, micro--macropore and micro--Jie-macropore boiling
Stone.Micro--large pore zeolite is usually made by hard template method, and common template has mesopore silicon oxide, PS bead and CaCO3Particle
Dosage Deng, blind hole, template is high and template hydrophobicity is the main problem in its synthesis process.Micro--mesoporous zeolite is
Most commonly used one kind HSZs is studied at present, and is widely used in all kinds of catalysis reactions.Its main preparation methods includes " from upper
Under and " and " from bottom to top " method, mesoporous pore size is usually in 2-20nm.And micro--super large mesoporous zeolite with the duct 30-50nm
Synthesis is but still difficult, is primarily limited to the mesoporous template and hole link of suitable dimension.Supramolecular is joined
With or system viscosity is biggish reacts, micro--super large mesoporous zeolite has important potential using value.On the other hand, multistage knot
The ideal model of structure zeolite is the zeolite skeleton that mesopore orbit three-dimensional runs through crystallization.
Schwieger etc. (Advanced Materials, 2015,27 (6), 1066-1070) is reported with mesoporous oxidation
Silicon particle (MSPs) is silicon source and macropore template, obtains micro--macropore Silicalite-1 zeolite list by steam auxiliary crystallization
It is brilliant.A kind of new thinking is provided for the synthesis of multilevel structure zeolite.In practical catalytic process, mesopore orbit is not only to mention
For the diffusion transport channel of macromolecular, the generation of carbon distribution in micropore canals is reduced, is more that can expose more catalysis to live
Property site, thus improve catalytic activity in addition select type selectivity.Therefore, compared to micro--large pore zeolite, micro--super large mesoporous zeolite
Not only diffusion admittance can be provided but also external surface area can be greatly increased.Although the mesoporous monox nanometer particle of 30-50nm
(MSNs) it can synthesize, it might even be possible to prepare micro--super large mesoporous Silicalite-1 zeolite as template.Due to
Silicalite-1 lacks effective activated centre, and application range is extremely limited, is more as a kind of ideal model material
Expect to verify the feasibility of synthetic method.If having with micro--super large mesoporous zeolite of the method preparation containing activated centre (hetero atom)
Two approach: one be in MSNs skeleton introducing hetero-atoms as template;The other is using MSNs as silicon source, object containing hetero atom
Matter is as activated centre presoma.First method, the preparation process of MSNs itself are miscellaneous with regard to comparatively laborious time-consuming and higher cost
What the introducing of atom has influence also to need to continue to grope the pattern of MSNs.For second method, since local hetero atom is dense
Height is spent, will cause zeolite nucleation crystallization difficulty, is only capable of obtaining the micro--super of hetero atom concentration lower (silicon/hetero atom is higher than 200)
Big mesoporous zeolite.
Summary of the invention
For the shortcoming of the existing super large mesoporous zeolite method of synthesis, the purpose of the present invention is to provide a kind of simple low costs
The preparation method containing super large mesoporous zeolite molecular sieve.
The present invention provides a kind of preparation methods with super large mesoporous hierarchical porous structure zeolite, which is characterized in that packet
Include following steps:
There is partial size for the solid SiO of 30~80nm (preferably 30~60nm, more preferably 40~50nm) for evenly dispersed2It is spherical
The aqueous solution of particle and structure directing agent carries out Crystallizing treatment 10~48 hours at 110~150 DEG C in steam condition;
Calcined material after Crystallizing treatment is removed into structure directing agent, obtains the hierarchical porous structure zeolite for having super large mesoporous.
Hard template preparation method different from the past, the present invention is with the solid SiO of greater particle size simple and easy to get2Spherical
Grain as silicon source and super large mesoporous template, greatly reduces the cost of template, improves combined coefficient, material yield simultaneously
Nearly 100%, synthesis process is more green, and resulting hierarchical porous structure zeolite has the super large mesoporous structure of three-dimensional perforation,
Spherical mesoporous aperture is between 30~50nm, that is, the mesoporous pore size of mesoporous zeolite expanded to the super large mesoporous range of 30~50nm,
Reaction process that is higher for reaction system viscosity or having larger reaction molecular to participate in, is remarkably improved the diffusion of mesopore orbit
Mass-transfer performance.This preparation method process is simple, template is at low cost, has high industrial applications prospect.
