CN105731489B - A kind of preparation method of the silica zeolites of Silicalite 2 - Google Patents
A kind of preparation method of the silica zeolites of Silicalite 2 Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of the silica zeolites of Silicalite 2, belongs to Zeolite synthesis field.The preparation method comprises the following steps：（1）Configure the seed-solutions of Silicalite 2：Alcohol and water is mixed to get alcoholic solution first, then adds solvent orange 2 A and solvent B, stirring adds the crystal seeds of Silicalite 2 to after dissolving completely, the seed-solutions of Silicalite 2 are obtained after stirring；（2）The solution containing alkali source is prepared, the pH value of solution is 9.0~14.0；（3）Silicon source and step are added into mixed solution（1）The obtained seed-solutions of Silicalite 2, then mixed solution is well mixed in confined conditions and obtains gel；The silica zeolites of Silicalite 2 are made in the gel 10~120h of crystallization at 100 DEG C~170 DEG C, then separating, washing, drying, roasting.The inventive method preparation process is simple, cost is low, and the silica zeolite crystallinity prepared is high, suitable for commercial Application.
Description
Technical field
The present invention relates to a kind of method for preparing silica zeolite, and it is quick to concretely relate to a kind of homogeneity crystal seed induction
The method for synthesizing silica zeolite Silicalite-2.
Background technology
Silicalite-2 is the molecular sieve for having MEL type skeleton structures, is ZSM-11 siliceous form, can be used as shape-selective
The inert carrier of property catalyst and the separation membrane material of organic matter aqueous phase etc., so as to receive extensive concern.
Chu P in 1973（USP3709979）Use Bu4N+Do template and successfully synthesize ZSM-11 molecular sieves, 1978
U.C.C. Flanigen E M of company etc. successfully synthesize last member of Pentasil families, total silicon ZSM-11- again
Silicalite-2, and then promoted the fast development in rich silicon molecular sieve by crystal synthesis field.Nineteen ninety Mc William
（USP4894212）Template is done using octylame, using the method for crystal seed is added in 100 ~ 350 DEG C of crystallization 12 hours ~ 10 days, is obtained
To relatively pure ZSM-11.Valyocsik（USP4941963）Synthesized using diquaternary amine salt (butyl pyrrolidine) for template
ZSM-11, crystallization temperature are 60 ~ 250 DEG C, and crystallization time is 1 ~ 30 day.Beck in 1993（USP5213786）Elaborate to use
Trimethylamine cation（CnN+(CH3)3, n 9,10,11,12）As organic formwork agent, preferable crystallization temperature is 80 ~ 200
DEG C, crystallization time is 1 ~ 30 day.United States Patent (USP)（USP6444191）With 3,5- dimethyl-N, N- diethyl pyrrolidines for template
Agent, crystallization temperature are 140 ~ 200 DEG C, and crystallization time is 2 ~ 20 days, has synthesized pure ZSM-11 molecular sieves.But above-mentioned side
Method technical process is relative complex, typically not high in relatively short time crystallinity, and contains stray crystal；Need longer crystalline substance
The ZSM-11 molecular sieves of no stray crystal, high-crystallinity, high conversion can just be prepared by changing the time, and energy consumption is higher, production efficiency is relatively low.
In order to solve the above problems, CN101423225A discloses a kind of preparation side of silica zeolite Silicalite-2
Method.Comprise the following steps：By organic formwork agent（Tetrabutylammonium hydroxide amine）, silicon source（Tetraethyl orthosilicate）Stirred with deionized water heating
Mix 0.5 ~ 10 hour, then keep the skin wet, crystallization 12 ~ 90 hours, is cooled to room under conditions of 100 ~ 200 DEG C of hydro-thermals are closed
Temperature, by washing, centrifuging, drying, being calcined, obtain silica zeolite Silicalite-2.Although this method shortens conjunction
Into the time, but process is complex, and gel process is needed to heat and gel time is partially long, it is also necessary to water is supplemented in gel；
Used silicon source is expensive tetraethyl orthosilicate, adds production cost.In addition, in order to obtain the complete of higher crystallinity
Si molecular sieves Silicalite-2, it is also necessary to longer crystallization time.
CN102442677A discloses a kind of preparation method of silica zeolite.Comprise the following steps：Match somebody with somebody pallet first
Agent（TBAH）And alkali source（Sodium hydroxide）Mixed solution, the pH value of mixed solution is between 12.10-13.20；
Then silicon source is added into mixed solution（White carbon or Ludox）, stir under confined conditions, mixing time 0.5-2 is small
When, obtain mixture gel rubber system；Final mixture gel rubber system crystallization 2.0-4.0 days, crystallization product at 170 DEG C -200 DEG C
Scrubbed, centrifugation, dry, the obtained Silicalite-2 silica zeolites of roasting.This method synthesis pH claimed ranges are narrower,
Gel process temperature is high, and crystallization time is partially long, obtains molecular sieve and mixed crystal state easily occurs.
