CN105731488B - A kind of method for preparing the silica zeolites of Silicalite 2 - Google Patents
A kind of method for preparing the silica zeolites of Silicalite 2 Download PDFInfo
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Abstract
The present invention provides a kind of method for preparing the silica zeolites of Silicalite 2, belongs to Zeolite synthesis field.The synthetic method comprises the following steps：（1）Configure MOR seed-solutions：Alcohol and water is mixed to get alcoholic solution first, then adds solvent orange 2 A and solvent B, stirring adds MOR crystal seeds to after dissolving completely, MOR seed-solutions are obtained after stirring；（2）The mixed solution containing template and alkali source is prepared, the pH value of mixed solution is 9.00~14.0；（3）Silicon source and step are added into mixed solution（1）Obtained seed-solution, then mixed solution is well mixed in confined conditions and obtains gel；Then 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, concretely relates to a kind of quick preparation of crystal seed induction
The method of 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 method for preparing Silicalite-2 silica zeolites, and the preparation method includes following step
Suddenly：
（1）Configure MOR seed-solutions：Alcohol and water is mixed to get alcoholic solution first, then adds A and B, stirring to dissolving
Completely after add MOR crystal seeds, MOR seed-solutions are obtained after stirring, wherein, the A be KBr, sodium bromide, potassium chloride,
One or more in sodium chloride, the B are the one or more in Tween 80, PEG400~PEG2000.
（2）The mixed solution containing template and alkali source is prepared, the pH value of mixed solution is 9.0~14.0, is preferably
12.0~13.2；
（3）To step（2）Silicon source and step are added in obtained mixed solution（1）Obtained MOR seed-solutions, wherein alkali
Source, template, silicon source, water mol ratio are 0.2~10: 5.0~50: 100: 1000~10000, preferably 0.5~3.5：3.0~
15：100：2500~6000, then mixed solution is well mixed in confined conditions and obtains gel；Then the gel exists
10~120h of crystallization, preferably 24~72h at 100 DEG C~170 DEG C, preferably 120 DEG C~140 DEG C, then separating, washing, dry
Silicalite-2 silica zeolites are made in dry, roasting.
The present invention is prepared in the method for Silicalite-2 silica zeolites, 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 in described alcoholic solution：100, preferably 10~80：100, more preferably
10~50：100.
The present invention is prepared in the method for Silicalite-2 silica zeolites, step（1）Described in A for KBr, bromine
Change the one or more in sodium, potassium chloride, sodium chloride, preferably KBr.Described A and the mass ratio of water are 0.5~20：
100, preferably 0.5~10：100, more preferably 0.5~5：100.
The present invention is prepared in the method for Silicalite-2 silica zeolites, step（1）Described in B for PEG400~
One or more in PEG2000, preferably PEG400.The mass ratio of B and water is 0.5~20：100, preferably 0.5~10：
100, more preferably 0.5~5：100.
The present invention is prepared in the method for Silicalite-2 silica zeolites, step（1）Described in MOR crystal seeds for grinding
The mass ratio of MOR crystal seeds below to 300 mesh, MOR crystal seeds and water is 0.5~50：100, preferably 0.5~20：100, it is more excellent
Elect 5~20 as：100.
The present invention is prepared in the method for Silicalite-2 silica zeolites, step（2）Described template be n-butylamine,
Hexamethylene diamine, 4-propyl bromide, TPAOH, tetraethyl ammonium hydroxide, tetrabutylammonium hydroxide amine, octadecyl front three
One or more in one or more in base ammonium bromide, preferably tetraethyl ammonium hydroxide, tetrabutylammonium hydroxide amine, it is more excellent
Elect tetrabutylammonium hydroxide amine as.
The present invention is prepared in the method for Silicalite-2 silica zeolites, 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.
The present invention is prepared in the method for Silicalite-2 silica zeolites, step（3）Described silicon source is positive silicic acid second
One or more in ester, Ludox, white carbon, preferably white carbon.