Preferably, the solid SiO2Spheric granules utilizesMethod is made.It utilizesMethod prepares SiO2Ball
It is relatively easy that shape particle can be such that its size adjusts, and is easy to carry out Heteroatom doping, and when carrying out Heteroatom doping
It can be in SiO2High degree of dispersion hetero atom in spheric granules, and can easily be accommodated heteroatomic doping.
Preferably, instilling ethyl orthosilicate (TEOS) to the mixed solution of ethyl alcohol, water and ammonium hydroxide, stir to get solid
SiO2Spheric granules, wherein ethyl alcohol, water, ammonium hydroxide volume ratio be (20~40): (5~20): (0.2~3.0), ethyl alcohol and positive silicon
The volume ratio of acetoacetic ester is 1:(0.02~0.05), the drop rate of ethyl orthosilicate is 0.5~2.0mL/ minutes.
Preferably, instill ethyl orthosilicate and stir 10~after sixty minutes, then hetero atom presoma is instilled, and stir 30~
90 minutes, to obtain containing heteroatomic solid SiO2Spheric granules, and then obtain that there is super large mesoporous multistage containing heteroatomic
Pore structure zeolite;Preferably, the hetero atom is selected from least one of Ti, Al, Fe, B, Ga, P etc..According to the invention, making
Standby solid SiO2When spheric granules, that is, introducing hetero-atoms, it is re-introduced into hetero atom therefore without when synthesizing hierarchical porous structure zeolite,
Avoid the problem of zeolite nucleation crystallization difficulty, controllable micro--super large mesoporous zeolite of available hetero atom concentration.
Preferably, solid SiO2The molar ratio of spheric granules and structure directing agent is 1:(0.05~0.25).
Preferably, the structure directing agent is tetrapropylammonium hydroxide, 4-propyl bromide, 4-propyl ammonium chloride and 4 third
At least one of base ammonium fluoride.
Preferably, the aqueous solution before Crystallizing treatment, is aged 10~48 hours at 20~40 DEG C.
Preferably, the calcining is calcined 6~48 hours at 450~600 DEG C.
Compared with prior art, the method that super large mesoporous zeolite molecular sieve is prepared in the present invention, the advantage is that:
(1) compared with existing mesoporous zeolite, the aperture in secondary duct is bigger, is more advantageous to the diffusion transport of substance;With macropore
Zeolite is compared, and external surface area is higher, can expose more activated centres;
(2) the secondary duct in super large mesoporous zeolite is interconnected, and is more advantageous to the progress of reaction;
(3) compared with existing hard template method, SiO2It is used as silicon source and template simultaneously, does not need to remove mesoporous template.
Detailed description of the invention
Fig. 1 schemes for the SEM of super large mesoporous Silicalite-1 zeolite molecular sieve obtained in embodiment one;
Fig. 2 schemes for the SEM of super large mesoporous Silicalite-1 zeolite molecular sieve cross section obtained in embodiment one;
Fig. 3 is electric for the TEM figure of super large mesoporous Silicalite-1 zeolite molecular sieve obtained in embodiment one and corresponding constituency
Sub- diffraction pattern (SAED);
Fig. 4 schemes for the SEM of super large mesoporous TS-1 zeolite molecular sieve obtained in embodiment two;
Fig. 5 schemes for the SEM of super large mesoporous TS-1 zeolite molecular sieve cross section obtained in embodiment two;
Fig. 6 is the nitrogen adsorption of TS-1 made from super large mesoporous TS-1 zeolite molecular sieve obtained and conventional hydrothermal in embodiment two
Thermoisopleth;
Fig. 7 adulterates SiO for super large mesoporous TS-1 zeolite molecular sieve obtained in embodiment two, unformed Ti2With conventional hydrothermal system
The UV-Vis figure of the TS-1 obtained;
Fig. 8 is SiO obtained in embodiment one2The SEM of particle schemes;
Fig. 9 is the SiO of the doping of Ti obtained in embodiment two2The SEM of particle schemes;
Figure 10 schemes for the SEM of super large mesoporous ZSM-5 obtained in embodiment three.
