CN106829991A - It is a kind of to change the method that skeleton hydrophilic and hydrophobic adjusts zeolite molecular sieve pore passage structure - Google Patents

It is a kind of to change the method that skeleton hydrophilic and hydrophobic adjusts zeolite molecular sieve pore passage structure Download PDF

Info

Publication number
CN106829991A
CN106829991A CN201611245176.9A CN201611245176A CN106829991A CN 106829991 A CN106829991 A CN 106829991A CN 201611245176 A CN201611245176 A CN 201611245176A CN 106829991 A CN106829991 A CN 106829991A
Authority
CN
China
Prior art keywords
molecular sieve
zeolite molecular
zeolite
hetero atom
skeleton
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201611245176.9A
Other languages
Chinese (zh)
Inventor
葛同广
华子乐
施剑林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Institute of Ceramics of CAS
Original Assignee
Shanghai Institute of Ceramics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Ceramics of CAS filed Critical Shanghai Institute of Ceramics of CAS
Priority to CN201611245176.9A priority Critical patent/CN106829991A/en
Publication of CN106829991A publication Critical patent/CN106829991A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter

Abstract

Change the method that skeleton hydrophilic and hydrophobic adjusts zeolite molecular sieve pore passage structure the present invention relates to a kind of, by add different valence state containing heteroatomic predecessor, and with reference to steam auxiliary crystallization treatment realize conversion of the zeolite molecular sieve between hierarchical porous structure and homogeneous zeolite granular by changing skeleton hydrophily；Including：Silicon source, water, microcellular structure directed agents are mixed, precursor sol is obtained；Different valence state is added in the precursor sol containing heteroatomic predecessor, aqueous precursor gel is obtained；After gained aqueous precursor gel is aged, Crystallizing treatment is carried out 1~120 hour at 100~220 DEG C in steam condition；By the aqueous precursor gel after Crystallizing treatment after drying, at 500~600 DEG C high-temperature calcination 6~24 hours.Compared with prior art, zeolite cavity structure is regulated and controled by hetero atom in the present invention, flow is simple, low cost, it is not easy to cause split-phase.

