CN104556089B - A kind of method for synthesizing silica zeolite - Google Patents
A kind of method for synthesizing silica zeolite Download PDFInfo
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- CN104556089B CN104556089B CN201410562157.3A CN201410562157A CN104556089B CN 104556089 B CN104556089 B CN 104556089B CN 201410562157 A CN201410562157 A CN 201410562157A CN 104556089 B CN104556089 B CN 104556089B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
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- 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
Abstract
A kind of method for synthesizing silica zeolite, including：By template, silicon source, optional inorganic ammonium salt, polyalcohol, peroxide and water formation mixture, crystallization reclaims silica zeolite；Wherein the mol ratio of polyalcohol and silicon source is 0.01~0.8：1, the mol ratio of peroxide and silicon source is 0.01~0.25:1, described silicon source is organic silicon source and/or solid silicon source.The method that the utilization that the present invention is provided synthesizes silica zeolite can reduce synthesized silica zeolite crystallite dimension.
Description
Technical field
The present invention relates to a kind of silica zeolite and its synthetic method.
Background technology
There is no the cation that can be exchanged on silica zeolite such as S-1, S-2, beta-molecular sieve, its skeleton, to hydrone
Adsorption capacity is well below the adsorption capacity to organic molecule, with high hydrophobicity, can be used as separation membrane and catalysis
Material, is also used as preparing the fertile material of other catalysis materials.For example, all-silica MFI structure molecular screen S-1 has been used as hexamethylene
Ketoxime rearrangement prepares the catalyst of caprolactam；Hetero atom is inserted using total silicon S-1 molecular sieves and total silicon beta molecular sieves as parent
The research of synthesis of molecular sieve is also in the ascendant, for example, synthesize TS-1 molecular sieves and Sn-beta molecular sieves.
Union carbide corporation of the U.S. in 1977 reports direct hydrothermal synthesis all-silica MFI structure molecular screen in USP4061724
Method, it is (0-6.5) M that it, which first prepares a mole composition,2O：(13-50)SiO2:Q2O：(150-700)H2O reactant mixture,
Then the mixture is placed at 100-250 DEG C crystallization 50-150 hours, wherein M is alkali metal ion, organic formwork agent Q=
R4X+, R is the alkyl of 2-6 carbon atom, and X is P or N.Then they disclose addition fluorine element in patent USP4073865 again
Method to reduce total silicon S-1 Crystallization of Zeolite temperature, but fluorine element has severe contamination to environment, and its application is restricted.
It is not high that silica zeolite prepared by above method is used for cyclohexanone oxime Beckmann rearrangement activity.
CN97100231.2 discloses a kind of synthetic method of crystalline silicon dioxide molecular sieve, this method using solid silicone as
Raw material, with amine organic matter (Q) for template, it is (0.02-0.3) that it is obtained by mixing into a mole composition with NaOH and water
Na2O:(0.05-0.8)SiO2:(1-10)H2O reactant mixture, then by the reactant mixture according to a conventional method in 100-
200 DEG C of crystallization 8 hours to 10 days.The silica zeolite that this method is obtained is used for cyclohexanone oxime Beckmann rearrangement activity very
It is low.
Patent CN201010616382 discloses a kind of S-1 silica zeolites and preparation method and in caprolactam is prepared
Application, S-1 silica zeolites are made of following methods：(1) synthesis of TPAOH template；(2) molecular sieve
Synthesis：By the TPAOH aqueous solution and tetraethyl orthosilicate and ethanol synthesis, filtering is washed with deionized, reacted
Liquid is dried, roasting, obtains molecular screen primary powder；Ludox, polyethylene glycol 2000, concentrated ammonia liquor, Tian Qing are added into molecular screen primary powder
Powder and active carbon powder, extruded moulding is carried out after being mediated with kneader；Roasting；Product after roasting is sequentially placed into NH3-
NH4NO3Soak, be washed with deionized in mixed solution and hydrofluoric acid aqueous solution；Dry, be calcined again, that is, a kind of S-1 is made
Silica zeolite.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of new silica zeolite synthetic method.
A kind of synthetic method of silica zeolite, including：By template, silicon source, optional inorganic ammonium salt, polyalcohol, mistake
Oxide and water formation mixture, crystallization reclaim silica zeolite；Wherein the mol ratio of polyalcohol and silicon source is 0.01~0.8：
1, the mol ratio of peroxide and silicon source is 0.01~0.25:1, described silicon source is organic silicon source and/or solid silicon source.
The synthetic method for the silica zeolite that the present invention is provided, wherein, template, silicon source, mole of inorganic source of ammonium and water
Than being preferably (0.04~0.5)：1：(0~0.1)：(3~100)；In wherein described mol ratio, silicon source is with SiO2Meter, be with
SiO2Meter organic silicon source and with SiO2The summation of the solid silicon source of meter, inorganic source of ammonium is with NH4 +Meter；Described inorganic source of ammonium is nothing
Machine ammonium salt and/or ammoniacal liquor.
The silica zeolite synthetic method that the present invention is provided, when described silicon source includes organic silicon source, in addition to hydrolysis
The step of catching up with alcohol.Described hydrolysis catches up with alcohol to be hydrolyzed including making organic silicon source be contacted with water, and reduces hydrolysate reclaimed water
Solve the content of the monohydric alcohol produced.The hydrolysis catches up with alcohol to be carried out before crystallization, described peroxide after alcohol is caught up with hydrolysis,
Crystallization is previously joined in mixture.
A kind of embodiment, it is described to form template, silicon source, optional inorganic ammonium salt, polyalcohol, peroxide and water
During mixture, silicon source is added in two times, wherein adding silicon source for the first time, (silicon source added for the first time is referred to as first time silicon
Source) aging afterwards, silicon source is then added for the second time (silicon source of second of addition is referred to as second of silicon source).It is preferred that, described silicon
Source includes organic silicon source and solid silicon source, and the solid silicon source is inorganic silicon source, and described organic silicon source is previously joined in aging,
Described solid silicon source is added after aging.The aging can be at room temperature~50 DEG C that step (1) products therefrom is quiet
Put 1~60 hour.The room temperature is 15~40 DEG C；Ageing time is for example, 2~50 hours 1~60 hour, and preferably 3~50 is small
When such as 3~15 hours, in ageing process without stirring, by the material be step (1) products therefrom stand.Described mistake
Oxide is preferably previously joined in aging.When the silicon source that first time adds includes organic silicon source, preferably it is hydrolyzed and catches up with alcohol
Described peroxide, then aging are added afterwards.