Specific embodiment
The present invention is further illustrated below in conjunction with attached drawing and following embodiments, it should be appreciated that attached drawing and following embodiments
It is merely to illustrate the present invention, is not intended to limit the present invention.
The present invention provides the preparation methods with super large mesoporous hierarchical porous structure zeolite.Here, super large mesoporous to refer to
Mesoporous pore size is 30~50nm, and multi-stage porous refers to micropore-mesopore.
In an embodiment of the present invention, two stages: SiO can be divided into2Preparation and steam auxiliary crystallization.Specifically,
First prepare solid SiO2Spheric granules then as mesoporous template and silicon source, and combines the strategy system of steam auxiliary crystallization
It is standby to go out to contain super large mesoporous zeolite.
In an embodiment of the present invention, utilizeMethod prepares solid SiO2Spheric granules.
Method prepares the SiO of varying particle size2Bead is highly developed, carries out Heteroatom doping to it and is also possible to.
If the SiO of Heteroatom doping2Bead can prepare HSZs, not only reduce the cost of template, and SiO2Height in bead
The hetero atom of dispersion also solves the problems, such as to be difficult to crystallization because local concentration is excessively high.In addition, can relate in actual application
And the molecule to different volumes, configuration and property, need to design the multilevel structure zeolite of Different Pore Structures and component to meet tool
The application demand of body.SiO2The adjusting of small spherical particles size is relatively simple, and heteroatomic doping is easy to adjust, therefore
SiO2The bead of base prepares micro--super large mesoporous zeolite and has more practical application value.
In one example, ethyl orthosilicate (TEOS) is instilled to the mixed solution of dehydrated alcohol, water, ammonium hydroxide, stirring makes it
It is fully hydrolyzed, obtains solid SiO2Spheric granules.By adjusting the ratio of dehydrated alcohol, water, ammonium hydroxide, adjustable gained is solid
SiO2The partial size of spheric granules.For example, the volume ratio of dehydrated alcohol, water, ammonium hydroxide can be (20~40): (5~20): (0.2~
3.0).Preferably, molar ratio CH3CH2OH:H2O:NH4OH=29.4:13.4:1.The volume of dehydrated alcohol and ethyl orthosilicate
Than that can be (0.5~2): (0.02~0.05).Wherein ammonium hydroxide can be the ammonium hydroxide that mass fraction is 25~28%.By adjusting just
The drop rate and/or mixing speed of silester can control the solid SiO of gained2The uniformity and pattern of spheric granules.Example
Such as, the drop rate of ethyl orthosilicate can be 0.5~2.0mL/ minutes, for example, 1mL min-1.In another example mixing speed can be
10000~20000r min-1, for example, 13000r min-1.Mixing time can be 10~60min.Reaction temperature can for 20~
40℃.In addition, water here may not need addition, and only add the ammonium hydroxide of suitable concentration.In addition, ethyl orthosilicate can also
To be added dropwise in mixed solution in the form of ethanol solution.
Solid SiO obtained2The partial size of spheric granules can be for 50nm or so, for example, 30~80nm, preferably 30~
60nm, more preferably 40~50nm.
