CN105731489A - Preparation method of Silicalite-2 all-silicon molecular sieve - Google Patents
Preparation method of Silicalite-2 all-silicon molecular sieve Download PDFInfo
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Abstract
The present invention provides a preparation method of Silicalite-2 all-silicon molecular sieve, and belongs to the field of molecular sieve synthesis. The preparation method comprises the steps of: (1) preparing a Silicalite-2 seed crystal solution by first mixing alcohol and water to obtain an alcohol solution, adding a solvent A and a solvent B, stirring to completely dissolve, adding the Silicalite-2 seed crystal and stirring evenly to obtain the Silicalite-2 crystal solution; (2) preparing a mixed solution containing a templating agent and an alkali source, wherein the pH value of the mixed solution is 9.0-14.0; (3) adding a silicon source and the Silicalite-2 seed crystal solution obtained in the step (1) into the mixed solution, then evenly mixing the mixed solution under enclosed conditions to obtain a gel; crystallizing the gel at 100-170 DEG C for 10-120 h, then separating, washing, drying and roasting to obtain the Silicalite-2 all-silicon molecular sieve. The preparation method has simple process and low cost; and the prepared all-silicon molecular sieve has high crystallinity and is applicable to industrial application.
Description
Technical field
The present invention relates to a kind of method preparing silica zeolite, the method concretely relating to a kind of homogeneity crystal seed induction Fast back-projection algorithm silica zeolite Silicalite-2.
Background technology
Silicalite-2 is the molecular sieve with MEL type framing structure, is the siliceous form of ZSM-11, can as the separation membrane material etc. of the inert carrier of shape selective catalyst and Organic substance aqueous phase, thus receiving extensive concern.
ChuP(USP3709979 in 1973) use Bu4N+Do template and successfully synthesize ZSM-11 molecular sieve, the FlanigenEM etc. of U.C.C. company in 1978 successfully synthesizes again last member of Pentasil family, total silicon ZSM-11-Silicalite-2, and then promoted the fast development in rich silicon molecular sieve by crystal synthesis field.Nineteen ninety McWilliam(USP4894212) use octylame to do template, adopt the way that adds crystal seed 100 ~ 350 DEG C of crystallization 12 hours ~ 10 days, obtain relatively pure ZSM-11.Valyocsik(USP4941963) using diquaternary amine salt (butyl pyrrolidine) to synthesize ZSM-11 for template, crystallization temperature is 60 ~ 250 DEG C, and crystallization time is 1 ~ 30 day.Beck(USP5213786 in 1993) elaborate to adopt Trimethylamine cation (CnN+(CH3)3, n is 9,10,11,12) and as organic formwork agent, it is preferred that crystallization temperature is 80 ~ 200 DEG C, and crystallization time is 1 ~ 30 day.United States Patent (USP) (USP6444191) is with 3,5-dimethyl-N, N-diethyl pyrrolidines for template, and crystallization temperature is 140 ~ 200 DEG C, and crystallization time is 2 ~ 20 days, has synthesized pure ZSM-11 molecular sieve.But, said method technical process relative complex, it is typically in relatively short time crystallinity not high, and containing stray crystal；Need longer crystallization time just can prepare without stray crystal, high-crystallinity, high conversion ZSM-11 molecular sieve, energy consumption is higher, production efficiency is relatively low.
In order to solve the problems referred to above, the preparation method that CN101423225A discloses a kind of silica zeolite Silicalite-2.Comprise the steps: organic formwork agent (tetrabutylammonium hydroxide amine), silicon source (tetraethyl orthosilicate) and deionized water heated and stirred 0.5 ~ 10 hour, then keep the skin wet, the crystallization 12 ~ 90 hours when 100 ~ 200 DEG C of hydro-thermals are airtight, it is cooled to room temperature, through washing, centrifugation, dry, roasting, obtain silica zeolite Silicalite-2.Although the method shortens generated time, but process is complex, and gel process needs heating and gel time partially long, in addition it is also necessary to supplement water in gel；The silicon source adopted is expensive tetraethyl orthosilicate, adds production cost.Additionally, for the silica zeolite Silicalite-2 obtaining higher crystallinity, in addition it is also necessary to longer crystallization time.