Description

It is a kind of to change the method that skeleton hydrophilic and hydrophobic adjusts zeolite molecular sieve pore passage structure
Technical field
The invention belongs to inorganic material synthesis and catalytic field, and in particular to one kind changes skeleton hydrophilic and hydrophobic adjustment zeolite The method of molecular sieve pore passage structure and the preparation method of zeolite molecular sieve.
Background technology
Micro-pore zeolite because with homogeneous micropore canals, specific surface area high and heat high and hydrothermal stability, existing The chemical processes such as absorption, separation, ion exchange and catalysis obtain extensive use, but the less aperture of micro-pore zeolite is (typically smaller than Transmission of the material in duct in course of reaction 1.2nm) is limited, particularly in the reaction for thering is bigger molecule to participate in, micropore The performance of zeolite then need to be improved.Ordered mesoporous material with M41s (Nature 1992,359,710) as representative is preferable Diffusion problem of the bigger molecule in duct is solved, but unfortunately, the crystalline state skeleton from micro-pore zeolite is different, mesoporous material Skeleton be generally in amorphous state, relatively low stability is very big with weaker acidic site to limit them as new catalyst The direct application of (carrier), adsorbent.Preparation has high stability, high activity and the mesoporous material high diffusibility of traditional zeolite concurrently Micro--mesoporous multilevel structure material turns into the common study hotspot of materials chemistry, inorganic chemistry, catalytic chemistry in recent years.
Ryoo etc. (Chem.Commun., 2006,4489) using particular design, synthesis amphiphilic organosilan as template And part silicon source, template carbochain is connected directly between by mesoporous wall by Si-C keys, synthesized a class polycrystalline structure, it is mesoporous Aperture is adjustable, hole wall has partially-crystallized zeolite structured micro--mesoporous multilevel structure material.Further, they design, synthesize The Gemini type surfactant of many ammonium type (quaternary ammonium salt functional group number is more than 3) for micro-, mesoporous difunctional template (Science, 2011,333,328) formed while, promoting crystallite skeleton with mesoporous ordered structure, be prepared for the orderly of crystallization hole wall Micro--mesoporous multilevel structure material.Xiao etc. (Angew.Chem.Int.Ed., 2006,45,3090) and Pinnavaia etc. (Angew.Chem.Int.Ed., 2006,45,7603) also reports the mesoporous zeolite with insertion pore structure respectively, synthesizes material Material embodies performance more more preferable than micro-pore zeolite in the alkylation of benzene or the catalytic cracking reaction of gas oil.It is existing It is to select, design new mesoporous template, by strengthening the interaction between template and inorganic species that research is more Power is come the problem of phase separation that solves to occur in self assembling process.On the other hand, arrived by reducing the zeolite granular size of crystalline phase Nano grade, it is also possible to expose more active sites and shorten residence time of the reaction species in micropore canals to subtract The possibility of carbon distribution in small catalytic reaction process, so as to extend catalyst life.In the report on nano zeolite at present, generally Substantial amounts of structure directing agent is needed, the synthesis cost of nano zeolite is substantially increased, while the separation of nano material needs height Speed centrifugation, is unfavorable for large-scale production.The synthetic method of the multi-stage porous or nano zeolite of developing a kind of simple low cost turns into One urgent problem.
The content of the invention
For the deficiency of existing synthetic method, it is an object of the invention to provide a kind of synthesis nanometer boiling of simple low cost The method of stone and multi-stage pore zeolite molecular sieve.
On the one hand, the invention provides a kind of method for adjusting zeolite molecular sieve pore passage structure, by adding different valence state Containing heteroatomic predecessor, and with reference to steam auxiliary crystallization treatment by changing skeleton hydrophily to realize zeolite molecular sieve Conversion between hierarchical porous structure and homogeneous zeolite granular；Including：
Silicon source, water, microcellular structure directed agents are mixed, precursor sol is obtained；
Different valence state is added in the precursor sol containing heteroatomic predecessor, aqueous precursor gel is obtained；
After gained aqueous precursor gel is aged, Crystallizing treatment is carried out 1~120 hour at 100~220 DEG C in steam condition；
By the aqueous precursor gel after Crystallizing treatment after drying, at 500~600 DEG C high-temperature calcination 6~24 hours.
The present invention uses the preparation method of quasi- solid phase, and the aqueous precursor gel to preparing carries out steam auxiliary crystallization treatment, steams Hetero atom can only be moved in less scope in vapour auxiliary crystallization processing procedure, therefore hetero atom can well enter into bone Exist in the middle of frame and in the form of being coordinated, while also ensure that the high yield of zeolite molecular sieve.By the sample after Crystallizing treatment Treatment is directly dried, final high temperature calcining removal organic formwork obtains zeolite molecular sieve.The present invention is miscellaneous by changing skeleton Atom achieves that the conversion between hierarchical porous structure and homogeneous zeolite granular.
It is preferred that it is only the tetravalence hetero atom that valence state is tetravalence to control the hetero atom for adding, make gained zeolite molecular sieve Pattern is homogeneous zeolite granular, and the tetravalence hetero atom is Zr and/or Ti.When heteroatomic valence state it is identical with Si atoms (be all+ 4 valencys) when, skeleton is externally presented electroneutral, shows hydrophobicity.And hydrophobic skeleton can then make the microcosmic " water in crystallization process Pond " is repelled to outside skeleton, and the conventional hydrothermal reaction similar to high alkalinity occurs, and what is obtained is the granule-morphology of single-size.
It is preferred that the hetero atom that control is added includes that valence state is not the non-tetravalence hetero atom of tetravalence, make gained zeolite molecules The pattern of sieve is hierarchical porous structure, and the non-tetravalence hetero atom is Fe and/or Al.In the middle of skeleton, when heteroatomic valence state with When Si atoms are different, skeleton is externally presented non-electroneutral, shows stronger hydrophily.In whole material synthesis processes, parent Hydrophobic framework can influence the existence of microcosmic " pond " in the middle of aqueous precursor gel, hydrophily bone during steam auxiliary crystallization Frame can adsorb microcosmic " pond " makes it play a part of mesoporous pore creating material, can obtain the zeolitic frameworks with hierarchical porous structure.