To obtain can be used containing heteroatomic super large mesoporous zeolite molecular sieve containing heteroatomic solid SiO2Spherical
Grain.In one embodiment, withMethod prepares solid SiO2When spheric granules, after silicon source complete hydrolysis, phase is added
The hetero atom presoma answered, the reaction was continued a period of time, obtains containing heteroatomic solid SiO2Spheric granules.In one example,
After dripping above-mentioned TEOS and complete hydrolysis, corresponding hetero atom presoma is added.Hetero atom is, for example, can be as super
The atom in the activated centre of big mesoporous zeolite molecular sieve, including but not limited at least one of Ti, Al, Fe, B, Ga, P.Miscellaneous original
Sub- presoma can be containing heteroatomic organic or inorganic compound, for example, the presoma of Ti can be titanate esters, such as titanium
Sour four butyl esters (TBOT), isopropyl titanate etc..The presoma of Al can be aluminium isopropoxide, meta-aluminic acid etc..The presoma of Fe can be
Iron chloride, ferrocene etc..The additional amount of hetero atom presoma can be to make the molar ratio (0.005~0.02) of hetero atom and Si:
1.By controlling the additional amount of hetero atom presoma, adjustable heteroatomic doping.Before reaction time can be according to hetero atom
It drives type and reactivity of body etc. and suitably determines, may be, for example, 30~90 minutes.In addition, for being particularly easy to hydrolysis
Presoma containing hetero atom can be diluted in the solution.On the one hand it is to control its hydrolysis rate, is on the other hand to pass through dilution
Reduce local hetero atom concentration, avoids the generation of hetero atom oxide.As the solvent of dilution presoma containing hetero atom, can be
Isopropanol, propyl alcohol, n-butanol etc..Specifically dilute strength can be determined according to the hydrolysis difficulty of the presoma containing hetero atom, for example,
For the presoma containing hetero atom of easier hydrolysis, can be diluted to diluter.In one example, precursor solution containing hetero atom
In the molar ratio of presoma containing hetero atom and retarder thinner can be 0.02~0.1.
By resulting solid SiO2Spheric granules and structure directing agent aqueous solution, which are uniformly mixed, obtains mixed liquor.Structure directing
Agent for example can be selected from tetrapropylammonium hydroxide (TPAOH), 4-propyl bromide, 4-propyl ammonium chloride and tetrapropyl ammonium fluoride
It is at least one.Solid SiO2The mass ratio of spheric granules and structure directing agent can be 1:(0.05~0.25).Structure directing agent water
The mass concentration of structure directing agent can be 25~35%, e.g., about 25% in solution.Optionally, above-mentioned mixed liquor is carried out old
Change, such as is stirred continuously until to form bulky powder at 20~40 DEG C (such as 40 DEG C).By ageing, it is solidifying to can control presoma
The content of water in glue, and the content of water directly affects the quality in hole, hypovolia crystallization is difficult, and hypervolia hole is unknown
It is aobvious.Above-mentioned mixed liquor is subjected to the processing of steam auxiliary crystallization.Vapor (steam) temperature can be 110~150 DEG C.Handling the time can be 10~48
Hour.In one particularly preferred example, molar ratio structure directing agent (such as TPAOH): TEOS=1:10, crystallization time are
110 DEG C, crystallization time 48h.Better hierarchical porous structure available in this way.
SiO2Spheric granules serves not only as super large mesoporous pore creating material, and provides silicon source for the growth of zeolite.Steam auxiliary is brilliant
After change processing, SiO2Spheric granules disappears, and spherical mesoporous structure, the size and SiO of mesoporous pore size are generated inside zeolite granular2
Spherical particle size is suitable.
It is the material washing that can will obtain after the processing of steam auxiliary crystallization, dry, such as 60~120 DEG C dry 10~24 small
When.
The structure directing agent in resulting materials can be removed by calcining, to obtain the hierarchical porous structure for having super large mesoporous
Zeolite.The temperature of calcining can be 450~600 DEG C.The time of calcining can be 6~48 hours.
The resulting super large mesoporous structure with super large mesoporous hierarchical porous structure zeolite with three-dimensional perforation, it is spherical mesoporous
Aperture is between 30~50nm.