The preparation method that CN102442677A discloses a kind of silica zeolite.Comprising the steps: the mixed solution first preparing template (TBAH) and alkali source (sodium hydroxide), the pH value of mixed solution is between 12.10-13.20；Then in mixed solution, add silicon source (white carbon or Ludox), stir under airtight condition, mixing time 0.5-2 hour, obtain mixture gel rubber system；Final mixture gel rubber system at 170 DEG C-200 DEG C crystallization 2.0-4.0 days, crystallization product is scrubbed, centrifugation, dry, roasting prepare Silicalite-2 silica zeolite.The method synthesis pH claimed range is narrower, and gel process temperature is high, and crystallization time is partially long, obtains molecular sieve and mixed crystal state easily occurs.
Summary of the invention
For the deficiencies in the prior art, in order to better control the nucleation and growth in sieve synthesis procedure, in Silicalite-2 silica zeolite preparation method of the present invention, crystal seed is carried out pretreatment.Preparation method process of the present invention is simple, cost is low, and the Silicalite-2 silica zeolite degree of crystallinity obtained is high, is suitable to commercial Application.
The preparation method that the present invention provides a kind of Silicalite-2 silica zeolite, described preparation method comprises the steps:
(1) configuration Silicalite-2 seed-solution: first alcohol and water is mixed to get alcoholic solution, it is subsequently adding solvent orange 2 A and solvent B, stirring adds Silicalite-2 crystal seed to dissolving completely, Silicalite-2 seed-solution is obtained after stirring, wherein, described solvent orange 2 A is one or more in potassium bromide, sodium bromide, potassium chloride, sodium chloride, and described solvent B is one or more in Tween 80, PEG400～PEG2000.
(2) preparation solution containing alkali source, the pH value of solution is 9.0～14.0, it is preferred to 12.0～13.2；
(3) solution obtained to step (2) adds silicon source and Silicalite-2 seed-solution that step (1) obtains, wherein alkali source, silicon source, water mol ratio are 0.2～10: 5.0～50: 100: 1000～10000, it is preferably 0.5～3.5 100 2500～6000, then mixed solution mix homogeneously in confined conditions is obtained gel；Then described gel is at 100 DEG C～180 DEG C, it is preferred to crystallization 10～120h at 150 DEG C～180 DEG C, it is preferred to 24～72h, and then separating, washing, drying, roasting prepare Silicalite-2 silica zeolite.
In the preparation method of Silicalite-2 silica zeolite of the present invention, alcohols described in step (1) is one or more in methanol, ethanol, normal propyl alcohol, isopropanol, butanol, it is preferably one or more in ethanol, normal propyl alcohol, isopropanol, more preferably ethanol.In described alcoholic solution, alcohol is 5～95 100 with the volume ratio of water, it is preferred to 10～80 100, more preferably 10～50 100.
In the preparation method of Silicalite-2 silica zeolite of the present invention, the solvent orange 2 A described in step (1) is one or more in potassium bromide, sodium bromide, it is preferred to potassium bromide.The mass ratio of described solvent orange 2 A and water is 0.5～20 100, it is preferred to 0.5～10 100, more preferably 0.5～5 100.
In the preparation method of Silicalite-2 silica zeolite of the present invention, the solvent B described in step (1) is one or more in PEG400～PEG2000, it is preferred to PEG400.The mass ratio of solvent B and water is 0.5～20 100, it is preferred to 0.5～10 100, more preferably 0.5～5 100.
In the preparation method of Silicalite-2 silica zeolite of the present invention, Silicalite-2 crystal seed described in step (1) is the Silicalite-2 crystal seed being ground to below 300 orders, the mass ratio of Silicalite-2 crystal seed and water is 0.5～50 100, it is preferably 0.5～20 100, more preferably 5～20 100.
In the preparation method of Silicalite-2 silica zeolite of the present invention, alkali source described in step (2) is one or more in ethamine, n-butylamine, sodium hydroxide, potassium hydroxide, it is preferably one or more in sodium hydroxide, potassium hydroxide, more preferably sodium hydroxid.
In the preparation method of Silicalite-2 silica zeolite of the present invention, the solution that step (2) described preparation contains alkali source adds template.Described template is one or more in n-butylamine, hexamethylene diamine, 4-propyl bromide, TPAOH, tetraethyl ammonium hydroxide, tetrabutyl hydrogen-oxygen oxyammonia, Cetyltrimethylammonium bromide, it is preferably one or more in tetraethyl ammonium hydroxide, tetrabutylammonium hydroxide amine, more preferably tetrabutylammonium hydroxide amine.The mol ratio of described alkali source and template is 0.2～10: 5.0～50, it is preferred to 0.5～3.5 3.0～15.