The content of the invention
In view of the shortcomings of the prior art, in order to preferably control the nucleation and growth in sieve synthesis procedure, the present invention
In Silicalite-2 silica zeolite preparation methods, crystal seed is pre-processed.Preparation method process of the present invention is simple, into
This is low, and obtained Silicalite-2 silica zeolites crystallinity is high, suitable for commercial Application.
The present invention provides a kind of preparation method of Silicalite-2 silica zeolites, and the preparation method includes following step
Suddenly：
（1）Configure Silicalite-2 seed-solutions：Alcohol and water is mixed to get alcoholic solution first, then adds solvent orange 2 A
With solvent B, stirring adds Silicalite-2 crystal seeds to after dissolving completely, it is molten that Silicalite-2 crystal seeds is obtained after stirring
Liquid, wherein, the solvent orange 2 A is the one or more in KBr, sodium bromide, potassium chloride, sodium chloride, and the solvent B is tween
80th, the one or more in PEG400~PEG2000.
（2）The solution containing alkali source is prepared, the pH value of solution is 9.0~14.0, preferably 12.0~13.2；
（3）To step（2）Silicon source and step are added in obtained solution（1）Obtained Silicalite-2 seed-solutions,
Wherein alkali source, silicon source, water mol ratio are 0.2~10: 5.0~50: 100: 1000~10000, the preferably ︰ of 0.5~3.5 ︰ 100
2500~6000, then mixed solution is well mixed in confined conditions and obtains gel；Then the gel 100 DEG C~
10~120h of crystallization, preferably 24~72h at 180 DEG C, preferably 150 DEG C~180 DEG C, then separating, washing, drying, roasting
Fire to obtain Silicalite-2 silica zeolites.
In the preparation method of Silicalite-2 silica zeolites of the present invention, step（1）Described in alcohols for methanol, second
One or more in one or more in alcohol, normal propyl alcohol, isopropanol, butanol, preferably ethanol, normal propyl alcohol, isopropanol, more
Preferably ethanol.The volume ratio of alcohol and water is 5~95 ︰ 100, preferably 10~80 ︰ 100 in described alcoholic solution, is more preferably
10~50 ︰ 100.
In the preparation method of Silicalite-2 silica zeolites of the present invention, step（1）Described in solvent orange 2 A be bromination
One or more in potassium, sodium bromide, preferably KBr.Described solvent orange 2 A and the mass ratio of water are 0.5~20 ︰ 100, excellent
Elect 0.5~10 ︰ 100, more preferably 0.5~5 ︰ 100 as.
In the preparation method of Silicalite-2 silica zeolites of the present invention, step（1）Described in solvent B be for
One or more in PEG400~PEG2000, preferably PEG400.The mass ratio of solvent B and water is 0.5~20 ︰ 100, excellent
Elect 0.5~10 ︰ 100, more preferably 0.5~5 ︰ 100 as.
In the preparation method of Silicalite-2 silica zeolites of the present invention, step（1）Described in Silicalite-2
Crystal seed is to be ground to the Silicalite-2 crystal seeds below 300 mesh, the mass ratio of Silicalite-2 crystal seeds and water for 0.5~
50 ︰ 100, preferably 0.5~20 ︰ 100, more preferably 5~20 ︰ 100.
In the preparation method of Silicalite-2 silica zeolites of the present invention, step（2）Described alkali source is ethamine, positive fourth
One or more in one or more in amine, sodium hydroxide, potassium hydroxide, preferably sodium hydroxide, potassium hydroxide, it is more excellent
Elect sodium hydroxid as.
In the preparation method of Silicalite-2 silica zeolites of the present invention, step（2）The preparation contains the molten of alkali source
Template is added in liquid.Described template is n-butylamine, hexamethylene diamine, 4-propyl bromide, TPAOH, tetraethyl
One or more in ammonium hydroxide, tetrabutyl hydrogen-oxygen oxyammonia, Cetyltrimethylammonium bromide, preferably tetraethyl hydrogen
One or more in amine-oxides, tetrabutylammonium hydroxide amine, more preferably tetrabutylammonium hydroxide amine.The alkali source and template
Mol ratio is 0.2~10: 5.0~50, preferably 0.5~3.5 ︰ 3.0~15.
In the preparation method of Silicalite-2 silica zeolites of the present invention, step（3）Described silicon source is positive silicic acid second
One or more in ester, Ludox, white carbon, preferably Ludox.
In the preparation method of Silicalite-2 silica zeolites of the present invention, step（3）Described Silicalite-2 is brilliant
Kind solution accounts for SiO used with Silicalite-2 crystal seeds contained in solution2Mass percent calculate, dosage be 0.1%~
10%, preferably 0.5%~5%, more preferably 2%~4%.
In the preparation method of Silicalite-2 silica zeolites of the present invention, step（3）Preparing gel process can add
Carry out, can also carry out at normal temperatures under heat condition, the gel preferably under normal temperature condition, described normal temperature refers in gel process
Without heating.