Also, it is preferred that as change the heteroatomic addition of the non-tetravalence adjust obtained by hierarchical porous structure.
In addition heteroatomic doping also has obvious influence, and with the increase of doping, hierarchical porous structure becomes more Plus substantially.
It is preferred that the mol ratio of the silicon source, hetero atom, water and microcellular structure directed agents is 1:(30~500):(10~ 50):(0.05~0.5).
It is preferred that the silicon source is at least one in tetraethyl orthosilicate, Ludox, silica and sodium metasilicate.
It is preferred that will be dissolved in alcoholic solution containing heteroatomic predecessor, and the presoma is added under cryogenic In colloidal sol, the cryogenic conditions are 0~10 DEG C, preferably 0~5 DEG C.
It is preferred that the microcellular structure directed agents be 4-propyl bromide, TPAOH, 4-propyl ammonium chloride and At least one in tetrapropyl ammonium fluoride.
It is preferred that the speed of the stirring is 100~800 revs/min.
It is preferred that the temperature of the ageing is 10~80 DEG C, the time is 10~240 hours.Digestion time is also required to strictly Control, during preparing hierarchical porous structure especially for hydrophilic back bone, the water in gel is played " mesoporous pore creating material " Effect, water content can occur to obtain pure zeolite phase similar to traditional hydro-thermal reaction too much, and pore-creating effect is not clear very little for water content It is aobvious.
It is preferred that the steam condition includes：Temperature be 100~220 DEG C, preferably 110~180 DEG C, more preferably 120~ 180℃。
There is greatly change in the present invention, by heteroatomic doping, not only zeolite granular pattern while pore structure parameter Can accordingly change, be only 0.22cm for homogeneous granule-morphology total pore volume3g-1Left and right, and pore volume increases to after Heteroatom doping 0.30~0.55cm3g-1Left and right, and material relative crystallinity be maintained at a level higher (>80%).
Compared with prior art, the method that nanometer or multi-stage pore zeolite molecular sieve are prepared in the present invention, the advantage is that：
(1) hetero atom regulation and control zeolite cavity structure, flow is simple, low cost, it is not easy to cause split-phase；
(2) due to being quasi- solid phase procedures, the preparation for nano material need not be centrifuged at a high speed, beneficial to large-scale production；
(3) compared to conventional hydrothermal technique, the method yield is very high.
Brief description of the drawings
Fig. 1 is the nitrogen adsorption-desorption isotherm a of obtained Silicalite-1 zeolite molecular sieve materials in embodiment 1 The SEM photograph b of sum；
Fig. 2 is the SEM photograph a and high-resolution of the Silicalite-1 zeolite molecular sieve materials of obtained Zr doping in embodiment 2 TEM photos b；
Fig. 3 is the XRD curves of zeolite molecular sieve material prepared by the present invention, and wherein a is obtained Zr doping in embodiment 2 Silicalite-1 zeolite molecular sieve materials, b are the Silicalite-1 zeolite molecular sieve materials of the Fe doping obtained by embodiment 3 Material；
Fig. 4 is SEM photograph a and the TEM photo of the Silicalite-1 zeolite molecular sieve materials of obtained Fe doping in embodiment 3 b；
Fig. 5 is the SEM photograph of zeolite molecular sieve material prepared by the present invention, and wherein a is obtained TS-1 zeolites point in embodiment 4 The SEM photograph of son sieve material, b is the TS-1 (Al of obtained Al doping in embodiment 5：Ti=0.75) zeolite molecular sieve material SEM photograph；
Fig. 6 is the SEM photograph of zeolite molecular sieve material prepared by the present invention, and wherein a is obtained Al doping in embodiment 6 TS-1(Al：Ti=0.50) the SEM photograph of zeolite molecular sieve material, b is the TS-1 (Al of obtained Al doping in embodiment 7：Ti The SEM photograph of=0.25) zeolite molecular sieve material.
Specific embodiment
The present invention is further illustrated below by way of following implementation methods, it should be appreciated that following implementation methods are merely to illustrate this Invention, is not intended to limit the present invention.
The present invention is prepared by changing the hydrophilic and hydrophobic (such as heteroatomic doping, forerunner modifies etc.) of zeolitic frameworks Desired granule-morphology is obtained, and realizes freely changing between the homogeneous particle of traditional zeolite molecular sieve and hierarchical porous structure.Institute It can be at least one in Zr, Fe, Ti and Al to state hetero atom.In the middle of skeleton, when heteroatomic valence state is different from Si atoms, Skeleton is externally presented non-electroneutral, shows stronger hydrophily, can obtain the zeolitic frameworks with hierarchical porous structure；When miscellaneous During the valence state of atom (being all+4 valencys) identical with Si atoms, skeleton is externally presented electroneutral, and what is obtained is the particle of single-size Pattern.Surface hydrophilicity skeleton obtains hierarchical porous structure, and surface hydrophobic skeleton is obtained without mesoporous traditional zeolite particle.For The Silicalite-1 of Silicalite-1 and the Zr doping of pure silica zeolites Silicalite-1, Ti doping, because skeleton is dredged Water only obtains pure zeolite phase；And the Silicalite-1 of Al doping, or it is hierarchical porous structure that Al, Ti be co-doped with obtaining.In addition What this method was utilized is xerogel steam auxiliary crystallization method, can reach raw material yield close to 100%.Mixed by heteroatomic Miscellaneous, not only there is greatly change in zeolite granular pattern, while pore structure parameter also can accordingly change, for homogeneous granule-morphology Total pore volume is only 0.22cm3g-1Left and right, and pore volume increases to 0.45cm after Heteroatom doping3g-1Left and right, and material relative knot Brilliant degree be maintained at a level higher (>80%).Additionally, heteroatomic doping also has obvious influence, with doping The increase of amount, hierarchical porous structure becomes readily apparent from.More importantly only by adjusting under conditions of without mesoporous template Whole surface hydrophilic and hydrophobic has obtained preferable hierarchical porous structure, for the synthesis of multi-stage pore zeolite molecular sieve provide one it is brand-new Thinking.
The preparation method of the zeolite molecular sieve that the explanation present invention in following exemplary ground is provided.