The silica zeolite synthetic method that the present invention is provided, can reduce the grain size of synthesized molecular sieve.
Brief description of the drawings
The XRD spectra for the total silicon S-1 molecular sieves that Fig. 1 is prepared for the present invention.
The XRD spectra for the total silicon beta-molecular sieve that Fig. 2 is prepared for the present invention.
Fig. 3 is the total silicon S-1 molecular sieves that prior art is synthesized with the present invention29Si NMR spectras.
Fig. 4 is the SEM scanning figures of total silicon S-1 molecular sieves of the present invention.
Total silicon beta-molecular sieve (also known as beta molecular sieves) SEM scanning figures that Fig. 5 synthesizes for the present invention
Fig. 6 is the TEM figures of the total silicon S-1 molecular sieves by resetting.
Embodiment
The synthetic method for the silica zeolite that the present invention is provided, can synthesize total silicon in the case of relatively low template agent consumption
Molecular sieve, thus template agent consumption can be with relatively low, the mol ratio of such as template agent and organic silicon source in terms of silica is
0.05~0.36:1, it is further 0.05~0.25:1, for example, 0.05~0.2:1；In the method that the present invention is provided, Ke Yi
Synthesize silica zeolite under high solids content, from can and reduce the usage amount of water, improve output per single reactor i.e. in same synthetic reaction
The more molecular sieves of the lower synthesis of body product, therefore described water and the mol ratio of silica can be 5~80:1 or (5~
50):1, further for example, 6~30:1 or for 6~20:1.
The synthetic method for the silica zeolite that the present invention is provided, described template, silicon source (also referred to as total silicon source), Inorganic Ammonium
The mol ratio of source and water is (0.05~0.36)：1：(0.01~0.1)：(5~80), further, described template, silicon source,
Inorganic source of ammonium and the mol ratio of water are (0.05~0.36)：1：(0.01~0.1)：(5~50).It is preferred that, described template,
The mol ratio of silicon source, inorganic source of ammonium and water is (0.05~0.25)：1：(0.01~0.07)：(6~30).Under preferable case, institute
The template and the mol ratio of silicon source stated are 0.05~0.20:1；The mol ratio of water and silicon source is 6~20：1, inorganic source of ammonium and silicon
The mol ratio in source is 0.01-0.05:1.The method that the present invention is provided, by template, silicon source, optional inorganic ammonium salt, polyalcohol,
During peroxide and water formation mixture, silicon source can be added in mixture in two times, added in two times when silicon source
When, organic silicon source and/or solid silicon source can be added for the first time, can add organic silicon source and/or solid silicon source for the second time,
The step of may also include aging between addition silicon source twice, preferably organic silicon source is added before aging, and solid silicon source is in aging
Add afterwards.
The synthetic method for the silica zeolite that the present invention is provided, described template agent is organic base or is organic base and organic
Quaternary ammonium salt, described organic base is the one or more in quaternary ammonium base, organic amine；Template can be to have to example as mentioned
Machine quaternary ammonium base, the mixture of quaternary ammonium base and organic amine, the mixture of quaternary ammonium base and organic quaternary ammonium salt, organic amine and have
Mixture or quaternary ammonium base, the mixture of organic quaternary ammonium salt and organic amine of machine quaternary ammonium salt.Described organic amine is fat
Fat amine, aromatic amine and/or hydramine, described fatty amine (present invention is also referred to as fat amine compound), its formula is R3(NH2)n,
Wherein R3For alkyl or alkylidene with 1~4 carbon atom, n=1 or 2；(present invention is also referred to as alcamines to described hydramine
Compound) its formula be (HOR4)mNH(3-m), wherein R4For the alkyl with 1~4 carbon atom, m=1,2 or 3.Described fat
One or more in fat amine such as ethamine, n-butylamine, butanediamine or hexamethylene diamine；Described aromatic amine refers to there is a fragrance
One or more in the amine of property substituent, such as aniline, toluidines, p-phenylenediamine；Described hydramine such as MEA, two
One or more in monoethanolamine or triethanolamine.
Described template agent, preferably comprises quaternary ammonium base, can be quaternary ammonium base or include organic quaternary ammonium
The mixture of alkali be, for example, mixture, quaternary ammonium base and the organic quaternary ammonium salt of quaternary ammonium base and organic amine mixture or
The mixture of person's quaternary ammonium base and organic quaternary ammonium salt and organic amine.Under preferable case, described template includes organic
Alkali, the organic base and the mol ratio of silicon source that template is introduced is not less than 0.05：1；The template include organic quaternary ammonium salt and/
Or quaternary ammonium base, wherein the mol ratio of organic quaternary amine alkali and organic quaternary ammonium salt sum and silicon source is not less than 0.05:1；Wherein, have
Machine quaternary ammonium base with SiO2The mol ratio of the silicon source of meter is 0~0.3:1, for example, 0.05~0.2:1, organic amine with SiO2Meter
Silicon source mol ratio be 0~0.45：1, for example, 0~0.35:1 or for 0.05~0.25:1, organic quaternary ammonium salt with
SiO2The mol ratio of the silicon source of meter is 0~0.45:1, for example, 0.05~0.3:1.In a kind of embodiment, described template
Including organic base, including quaternary organic ammonium compounds, the organic base and the mol ratio of silicon source introduced in template is not less than 0.04:1
For example, 0.05~0.45；1, described organic base is quaternary ammonium base and/or organic amine；Quaternary organic ammonium compounds and and silicon source
Mol ratio be not less than 0.04:1, for example, 0.05~0.45:1, described quaternary organic ammonium compounds for quaternary ammonium base and/or
Organic quaternary ammonium salt.
In described quaternary ammonium base such as TPAOH, TBAH or tetraethyl ammonium hydroxide
One or more mixtures；Described organic quaternary ammonium salt such as 4-propyl bromide, TBAB, tetraethyl bromination
One or more in ammonium, 4-propyl ammonium chloride, tetrabutylammonium chloride or etamon chloride.
A kind of embodiment, described silica zeolite is S-1 molecular sieves, and described template agent is TPAOH
Or be TPAOH and one or more institute's groups in organic amine, 4-propyl ammonium chloride, 4-propyl bromide
Into mixture.
A kind of embodiment, described silica zeolite is S-2 molecular sieves, and described template is TBAH
Or one or more institute's groups for TBAH and in organic amine, tetrabutylammonium chloride, TBAB
Into mixture.