In the preparation method of Silicalite-2 silica zeolite of the present invention, the silicon source described in step (3) is one or more in tetraethyl orthosilicate, Ludox, white carbon, it is preferred to Ludox.
In the preparation method of Silicalite-2 silica zeolite of the present invention, the Silicalite-2 seed-solution described in step (3) accounts for SiO used with Silicalite-2 crystal seed contained in solution2Mass percent calculate, consumption is 0.1%～10%, it is preferred to 0.5%～5%, more preferably 2%～4%.
In the preparation method of Silicalite-2 silica zeolite of the present invention, step (3) is prepared gel process and can be carried out in a heated condition, it is also possible to carry out at normal temperatures, it is preferable that gel under normal temperature condition, and described room temperature refers in gel process without heating.
In the preparation method of Silicalite-2 silica zeolite of the present invention, step is separated into centrifugation described in (3)；Described washing is for using deionized water wash；Described drying as 6h ~ 12h dry under 100 DEG C～120 DEG C conditions, described roasting is roasting 8h ~ 12h under 500 DEG C～600 DEG C conditions.
The Silicalite-2 silica zeolite that the inventive method is prepared may be used for synthesis gas olefin hydrocarbon, it is also possible to for other petrochemical industry catalytic process.
The preparation method of Silicalite-2 silica zeolite of the present invention compared with prior art has the advantage that
1, crystal seed is carried out pretreatment by the present invention; synergism by solvent orange 2 A and solvent B; crystal seed dispersion in the solution can be improved; outside crystal seed, provide a protective layer simultaneously; make in the nucleation generation protective layer of molecular sieve, it is possible to the purity of significantly more efficient raising molecular sieve, it is to avoid generate stray crystal phase; but also crystal growth can be suppressed, obtain the molecular sieve that particle diameter is less.
2, the inventive method is carried out the pH value of controlling crystallizing material by appropriate alkali source and selects suitable building-up process, particularly synthesize the addition sequence of material, prepare the Silicalite-2 silica zeolite of high-crystallinity, from embodiment and comparative example, at identical crystallization temperature with in the time, the degree of crystallinity of the Silicalite-2 silica zeolite that the present invention prepares is apparently higher than comparative example.
3, the inventive method substantially shortens gel and the crystallization time of mixed material, gel process is without carrying out in a heated condition, and cheap Ludox can be used as silicon source, compared with the preparation method of conventional Silicalite-2 silica zeolite, the inventive method preparation process time is short, easily operated, cost is low, is suitable to commercial Application.
Accompanying drawing explanation
Fig. 1 is the Silicalite-2 silica zeolite XRD diffraction pattern of the embodiment of the present invention 1 synthesis.
Fig. 2 is the Silicalite-2 silica zeolite XRD diffraction pattern of comparative example 1 of the present invention, the 2-in-1 one-tenth of comparative example.
Detailed description of the invention
The method further illustrating Fast back-projection algorithm Silicalite-2 silica zeolite of the present invention by the examples below, but invention should not be deemed limited to following examples in.
Embodiment 1
Configuration Silicalite-2 seed-solution: by ethanol water according to volume ratio be 40 100 be mixed to get alcoholic solution, according to the ratio that mass ratio is 2.0KBr 1.2PEG400 100 water, material added stirring 1h in alcoholic solution, then Silicalite-2 molecular sieve is ground to below 300 orders, according to the ratio that mass ratio is 10Silicalite-2 100 water, Silicalite-2 crystal seed is joined in above-mentioned solution, prepare Silicalite-2 seed-solution.
Secure ph is the sodium hydroxide mixed solution of 12.6, then adds Ludox in material and (amount of seed accounts for SiO used with Silicalite-2 with Silicalite-2 seed-solution2Mass percent be 2.3% calculating), airtight uniform stirring 2 hours, obtain mixture gel rubber system, each molar ratio of material 4.1NaOH 100SiO-in gel26550H2O, final mixture gel rubber system is crystallization 2 days at 150 DEG C, and crystallization product is performing centrifugal separation on, deionized water wash, dry 12h under 120 DEG C of conditions, and under 550 DEG C of conditions, roasting 8h prepares Silicalite-2 silica zeolite, and specific surface area is 477m2/ g, relative crystallinity is 166%, and XRD spectra is as shown in Figure 1.