In the preparation method of Silicalite-2 silica zeolites of the present invention, step（3）Described in be separated into centrifugation；
The washing is to be washed with deionized；The drying is that the h of 6 h ~ 12, the roasting are dried under the conditions of 100 DEG C~120 DEG C
To be calcined the h of 8 h ~ 12 under the conditions of 500 DEG C~600 DEG C.
The Silicalite-2 silica zeolites that the inventive method is prepared can be used for synthesis gas olefin hydrocarbon, also may be used
For other petrochemical industry catalytic process.
The preparation method of Silicalite-2 silica zeolites of the present invention has the following advantages that compared with prior art：
1st, the present invention pre-processes to crystal seed, by the synergy of solvent orange 2 A and solvent B, can improve crystal seed molten
Decentralization in liquid, while a protective layer is provided outside crystal seed, the nucleation of molecular sieve is occurred in protective layer, Ke Yigeng
Add the effective purity for improving molecular sieve, avoid generating stray crystal phase, but also crystal growth can be suppressed, it is less to obtain particle diameter
Molecular sieve.
2nd, the inventive method come the pH values of controlling crystallizing material and selects suitable building-up process by appropriate alkali source,
The addition sequence of material is particularly synthesized, the Silicalite-2 silica zeolites of high-crystallinity are prepared, by embodiment and ratio
Understood compared with example, in identical crystallization temperature and in the time, the crystallization for the Silicalite-2 silica zeolites that the present invention prepares
Spend apparently higher than comparative example.
3rd, the inventive method substantially shortens the gel and crystallization time of mixed material, and gel process is without in heating condition
Lower progress, and cheap Ludox can be used as silicon source, the preparation with the Silicalite-2 silica zeolites of routine
Method is compared, and the inventive method preparation process time is short, easily operated, and cost is low, suitable for commercial Application.
Brief description of the drawings
Fig. 1 is the Silicalite-2 silica zeolite XRD diffraction patterns that the embodiment of the present invention 1 synthesizes.
Fig. 2 be comparative example 1 of the present invention, comparative example it is 2-in-1 into Silicalite-2 silica zeolite XRD diffraction patterns.
Embodiment
The method that Fast back-projection algorithm Silicalite-2 silica zeolites of the present invention are further illustrated below by embodiment,
But it invention should not be deemed limited in following example.
Embodiment 1
Configure Silicalite-2 seed-solutions：Yi Chun ︰ water is mixed to get alcoholic solution according to volume ratio for 40 ︰ 100,
Material is added in alcoholic solution for the ratio of the water of 2.0KBr ︰ 1.2PEG400 ︰ 100 according to mass ratio and stirs 1 h, then will
Silicalite-2 molecular sieves are ground to below 300 mesh, will according to the ratio that mass ratio is the water of 10 Silicalite-2 ︰ 100
Silicalite-2 crystal seeds are added in above-mentioned solution, and Silicalite-2 seed-solutions are made.
Secure ph be 12.6 sodium hydroxide mixed solution, then into material add Ludox and and
Silicalite-2 seed-solutions（Amount of seed accounts for SiO used with Silicalite-22Mass percent for 2.3% calculate）,
Closed uniform stirring 2 hours, obtains mixture gel rubber system, each molar ratio of material 4.1NaOH ︰ 100SiO in gel2︰
6550H2O, final mixture gel rubber system crystallization 2 days at 150 DEG C, crystallization product is centrifuged, deionized water is washed,
12 h are dried under the conditions of 120 DEG C, 8 h is calcined under the conditions of 550 DEG C Silicalite-2 silica zeolites, specific surface area is made
For 477 m2/ g, relative crystallinity 166%, XRD spectra is as shown in Figure 1.
Embodiment 2
Configure Silicalite-2 seed-solutions：By positive Bing Chun ︰ water according to volume ratio be 35 ︰ 100 to be mixed to get alcohol molten
Liquid, material is added in alcoholic solution for the ratio of the water of 0.5KBr ︰ 0.5PEG400 ︰ 100 according to mass ratio and stirs 1 h, then will
Silicalite-2 molecular sieves are ground to below 300 mesh, will according to the ratio that mass ratio is the water of 5 Silicalite-2 ︰ 100
Silicalite-2 crystal seeds are added in above-mentioned solution, and Silicalite-2 seed-solutions are made.
Secure ph is 12.6 sodium hydroxide mixed solution, and Ludox and Silicalite-2 are then added into material
Seed-solution（Amount of seed accounts for SiO used with Silicalite-22Mass percent for 2.3% calculate）, closed uniform stirring
2 hours, obtain mixture gel rubber system, each molar ratio of material 4.1NaOH ︰ 100SiO in gel2︰ 6550H2O, final mixture
Gel rubber system crystallization 2 days at 150 DEG C, crystallization product is centrifuged, deionized water is washed, 12 are dried under the conditions of 120 DEG C
H, 8 h are calcined under the conditions of 550 DEG C Silicalite-2 silica zeolites are made, specific surface area is 459 m2/ g, relative crystallization
Spend for 159%.