The present invention is prepared in the method for Silicalite-2 silica zeolites, step（3）Described MOR seed-solutions are with molten
Contained MOR crystal seeds account for SiO used in liquid2Mass percent calculate, dosage be 0.1%~10%, preferably 0.5%~5%, more
Preferably 2%~4%.
The present invention is prepared in the method for Silicalite-2 silica zeolites, 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 synthetic 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 method that the present invention prepares Silicalite-2 silica zeolites has the following advantages that compared with prior art：
1st, the present invention pre-processes to crystal seed, by A and B synergy, can improve point of crystal seed in the solution
Divergence, while a protective layer is provided outside crystal seed, the nucleation of molecular sieve is occurred in protective layer, can be with significantly more efficient
The purity of molecular sieve is improved, avoids generating stray crystal phase, but also crystal growth can be suppressed, obtains the less molecular sieve of particle diameter.
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 white carbon 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.
4th, compared with conventional hydrothermal crystallization method, the method for crystal seed induction synthesis Silicalite-2 silica zeolites can add
Fast crystallization rate, shorten crystallization time；Organic formwork dosage needed for synthetic method is reduced, the charge ratio scope of each raw material compared with
Width, while also improve the crystallinity of Silicalite-2 silica zeolites.
Brief description of the drawings
Fig. 1 is the 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 silica zeolite XRD diffraction patterns.
Embodiment
The preparation method of Silicalite-2 silica zeolites of the present invention is further illustrated below by embodiment, but not
It is considered as that present invention is limited only by following example.
Embodiment 1
Configure MOR seed-solutions：By ethanol：Water is 40 according to volume ratio：100 are mixed to get alcoholic solution, according to quality
Than for 2.0KBr：1.2PEG400：Material is added in alcoholic solution and stirs 1 h by the ratio of 100 water, then grinds MOR molecular sieves
It is 10 MOR according to mass ratio to 300 mesh：MOR crystal seeds are added in above-mentioned solution by the ratio of 100 water, and it is brilliant that MOR is made
Kind solution.
The mixed solution of tetrabutylammonium hydroxide amine and sodium hydroxide is prepared, white carbon is then added into material and MOR is brilliant
Kind solution（Amount of seed accounts for SiO used with MOR2Mass percent for 2.0% calculate）, the closed h of uniform stirring 1.5, obtain
Mixture gel rubber system, each molar ratio of material 3.0NaOH in gel：9.0TBAOH：100SiO2：5200H2O, final mixture coagulate
Colloid lies in the h of crystallization 48 at 130 DEG C, and 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 463 m2/ g, relative crystallization
Spend for 161%, XRD spectra is as shown in Figure 1.
Embodiment 2
Configure MOR seed-solutions：By ethanol：Water is 10 according to volume ratio：100 are mixed to get alcoholic solution, according to quality
Than for 0.5KBr：0.5PEG400：Material is added in alcoholic solution and stirs 1 h by the ratio of 100 water, then grinds MOR molecular sieves
It is 5 MOR according to mass ratio to 300 mesh：MOR crystal seeds are added in above-mentioned solution by the ratio of 100 water, and it is brilliant that MOR is made
Kind solution.
The mixed solution of tetrabutylammonium hydroxide amine and sodium hydroxide is prepared, white carbon is then added into material and MOR is brilliant
Kind solution（Amount of seed accounts for SiO used with MOR2Mass percent for 3.0% calculate）, closed uniform stirring 1.5 hours, obtain
To mixture gel rubber system, each molar ratio of material 3.0NaOH in gel：9.0TBAOH：100SiO2：5200H2O, final mixture
Gel rubber system h of crystallization 36 at 135 DEG C, crystallization product is centrifuged, deionized water is washed, 10 are dried under the conditions of 100 DEG C
H, 12 h are calcined under the conditions of 600 DEG C Silicalite-2 silica zeolites are made, specific surface area is 407 m2/ g, relative knot
Brilliant degree is 142%.