A kind of embodiment, described silica zeolite is total silicon beta molecular sieves (total silicon beta-molecular sieve), described template
Agent is tetraethyl ammonium hydroxide or is tetraethyl ammonium hydroxide and is selected from tetraethylammonium bromide, etamon chloride and organic amine
In one or more compositions mixtures.
The silica zeolite synthetic method that the present invention is provided, described organic silicon source is organo-silicon ester, described organosilicon
Ester, its formula is Si (OR1)4, R1Selected from such as R of the alkyl with 1~6 carbon atom1For C1-C4Alkyl, described alkyl
Can be branched alkyl or straight chained alkyl.Described organo-silicon ester for example quanmethyl silicate, tetraethyl orthosilicate, the butyl ester of silicic acid four,
One or more in dimethyl diethyl estersil；Wherein preferred quanmethyl silicate, tetraethyl orthosilicate, dimethyl diethyl estersil
In one or more.Solid silicon source described in the present invention is the silica solid or powder of high-purity, for example, can be
White carbon and/or high-purity silica gel.Under preferable case, the SiO in the solid silicon source on the basis of butt weight2Content is not low
It is less than 10ppm in 99.99 weight %, and Fe, Al and Na impurity gross mass content；Such as SiO2Content is 99.99~100 weights
Measure %, typically greater than 99.99 and less than 100 weight %.Described solid silicon source can be high-purity silica gel and/or hard charcoal
It is black, preferred white carbon, wherein SiO in the high-purity silica gel2It is, for example, to be more than that content, which is preferably greater than or equal to 99.99 weight %,
The 99.99 weight % and mass content of Fe, Al and Na impurity is less than 10ppm less than 100 weight %, and in terms of element.It is described white
The specific surface area of carbon black is preferably between 20-1000m2The preferred 50-400m of/g2Between/g, on the basis of the butt weight of white carbon,
SiO in the white carbon2It is, for example, that 99.99~100 weight % are, for example, to be more than that content, which is preferably greater than or equal to 99.99 weight %,
99.99 weight % and less than 100 weight %, the mass content of Fe, Al and Na impurity is less than in terms of simple substance in the white carbon
10ppm.The white carbon can be commercially available, or is prepared according to existing method, for example, carried according to patent CN200910227646.2
Prepared by the method for confession, a kind of preparation method is that silicon tetrachloride into combustion reaction occur with hydrogen and oxygen to obtain.
The silica zeolite synthetic method that the present invention is provided, described inorganic source of ammonium is inorganic ammonium salt and/or ammoniacal liquor, described
Inorganic ammonium salt such as ammonium chloride, ammonium nitrate, ammonium sulfate in one or more.Described inorganic source of ammonium is preferably ammoniacal liquor, with
NH4 +The ammoniacal liquor of meter with SiO2The mol ratio of the silicon source (being counted using organic silicon source and the solid silicon source total amount) of meter as 0~
0.11:1, for example, 0.01~0.07:1 is further 0.01~0.05:1.
In the silica zeolite synthetic method that the present invention is provided, by template, organic silicon source, inorganic source of ammonium, polyalcohol
With water by mixing, stirred at least 10 minutes at 0~150 DEG C such as 0~100 DEG C such as 50~95 DEG C, so that organic silicon source is hydrolyzed,
The content for the alcohol (being usually monohydric alcohol) that the wherein organic silicon source hydrolysis of reduction is produced.Usual mixing time is 10~3000 minutes,
For example, 2~30 hours.By hydrolysis, the organosilicon hydrolyzation liquid of clear is obtained.Organosilicon in the organosilicon hydrolyzation liquid
The content that the mass content for the monohydric alcohol that source hydrolysis is produced is preferably more than monohydric alcohol in 10ppm, the organosilicon hydrolyzation liquid is excellent
Choosing is no more than 10ppm.Then add peroxide to stir, usual mixing time is 10~60 minutes.
In the silica zeolite synthetic method that the present invention is provided, the polyalcohol be molecule in have 2 or more than 2 hydroxyls
The carbon atom number having in the alcohol of base, the polyol molecule is preferably 2~8；Described peroxide is tool in molecule
There is the compound of peroxide bridge.One or more in described polyhydric alcohols such as glycerine, ethylene glycol, hexylene glycol, diethylene glycol (DEG).Institute
One or more in the preferred hydrogen peroxide of peroxide, tert-butyl peroxide, Peracetic acid, trifluoro Peracetic acid for stating etc..It is many
The mol ratio of first alcohol and silicon source is 0.01~0.8, preferably 0.05~0.6:1, the mol ratio of peroxide and silicon source for 0.05~
0.25：1, for example, 0.05~0.15：1.
The silica zeolite synthetic method that the present invention is provided, the crystallization, the temperature of crystallization is 110~200 DEG C, crystallization pressure
Power is self-generated pressure, and the time of crystallization is 2 hours~20 days, and the time of the usual crystallization is 0.5~20 day, such as during crystallization
Between be 0.5~10 day, the temperature of crystallization described further is, for example, 160~180 DEG C for 140~180 DEG C, and crystallization time is
It is, for example, within 0.5~10 day 0.5~6 day, or for 0.5~3 day.Crystallization pressure is self-generated pressure.The crystallization can be in stainless steel
Carried out in stirred tank.Crystallization heating can be heated up with one section can also multistage heating mode.Heating rate can be according to existing crystallization liter
Warm method is carried out, for example, 0.5-1 DEG C/min.The crystallization can be carried out in stainless steel stirred tank.A kind of embodiment, institute
The crystallization temperature for stating crystallization is 160~180 DEG C, and it 0.5~10 day is, for example, 0.5~6 day or 0.5~3 day, crystallization that crystallization time, which is,
Pressure is self-generated pressure.A kind of embodiment, the crystallization described in step is：The crystallization at 100~130 DEG C such as 110~130 DEG C
0.5~1.5 day, then crystallization 1~3 day at 160~180 DEG C, crystallization pressure was self-generated pressure.