Embodiment 3
Configure Silicalite-2 seed-solutions：By Yi Bing Chun ︰ water according to volume ratio be 26 ︰ 100 to be mixed to get alcohol molten
Liquid, material is added in alcoholic solution for the ratio of the water of 1.0KBr ︰ 2.8PEG400 ︰ 100 according to mass ratio and stirs 1 h, then will
Silicalite-2 molecular sieves are ground to below 300 mesh, will according to the ratio that mass ratio is the water of 15 Silicalite-2 ︰ 100
Silicalite-2 crystal seeds are added in above-mentioned solution, and Silicalite-2 seed-solutions are made.
Secure ph is 12.1 sodium hydroxide mixed solution, and Ludox and Silicalite-2 are then added into material
Seed-solution（Amount of seed accounts for SiO used with Silicalite-22Mass percent for 2.3% calculate）, closed uniform stirring
1.5 hours, obtain mixture gel rubber system, each molar ratio of material 1.2NaOH ︰ 100SiO in gel2︰ 7550H2O, finally mix
Thing gel rubber system crystallization 1 day at 150 DEG C, crystallization product is centrifuged, deionized water is washed, is dried under the conditions of 120 DEG C
12 h, 8 h are calcined under the conditions of 550 DEG C Silicalite-2 silica zeolites are made, specific surface area is 453 m2/ g, relatively
Crystallinity is 157%.
Embodiment 4
Configure Silicalite-2 seed-solutions：Yi Chun ︰ water is mixed to get alcoholic solution according to volume ratio for 10 ︰ 100,
Material is added in alcoholic solution for the ratio of the water of 4.5NaBr ︰ 4.0PEG400 ︰ 100 according to mass ratio and stirs 1 h, then will
Silicalite-2 molecular sieves are ground to below 300 mesh, will according to the ratio that mass ratio is the water of 5 Silicalite-2 ︰ 100
Silicalite-2 crystal seeds are added in above-mentioned solution, and Silicalite-2 seed-solutions are made.
Secure ph is 12.8 sodium hydroxide mixed solution, and Ludox and Silicalite-2 are then added into material
Seed-solution（Amount of seed accounts for SiO used with Silicalite-22Mass percent for 2.5% calculate）, closed uniform stirring
2 hours, obtain mixture gel rubber system, each molar ratio of material 2.6NaOH ︰ 100SiO in gel2︰ 5600H2O, final mixture
Gel rubber system crystallization 3 days at 150 DEG C, crystallization product is centrifuged, deionized water is washed, 12 are dried under the conditions of 120 DEG C
H, 8 h are calcined under the conditions of 550 DEG C Silicalite-2 silica zeolites are made, specific surface area is 468 m2/ g, relative crystallization
Spend for 163%.
Embodiment 5
Configure Silicalite-2 seed-solutions：Yi Chun ︰ water is mixed to get alcoholic solution according to volume ratio for 80 ︰ 100,
Material is added in alcoholic solution for the ratio of the water of 10KBr ︰ 10PEG600 ︰ 100 according to mass ratio and stirs 1 h, then will
Silicalite-2 molecular sieves are ground to below 300 mesh, will according to the ratio that mass ratio is the water of 20 Silicalite-2 ︰ 100
Silicalite-2 crystal seeds are added in above-mentioned solution, and Silicalite-2 seed-solutions are made.
Secure ph is 13.1 sodium hydroxide mixed solution, and Ludox and Silicalite-2 are then added into material
Seed-solution（Amount of seed accounts for SiO used with Silicalite-22Mass percent for 2.3% calculate）, closed uniform stirring
1.5 hours, obtain mixture gel rubber system, each molar ratio of material 3.2NaOH ︰ 100SiO in gel2︰ 3000H2O, finally mix
Thing gel rubber system crystallization 2 days at 120 DEG C, crystallization product is centrifuged, deionized water is washed, is dried under the conditions of 120 DEG C
12 h, 8 h are calcined under the conditions of 550 DEG C Silicalite-2 silica zeolites are made, specific surface area is 389 m2/ g, relatively
Crystallinity is 135%.
Embodiment 6
Configure Silicalite-2 seed-solutions：Yi Chun ︰ water is mixed to get alcoholic solution according to volume ratio for 40 ︰ 100,
Material is added in alcoholic solution for the ratio of the water of 1.2 tweens of 2KBr ︰, 80 ︰ 100 according to mass ratio and stirs 1 h, then will
Silicalite-2 molecular sieves are ground to below 300 mesh, will according to the ratio that mass ratio is the water of 10 Silicalite-2 ︰ 100
Silicalite-2 crystal seeds are added in above-mentioned solution, and Silicalite-2 seed-solutions are made.