Silicon source, water, microcellular structure directed agents are mixed, precursor sol is obtained.10 DEG C -80 of the preparation temperature of presoma ℃.The silicon source, water, the mol ratio of microcellular structure directed agents can be 1:10~50:0.05~0.5.The silicon source and micropore knot Structure directed agents respectively can be for tetraethyl orthosilicate, Ludox, sodium metasilicate and TPAOH, 4-propyl bromide etc., but not Only place restrictions in this.Used as an example, silicon source, water, structure directing agent are uniformly mixed with what is clarified at ambient temperature Precursor sol, then stirs at a certain temperature.
To be added in the precursor sol containing heteroatomic predecessor, agitated (mixing speed can be 100- 800r min-1) after obtain aqueous precursor gel, the hetero atom is at least one in Zr, Fe, Ti and Al.Wherein contain miscellaneous original The alcoholic solution of the optional aluminium isopropoxide of predecessor of son, the alcoholic solution of butyl titanate, the alcoholic solution of ferric nitrate, zirconium iso-propoxide Alcoholic solution etc..Wherein solvent alcohol can select isopropanol, normal propyl alcohol, n-butanol etc..Wherein hetero atom can be with the mol ratio of silicon source 1:30~500, for the hetero atom predecessor of easy hydrolysis should dilute in alcoholic solution simultaneously cryogenic conditions (can be 0~ 10 DEG C, preferably 0~5 DEG C) under add reaction system, and accelerate mixing speed, it is to avoid the generation of non-skeleton composition.As one Individual example, will be added to precursor sol containing corresponding heteroatomic predecessor, it is sufficiently mixed uniformly under agitation And hydrolyze enough time.And by precursor sol be transferred to 40 DEG C of waters, stirring is to forming gel.
(presoma xerogel is obtained after gained aqueous precursor gel is aged), enter at 100~220 DEG C in steam condition Row Crystallizing treatment 1~120 hour.Gel Aging Temperature is 10 DEG C~80 DEG C, digestion time 10h~240h, Crystallizing treatment temperature It can be 100-220 DEG C, preferably 110~180 DEG C, crystallization time can be 1-120 hours.Wherein high temperature and high pressure steam condition is specific Can be that temperature is 100~220 DEG C, preferably 110~180 DEG C, more preferably 120~180 DEG C, and Crystallizing treatment temperature keeps substantially Unanimously.Specifically, added outside the crucible in reactor (water heating kettle volume can select 10~200ml) a certain amount of (wherein brilliant It is 0.1-20g to change added water) water, gel is in the high temperature and high pressure environment of water vapour.After being aged in a kettle. The addition of presoma xerogel the final structure of material is had no significant effect.Used as an example, gel is simultaneously aged After treatment, the presoma xerogel for obtaining is transferred to 80ml water heating kettles crystallization under high-temperature and high-pressure conditions.
By dried process under the high temperature conditions after the material washing after crystallization, organic mould is then removed by high-temperature calcination Plate, obtains target material.Wherein calcining heat can be 500 DEG C~600 DEG C, and calcination time can be 6h~24h, and heating rate can be 1-20℃min-1.What the material of surface relative hydrophobicity was prepared is the homogeneous pure zeolite phase of particle size, relative hydropathy Material obtains being hierarchical porous structure zeolite.
For the preparation of the nano Si licalite-1 zeolites without hetero atom with single-size, can be by following steps It is prepared from：(1) weigh appropriate water to be well mixed with a certain amount of silicon source, and add microcellular structure directed agents, in 40 DEG C of water-baths Pot 2~10h of stirring, makes silicon source be fully hydrolyzed with this understanding；(2) under conditions of step (1), it is stirred continuously until to form boiling The presoma clear gel of stone, then still aging regular hour；(3) the zeolite precursor soma gel dress that will be obtained in (2) To enter be put into 80ml water heating kettle liners in crucible, and a certain amount of water is added outside crucible, carry out steam auxiliary crystallization treatment. (4) material obtained in (3) is dried into 24h at 100 DEG C, then 600 DEG C of calcining 6h removal microcellular structure directed agents, obtain zeolite Molecular sieve.
As a preferred example, the preparation of precursor liquid, it is preferable that microcellular structure directed agents are added into silicon source and water Mixed solution in, stir 4h under the conditions of 40 DEG C.
The zeolite of different pore passage structures is prepared if necessary to doping hetero atom.Then need to be added in upper precursor sol and contain There is heteroatomic predecessor.For the hetero atom raw material (containing heteroatomic predecessor) of easy hydrolysis, need to be molten in corresponding alcohol After liquid dilution (6ml alcoholic solutions), under the conditions of 0-10 DEG C (preferably 0-5 DEG C), with 0.1-2ml min-1Speed be added dropwise over To in precursor sol, it is to avoid the fast hydrolyzing of hetero atom raw material, non-skeleton is formed；For not allowing the hetero atom of facile hydrolysis former Material can be added directly into precursor sol.
Used as a preferred example, in gelation process of the invention, hetero atom raw material preferentially uses hydrolysis rate ratio Slower corresponding alkoxide, so that hetero atom smoothly enters skeleton.
The method of the invention is different from and prepare in the past many mesoporous zeolites (mesoporous template pore-creating), and the present invention both need not Mesoporous template only adjusts the hydrophilic and hydrophobic of zeolitic frameworks also without special structure directing agent on the basis of conventional method Homogeneous zeolite granular or porous zeotile is can be obtained by, and microcellular structure directed agents consumption is low, is porous zeotile Synthesis provides a kind of brand-new synthesis thinking, simple, convenient, be easily controlled, at the same nano zeolite can also reach it is non- Yield (close to 100%) often high, is expected to scale application.
The specific surface area of the catalyst that the present invention can obtain preparation of the present invention by BET methods can be 354~536m2/g。
The present invention can be 10~20nm by the catalyst pore size that BJH methods can obtain preparation of the present invention, and pore volume can be 0.30~0.55cm3/g。
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this Invention is further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to this hair Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific Technological parameter etc. is also only that 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 the concrete numerical value of hereafter example.
Embodiment 1
The preparation of Silicalite-1, whole pure Si skeletons are externally presented relative hydrophobicity, therefore obtain smooth homogeneous in surface Zeolite granular；
A) by 18g water with 10.4165g tetraethyl orthosilicates (TEOS), (25%wt's is water-soluble for 4.1g TPAOHs solution Liquid), 2h is uniformly mixed at room temperature, it is stirred continuously until to form clear gel in 40 DEG C of water-baths；