The silica zeolite synthetic method that the present invention is provided, the recovery silica zeolite is existing method, including by crystalline substance
Change product filtering, washing and roasting or crystallization product is filtered, washed, is dried and then is calcined.The purpose of filtering is by crystallization
Obtained silica zeolite is separated with crystallization mother liquor, and the purpose of washing is the siliceous mould for washing away absorption on sieve particle surface
Version agent solution, for example, can be room temperature~50 DEG C in temperature, and the weight of molecular sieve and water compares 1:1~20 such as 1:Enter under (1-15)
Row mixing, washing or elution.Dry purpose is to remove the most of moisture in molecular sieve, is steamed with reducing moisture when roasting
Hair amount, dry temperature can be 100~200 DEG C.The purpose of roasting is to remove the template in molecular sieve, and example is roasted as mentioned
The temperature of burning is 350~650 DEG C, and roasting time is 2-10 hours.Silica zeolite product is obtained by reclaiming.
A kind of synthetic method for the silica zeolite that the present invention is provided, embodiment, comprises the following steps：(1) by template
Then agent, organic silicon source, inorganic ammonium salt, the mixing of polynary alcohol and water, hydrolysis add peroxide, (2) aging, and (3) have been added
Machine silicon source and/or solid silicon source, stir, crystallization reclaims silica zeolite；The mol ratio of wherein polyalcohol and silicon source is
0.01~0.8：1, the mol ratio of peroxide and silicon source is 0.01~0.25：1；Silicon source is with SiO2Meter, is with SiO2That counts is organic
Silicon source and with SiO2The summation of the solid silicon source of meter.
The synthetic method for the silica zeolite that the present invention is provided, it is a kind of preferred embodiment, including：(1) by template,
Then organic silicon source, inorganic ammonium salt, the mixing of polynary alcohol and water, hydrolysis add peroxide, (2) aging, and (3) add solid
Silicon source, stir, crystallization reclaims silica zeolite；Wherein the mol ratio of polyalcohol and silicon source is 0.01~0.8：1, peroxide
The mol ratio of compound and silicon source is 0.01~0.25：1；Silicon source is with SiO2Meter, is with SiO2Meter organic silicon source and with SiO2Meter
The summation of solid silicon source.
In the silica zeolite synthetic method that the present invention is provided, the embodiment of the choosing, by using organic silicon source and
Two kinds of silicon sources of solid silicon source (inoganic solids silicon source), add first time silicon source before ageing, and the first time silicon source is organosilicon
Second of silicon source is added after source, aging, second of silicon source is solid silicon source, can have synthesized molecular sieve more
Surface hydroxyl nest defect.The Q of resulting silica zeolite4/Q3For 10~90:1, wherein Q4For the silica zeolite29Chemical shift is the peak intensity at -112 ± 2ppm in Si NMR spectras, is represented with peak height, Q3For the silica zeolite29Chemical shift is the peak intensity at -103 ± 2ppm in Si NMR spectras, is represented with peak height.
In silica zeolite, a silicon atom is connected with four additional silicon atom by oxygen, is represented by Si (OSi)4,
Its29It is that there is peak at -112 ± 2ppm in chemical shift, its peak intensity (being represented with peak height value) is expressed as Q in SiNMR spectrograms4；
One silicon source (is represented by SiOH (OSi) from being connected with the other three silicon atom by oxygen3), its29In Si NMR spectras, chemistry
Displacement is to have peak at -103 ± 2ppm, and its peak intensity (being represented with peak height value) is expressed as Q3；Q4/Q3Reflect to a certain extent
The quantity of defective bit contained by silica zeolite, the ratio is bigger, represents that defective bit is fewer.Total silicon prepared by prior art
The molecular sieve ratio is more than 95.
More 3 silicon originals of connection are provided in the silica zeolite of the present invention preferred embodiment provided, lattice
The defect silicon position of son, has higher catalytic activity for cyclohexanone oxime Beckmann rearrangement.It is described preferred embodiment,
Zeolite crystal size can be reduced.In addition, using the relatively inexpensive solid silicon source being easy to get such as high-purity silica gel or/and hard charcoal
It is black, partly instead of expensive organic silicon source, the waste discharge of process of producing molecular sieve can be reduced and cost of material is saved.This
Invent provide silica zeolite synthetic method, it is described preferred embodiment, use solid silicon source and organic silicon source, Ke Yiling
The particle size of silica zeolite prepared by modulation living, can be obtained and all using organosilicon as the silica zeolite of Material synthesis
The suitable silica zeolite of grain size.The silica zeolite synthetic method that the present invention is provided, can be used in relatively low template agent
Silica zeolite is synthesized in the case of amount and relatively low water silicon ratio, the synthesis cost of silica zeolite can be substantially reduced, improves and closes
Into the solid content of molecular sieve crystallization product, one-pot molecular sieve yield is improved.
The synthetic method for the silica zeolite that the present invention is provided, it is described preferred embodiment, under preferable case, including such as
Lower step：
(1) template, organic silicon source, inorganic source of ammonium, polynary alcohol and water are mixed, at 0~150 DEG C such as 10~100 DEG C
Stirring at least 10 minutes；The mixing time of the stirring is for example stirred 10 minutes~50 hours；Then peroxide stirring is added
Uniformly, for example stir 10~30 minutes；(2) by step (1) products therefrom aging, the aging is by step (1) products therefrom
Stand such as 3~15 hours preferably 3~30 hours such as 2~50 hours 1~60 hour at room temperature；(3) by obtained by step (2)
The ageing products arrived are with solid silicon source according to 1：0.1~20 weight is than being well mixed, and then the crystallization in closed reactor, is returned
Receive si molecular sieves；In wherein described part by weight, the ageing products and solid silicon source obtained by step (2) are with SiO2
Meter；
Wherein, the mol ratio of template, silicon source, inorganic source of ammonium and water is (0.04~0.5)：1：(0.01~0.1)：(3~
100), wherein in described mol ratio, silicon source is with SiO2Meter organic silicon source and with SiO2The total moles of the solid silicon source of meter
Number, inorganic source of ammonium is with NH4 +Meter, inorganic source of ammonium can be inorganic ammonium salt and/or ammoniacal liquor, and water is with H2O is counted.
The silica zeolite synthetic method that the present invention is provided, it is described preferred embodiment, by step (1) in step (2)
Products therefrom aging, the aging be at room temperature~50 DEG C by step (1) products therefrom stand 1~60 hour.The room temperature
For 15~40 DEG C；It 1~60 hour is, for example, 2~50 hours, preferably 3~50 hours such as 3~15 hours, aging that ageing time, which is,
During without stirring, by the material be step (1) products therefrom stand.
The silica zeolite synthetic method that the present invention is provided, it is described preferred embodiment, by step (2) in step (3)
Obtained ageing products are mixed with solid silicon source, with SiO2Meter, the product and the mol ratio of solid silicon source that step (2) is obtained are (i.e.