Secure ph is 13.5 sodium hydroxide mixed solution, and Ludox and Silicalite-2 are then added into material
Seed-solution（Amount of seed accounts for SiO used with Silicalite-22Mass percent for 2.0% calculate）, closed uniform stirring
1.5 hours, obtain mixture gel rubber system, each molar ratio of material 3.8NaOH ︰ 100SiO in gel2︰ 7000H2O, finally mix
Thing gel rubber system crystallization 2 days at 180 DEG C, crystallization product is centrifuged, deionized water is washed, is dried under the conditions of 100 DEG C
10 h, 12 h are calcined under the conditions of 600 DEG C Silicalite-2 silica zeolites are made, specific surface area is 450 m2/ g, relatively
Crystallinity is 156%.
Embodiment 7
Configure Silicalite-2 seed-solutions：Yi Chun ︰ water is mixed to get alcoholic solution according to volume ratio for 40 ︰ 100,
Material is added in alcoholic solution for the ratio of the water of 2KBr ︰ 1.2PEG400 ︰ 100 according to mass ratio and stirs 1 h, then will
Silicalite-2 molecular sieves are ground to below 300 mesh, will according to the ratio that mass ratio is the water of 10 Silicalite-2 ︰ 100
Silicalite-2 crystal seeds are added in above-mentioned solution, and Silicalite-2 seed-solutions are made.
Secure ph is 13.8 sodium hydroxide mixed solution, and Ludox and Silicalite-2 are then added into material
Seed-solution（Amount of seed accounts for SiO used with Silicalite-22Mass percent for 0.6% calculate）, closed uniform stirring
2 hours, obtain mixture gel rubber system, each molar ratio of material 4.2NaOH ︰ 100SiO in gel2︰ 5000H2O, final mixture
Gel rubber system crystallization 2 days at 150 DEG C, crystallization product is centrifuged, deionized water is washed, 12 are dried under the conditions of 110 DEG C
H, 10 h are calcined under the conditions of 500 DEG C Silicalite-2 silica zeolites are made, specific surface area is 465 m2/ g, relative knot
Brilliant degree is 161%.
Embodiment 8
Configure Silicalite-2 seed-solutions：Yi Chun ︰ water is mixed to get alcoholic solution according to volume ratio for 40 ︰ 100,
Material is added in alcoholic solution for the ratio of the water of 2.0KBr ︰ 1.2PEG400 ︰ 100 according to mass ratio and stirs 1 h, then will
Silicalite-2 molecular sieves are ground to below 300 mesh, will according to the ratio that mass ratio is the water of 10 Silicalite-2 ︰ 100
Silicalite-2 crystal seeds are added in above-mentioned solution, and Silicalite-2 seed-solutions are made.
Secure ph is 12.2 sodium hydroxide mixed solution, and Ludox and Silicalite-2 are then added into material
Seed-solution（Amount of seed accounts for SiO used with Silicalite-22Mass percent for 2.3% calculate）, closed uniform stirring
2 hours, obtain mixture gel rubber system, each molar ratio of material 3.0NaOH ︰ 100SiO in gel2︰ 3500H2O, final mixture
Gel rubber system crystallization 2 days at 150 DEG C, crystallization product is centrifuged, deionized water is washed, 12 are dried under the conditions of 120 DEG C
H, 8 h are calcined under the conditions of 550 DEG C Silicalite-2 silica zeolites are made, specific surface area is 426 m2/ g, relative crystallization
Spend for 148%.
Embodiment 9
Configure Silicalite-2 seed-solutions：Yi Chun ︰ water is mixed to get alcoholic solution according to volume ratio for 40 ︰ 100,
Material is added in alcoholic solution for the ratio of the water of 2.0KBr ︰ 1.2PEG400 ︰ 100 according to mass ratio and stirs 1 h, then will
Silicalite-2 molecular sieves are ground to below 300 mesh, will according to the ratio that mass ratio is the water of 10 Silicalite-2 ︰ 100
Silicalite-2 crystal seeds are added in above-mentioned solution, and Silicalite-2 seed-solutions are made.
Secure ph is 12.3 sodium hydroxide mixed solution, and Ludox and Silicalite-2 are then added into material
Seed-solution（Amount of seed accounts for SiO used with Silicalite-22Mass percent for 6.5% calculate）, closed uniform stirring
2 hours, obtain mixture gel rubber system, each molar ratio of material 3.5NaOH ︰ 100SiO in gel2︰ 7200H2O, final mixture
Gel rubber system crystallization 2 days at 150 DEG C, crystallization product is centrifuged, deionized water is washed, 12 are dried under the conditions of 120 DEG C
H, 8 h are calcined under the conditions of 550 DEG C Silicalite-2 silica zeolites are made, specific surface area is 447 m2/ g, relative crystallization
Spend for 155%.
Embodiment 10
Configure Silicalite-2 seed-solutions：Yi Chun ︰ water is mixed to get alcoholic solution according to volume ratio for 40 ︰ 100,
Material is added in alcoholic solution for the ratio of the water of 2.0KBr ︰ 1.2PEG400 ︰ 100 according to mass ratio and stirs 1 h, then will
Silicalite-2 molecular sieves are ground to below 300 mesh, will according to the ratio that mass ratio is the water of 10 Silicalite-2 ︰ 100
Silicalite-2 crystal seeds are added in above-mentioned solution, and Silicalite-2 seed-solutions are made.