B) the clear gel ripening 24h in a) is obtained into presoma xerogel, then Crystallizing treatment, every before crystallization The bottom (outside of crucible, sample is put in crucible) of individual liner adds 0.7g deionized waters, is put into 150 DEG C of baking ovens, steam Auxiliary crystallization processes 24h；
C) sample after crystallization is taken out, 8h is dried in 100 DEG C of baking ovens, finally calcine 6h in 600 DEG C of air atmosphere, heated up Speed is about 1 DEG C of min-1, obtain final product the Silicalite-1 zeolite molecular sieve materials described in 2.92g.
A is the nitrogen adsorption-desorption isothermal of obtained Silicalite-1 zeolite molecular sieve materials in embodiment 1 in Fig. 1 Line, as seen from the figure, material is typical pure zeolite structured, without obvious nitrogen adsorption in macropore range, is surveyed by BET methods Total specific surface area 462m2.g-1, pore volume is measured for 0.22cm by BJH methods3.g-1；
B is the SEM photograph of obtained Silicalite-1 zeolite molecular sieve materials in embodiment 1 in Fig. 1, as seen from the figure, is prepared Material particle size it is homogeneous, at 2 μm or so.
Embodiment 2
The preparation of the Silicalite-1 of Zr doping, Zr is presented+4 valencys in skeleton, and whole skeleton is externally presented relative hydrophobicity, Therefore what is obtained is still the smooth single zeolite phase in homogeneous surface；
A) by 18g water, 4.1g TPAOHs solution (aqueous solution of 25%wt) and 10.4165g tetraethyl orthosilicates in room 2h is uniformly mixed under temperature, is subsequently transferred to persistently stir 4h in 40 DEG C of water-baths, be then transferred in 0 DEG C of ice bath；
B) 0.3276g zirconium iso-propoxides are added in 6g aqueous isopropanols, are cooled to 0 DEG C or so, in being then added dropwise to a), And quickly stir, until forming vitreosol；
C) vitreosol in b) is transferred in 40 DEG C of water-baths, the row's of carrying out alcohol and ripening, until desiccant gel is formed, Then Crystallizing treatment is carried out, was added in the bottom (outside of crucible, sample is put in crucible) of each liner before crystallization 0.7g deionized waters, are put into 150 DEG C of baking ovens, steam auxiliary crystallization treatment 24h；
D) sample after crystallization is taken out, 8h is dried in 100 DEG C of baking ovens, finally calcine 6h in 600 DEG C of air atmosphere, heated up Speed is about 1 DEG C of min-1, the Silicalite-1 zeolite molecular sieve materials of the Zr doping described in 3.0g are obtained final product, by BET methods The total specific surface area 434m for surveying2.g-1, pore volume is measured for 0.24cm by BJH methods3.g-1。
A is the SEM photograph of the Silicalite-1 zeolite molecular sieve materials of obtained Zr doping in embodiment 2 in Fig. 2, by Figure is visible, and material surface is smooth, without meso-hole structure；
B is the high-resolution TEM photos of the Silicalite-1 zeolite molecular sieve materials of obtained Zr doping in embodiment 2 in Fig. 2, As seen from the figure, material internal is without meso-hole structure；
A is the XRD of the Silicalite-1 zeolite molecular sieve materials of obtained Zr doping in embodiment 2 in Fig. 3, can by figure See, material crystalline is good.
Embodiment 3
The present embodiment the difference is that only with embodiment 2：The hetero atom of doping is become Fe by Zr, Fe doping is prepared Silicalite-1 zeolite molecular sieves, because skeleton is in electronegativity, with relative hydropathic effect, what is obtained is hierarchical porous structure. Specific implementation step is as follows：
A) 18g water and 10.4165g tetraethyl orthosilicates are uniformly mixed into 2h at room temperature；
B) by the water ferric nitrate (Fe (NO of 0.404g nine3)3·9H2O in) being added to a), stirring to TEOS complete hydrolysis is formed clarifies Colloidal sol；
C) 4.1g TPAOHs solution (aqueous solution of 25%wt) is added dropwise to b) in, and it is transferred to 40 DEG C of water-baths In, the row's of carrying out alcohol and ripening, until forming desiccant gel, then carry out Crystallizing treatment, in each liner before crystallization Bottom (outside of crucible, sample is put in crucible) add 0.7g deionized waters, be put into 150 DEG C of baking ovens, steam auxiliary is brilliant Change treatment 24h；
D) sample after crystallization is taken out, 8h is dried in 100 DEG C of baking ovens, finally calcine 6h in 600 DEG C of air atmosphere, heated up Speed is about 1 DEG C of min-1, the Silicalite-1 zeolite molecular sieve materials of the Fe doping described in 3.0g are obtained final product, by BET methods The total specific surface area 354m for surveying2.g-1, pore size is 10nm or so, and pore volume is measured for 0.54cm by BJH methods3.g-1。
B is the XRD of the Silicalite-1 zeolite molecular sieve materials of the Fe doping obtained by the present embodiment 3 in Fig. 3, by Figure is visible, and material is typical MFI type zeolite structure, and crystallinity is of a relatively high；
A is the SEM photograph of the Silicalite-1 zeolite molecular sieve materials of obtained Fe doping in embodiment 3 in Fig. 4, can by figure See, material is coarse, meso-hole structure is obvious；
B is the TEM photos of the Silicalite-1 zeolite molecular sieve materials of obtained Fe doping in embodiment 3 in Fig. 4, can by figure See, material internal presence is substantially mesoporous and skeleton crystal is good.
Embodiment 4
The present embodiment is similar with the synthesis technique of embodiment 2, and the hetero atom of doping is become Ti by Zr to prepare TS-1 zeolites point Son sieve, exists in skeleton in+4 valency forms, and relative hydrophobic property is externally presented, and specific implementation step is as follows：
A) by 18g water, 4.1g TPAOHs solution (aqueous solution of 25%wt) and 10.4165g tetraethyl orthosilicates in room 2h is uniformly mixed under temperature, is subsequently transferred to persistently stir 4h in 40 DEG C of water-baths, be then transferred in 0 DEG C of ice bath；
B) 0.34g butyl titanates are added in 6g aqueous isopropanols, are cooled to 0 DEG C or so, in being then added dropwise to a), And quickly stir, until forming vitreosol；
C) vitreosol in b) is transferred in 40 DEG C of water-baths, the row's of carrying out alcohol and ripening, until desiccant gel is formed, Then Crystallizing treatment is carried out, was added in the bottom (outside of crucible, sample is put in crucible) of each liner before crystallization 0.7g deionized waters, are put into 150 DEG C of baking ovens, steam auxiliary crystallization treatment 24h；
D) sample after crystallization is taken out, 8h is dried in 100 DEG C of baking ovens, finally calcine 6h in 600 DEG C of air atmosphere, heated up Speed is about 1 DEG C of min-1, the TS-1 zeolite molecular sieve materials described in 3.0g are obtained final product, the total specific surface area surveyed by BET methods 515m2.g-1, pore volume is measured for 0.55cm by BJH methods3.g-1。