Embodiment 3
Configure MOR seed-solutions：By ethanol：Water is 80 according to volume ratio：100 are mixed to get alcoholic solution, according to quality
Than for 15KBr：15PEG400：Material is added in alcoholic solution and stirs 1 h by the ratio of 100 water, is then ground to MOR molecular sieves
It is 20 MOR according to mass ratio below 300 mesh：MOR crystal seeds are added in above-mentioned solution by the ratio of 100 water, and MOR crystal seeds are made
Solution.
The mixed solution of tetrabutylammonium hydroxide amine and sodium hydroxide is prepared, white carbon is then added into material and MOR is brilliant
Kind solution（Amount of seed accounts for SiO used with MOR2Mass percent for 4.0% calculate）, the closed h of uniform stirring 1.5, obtain
Mixture gel rubber system, each molar ratio of material 3.0NaOH in gel：9.0TBAOH：100SiO2：5200H2O, final mixture coagulate
Colloid lies in the h of crystallization 72 at 140 DEG C, and 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 454 m2/ g, relative knot
Brilliant degree is 158%.
Embodiment 4
Configure MOR seed-solutions：By normal propyl alcohol：Water is 40 according to volume ratio：100 are mixed to get alcoholic solution, according to matter
It is 2.0KBr to measure ratio：1.2PEG400：Material is added in alcoholic solution and stirs 1 h by the ratio of 100 water, then grinds MOR molecular sieves
It is milled to below 300 mesh, is 10 MOR according to mass ratio：MOR crystal seeds are added in above-mentioned solution by the ratio of 100 water, and MOR is made
Seed-solution.
The mixed solution of tetrabutylammonium hydroxide amine and sodium hydroxide is prepared, white carbon is then added into material and MOR is brilliant
Kind solution（Amount of seed accounts for SiO used with MOR2Mass percent for 2.0% calculate）, the closed h of uniform stirring 1.5, obtain
Mixture gel rubber system, each molar ratio of material 3.0NaOH in gel：7.8TBAOH：100SiO2：5050H2O, final mixture coagulate
Colloid lies in the h of crystallization 48 at 130 DEG C, and 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 413 m2/ g, relative crystallization
Spend for 144%.
Embodiment 5
Configure MOR seed-solutions：By isopropanol：Water is 40 according to volume ratio：100 are mixed to get alcoholic solution, according to matter
It is 2.0KBr to measure ratio：1.2PEG400：Material is added in alcoholic solution and stirs 1 h by the ratio of 100 water, then grinds MOR molecular sieves
It is milled to below 300 mesh, is 10 MOR according to mass ratio：MOR crystal seeds are added in above-mentioned solution by the ratio of 100 water, and MOR is made
Seed-solution.
The mixed solution of tetrabutylammonium hydroxide amine and sodium hydroxide is prepared, white carbon is then added into material and MOR is brilliant
Kind solution（Amount of seed accounts for SiO used with MOR2Mass percent for 2.0% calculate）, the closed h of uniform stirring 1.5, obtain
Mixture gel rubber system, each molar ratio of material 2.5NaOH in gel：7.1TBAOH：100SiO2：3800H2O, final mixture coagulate
Colloid lies in the h of crystallization 48 at 130 DEG C, and 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 434 m2/ g, relative crystallization
Spend for 151%.
Embodiment 6
Configure MOR seed-solutions：By Yi Chun ︰ water according to volume ratio be 40：100 are mixed to get alcoholic solution, according to quality
Than for 2.0KBr：1.2PEG600：Material is added in alcoholic solution and stirs 1 h by the ratio of 100 water, then grinds MOR molecular sieves
It is 10 MOR according to mass ratio to 300 mesh：MOR crystal seeds are added in above-mentioned solution by the ratio of 100 water, and it is brilliant that MOR is made
Kind solution.