Secure ph is 12.1 sodium hydroxide mixed solution, and Ludox and Silicalite-2 are then added into material
Seed-solution（Amount of seed accounts for SiO used with Silicalite-22Mass percent for 8.9% calculate）, closed uniform stirring
1.5 hours, obtain mixture gel rubber system, each molar ratio of material 2.9NaOH ︰ 100SiO in gel2︰ 4860H2O, finally mix
Thing gel rubber system crystallization 2 days at 150 DEG C, crystallization product is centrifuged, deionized water is washed, is dried under the conditions of 120 DEG C
12 h, 8 h are calcined under the conditions of 550 DEG C Silicalite-2 silica zeolites are made, specific surface area is 453 m2/ g, relatively
Crystallinity is 157%.
Embodiment 11
Configure Silicalite-2 seed-solutions：Yi Chun ︰ water is mixed to get alcoholic solution according to volume ratio for 35 ︰ 100,
Material is added in alcoholic solution for the ratio of the water of 0.5KBr ︰ 0.5PEG400 ︰ 100 according to mass ratio and stirs 1 h, then will
Silicalite-2 molecular sieves are ground to below 300 mesh, will according to the ratio that mass ratio is the water of 5 Silicalite-2 ︰ 100
Silicalite-2 crystal seeds are added in above-mentioned solution, and Silicalite-2 seed-solutions are made.
Prepare the mixed solution of tetrabutylammonium hydroxide amine and sodium hydroxide, then added into material Ludox and
Silicalite-2 seed-solutions（Amount of seed accounts for SiO used with Silicalite-22Mass percent for 3.0% calculate）,
The closed h of uniform stirring 1.5, obtains mixture gel rubber system, each molar ratio of material 3.0NaOH ︰ 9.0TBAOH ︰ in gel
100SiO2︰ 5200H2O, final mixture gel rubber system h of crystallization 40 at 125 DEG C, crystallization product is centrifuged, deionization
Water washing, 12 h are dried under the conditions of 120 DEG C, 8 h are calcined under the conditions of 550 DEG C Silicalite-2 silica zeolites are made,
Specific surface area is 472 m2/ g, relative crystallinity 164%.
Embodiment 12
Configure Silicalite-2 seed-solutions：Yi Chun ︰ water is mixed to get alcoholic solution according to volume ratio for 26 ︰ 100,
Material is added in alcoholic solution for the ratio of the water of 1.0KBr ︰ 2.8PEG400 ︰ 100 according to mass ratio and stirs 1 h, then will
Silicalite-2 molecular sieves are ground to below 300 mesh, will according to the ratio that mass ratio is the water of 15 Silicalite-2 ︰ 100
Silicalite-2 crystal seeds are added in above-mentioned solution, and Silicalite-2 seed-solutions are made.
Prepare the mixed solution of tetrabutylammonium hydroxide amine and sodium hydroxide, then added into material Ludox and
Silicalite-2 seed-solutions（Amount of seed accounts for SiO used with Silicalite-22Mass percent for 4.0% calculate）,
The closed h of uniform stirring 1.5, obtains mixture gel rubber system, each molar ratio of material 3.0NaOH ︰ 9.0TBAOH ︰ in gel
100SiO2︰ 5200H2O, final mixture gel rubber system h of crystallization 40 at 125 DEG C, crystallization product is centrifuged, deionization
Water washing, 12 h are dried under the conditions of 120 DEG C, 8 h are calcined under the conditions of 550 DEG C Silicalite-2 silica zeolites are made,
Specific surface area is 466 m2/ g, relative crystallinity 162%.
Embodiment 13
Configure Silicalite-2 seed-solutions：Yi Chun ︰ water is mixed to get alcoholic solution according to volume ratio for 10 ︰ 100,
Material is added in alcoholic solution for the ratio of the water of 4.5KBr ︰ 4.0PEG400 ︰ 100 according to mass ratio and stirs 1 h, then will
Silicalite-2 molecular sieves are ground to below 300 mesh, will according to the ratio that mass ratio is the water of 5 Silicalite-2 ︰ 100
Silicalite-2 crystal seeds are added in above-mentioned solution, and Silicalite-2 seed-solutions are made.
Prepare the mixed solution of tetrabutylammonium hydroxide amine and sodium hydroxide, then added into material Ludox and
Silicalite-2 seed-solutions（Amount of seed accounts for SiO used with Silicalite-22Mass percent for 2.5% calculate）,
The closed h of uniform stirring 1.5, obtains mixture gel rubber system, each molar ratio of material 3.0NaOH ︰ 9.0TBAOH ︰ in gel
100SiO2︰ 5200H2O, final mixture gel rubber system h of crystallization 40 at 125 DEG C, crystallization product is centrifuged, deionization
Water washing, 12 h are dried under the conditions of 120 DEG C, 8 h are calcined under the conditions of 550 DEG C Silicalite-2 silica zeolites are made,
Specific surface area is 481 m2/ g, relative crystallinity 167%.