According to solid SiO2Whether spheric granules contains hetero atom, and finally obtained zeolite molecular sieve for example can be pure silica zeolites
Silicalite-1(SiO2In be free of hetero atom), Ti-Si zeolite molecular sieve TS-1 (SiO2In have Ti doping), ZSM-5 (SiO2In
Have Al doping) etc..Other types of zeolite can be obtained in the type for changing structure directing agent, for example structure directing agent is tetrapropyl hydrogen
When amine-oxides, BEA type zeolite can be obtained.Of the invention has silicon/heteroatomic original in super large mesoporous hierarchical porous structure zeolite
Son is than that can be 50~200.
The present invention is with solid SiO2For super large mesoporous template, and silicon source, gained zeolite granular are provided for the growth of zeolite
Internal spherical mesoporous duct rich in.The method has not only filled up the blank in super large mesoporous zeolite synthesis field, more contains
The synthesis of the hierarchical porous structure zeolite in hetero atom activated centre provides a kind of preparation method of simple low cost.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Embodiment one
The preparation of super large mesoporous Silicalite-1:
A) by 35.7mL dehydrated alcohol and 5mL deionized water, 0.8mL ammonium hydroxide in 20 DEG C of stirring 10min;
B) by 1.0mL TEOS with 1mL min-1Speed be added dropwise in a), and in 13000r min-1Mixing speed under stir
Mix 30min;
C) SiO obtained in 3g (b) is taken2Particle (its SEM figure is referring to Fig. 8) is water-soluble with 4.1g tetrapropylammonium hydroxide (TPAOH)
Liquid is uniformly mixed, and is then transferred to 40 DEG C of water-baths, is stirred continuously until to form bulky powder, and then steam assists at 110 DEG C
Crystallization 48h;
D) material obtained in (c) is dried for 24 hours at 100 DEG C, then 600 DEG C of calcining 6h remove structure directing agent, obtain super large
Mesoporous Silicalite-1.
Fig. 1 schemes for the SEM of super large mesoporous Silicalite-1 zeolite molecular sieve obtained in embodiment one, as seen from the figure,
There are the spherical mesoporous structures of abundant~50nm on spherical zeolite granular surface.
Fig. 2 schemes for the SEM of super large mesoporous Silicalite-1 zeolite molecular sieve cross section obtained in embodiment one, by scheming
As it can be seen that equally existed inside zeolite granular~the spherical mesoporous structure of 50nm, and duct is interconnected.
TEM figure and corresponding choosing of the Fig. 3 for super large mesoporous Silicalite-1 zeolite molecular sieve obtained in embodiment one
Area's electron diffraction diagram (SAED), as seen from the figure, spherical mesoporous structure is present in inside entire zeolite granular, and this is super large mesoporous
Silicalite-1 is mono-crystalline structures.
Embodiment two
The synthesis of the Silicalite-1 zeolite in the activated centre Ti containing hetero atom, i.e., the preparation of super large mesoporous TS-1:
A) by 35.7mL dehydrated alcohol and 5mL deionized water, 0.8mL ammonium hydroxide in 20 DEG C of stirring 10min;
B) by 1.0mL TEOS with 1mL min-1Speed be added dropwise in a), and in 13000r min-1Mixing speed under stir
10min is mixed to TEOS complete hydrolysis, then, the mixed liquor of 340 μ L TBOT and 3g isopropanols is added dropwise, and continues to stir
30min;
C) SiO for taking Ti obtained in 3g (b) to adulterate2Particle (its SEM figure is referring to Fig. 9) and 4.1g tetrapropylammonium hydroxide
(TPAOH) aqueous solution is uniformly mixed, and is then transferred to 40 DEG C of water-baths, is stirred continuously until to form bulky powder, then at 110 DEG C
Lower steam auxiliary crystallization 48h;
D) material obtained in (c) is dried for 24 hours at 100 DEG C, then 600 DEG C of calcining 6h remove structure directing agent, obtain super large
Mesoporous TS-1.
Fig. 4 schemes for the SEM of super large mesoporous TS-1 zeolite molecular sieve obtained in embodiment two, as seen from the figure, spheric granules
There are spherical mesoporous ducts abundant on surface.