Have the mol ratio of solid silicon source described in the machine silicon source and step (3) in step (1)) it is 1:0.1~20, for example can be 1:
1~19, or 1:2~18, or 1:3~17, or 1:5~15 or 1:11~20.Organic silicon source and solid silicon
The mol ratio in source preferably 1:5~15.The method that the present invention is provided, can use the solid silicon source of higher proportion, can improve conjunction
Into the solid content of product, so as to improve the yield of single synthesis in the case where synthesis reaction vessel is constant.Obtain product more existing
The production die obtained using the synthetic method of solid silicon source is smaller, can reach the crystal grain level all using organic silicon source.
The ageing products that step (2) is obtained are mixed with solid silicon source, are stirred, generally stirring at least 15 minutes, for example, stir 0.5
~5 hours.
In the silica zeolite synthetic method that the present invention is provided, reclaiming obtained silica zeolite can also be by further place
Reason, such as step (3) reclaim obtained silica zeolite and also can be further processed, i.e., the silica zeolite that the present invention is provided
Synthetic method, can also comprise the following steps (present invention is referred to as molecular sieve rearrangement step)：
Obtained silica zeolite will be reclaimed with organic base, water according to 1：0.02~0.5：2~50 mol ratio forms mixed
Compound, in 100~200 DEG C such as 100~150 DEG C or 120~200 DEG C of crystallization (these in closed reactor and under self-generated pressure
Invention is referred to as the second crystallization) 0.1~10 day, then reclaim product.In above-mentioned steps (molecular sieve rearrangement step), it is preferable that having
Obtained silica zeolite is reclaimed in machine quaternary ammonium alkali solution described in Crystallizing treatment, silica zeolite, wherein molecular sieve is then reclaimed
(with SiO2Meter) with the molar ratio of organic base it is 1：0.02~0.5 is, for example, 1：0.05~0.2, with SiO2The molecular sieve of meter with
The mol ratio of water is 1：2~50 be, for example, 1：2~20 or 1：5~10, crystallization temperature (the second crystallization) is 120~200 DEG C, time
For 0.5~8 day, crystallization pressure was self-generated pressure；It is preferred that, described crystallization temperature is 150-200 DEG C, and crystallization time is 0.5~6
My god.Recovery method is existing method, can refer to foregoing recovery method, generally includes to filter crystallization product, washs, does
Dry right and roasting.Described organic base is quaternary ammonium base and/or organic amine, described quaternary ammonium base such as tetrapropyl hydrogen-oxygen
Change one or more mixtures in ammonium, TBAH or tetraethyl ammonium hydroxide.Described organic amine is fat
One or more in amine, aromatic amine and hydramine, described fatty amine (present invention is also referred to as fat amine compound), its formula is
R3(NH2)n, wherein R3For alkyl or alkylidene with 1~4 carbon atom, n=1 or 2；Described hydramine (the present invention
Alcamine compound) its formula is called (HOR4)mNH(3-m), wherein R4For the alkyl with 1~4 carbon atom, m=1,2 or 3.
One or more in described fatty amine such as ethamine, n-butylamine, butanediamine or hexamethylene diamine；Described aromatic amine refers to have
One or more in the amine of one armaticity substituent, such as aniline, toluidines, p-phenylenediamine；Described hydramine is for example single
One or more in monoethanolamine, diethanol amine or triethanolamine.A kind of embodiment, described silica zeolite is S-1 points
Son sieve, described quaternary ammonium base is TPAOH.A kind of embodiment, described silica zeolite is S-2 molecules
Sieve, described quaternary ammonium base is TBAH.A kind of embodiment, described silica zeolite divides for total silicon beta
Son sieve (total silicon beta-molecular sieve), described quaternary ammonium base is tetraethyl ammonium hydroxide.
The above-mentioned molecular sieve for obtaining recovery is contacted with organic base and water to be handled, and the present invention is referred to as molecular sieve weight
Row, this process can be carried out once, can also be repeated one or more times, and the repetition will handle obtained silica zeolite
Further according to above method processing.Handled by rearrangement, the silica zeolite with secondary pore structure can be obtained, gained is complete
The crystal grain of si molecular sieves is hollow-core construction, and the radical length of the chamber portion of the hollow crystal grain is 5~300nm, in 25 DEG C, P/P0
=0.10, the benzene adsorbance that adsorption time is measured under conditions of 1 hour is at least 70 milligrams per grams, and the cryogenic nitrogen of the molecular sieve is inhaled
There is hysteresis loop between attached adsorption isotherm and desorption isotherm.With higher pore volume and specific surface area.
The silica zeolite that the present invention is provided, the Q of the silica zeolite4/Q3For 10~90:1, for example, 10~70:1,
Wherein Q4For the silica zeolite29Chemical shift is the peak intensity at -112 ± 2ppm in SiNMR spectrograms, with peak height table
Show, Q3For the silica zeolite29Chemical shift is the peak intensity at -103 ± 2ppm in SiNMR spectrograms, is represented with peak height.
The Q4/Q3Preferably 10~50:1.The grain size (short-axis direction) of the silica zeolite can be for 140nm~2 μm for example
200nm~2 μm, for example, 200nm~700nm.The particle of the silica zeolite is that single crystal grain or multiple crystal grain are assembled
Form.
The present invention is further illustrated for the following examples, but and is not so limited the present invention.Institute in embodiment
What the reagent used was not described further is commercially available AR.In comparative example 1 silica zeolite used be by
S-1 sieve samples prepared by the method described in prior art CN1338427A method.
Q in embodiment4/Q3Measuring method use29Si MAS NMR methods.Using Varian INOVA300 type nuclear-magnetisms
Resonance spectrometer.Popped one's head in using solid double resonance, Φ 6mm ZrO2Rotor.29The resonance spectrum of Si detection cores is 59.588MHz,
Magic angle rotating speed is 3kHz, sampling time 0.02s, pulsewidth 1.5 μ s, circulation delay time 3s, scanning times 3000 times.
The measuring method of grain size：Using SEM Electronic Speculum characterizing methods, the Quanta 200F types scanning of FEI Co.'s production
Electronic Speculum：After sample drying processing, metal spraying is evaporated in vacuo, to increase electric conductivity and contrast effect；Analytic electron microscope accelerating potential is
20.0kV, 1~30k of multiplication factor.