B is the SEM photograph of obtained TS-1 zeolite molecular sieve materials in embodiment 4 in a and Fig. 6 in Fig. 5, as seen from the figure, Material surface is smooth, without meso-hole structure.
Embodiment 5
The present embodiment adulterated on the basis of embodiment 4 Al elements adjustment skeleton hydrophilic and hydrophobic, because Al is+trivalent in skeleton, Skeleton is in externally electronegativity, and relative hydropathy is externally presented, therefore can obtain hierarchical porous structure, while the doping of Al is to knot The influence of structure is also obvious, and Al is only listed here:The specific implementation step of Ti (mol ratio)=0.75, specific implementation step is such as Under：
A) by 18g water, 0.1532g aluminium isopropoxides uniformly mix 2h at room temperature with 10.4165g tetraethyl orthosilicates, then 10.98g TPAOHs solution (aqueous solution of 25%wt) is added dropwise over, 4h is persistently stirred in 40 DEG C of water-baths, so It is transferred to afterwards in 0 DEG C of ice bath；
B) 0.34g butyl titanates are added in the aqueous isopropanol of 6g (0 DEG C of temperature), in being then added dropwise to a), and Quick stirring, until forming vitreosol；
C) vitreosol in b) is transferred in 40 DEG C of water-baths, the row's of carrying out alcohol and ripening, until desiccant gel is formed, Then Crystallizing treatment is carried out, was added in the bottom (outside of crucible, sample is put in crucible) of each liner before crystallization 0.7g deionized waters, are put into 150 DEG C of baking ovens, steam auxiliary crystallization treatment 24h；
D) sample after crystallization is taken out, 8h is dried in 100 DEG C of baking ovens, finally calcine 6h in 600 DEG C of air atmosphere, heated up Speed is about 1 DEG C of min-1, obtain final product described in 3.0g Al doping TS-1 zeolite molecular sieve materials, by BET methods survey it is total Specific surface area 496m2.g-1, pore size is~15nm, and pore volume is measured for 0.45cm by BJH methods3.g-1。
B is the SEM photograph of the TS-1 zeolite molecular sieve materials of obtained Al doping in embodiment 5 in Fig. 5, as seen from the figure, Material surface is coarse, and meso-hole structure occurs.
Embodiment 6
The present embodiment adulterated on the basis of embodiment 4 Al elements adjustment skeleton hydrophilic and hydrophobic, because Al is+trivalent in skeleton, Skeleton is in externally electronegativity, and relative hydropathy is externally presented, therefore can obtain hierarchical porous structure, while the doping of Al is to knot The influence of structure is also obvious, and Al is only listed here:The specific implementation step of Ti (mol ratio)=0.50, specific implementation step is such as Under：
A) by 18.0g water, 0.1021g aluminium isopropoxides uniformly mix 2h at room temperature with 10.4165g tetraethyl orthosilicates, with 10.98g TPAOHs solution (aqueous solution of 25%wt) is added dropwise over afterwards, and 4h is persistently stirred in 40 DEG C of water-baths, It is then transferred in 0 DEG C of ice bath；
B) 0.34g butyl titanates are added in the aqueous isopropanol of 6g (0 DEG C of temperature), in being then added dropwise to a), and Quick stirring, until forming vitreosol；
C) vitreosol in b) is transferred in 40 DEG C of water-baths, the row's of carrying out alcohol and ripening, until desiccant gel is formed, Then Crystallizing treatment is carried out, was added in the bottom (outside of crucible, sample is put in crucible) of each liner before crystallization 0.7g deionized waters, are put into 150 DEG C of baking ovens, steam auxiliary crystallization treatment 24h；
D) sample after crystallization is taken out, 8h is dried in 100 DEG C of baking ovens, finally calcine 6h in 600 DEG C of air atmosphere, heated up Speed is about 1 DEG C of min-1, obtain final product described in 3.0g Al doping TS-1 zeolite molecular sieve materials, by BET methods survey it is total Specific surface area 475m2.g-1, pore size is 10~15nm, and pore volume is measured for 0.34cm by BJH methods3.g-1。
A is the SEM photograph of the TS-1 zeolite molecular sieve materials of obtained Al doping in embodiment 6 in Fig. 6, as seen from the figure, Material surface is coarse, and meso-hole structure occurs.
Embodiment 7
The present embodiment adulterated on the basis of embodiment 4 Al elements adjustment skeleton hydrophilic and hydrophobic, because Al is+trivalent in skeleton, Skeleton is in externally electronegativity, and relative hydropathy is externally presented, therefore can obtain hierarchical porous structure, while the doping of Al is to knot The influence of structure is also obvious, and Al is only listed here:The specific implementation step of Ti (mol ratio)=0.25, specific implementation step is such as Under：
A) by 18g water, 0.051g aluminium isopropoxides and 10.4165g tetraethyl orthosilicates uniformly mix 2h at room temperature, then by 10.98g TPAOHs solution (aqueous solution of 25%wt) is added dropwise to, 4h is persistently stirred in 40 DEG C of water-baths, then It is transferred in 0 DEG C of ice bath；
B) 0.34g butyl titanates are added in the aqueous isopropanol of 6g (0 DEG C of temperature), in being then added dropwise to a), and Quick stirring, until forming vitreosol；
C) vitreosol in b) is transferred in 40 DEG C of water-baths, the row's of carrying out alcohol and ripening, until desiccant gel is formed, Then Crystallizing treatment is carried out, was added in the bottom (outside of crucible, sample is put in crucible) of each liner before crystallization 0.7g deionized waters, are put into 150 DEG C of baking ovens, steam auxiliary crystallization treatment 24h；
D) sample after crystallization is taken out, 8h is dried in 100 DEG C of baking ovens, finally calcine 6h in 600 DEG C of air atmosphere, heated up Speed is about 1 DEG C of min-1, obtain final product described in 3.0g Al doping TS-1 zeolite molecular sieve materials, by BET methods survey it is total Specific surface area 432m2.g-1, pore volume is measured for 0.27cm by BJH methods3.g-1。
B is the SEM photograph of the TS-1 zeolite molecular sieve materials of obtained Al doping in embodiment 7 in Fig. 6, as seen from the figure, Material surface still smoother, does not observe meso-hole structure.
As fully visible, the zeolite molecular sieve material with homogeneous particle size and hierarchical porous structure for being prepared in the present invention Method, need not only add mesoporous template, and material yield close to 100%, it is possible to realize mass production.This side Method has overturned the thinking of conventional synthesis porous zeotile completely, there is provided a kind of simple efficient completely new approach, and with pervasive Property, it is that industrial applications have established solid foundation.
Finally be necessary explanation be：Above example is served only for saying technical scheme in further detail Bright, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art's the above of the invention is made Some nonessential modifications and adaptations belong to protection scope of the present invention.