Embodiment 2
Configuration Silicalite-2 seed-solution: by normal propyl alcohol water according to volume ratio be 35 100 be mixed to get alcoholic solution, according to the ratio that mass ratio is 0.5KBr 0.5PEG400 100 water, material added stirring 1h in alcoholic solution, then Silicalite-2 molecular sieve is ground to below 300 orders, according to the ratio that mass ratio is 5Silicalite-2 100 water, Silicalite-2 crystal seed is joined in above-mentioned solution, prepare Silicalite-2 seed-solution.
Secure ph is the sodium hydroxide mixed solution of 12.6, and (amount of seed accounts for SiO used with Silicalite-2 then to add Ludox and Silicalite-2 seed-solution in material2Mass percent be 2.3% calculating), airtight uniform stirring 2 hours, obtain mixture gel rubber system, each molar ratio of material 4.1NaOH 100SiO-in gel26550H2O, final mixture gel rubber system is crystallization 2 days at 150 DEG C, and crystallization product is performing centrifugal separation on, deionized water wash, dry 12h under 120 DEG C of conditions, and under 550 DEG C of conditions, roasting 8h prepares Silicalite-2 silica zeolite, and specific surface area is 459m2/ g, relative crystallinity is 159%.
Embodiment 3
Configuration Silicalite-2 seed-solution: by isopropanol water according to volume ratio be 26 100 be mixed to get alcoholic solution, according to the ratio that mass ratio is 1.0KBr 2.8PEG400 100 water, material added stirring 1h in alcoholic solution, then Silicalite-2 molecular sieve is ground to below 300 orders, according to the ratio that mass ratio is 15Silicalite-2 100 water, Silicalite-2 crystal seed is joined in above-mentioned solution, prepare Silicalite-2 seed-solution.
Secure ph is the sodium hydroxide mixed solution of 12.1, and (amount of seed accounts for SiO used with Silicalite-2 then to add Ludox and Silicalite-2 seed-solution in material2Mass percent be 2.3% calculating), airtight uniform stirring 1.5 hours, obtain mixture gel rubber system, each molar ratio of material 1.2NaOH 100SiO-in gel27550H2O, final mixture gel rubber system is crystallization 1 day at 150 DEG C, and crystallization product is performing centrifugal separation on, deionized water wash, dry 12h under 120 DEG C of conditions, and under 550 DEG C of conditions, roasting 8h prepares Silicalite-2 silica zeolite, and specific surface area is 453m2/ g, relative crystallinity is 157%.
Embodiment 4
Configuration Silicalite-2 seed-solution: by ethanol water according to volume ratio be 10 100 be mixed to get alcoholic solution, according to the ratio that mass ratio is 4.5NaBr 4.0PEG400 100 water, material added stirring 1h in alcoholic solution, then Silicalite-2 molecular sieve is ground to below 300 orders, according to the ratio that mass ratio is 5Silicalite-2 100 water, Silicalite-2 crystal seed is joined in above-mentioned solution, prepare Silicalite-2 seed-solution.
Secure ph is the sodium hydroxide mixed solution of 12.8, and (amount of seed accounts for SiO used with Silicalite-2 then to add Ludox and Silicalite-2 seed-solution in material2Mass percent be 2.5% calculating), airtight uniform stirring 2 hours, obtain mixture gel rubber system, each molar ratio of material 2.6NaOH 100SiO-in gel25600H2O, final mixture gel rubber system is crystallization 3 days at 150 DEG C, and crystallization product is performing centrifugal separation on, deionized water wash, dry 12h under 120 DEG C of conditions, and under 550 DEG C of conditions, roasting 8h prepares Silicalite-2 silica zeolite, and specific surface area is 468m2/ g, relative crystallinity is 163%.
Embodiment 5
Configuration Silicalite-2 seed-solution: by ethanol water according to volume ratio be 80 100 be mixed to get alcoholic solution, according to the ratio that mass ratio is 10KBr 10,PEG,600 100 water, material added stirring 1h in alcoholic solution, then Silicalite-2 molecular sieve is ground to below 300 orders, according to the ratio that mass ratio is 20Silicalite-2 100 water, Silicalite-2 crystal seed is joined in above-mentioned solution, prepare Silicalite-2 seed-solution.