TEM methods：Electron microscope experiment is carried out on FEI Co.'s Tecnai F20G2S-TWIN type transmission electron microscopes, is matched somebody with somebody
There is the energy filter system GIF2001 of Gatan companies, annex is equipped with X-ray energy spectrometer.Electron microscopic sample uses the side of suspended dispersed
Method is prepared in diameter 3mm micro-grid.
XRD measuring methods：The X-ray diffraction (XRD) of sample is carried out on Siemens D5005 type x-ray diffractometers
Crystalline phase figure determine, radiographic source be CuK α (λ=), tube voltage 40kV, tube current 40mA, 0.5 °/min of sweep speed,
θ=4 °~40 ° of scanning range 2.
BET specific surface area and the method for testing of pore volume use N2 adsorption volumetric method, according to BJH computational methods.(referring to stone
Oily chemical analysis method (RIPP test methods), RIPP151-90)
Raw materials used property is as follows in embodiment and comparative example：
TPAOH, Guangdong great You chemical plant, concentration is 25.05 weight %,
Tetraethyl orthosilicate, analyzes pure, Chemical Reagent Co., Ltd., Sinopharm Group.
Ammoniacal liquor, analyzes pure, the weight % of concentration 20.
White carbon, Zhejiang Ju Hua groups product, model AS-150；Solid content is more than silica in 95 weight %, butt
Content is more than 99.99 weight %, and the total content of iron, sodium and Al is less than 10ppm, and specific surface area is 195m2/g。
Embodiment 1
(1) by the TPAOH aqueous solution that 9.8g concentration is 25.05 weight %, 4.16g tetraethyl orthosilicates,
0.21g concentration is added sequentially in 500ml beaker for 20 weight % ammoniacal liquor, 2.83 grams hexylene glycols and 32g deionized waters, is put
Enter the magnetic stirring apparatus with heating and agitating function, stirred 4 hours at 80 DEG C, supplement the water of evaporation in whipping process at any time
Point, the mass content of monohydric alcohol is no more than 10ppm in obtained product, then adds 2.83 grams of (the weight % of concentration 30) dioxygens
Water, stirs 15 minutes, obtains organic alkaline hydrolyzate of silicon；
(2) organic alkaline hydrolyzate of gained silicon is cooled to room temperature (26 DEG C) under agitation, 12 is then stood at room temperature
Hour aging, obtains ageing products；
(3) under stirring, 13.2g white carbon powder is added in the ageing products, stirs 2 hours, is transferred into not
Become rusty in steel closed reactor, in 165 DEG C of thermostatic crystallizations 12 hours, you can total silicon S-1 Crystallization of Zeolite products, by obtained S-
1 Crystallization of Zeolite product is filtered, and is washed with the deionized water for decupling molecular sieve, is dried 24 hours, 550 DEG C at 120 DEG C
Roasting 6 hours, obtains S-1 samples S-1-Y1；Its XRD analysis spectrogram is as shown in Figure 1；29Si NMR characterization results as shown in figure 3,
SEM is as shown in Figure 4.Its BET specific surface area is 415m2.g-1, mesopore volume is 0.088mL.g-1Micro pore volume is 0.168mL.g-1。
(4) 6g S-1-Y1 samples are uniformly mixed with the 10 mass % TPAOH aqueous solution, wherein TPAOH amount of aqueous solution used
For 25.2g, in closed reactor, 150 DEG C of crystallization 3 days, filtering, washing are dried 24 hours at 120 DEG C, 550 DEG C of roastings 6
Hour, obtain sample S-1-Y1P.Its XRD analysis spectrogram is as shown in figure 1, its BET specific surface area is 428m2/ g, micro pore volume is
0.164mL.g-1, mesopore volume is 0.170mL.g-1, its in transmission electron microscope photo is hollow-core construction (shown in Fig. 6).
The characterization result of the preparation condition of embodiment 1 and resulting molecular sieve is shown in Table 1.
Embodiment 2~6
Method according to embodiment 1 prepares molecular sieve, the difference is that adjustment proportioning and preparation condition, wherein step (4)
Condition is constant, and it is matched and characterization result is shown in Table 1.
Embodiment 7
Template is TPAOH (TPAOH) and ethamine, TPAOH：Mol ratio=0.1 of ethamine:0.15, prepare
Method reference implementation example 1, preparation condition and characterization result are shown in Table 1.
Embodiment 8
The method of reference implementation example 1, changes proportioning and template prepares S-2 molecular sieves, and preparation condition and characterization result are shown in
Table 1.
Embodiment 9
The method of reference implementation example 1, changes proportioning and template prepares beta-molecular sieve, and preparation condition and characterization result are shown in Table
1。
Embodiment 10
According to the method for embodiment 1, unlike first crystallization 24 hours at 110 DEG C, then crystallization 48 is small at 170 DEG C
When.
Comparative example 1
This comparative example illustrates to prepare conventional silica zeolite S-1 according to CN1338427A method.
It is that 22.05% TPAOH solution is mixed by 208g tetraethyl orthosilicates and 180g concentration, adds 64.5g and go
Ionized water is uniformly mixed；Then in hydrolyzing 5-9h at 60-80 DEG C, hydrating solution containing tetraethyl orthosilicate is obtained；What is be stirred vigorously
Under effect, by the mixture in continuing to stir 7h at 75 DEG C, colloid is obtained, then the colloid is moved into stainless steel closed reactor
In, thermostatic crystallization 2 days at 170 DEG C, you can obtain conventional S-1 molecular sieves；
By obtained S-1 sample filterings, wash, dried at 120 DEG C 24 hours, 550 DEG C are calcined 6 hours.After 6g is calcined
S-1 samples and 22 grams of concentration uniformly mixed for the 22.05 weight % TPAOH aqueous solution, 150 DEG C of crystalline substances in closed reactor
Change 1 day, filtering, washing, dried at 120 DEG C 24 hours, 550 DEG C are calcined 6 hours, you can obtain the product described in the patent.
Preparation condition and characterization result are shown in Table 1.
Comparative example 2
Method according to comparative example 1 prepares silica zeolite, the difference is that with the white carbon of equivalent (with SiO2Meter) replace
Tetraethyl orthosilicate described in comparative example 1 is (with SiO2Meter).Preparation condition and characterization result are shown in Table 1.It is added without polyalcohol and dioxygen
Water.Preparation condition and characterization result are shown in Table 1.
Comparative example 1
According to the method for embodiment 2, the difference is that not introducing hydrogen peroxide, preparation condition and characterization result are shown in Table 1.