The mixed solution of tetrabutylammonium hydroxide amine and sodium hydroxide is prepared, white carbon is then added into material and MOR is brilliant
Kind solution（Amount of seed accounts for SiO used with MOR2Mass percent for 2.0% calculate）, the closed h of uniform stirring 1.5, obtain
Mixture gel rubber system, each molar ratio of material 3.0NaOH in gel：8.5TBAOH：100SiO2：3800H2O, final mixture coagulate
Colloid lies in the h of crystallization 48 at 130 DEG C, and 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 440 m2/ g, relative crystallization
Spend for 153%.
Embodiment 7
Configure MOR seed-solutions：By ethanol：Water is 40 according to volume ratio：100 are mixed to get alcoholic solution, according to quality
Than for 2.0KBr：1.2PEG1000：Material is added in alcoholic solution and stirs 1 h by the ratio of 100 water, then grinds MOR molecular sieves
It is milled to below 300 mesh, is 10 MOR according to mass ratio：MOR crystal seeds are added in above-mentioned solution by the ratio of 100 water, and MOR is made
Seed-solution.
The mixed solution of tetrabutylammonium hydroxide amine and sodium hydroxide is prepared, white carbon is then added into material and MOR is brilliant
Kind solution（Amount of seed accounts for SiO used with MOR2Mass percent for 2.0% calculate）, the closed h of uniform stirring 1.5, obtain
Mixture gel rubber system, each molar ratio of material 2.0NaOH in gel：5.8TBAOH：100SiO2：5400H2O, final mixture coagulate
Colloid lies in the h of crystallization 48 at 130 DEG C, and 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 425 m2/ g, relative crystallization
Spend for 148%.
Embodiment 8
Configure MOR seed-solutions：By ethanol：Water is 40 according to volume ratio：100 are mixed to get alcoholic solution, according to quality
Than for 2.0KBr：1.2 Tween 80：Material is added in alcoholic solution and stirs 1 h by the ratio of 100 water, then grinds MOR molecular sieves
It is 10 MOR according to mass ratio to 300 mesh：MOR crystal seeds are added in above-mentioned solution by the ratio of 100 water, and it is brilliant that MOR is made
Kind solution.
The mixed solution of tetrabutylammonium hydroxide amine and sodium hydroxide is prepared, white carbon is then added into material and MOR is brilliant
Kind solution（Amount of seed accounts for SiO used with MOR2Mass percent for 2.0% calculate）, the closed h of uniform stirring 1.5, obtain
Mixture gel rubber system, each molar ratio of material 3.0NaOH in gel：7.4TBAOH：100SiO2：4800H2O, final mixture coagulate
Colloid lies in the h of crystallization 48 at 130 DEG C, and 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 393 m2/ g, relative crystallization
Spend for 137%.
Embodiment 9
Configure MOR seed-solutions：By Yi Chun ︰ water according to volume ratio be 40：100 are mixed to get alcoholic solution, according to quality
Than for 2.0NaBr：1.2PEG400：Material is added in alcoholic solution and stirs 1 h by the ratio of 100 water, then grinds MOR molecular sieves
It is milled to below 300 mesh, is 10 MOR according to mass ratio：MOR crystal seeds are added in above-mentioned solution by the ratio of 100 water, and MOR is made
Seed-solution.
The mixed solution of tetrabutylammonium hydroxide amine and sodium hydroxide is prepared, white carbon is then added into material and MOR is brilliant
Kind solution（Amount of seed accounts for SiO used with MOR2Mass percent for 2.0% calculate）, the closed h of uniform stirring 1.5, obtain
Mixture gel rubber system, each molar ratio of material 3.0NaOH in gel：8.2TBAOH：100SiO2：5500H2O, final mixture coagulate
Colloid lies in the h of crystallization 48 at 130 DEG C, and 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 399 m2/ g, relative crystallization
Spend for 139%.