Fig. 5 boils as seen from the figure for the SEM figure of super large mesoporous TS-1 zeolite molecular sieve cross section obtained in embodiment two
~spherical mesoporous the structure of 50nm is equally existed inside stone particle, and duct is interconnected.
One conventional hydrothermal method of comparative example
10.4165g TEOS, 18g deionized water and 4.1g tetrapropylammonium hydroxide solution (mass fraction 25%) are at room temperature
2h is mixed;0.34g butyl titanate is dissolved in 6g isopropanol;Above-mentioned two solution is cooled to 4 DEG C or less respectively;By this
Two solution mix and are stirred continuously until to form gel;Gel is placed in 150 DEG C of water heating kettles and carries out steam auxiliary crystallization for 24 hours,
It is washed after crystallization three times and in 100 DEG C of dry 10h;Finally 550 DEG C of calcining 10h in Muffle furnace, obtain TS-1.
Fig. 6 be in embodiment two super large mesoporous TS-1 zeolite molecular sieve (label is in figure) obtained with it is right
The nitrogen adsorption isotherm of TS-1 made from ratio one (conventional hydrothermal) (label is in figure), as seen from the figure, super large
There are apparent hysteresis loops by mesoporous TS-1, increase external surface area compared to pure zeolite and to the diffusion transport spy of macromolecular
Property, and TS-1 then shows typical pure zeolite feature.
Fig. 7 adulterates SiO for super large mesoporous TS-1 zeolite molecular sieve obtained in embodiment two, unformed Ti2(i.e. comparative example
The presoma of TS-1 in one, label is doping SiO in figure2) and comparative example one (conventional hydrothermal) made from TS-1 UV-
Vis figure, as seen from the figure, Ti atom is successfully introduced into super large mesoporous TS-1 zeolite skeleton, and exists in the form of four-coordination.
Embodiment three
The synthesis of the Silicalite-1 zeolite in the activated centre Al containing hetero atom, i.e., the preparation of super large mesoporous ZSM-5:
A) by 35.7mL dehydrated alcohol and 5mL deionized water, 0.8mL ammonium hydroxide in 20 DEG C of stirring 10min;
B) by 1.0mL TEOS with 1mL min-1Speed be added dropwise in a), and in 13000r min-1Mixing speed under stir
10min is mixed to TEOS complete hydrolysis, then, the mixed liquor of 0.2042g TEOS and 3g isopropanol is added dropwise, and continues to stir
30min;
C) SiO for taking Al obtained in 3g (b) to adulterate2Particle mixes with 4.1g tetrapropylammonium hydroxide (TPAOH) aqueous solution
It is even, 40 DEG C of water-baths are then transferred to, are stirred continuously until to form bulky powder, then the steam auxiliary crystallization 48h at 110 DEG C;
D) material obtained in (c) is dried for 24 hours at 100 DEG C, then 600 DEG C of calcining 6h remove structure directing agent, obtain super large
Mesoporous ZSM-5.
The SEM that Figure 10 is super large mesoporous ZSM-5 obtained schemes, and as seen from the figure, there are abundant transgranular inside zeolite granular
Mesoporous, size is in 50nm or so.
Preparation has the method for super large mesoporous hierarchical porous structure zeolite molecular sieve, SiO in the present invention2Simultaneously as mesoporous
Template and silicon source.The blank field between mesoporous zeolite and large pore zeolite has been filled up in the successful preparation of super large mesoporous zeolite, is mentioned
A kind of synthetic method being simple and efficient has been supplied, and there is universality, has established solid foundation for industrial applications.
Finally it is necessary to explanations: above embodiments are served only for saying technical solution of the present invention in further detail
It is bright, it should not be understood as limiting the scope of the invention, for example contain the super large mesoporous zeolite of other hetero atoms (such as Al, Fe)
Or other zeolite types (BEA, FAU etc.) etc. belong to the protection scope of this patent, those skilled in the art is according to the present invention
Some nonessential modifications and adaptations for making of above content all belong to the scope of protection of the present invention.