Comparative example 2
According to the method for embodiment 2, unlike, it is added without polyalcohol.Preparation condition and characterization result are shown in Table 1.
Comparative example 3
According to the method for embodiment 2, unlike, it is added without polyalcohol and hydrogen peroxide.Preparation condition and characterization result are shown in
Table 1.
Embodiment 11
By 59.9g white carbons (with SiO2Meter) mixed with 180g concentration for 22.05% TPAOH solution, add
64.5g deionized waters, 2.83 grams hexylene glycols are uniformly mixed；Then the mixture is added 2.18 in continuing to stir 7h at 75 DEG C
Gram concentration is 30 weight % hydrogen peroxide, is stirred 30 minutes, obtains colloid, then the colloid is moved into stainless steel closed reactor,
Thermostatic crystallization 2 days at 170 DEG C, you can obtain S-1 molecular sieves；
By obtained S-1 sample filterings, wash, dried at 120 DEG C 24 hours, 550 DEG C are calcined 6 hours.After 6g is calcined
S-1 samples and 22 grams of concentration uniformly mixed for the 22.05 weight % TPAOH aqueous solution, 150 DEG C of crystalline substances in closed reactor
Change 1 day, filtering, washing, dried at 120 DEG C 24 hours, 550 DEG C are calcined 6 hours, produce hollow S-1 samples product.
Preparation condition and it the results are shown in Table 1.
Embodiment 12
According to the method for embodiment 1, unlike in step (3) by white carbon with equivalent (with SiO2Meter) silicic acid tetrem
Ester is replaced.Preparation condition and it the results are shown in Table 1.
Embodiment 13
According to the method for embodiment 1, unlike in step (1) by tetraethyl orthosilicate with equivalent (with SiO2Meter) hard charcoal
It is black to replace.Preparation condition and it the results are shown in Table 1.
Evaluate embodiment
Molecular sieve after the silica zeolite do not reset provided above-described embodiment and comparative example and rearrangement is evaluated.
The catalytic performance of gained silica zeolite is evaluated using cyclohexanone oxime Beckmann rearrangement.Silica zeolite tabletting, then breaks
It is broken, the particle of 20-60 mesh is taken as catalyst.Evaluation result is shown in Table 1.Appreciation condition is as follows：
Reaction unit is that normal pressure continuously flows fixed bed, and reactor inside diameter is 5 millimeters, catalyst (silica zeolite) filling
Measure as 0.5g, the grain graininess of catalyst is 20-60 mesh.
Catalyst loads after reaction tube, is pre-processed 2 hours in normal pressure, 350 DEG C of nitrogen atmosphere.
The concentration of cyclohexanone oxime is 35.7 weight %, and weight space velocity (WHSV) is 7.5h-1, solvent is methanol, reaction temperature
For 350 DEG C, the flow velocity of nitrogen is 1.8 ls/h, the sampling of 3 hours reaction time.
Reaction product is collected after being condensed by water circulation, hydrogen flame detector, and gas chromatography measures its composition.
It should be noted that various embodiments of the present invention can be combined randomly, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (30)
1. a kind of synthetic method of silica zeolite, including：By template, silicon source, optional inorganic source of ammonium, polyalcohol, peroxide
Compound and water formation mixture, crystallization reclaim silica zeolite；Wherein the mol ratio of polyalcohol and silicon source is 0.01~0.8：1,
The mol ratio of peroxide and silicon source is 0.01~0.25:1, described silicon source is organic silicon source and/or solid silicon source, described solid
Body silicon source is inorganic silicon source.
2. in accordance with the method for claim 1, it is characterised in that by silicon source, template, optional inorganic source of ammonium, polyalcohol,
During peroxide and water formation mixture, described silicon source is added in two times, and add also includes aging twice between silicon source
The step of.
3. in accordance with the method for claim 1, it is characterised in that the mol ratio of polyalcohol and silicon source is 0.05~0.6:1, mistake
The mol ratio of oxide and silicon source is 0.05~0.25:1.
4. in accordance with the method for claim 1, it is characterised in that template, silicon source, the mol ratio of inorganic source of ammonium and water are
(0.04~0.5)：1：(0.01~0.1)：(3~100)；In wherein described mol ratio, silicon source is with SiO2Meter, is with SiO2Meter
Organic silicon source and with SiO2The summation of the solid silicon source of meter, inorganic source of ammonium is with NH4 +Meter；Described inorganic source of ammonium is inorganic ammonium salt
And/or ammoniacal liquor.
5. in accordance with the method for claim 4, it is characterised in that described template, silicon source, mole of inorganic source of ammonium and water
Than for (0.05~0.36)：1：(0.01~0.1)：(5~50).
6. in accordance with the method for claim 5, it is characterised in that described template, silicon source, mole of inorganic source of ammonium and water
Than for (0.05~0.25)：1：(0.01~0.07)：(6~30).
7. in accordance with the method for claim 6, it is characterised in that described template and the mol ratio of silicon source be 0.05~
0.2:1；The mol ratio of water and silicon source is 6~20：1, the mol ratio of inorganic source of ammonium and silicon source is 0.01-0.07:1.
8. in accordance with the method for claim 1, it is characterised in that described template is organic base or is organic base and organic
Quaternary ammonium salt；Described organic silicon source is organo-silicon ester, and described organo-silicon ester, its formula is Si (OR1)4, R1Selected from 1~6
The alkyl of individual carbon atom, described alkyl is branched-chain or straight-chain alkyl；Described solid silicon source is high-purity silicon dioxide granule
Or SiO 2 powder, on the basis of butt weight, the SiO of the solid silicon source2Content is more than 99.99 weight %, with atom
Fe, Al and Na of meter total content are less than 10ppm silica gel.
9. in accordance with the method for claim 8, it is characterised in that described organo-silicon ester is quanmethyl silicate, silicic acid tetrem
One or more in ester, the butyl ester of silicic acid four, dimethyl diethyl estersil.
10. in accordance with the method for claim 8, it is characterised in that described solid silicon source is white carbon, the white carbon
Specific surface area is 20~1000m2/ g is 50~400m2/g。
11. in accordance with the method for claim 8, it is characterised in that described organic base is in quaternary ammonium base, organic amine
It is one or more；Described organic amine is the one or more in fatty amine, aromatic amine and hydramine.
12. in accordance with the method for claim 11, it is characterised in that the formula of described fatty amine is R3(NH2)n, wherein R3
For alkyl or alkylidene with 1~4 carbon atom, n=1 or 2；Its formula of described hydramine is (HOR4)mNH(3-m), its
Middle R4For the alkyl with 1~4 carbon atom, m=1,2 or 3；Described aromatic amine is with an armaticity substituent
Amine.