Embodiment 10
Configure MOR seed-solutions：By ethanol：Water is 40 according to volume ratio：100 are mixed to get alcoholic solution, according to quality
Than for 2.0NaCl：1.2PEG400：Material is added in alcoholic solution and stirs 1 h by the ratio of 100 water, then grinds MOR molecular sieves
It is milled to below 300 mesh, is 10 MOR according to mass ratio：MOR crystal seeds are added in above-mentioned solution by the ratio of 100 water, and MOR is made
Seed-solution.
The mixed solution of tetrabutylammonium hydroxide amine and sodium hydroxide is prepared, white carbon is then added into material and MOR is brilliant
Kind solution（Amount of seed accounts for SiO used with MOR2Mass percent for 2.0% calculate）, the closed h of uniform stirring 1.5, obtain
Mixture gel rubber system, each molar ratio of material 3.0NaOH in gel：8.2TBAOH：100SiO2：5500H2O, final mixture coagulate
Colloid lies in the h of crystallization 48 at 130 DEG C, and 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 390 m2/ g, relative crystallization
Spend for 136%.
Embodiment 11
Configure MOR seed-solutions：By ethanol:Water is 40 according to volume ratio:100 are mixed to get alcoholic solution, according to quality
Than for 2.0KCl：1.2PEG400：Material is added in alcoholic solution and stirs 1 h by the ratio of 100 water, then grinds MOR molecular sieves
It is 10 MOR according to mass ratio to 300 mesh：MOR crystal seeds are added in above-mentioned solution by the ratio of 100 water, and it is brilliant that MOR is made
Kind solution.
The mixed solution of tetrabutylammonium hydroxide amine and sodium hydroxide is prepared, white carbon is then added into material and MOR is brilliant
Kind solution（Amount of seed accounts for SiO used with MOR2Mass percent for 2.0% calculate）, the closed h of uniform stirring 1.5, obtain
Mixture gel rubber system, each molar ratio of material 3.0NaOH in gel：8.2TBAOH：100SiO2：5500H2O, final mixture coagulate
Colloid lies in the h of crystallization 48 at 130 DEG C, and 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 378 m2/ g, relative crystallization
Spend for 132%.
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
It is same as Example 1, difference be the crystal seed not by pretreatment, be solid MOR crystal seeds, gained
The relative crystallinity of Silicalite-2 silica zeolites is 123%.
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, template dosage are reduced, the time of gel is few, gel rubber system need not heat, and are shortened generated time, are reduced energy consumption.
Claims (37)
1. a kind of synthetic method of Silicalite-2 silica zeolites, the synthetic method comprise the following steps：
（1）Configure MOR seed-solutions：Alcohol and water is mixed to get alcoholic solution first, then adds A and B, stirring is complete to dissolving
MOR crystal seeds are added afterwards, and MOR seed-solutions are obtained after stirring, wherein, the A is KBr, sodium bromide, potassium chloride, chlorination
One or more in sodium, the B are the one or more in Tween 80, PEG400~PEG2000；
（2）The mixed solution containing template and alkali source is prepared, the pH value of mixed solution is 9.0~14.0；
（3）To step（2）Silicon source and step are added in obtained mixed solution（1）Obtained MOR seed-solutions, wherein alkali source,
Template, silicon source, water mol ratio are 0.2~10：5.0~50：100：1000~10000, then by mixed solution in closed bar
It is well mixed under part and obtains gel；Then the gel 10~120h of crystallization at 100 DEG C~170 DEG C, then through separating, washing
Wash, dry, being calcined obtained Silicalite-2 silica zeolites.
2. synthetic method according to claim 1, it is characterised in that：Step（2）Described in the pH value of mixed solution be
12.0~13.2.
3. synthetic method according to claim 1, it is characterised in that：Step（3）Described in alkali source, template, silicon source, water
Mol ratio is 0.5~3.5：3.0~15：100：2500~6000.
4. synthetic method according to claim 1, it is characterised in that：Step（3）Described in gel at 120 DEG C~140 DEG C
24~72h of lower crystallization.
5. synthetic 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. synthetic 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. synthetic method according to claim 6, it is characterised in that：Step（1）Described in alcohols be ethanol.