Embodiment 14
Configure Silicalite-2 seed-solutions：Yi Chun ︰ water is mixed to get alcoholic solution according to volume ratio for 40 ︰ 100,
Material is added in alcoholic solution for the ratio of the water of 2KBr ︰ 1.2PEG400 ︰ 100 according to mass ratio and stirs 1 h, then will
Silicalite-2 molecular sieves are ground to below 300 mesh, will according to the ratio that mass ratio is the water of 10 Silicalite-2 ︰ 100
Silicalite-2 crystal seeds are added in above-mentioned solution, and Silicalite-2 seed-solutions are made.
Prepare the mixed solution of tetrabutylammonium hydroxide amine and sodium hydroxide, then added into material Ludox and
Silicalite-2 seed-solutions（Amount of seed accounts for SiO used with Silicalite-22Mass percent for 2.0% calculate）,
Closed uniform stirring 1.5 hours, obtains mixture gel rubber system, each molar ratio of material 3.0NaOH ︰ 9.0TBAOH ︰ in gel
100SiO2︰ 5200H2O, final mixture gel rubber system h of crystallization 36 at 135 DEG C, crystallization product is centrifuged, deionization
Water washing, 10 h are dried under the conditions of 100 DEG C, 12 h are calcined under the conditions of 600 DEG C Silicalite-2 total silicon molecules are made
Sieve, specific surface area is 464 m2/ g, relative crystallinity 161%.
Comparative example 1
It is 10% by 9.56g tetraethyl orthosilicates and 32.44g mass concentrations by patent CN101423225 preparation method
Tetrabutylammonium hydroxide amine aqueous solution is added in the retort of polytetrafluoroethylene (PTFE), and in 60 DEG C of heating stirring 4.5h, keeping the skin wet makes body
SiO in system2Mass concentration is 13%, and 180 DEG C of closed crystallization 2.5 days, crystallization product is scrubbed, centrifuges, dries, roasting system
Silicalite-2 silica zeolites are obtained, using the molecular sieve as reference, for calculating relative crystallinity.
Comparative example 2
Same as Example 1, difference is that the crystal seed does not pass through pretreatment, is solid Silicalite-2 brilliant
Kind, the relative crystallinity of gained Silicalite-2 silica zeolites is 121%.
Comparative example 1, comparative example 2 and embodiment 1, which are compared, to be understood, the embodiment Silicalite-2 under identical crystallization condition
The crystallinity of silica zeolite is generally higher than comparative example, in addition, using crystal seed induction synthesis total silicon molecule in the embodiment of the present invention
Sieve, the time of gel is few, gel rubber system without heating, shorten generated time, reduce energy consumption.
Claims (40)
1. a kind of preparation method of Silicalite-2 silica zeolites, the preparation method comprise the following steps：
（1）Configure Silicalite-2 seed-solutions：Alcohol and water is mixed to get alcoholic solution first, then adds A and B, stirring
Silicalite-2 crystal seeds are added after to dissolving completely, Silicalite-2 seed-solutions are obtained after stirring, wherein, it is described
A is the one or more in KBr, sodium bromide, potassium chloride, sodium chloride, and the B is in Tween 80, PEG400~PEG2000
One or more；
（2）The solution containing alkali source is prepared, the pH value of solution is 9.0~14.0；
（3）To step（2）Silicon source and step are added in obtained solution（1）Obtained Silicalite-2 seed-solutions, wherein
Alkali source, silicon source, water mol ratio are 0.2~10：100：1000~10000, then mixed solution is mixed in confined conditions
It is even to obtain gel；Then the gel 10~120h of crystallization at 100 DEG C~180 DEG C, then separating, washing, drying, roasting
Silicalite-2 silica zeolites are made.
2. preparation method according to claim 1, it is characterised in that：Step（2）The solution containing alkali source is prepared, solution
PH value is 12.0~13.2.
3. preparation method according to claim 1, it is characterised in that：Step（3）Middle alkali source, silicon source, water mol ratio are 0.5
~3.5：100：2500~6000.
4. preparation method according to claim 1, it is characterised in that：Step（3）Described in gel at 150 DEG C~180 DEG C
24~72h of lower crystallization.
5. preparation method according to claim 1, it is characterised in that：Step（1）Described in alcohols for methanol, ethanol,
One or more in normal propyl alcohol, isopropanol, butanol.
6. preparation method according to claim 5, it is characterised in that：Step（1）Described in alcohols for ethanol, positive third
One or more in alcohol, isopropanol.
7. preparation method according to claim 6, it is characterised in that：Step（1）Described in alcohols be ethanol.