13. in accordance with the method for claim 11, it is characterised in that described fatty amine be ethamine, n-butylamine, butanediamine or
One or more in hexamethylene diamine；Described hydramine is the one or more in MEA, diethanol amine or triethanolamine；Institute
The aromatic amine stated is the one or more in aniline, toluidines, p-phenylenediamine.
14. in accordance with the method for claim 8, it is characterised in that described template agent includes quaternary ammonium base and optional
Organic amine and/or organic quaternary ammonium salt, described quaternary ammonium base with SiO2The mol ratio of the silicon source of meter is 0.05~0.3:1,
Organic amine with SiO2The mol ratio of the silicon source of meter is 0~0.45:1, organic quaternary ammonium salt with SiO2The mol ratio of the silicon source of meter is
0~0.45:1.
15. in accordance with the method for claim 14, it is characterised in that described template is quaternary ammonium base, organic quaternary ammonium
The mixture of alkali and organic amine, the mixture or organic amine of quaternary ammonium base and organic quaternary ammonium salt and the mixing of organic quaternary ammonium salt
Thing.
16. in accordance with the method for claim 14, it is characterised in that described quaternary ammonium base be TPAOH,
One or more in TBAH or tetraethyl ammonium hydroxide；Described organic quaternary ammonium salt be 4-propyl bromide,
One kind or many in TBAB, tetraethylammonium bromide, 4-propyl ammonium chloride, tetrabutylammonium chloride or etamon chloride
Kind.
17. in accordance with the method for claim 14, it is characterised in that described silica zeolite is S-1 molecular sieves, described
Template agent be TPAOH or be one kind in organic amine, 4-propyl bromide, 4-propyl ammonium chloride or more with kind
The mixture that TPAOH is constituted；Or, described silica zeolite is S-2 molecular sieves, and described template is
TBAH is the one or more and tetrabutylammonium hydrogen in organic amine, TBAB, tetrabutylammonium chloride
The mixture of amine-oxides；Or, described silica zeolite is total silicon beta molecular sieves, and described template is tetraethyl hydrogen-oxygen
Change ammonium or mixing for the one or more and tetraethyl ammonium hydroxide in organic amine, tetraethylammonium bromide, etamon chloride
Compound.
18. in accordance with the method for claim 1, be characterised by, the polyalcohol is to have 2 or more than 2 hydroxyls in molecule
The carbon atom number having in the alcohol of base, the polyol molecule is preferably 2~8；Described peroxide is tool in molecule
There is the compound of peroxide bridge.
19. in accordance with the method for claim 1, it is characterised in that described peroxide is hydrogen peroxide, the tertiary fourth of peroxidating
One or more in base, Peracetic acid, trifluoro Peracetic acid, described polyalcohol is glycerine, ethylene glycol, hexylene glycol, two
One or more in glycol.
20. in accordance with the method for claim 1, it is characterised in that the crystallization, the temperature of crystallization is 110~200 DEG C, brilliant
Change pressure is self-generated pressure, and the time of crystallization is 2 hours~20 days or 0.5~10 day or 0.5~6 day.
21. in accordance with the method for claim 18, it is characterised in that the crystallization temperature of the crystallization is 140~180 DEG C or is
160~180 DEG C.
22. in accordance with the method for claim 1, it is characterised in that described crystallization is：The crystallization 0.5 at 100~130 DEG C
~1.5 days, then crystallization 1~3 day at 160~180 DEG C, crystallization pressure was self-generated pressure.
23. according to the synthetic method of the silica zeolite described in claim 1, comprise the following steps, (1) is by template, organic
Then silicon source, inorganic source of ammonium, the mixing of polynary alcohol and water, hydrolysis add peroxide, (2) aging, and it is old that (3) step (2) is obtained
Change in product and add organic silicon source and/or solid silicon source, stir, crystallization reclaims silica zeolite；Wherein polyalcohol and silicon
The mol ratio in source is 0.01~0.8：1, the mol ratio of peroxide and silicon source is 0.01~0.25:1, described silicon source is organic
The summation of silicon source and solid silicon source.
24. in accordance with the method for claim 4, it is characterised in that comprise the following steps:
(1) by template, organic silicon source, inorganic source of ammonium, polynary alcohol and water mix, 0~150 DEG C stir at least 10 minutes, directly
Catch up with alcohol process to terminate to hydrolysis, add peroxide；
(2) by step (1) products therefrom aging, the aging is small for step (1) products therefrom is stood into 1~60 at room temperature
When；
(3) by the ageing products obtained by step (2) and solid silicon source according to 1：0.1~20 weight is than being well mixed, then
The crystallization in closed reactor, reclaims silica zeolite；It is old obtained by the step (2) in wherein described part by weight
Change product with SiO2Meter, solid silicon source is with SiO2Meter.
25. in accordance with the method for claim 23, it is characterised in that the temperature of step (1) described stirring is 50~90 DEG C, is stirred
The time is mixed for 2~30 hours.
26. in accordance with the method for claim 23, it is characterised in that organic silicon source hydrolysis production in the product that step (1) is obtained
The mass content of raw alcohol is no more than 10ppm.
27. according to the method described in claim 2,23 or 24, it is characterised in that the ageing time of the aging is 2~50 small
When or be 3~30 hours or be 3~15 hours, the temperature of aging is room temperature~50 DEG C.
28. according to the method described in claim 23 or 24, it is characterised in that the mol ratio of the organic silicon source and solid silicon source
For 1：1~19 or for 1:5~15.
29. according to the method described in claim 1,23 or 24, it is characterised in that described method is further comprising the steps of：
By obtained silica zeolite in organic aqueous alkali crystallization 0.5~10 day, the temperature of crystallization is 110~200 DEG C；Its
Described in silica zeolite (with SiO2Meter) with the mol ratio of the organic base it is 1:0.02-0.5, described silica zeolite
(with SiO2Meter) with the mol ratio of water it is 1：2~50.
30. in accordance with the method for claim 29, it is characterised in that described that obtained silica zeolite is water-soluble in organic base
The crystallization temperature of crystallization is 150~200 DEG C in liquid, and pressure is self-generated pressure, described silica zeolite and the organic base
Mol ratio is 1:0.02-0.2, described silica zeolite and the mol ratio of water are 1：2~20.
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