8. synthetic 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. synthetic 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. synthetic 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. synthetic method according to claim 1, it is characterised in that：Step（1）Described in A for KBr, sodium bromide
In one or more.
12. synthetic method according to claim 11, it is characterised in that：Step（1）Described in A be KBr.
13. synthetic 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. synthetic 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. synthetic 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. synthetic method according to claim 1, it is characterised in that：Step（1）Described in B for PEG400~
One or more in PEG2000.
17. synthetic method according to claim 16, it is characterised in that：Step（1）Described in B be PEG400.
18. synthetic 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. synthetic 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. synthetic 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. synthetic method according to claim 1, it is characterised in that：Step（1）Described in MOR crystal seeds to be ground to
The mass ratio of MOR crystal seeds below 300 mesh, MOR crystal seeds and water is 0.5~50：100.
22. synthetic method according to claim 21, it is characterised in that：Step（1）Described in the quality of MOR crystal seeds and water
Than for 0.5~20：100.
23. synthetic method according to claim 22, it is characterised in that：Step（1）Described in the quality of MOR crystal seeds and water
Than for 5~20：100.
24. synthetic method according to claim 1, it is characterised in that：Step（2）Described template is n-butylamine, oneself
Diamines, 4-propyl bromide, TPAOH, tetraethyl ammonium hydroxide, tetrabutylammonium hydroxide amine, octadecyl trimethyl
One or more in ammonium bromide.
25. synthetic method according to claim 24, it is characterised in that：Step（2）Described template is tetraethyl hydrogen
One or more in amine-oxides, tetrabutylammonium hydroxide amine.
26. synthetic method according to claim 25, it is characterised in that：Step（2）Described template is tetrabutylammonium hydrogen
Amine oxide.
27. synthetic 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.
28. synthetic method according to claim 27, it is characterised in that：Step（2）Described alkali source is sodium hydroxide, hydrogen
One or more in potassium oxide.
29. synthetic method according to claim 28, it is characterised in that：Step（2）Described alkali source is sodium hydroxid.
30. synthetic 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.
31. synthetic method according to claim 30, it is characterised in that：Step（3）Described silicon source is white carbon.
32. synthetic method according to claim 1, it is characterised in that：Step（3）Described MOR seed-solutions are with solution
In contained crystal seed account for SiO used2Mass percent calculate, dosage be 0.1%~10%.
33. synthetic method according to claim 32, it is characterised in that：Step（3）Described MOR seed-solutions are with solution
In contained crystal seed account for SiO used2Mass percent calculate, dosage be 0.5%~5%.
34. synthetic method according to claim 33, it is characterised in that：Step（3）Described MOR seed-solutions are with solution
In contained crystal seed account for SiO used2Mass percent calculate, dosage be 2%~4%.
35. synthetic 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.
36. synthetic method according to claim 35, it is characterised in that：Step（3）Gel is prepared under normal temperature condition to enter
OK.
37. synthetic 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 6h ~ 12h is dried under the conditions of 100 DEG C~120 DEG C, described to be roasted to
8h ~ 12h is calcined under the conditions of 500 DEG C~600 DEG C.
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| CN101423225A (en) * | 2008-11-27 | 2009-05-06 | 中国科学院过程工程研究所 | Method for preparing silica zeolite Silicalite-2 |
| CN102442677A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing silicalite-2 |
| CN102774851A (en) * | 2012-08-06 | 2012-11-14 | 黑龙江省科学院高技术研究院 | Method for preparing nano sillicalite-1 type total-silicalite molecular sieve |
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| CN101423225A (en) * | 2008-11-27 | 2009-05-06 | 中国科学院过程工程研究所 | Method for preparing silica zeolite Silicalite-2 |
| CN102442677A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing silicalite-2 |
| CN102774851A (en) * | 2012-08-06 | 2012-11-14 | 黑龙江省科学院高技术研究院 | Method for preparing nano sillicalite-1 type total-silicalite molecular sieve |
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