Secure ph is the sodium hydroxide mixed solution of 13.1, and (amount of seed accounts for SiO used with Silicalite-2 then to add Ludox and Silicalite-2 seed-solution in material2Mass percent be 2.3% calculating), airtight uniform stirring 1.5 hours, obtain mixture gel rubber system, each molar ratio of material 3.2NaOH 100SiO-in gel23000H2O, final mixture gel rubber system is crystallization 2 days at 120 DEG C, and crystallization product is performing centrifugal separation on, deionized water wash, dry 12h under 120 DEG C of conditions, and under 550 DEG C of conditions, roasting 8h prepares Silicalite-2 silica zeolite, and specific surface area is 389m2/ g, relative crystallinity is 135%.
Embodiment 6
Configuration Silicalite-2 seed-solution: by ethanol water according to volume ratio be 40 100 be mixed to get alcoholic solution, according to the ratio that mass ratio is 2KBr 1.2 Tween 80 100 water, material added stirring 1h in alcoholic solution, then Silicalite-2 molecular sieve is ground to below 300 orders, according to the ratio that mass ratio is 10Silicalite-2 100 water, Silicalite-2 crystal seed is joined in above-mentioned solution, prepare Silicalite-2 seed-solution.
Secure ph is the sodium hydroxide mixed solution of 13.5, and (amount of seed accounts for SiO used with Silicalite-2 then to add Ludox and Silicalite-2 seed-solution in material2Mass percent be 2.0% calculating), airtight uniform stirring 1.5 hours, obtain mixture gel rubber system, each molar ratio of material 3.8NaOH 100SiO-in gel27000H2O, final mixture gel rubber system is crystallization 2 days at 180 DEG C, and crystallization product is performing centrifugal separation on, deionized water wash, dry 10h under 100 DEG C of conditions, and under 600 DEG C of conditions, roasting 12h prepares Silicalite-2 silica zeolite, and specific surface area is 450m2/ g, relative crystallinity is 156%.
Embodiment 7
Configuration Silicalite-2 seed-solution: by ethanol water according to volume ratio be 40 100 be mixed to get alcoholic solution, according to the ratio that mass ratio is 2KBr 1.2PEG400 100 water, material added stirring 1h in alcoholic solution, then Silicalite-2 molecular sieve is ground to below 300 orders, according to the ratio that mass ratio is 10Silicalite-2 100 water, Silicalite-2 crystal seed is joined in above-mentioned solution, prepare Silicalite-2 seed-solution.
Secure ph is the sodium hydroxide mixed solution of 13.8, and (amount of seed accounts for SiO used with Silicalite-2 then to add Ludox and Silicalite-2 seed-solution in material2Mass percent be 0.6% calculating), airtight uniform stirring 2 hours, obtain mixture gel rubber system, each molar ratio of material 4.2NaOH 100SiO-in gel25000H2O, final mixture gel rubber system is crystallization 2 days at 150 DEG C, and crystallization product is performing centrifugal separation on, deionized water wash, dry 12h under 110 DEG C of conditions, and under 500 DEG C of conditions, roasting 10h prepares Silicalite-2 silica zeolite, and specific surface area is 465m2/ g, relative crystallinity is 161%.
Embodiment 8
Configuration Silicalite-2 seed-solution: by ethanol water according to volume ratio be 40 100 be mixed to get alcoholic solution, according to the ratio that mass ratio is 2.0KBr 1.2PEG400 100 water, material added stirring 1h in alcoholic solution, then Silicalite-2 molecular sieve is ground to below 300 orders, according to the ratio that mass ratio is 10Silicalite-2 100 water, Silicalite-2 crystal seed is joined in above-mentioned solution, prepare Silicalite-2 seed-solution.
Secure ph is the sodium hydroxide mixed solution of 12.2, and (amount of seed accounts for SiO used with Silicalite-2 then to add Ludox and Silicalite-2 seed-solution in material2Mass percent be 2.3% calculating), airtight uniform stirring 2 hours, obtain mixture gel rubber system, each molar ratio of material 3.0NaOH 100SiO-in gel23500H2O, final mixture gel rubber system is crystallization 2 days at 150 DEG C, and crystallization product is performing centrifugal separation on, deionized water wash, dry 12h under 120 DEG C of conditions, and under 550 DEG C of conditions, roasting 8h prepares Silicalite-2 silica zeolite, and specific surface area is 426m2/ g, relative crystallinity is 148%.