8. preparation method according to claim 1, it is characterised in that：Step（1）Described in alcoholic solution in alcohol and water
Volume ratio is 5~95：100.
9. preparation method according to claim 8, it is characterised in that：Step（1）Described in alcoholic solution in alcohol and water
Volume ratio is 10~80：100.
10. preparation method according to claim 9, it is characterised in that：Step（1）Described in alcoholic solution in alcohol and water
Volume ratio is 10~50：100.
11. preparation method according to claim 1, it is characterised in that：Step（1）Described in A for KBr, sodium bromide
In one or more.
12. preparation method according to claim 11, it is characterised in that：Step（1）Described in A be KBr.
13. preparation method according to claim 1, it is characterised in that：Step（1）Described in A and the mass ratio of water be
0.5~20：100.
14. preparation method according to claim 13, it is characterised in that：Step（1）Described in A and the mass ratio of water be
0.5~10：100.
15. preparation method according to claim 14, it is characterised in that：Step（1）Described in A and the mass ratio of water be
0.5~5：100.
16. preparation method according to claim 1, it is characterised in that：Step（1）Described in B for PEG400~
One or more in PEG2000.
17. preparation method according to claim 1, it is characterised in that：Step（1）Described in B be PEG400.
18. preparation method according to claim 1, it is characterised in that：Step（1）Described in the mass ratio of B and water be 0.5
~20：100.
19. preparation method according to claim 18, it is characterised in that：Step（1）Described in the mass ratio of B and water be
0.5~10：100.
20. preparation method according to claim 19, it is characterised in that：Step（1）Described in the mass ratio of B and water be
0.5~5：100.
21. preparation method according to claim 1, it is characterised in that：Step（1）Described in Silicalite-2 crystal seeds
To be ground to the Silicalite-2 crystal seeds below 300 mesh, the mass ratio of Silicalite-2 crystal seeds and water is 0.5~50：
100。
22. preparation method according to claim 21, it is characterised in that：Step（1）Described in Silicalite-2 it is brilliant
The mass ratio of kind and water is 0.5~20：100.
23. preparation method according to claim 22, it is characterised in that：Step（1）Described in Silicalite-2 crystal seeds
Mass ratio with water is 5~20：100.
24. preparation method according to claim 1, it is characterised in that：Step（2）Described alkali source be ethamine, n-butylamine,
One or more in sodium hydroxide, potassium hydroxide.
25. preparation method according to claim 4, it is characterised in that：Step（2）Described alkali source is sodium hydroxide, hydrogen
One or more in potassium oxide.
26. preparation method according to claim 25, it is characterised in that：Step（2）Described alkali source is sodium hydroxid.
27. preparation method according to claim 1, it is characterised in that：Step（2）In the solution of the preparation containing alkali source
Add template.
28. preparation method according to claim 27, it is characterised in that：Described template is n-butylamine, hexamethylene diamine, four
Propyl group ammonium bromide, TPAOH, tetraethyl ammonium hydroxide, TBAH, Cetyltrimethylammonium bromide
In one or more.
29. preparation method according to claim 28, it is characterised in that：Described template be tetraethyl ammonium hydroxide,
One or more in TBAH.
30. preparation method according to claim 29, it is characterised in that：Described template is TBAH.
31. preparation method according to claim 27, it is characterised in that：The mol ratio of the alkali source and template is 0.2
~10：5.0~50.
32. preparation method according to claim 31, it is characterised in that：The mol ratio of the alkali source and template is 0.5
~3.5：3.0~15.
33. preparation method according to claim 1, it is characterised in that：Step（3）Described silicon source be tetraethyl orthosilicate,
One or more in Ludox, white carbon.
34. preparation method according to claim 33, it is characterised in that：Step（3）Described silicon source is Ludox.
35. preparation method according to claim 1, it is characterised in that：Step（3）Described seed-solution is with institute in solution
The Silicalite-2 crystal seeds contained account for SiO used2Mass percent calculate, dosage be 0.1%~10%.
36. preparation method according to claim 35, it is characterised in that：Step（3）Described seed-solution is with solution
Contained Silicalite-2 crystal seeds account for SiO used2Mass percent calculate, dosage be 0.5%~5%.
37. preparation method according to claim 36, it is characterised in that：Step（3）Described seed-solution is with solution
Contained Silicalite-2 crystal seeds account for SiO used2Mass percent calculate, dosage be 2%~4%.
38. preparation method according to claim 1, it is characterised in that：Step（3）Prepare gel in a heated condition or often
Temperature is lower to be carried out.
39. the preparation method according to claim 38, it is characterised in that：Step（3）Gel is prepared under normal temperature condition to enter
OK.
40. preparation method according to claim 1, it is characterised in that：Step（3）Described in be separated into centrifugation；Institute
Washing is stated to be washed with deionized；The drying is that the h of 6 h ~ 12 is dried under the conditions of 100 DEG C~120 DEG C, described to be roasted to
The h of 8 h ~ 12 is calcined under the conditions of 500 DEG C~600 DEG C.
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