Claims (10)

1. a kind of method for adjusting zeolite molecular sieve pore passage structure, it is characterised in that contain miscellaneous original by add different valence state The predecessor of son, and with reference to the treatment of steam auxiliary crystallization by changing skeleton hydrophily to realize zeolite molecular sieve from multi-stage porous knot Conversion between structure and homogeneous zeolite granular；Including：
Silicon source, water, microcellular structure directed agents are mixed, precursor sol is obtained；
Different valence state is added in the precursor sol containing heteroatomic predecessor, aqueous precursor gel is obtained；
After gained aqueous precursor gel is aged, Crystallizing treatment is carried out 1~120 hour at 100~220 DEG C in steam condition；
By the aqueous precursor gel after Crystallizing treatment after drying, at 500~600 DEG C high-temperature calcination 6~24 hours.
2. method according to claim 1, it is characterised in that it is only the tetravalence that valence state is tetravalence to control the hetero atom for adding Hetero atom, the pattern for making gained zeolite molecular sieve is homogeneous zeolite granular, and the tetravalence hetero atom is Zr and/or Ti.
3. method according to claim 1, it is characterised in that it is non-for tetravalence that the hetero atom that control is added includes valence state Tetravalence hetero atom, the pattern for making gained zeolite molecular sieve is hierarchical porous structure, and the non-tetravalence hetero atom is Fe and/or Al.
4. method according to claim 3, it is characterised in that adjusted by changing the heteroatomic addition of the non-tetravalence Gained hierarchical porous structure.
5. the preparation method according to any one of claim 1-4, it is characterised in that the silicon source, hetero atom, water with it is micro- The mol ratio of pore structure directed agents is 1:（30~500）:（10~50）:（0.05~0.5）.
6. the preparation method according to any one of claim 1-5, it is characterised in that the silicon source be tetraethyl orthosilicate, At least one in Ludox and sodium metasilicate.
7. the preparation method according to any one of claim 1-6, it is characterised in that will be molten containing heteroatomic predecessor In alcoholic solution, and add the precursor sol under cryogenic, the cryogenic conditions are 0~10 DEG C, preferably 0~ 5℃。
8. the preparation method according to any one of claim 1-7, it is characterised in that the microcellular structure directed agents are four At least one in propyl group ammonium bromide, TPAOH, 4-propyl ammonium chloride and tetrapropyl ammonium fluoride.
9. the preparation method according to any one of claim 1-8, it is characterised in that the temperature of the ageing is 10~80 DEG C, the time is 10~240 hours.
10. the preparation method according to any one of claim 1-9, it is characterised in that the steam condition includes：Temperature It is 100~220 DEG C, preferably 110~180 DEG C.
CN201611245176.9A 2016-12-29 2016-12-29 It is a kind of to change the method that skeleton hydrophilic and hydrophobic adjusts zeolite molecular sieve pore passage structure Pending CN106829991A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611245176.9A CN106829991A (en) 2016-12-29 2016-12-29 It is a kind of to change the method that skeleton hydrophilic and hydrophobic adjusts zeolite molecular sieve pore passage structure