Claims (9)
1. a kind of preparation method with super large mesoporous hierarchical porous structure zeolite, which comprises the following steps:
There is partial size for the solid SiO of 30~80nm for evenly dispersed2The aqueous solution of spheric granules and structure directing agent is in steam condition
In carried out Crystallizing treatment 10~48 hours at 110~150 DEG C;
Calcined material after Crystallizing treatment is removed into structure directing agent, obtains the hierarchical porous structure zeolite for having super large mesoporous.
2. preparation method according to claim 1, which is characterized in that the solid SiO2Spheric granules utilizes the side ber St
Method is made.
3. preparation method according to claim 2, which is characterized in that instilled just to the mixed solution of ethyl alcohol, water and ammonium hydroxide
Silester stirs to get solid SiO2Spheric granules, wherein ethyl alcohol, water, ammonium hydroxide volume ratio be (20~40): (5~20):
The volume ratio of (0.2~3.0), ethyl alcohol and ethyl orthosilicate is 1:(0.02~0.05), the drop rate of ethyl orthosilicate is 0.5
~2.0 mL/ minutes.
4. preparation method according to claim 3, which is characterized in that instill ethyl orthosilicate and stir 10~60 minutes
Afterwards, then hetero atom presoma is instilled, and stirred 30~90 minutes, to obtain containing heteroatomic solid SiO2Spheric granules, in turn
Obtain that there is super large mesoporous hierarchical porous structure zeolite containing heteroatomic;Preferably, the hetero atom be selected from Ti, Al, Fe, B,
At least one of Ga, P.
5. preparation method according to any one of claim 1 to 4, which is characterized in that solid SiO2Spheric granules and structure
The molar ratio of directed agents is 1:(0.05~0.25).
6. preparation method according to any one of claim 1 to 5, which is characterized in that the structure directing agent is 4 third
At least one of base ammonium hydroxide, 4-propyl bromide, 4-propyl ammonium chloride.
7. preparation method according to any one of claim 1 to 6, which is characterized in that the aqueous solution is in Crystallizing treatment
Before, it is aged 10~48 hours at 20~40 DEG C.
8. preparation method according to any one of claim 1 to 7, which is characterized in that the calcining is 450~600
DEG C calcining 6~48 hours.
9. preparation method according to any one of claim 1 to 8, which is characterized in that resulting hierarchical porous structure zeolite
Super large mesoporous structure with three-dimensional perforation, spherical mesoporous aperture is between 30~50 nm.
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CN112624142A (en) * | 2021-01-19 | 2021-04-09 | 吉林大学 | Preparation method of nano hierarchical pore Beta molecular sieve |
CN112978755A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Preparation method and application of titanium silicalite TS-1 |
CN113880103A (en) * | 2020-07-01 | 2022-01-04 | 中国石油化工股份有限公司 | Beta molecular sieve and synthetic method and application thereof |
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CN107082436A (en) * | 2017-04-14 | 2017-08-22 | 武汉理工大学 | A kind of preparation method of mesoporous micro porous molecular sieve |
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CN103539145A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Preparation method of SAPO (Si, Al, P, O)-34 molecular sieve |
CN104617270A (en) * | 2015-01-29 | 2015-05-13 | 扬州大学 | Preparation method of spherical hollow lithium titanate/graphene composite material as lithium battery negative material |
CN107082436A (en) * | 2017-04-14 | 2017-08-22 | 武汉理工大学 | A kind of preparation method of mesoporous micro porous molecular sieve |
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CN112978755A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Preparation method and application of titanium silicalite TS-1 |
CN113880103A (en) * | 2020-07-01 | 2022-01-04 | 中国石油化工股份有限公司 | Beta molecular sieve and synthetic method and application thereof |
CN112624142A (en) * | 2021-01-19 | 2021-04-09 | 吉林大学 | Preparation method of nano hierarchical pore Beta molecular sieve |
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