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611245176.9A CN106829991A (en) 2016-12-29 2016-12-29 It is a kind of to change the method that skeleton hydrophilic and hydrophobic adjusts zeolite molecular sieve pore passage structure

Publications (1)

Publication Number Publication Date
CN106829991A true CN106829991A (en) 2017-06-13

Family

ID=59114595

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611245176.9A Pending CN106829991A (en) 2016-12-29 2016-12-29 It is a kind of to change the method that skeleton hydrophilic and hydrophobic adjusts zeolite molecular sieve pore passage structure

Country Status (1)

Country Link
CN (1) CN106829991A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110787767A (en) * 2019-08-15 2020-02-14 北京科技大学 Hydrophobic adsorbent and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101618877A (en) * 2009-07-28 2010-01-06 中国科学院上海硅酸盐研究所 Micropore-mesopore grading structural material and preparation method thereof
CN102795635A (en) * 2012-09-10 2012-11-28 中国科学院上海硅酸盐研究所 Multi-orifice zeolite material as well as preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101618877A (en) * 2009-07-28 2010-01-06 中国科学院上海硅酸盐研究所 Micropore-mesopore grading structural material and preparation method thereof
CN102795635A (en) * 2012-09-10 2012-11-28 中国科学院上海硅酸盐研究所 Multi-orifice zeolite material as well as preparation method and application thereof

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
JINGUI WANG ET AL.: "Titanium(IV) in the Organic-Structure-Directing-Agent-Free Synthesis of Hydrophobic and Large-Pore Molecular Sieves as Redox Catalysts", 《CHEMSUSCHEM》 *
JUNGKYU CHOI ET AL.: "Grain Boundary Defect Elimination in a Zeolite Membrane by Rapid Thermal Processing", 《SCIENCE》 *
LIANG WANG ET AL.: "A significant enhancement of catalytic activities in oxidation with H2O2 over the TS-1 zeolite by adjusting the catalyst wettability†", 《CHEM. COMMUN.》 *
TONGGUANG GE ET AL.: "On the Mesoporogen-Free Synthesis of Single-Crystalline Hierarchically Structured ZSM-5 Zeolites in a Quasi-Solid-State System", 《CHEM. EUR. J.》 *
WEIBIN FAN ET AL.: "Synthesis, Crystallization Mechanism, and Catalytic Properties of Titanium-Rich TS-1 Free of Extraframework Titanium Species", 《J. AM. CHEM. SOC.》 *
XUE GAO ET AL.: "Eco-friendly fabrication of hydrophilic ZSM-5 membranes for alcohol upgrading†", 《CHEM. COMMUN.》 *
于文静: "ZSM-5分子膜的合成与应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110787767A (en) * 2019-08-15 2020-02-14 北京科技大学 Hydrophobic adsorbent and preparation method thereof
CN110787767B (en) * 2019-08-15 2021-03-23 北京科技大学 Hydrophobic adsorbent and preparation method thereof

Similar Documents

Publication Publication Date Title
CN107555446B (en) Preparation method of hierarchical pore Y-type molecular sieve
CN107915234B (en) Preparation method of hierarchical porous TS-1 nano zeolite aggregate molecular sieve
CN102001681A (en) Method for synthesizing ZSM-5 zeolite
CN103665024B (en) A kind of double carbamate aliphatic chain organosilan quaternary ammonium compound and preparation thereof and application
CN109368657A (en) Framework metal high dispersive type multi-stage porous H-ZSM-5 molecular sieve preparation method
CN102745710B (en) The preparation method of hierarchical pore structure titanium-silicon molecular sieve material
CN107082436A (en) A kind of preparation method of mesoporous micro porous molecular sieve
CN105271299A (en) Mesoporous ZSM-5 zeolite preparing method
CN109437232A (en) A kind of preparation method of the ZSM-5 molecular sieve of multilevel structure
JP6075896B2 (en) Preparation of molecular sieve SSZ-23
CN108658087B (en) Hierarchical pore TS-1 zeolite material and preparation method thereof
CN108786767A (en) A kind of preparation method of nanoscale molecular sieve@graphene oxide coupling materials
CN102942193A (en) Method for synthesizing novel thin layer ZSM-5 zeolite with boron-containing framework
CN106745039B (en) A kind of size adjustable and the nanometer Ti-Si zeolite molecular sieve and preparation method thereof with ultra-high yield
US11434140B2 (en) Hierarchical zeolites and preparation method therefor
CN100360405C (en) LTA and FAU molecular screen nanocrystalline preparation method
CN105347358B (en) A kind of preparation method that there is three-dimensional through the zeolite molecular sieve material of mesoporous multi-stage artery structure
CN106829991A (en) It is a kind of to change the method that skeleton hydrophilic and hydrophobic adjusts zeolite molecular sieve pore passage structure
CN106276967A (en) A kind of synthetic method of mesoporous zeolite
CN103466653A (en) Preparation method of all-silicon-type silicalite-1 zeolite molecular sieve containing intracrystalline mesoporous
CN102502685B (en) Preparation method of mesoporous LTA zeolite
CN109694086B (en) Preparation method of nano ZSM-5 zeolite molecular sieve aggregate
CN112125318B (en) Method for preparing MFI zeolite based on imidazolyl ionic liquid
CN105905919A (en) Meso-porous EU-1 zeolite molecular sieve and preparation method thereof
Zhang et al. A novel method for synthesis of mesoporous ZSM-5 from iron ore tailings

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20170613