Embodiment 9
Configuration Silicalite-2 seed-solution: by ethanol water according to volume ratio be 40 100 be mixed to get alcoholic solution, according to the ratio that mass ratio is 2.0KBr 1.2PEG400 100 water, material added stirring 1h in alcoholic solution, then Silicalite-2 molecular sieve is ground to below 300 orders, according to the ratio that mass ratio is 10Silicalite-2 100 water, Silicalite-2 crystal seed is joined in above-mentioned solution, prepare Silicalite-2 seed-solution.
Secure ph is the sodium hydroxide mixed solution of 12.3, and (amount of seed accounts for SiO used with Silicalite-2 then to add Ludox and Silicalite-2 seed-solution in material2Mass percent be 6.5% calculating), airtight uniform stirring 2 hours, obtain mixture gel rubber system, each molar ratio of material 3.5NaOH 100SiO-in gel27200H2O, final mixture gel rubber system is crystallization 2 days at 150 DEG C, and crystallization product is performing centrifugal separation on, deionized water wash, dry 12h under 120 DEG C of conditions, and under 550 DEG C of conditions, roasting 8h prepares Silicalite-2 silica zeolite, and specific surface area is 447m2/ g, relative crystallinity is 155%.
Embodiment 10
Configuration Silicalite-2 seed-solution: by ethanol water according to volume ratio be 40 100 be mixed to get alcoholic solution, according to the ratio that mass ratio is 2.0KBr 1.2PEG400 100 water, material added stirring 1h in alcoholic solution, then Silicalite-2 molecular sieve is ground to below 300 orders, according to the ratio that mass ratio is 10Silicalite-2 100 water, Silicalite-2 crystal seed is joined in above-mentioned solution, prepare Silicalite-2 seed-solution.
Secure ph is the sodium hydroxide mixed solution of 12.1, and (amount of seed accounts for SiO used with Silicalite-2 then to add Ludox and Silicalite-2 seed-solution in material2Mass percent be 8.9% calculating), airtight uniform stirring 1.5 hours, obtain mixture gel rubber system, each molar ratio of material 2.9NaOH 100SiO-in gel24860H2O, final mixture gel rubber system is crystallization 2 days at 150 DEG C, and crystallization product is performing centrifugal separation on, deionized water wash, dry 12h under 120 DEG C of conditions, and under 550 DEG C of conditions, roasting 8h prepares Silicalite-2 silica zeolite, and specific surface area is 453m2/ g, relative crystallinity is 157%.
Embodiment 11
Configuration Silicalite-2 seed-solution: by ethanol water according to volume ratio be 35 100 be mixed to get alcoholic solution, according to the ratio that mass ratio is 0.5KBr 0.5PEG400 100 water, material added stirring 1h in alcoholic solution, then Silicalite-2 molecular sieve is ground to below 300 orders, according to the ratio that mass ratio is 5Silicalite-2 100 water, Silicalite-2 crystal seed is joined in above-mentioned solution, prepare Silicalite-2 seed-solution.
Preparation tetrabutylammonium hydroxide amine and the mixed solution of sodium hydroxide, (amount of seed accounts for SiO used with Silicalite-2 then to add Ludox and Silicalite-2 seed-solution in material2Mass percent be 3.0% calculating), airtight uniform stirring 1.5h, obtain mixture gel rubber system, each molar ratio of material 3.0NaOH 9.0TBAOH 100SiO-in gel25200H2O, final mixture gel rubber system is crystallization 40h at 125 DEG C, and crystallization product is performing centrifugal separation on, deionized water wash, dry 12h under 120 DEG C of conditions, and under 550 DEG C of conditions, roasting 8h prepares Silicalite-2 silica zeolite, and specific surface area is 472m2/ g, relative crystallinity is 164%.
Embodiment 12
Configuration Silicalite-2 seed-solution: by ethanol water according to volume ratio be 26 100 be mixed to get alcoholic solution, according to the ratio that mass ratio is 1.0KBr 2.8PEG400 100 water, material added stirring 1h in alcoholic solution, then Silicalite-2 molecular sieve is ground to below 300 orders, according to the ratio that mass ratio is 15Silicalite-2 100 water, Silicalite-2 crystal seed is joined in above-mentioned solution, prepare Silicalite-2 seed-solution.
Preparation tetrabutylammonium hydroxide amine and the mixed solution of sodium hydroxide, (amount of seed accounts for SiO used with Silicalite-2 then to add Ludox and Silicalite-2 seed-solution in material2Mass percent be 4.0% calculating), airtight uniform stirring 1.5h, obtain mixture gel rubber system, each molar ratio of material 3.0NaOH 9.0TBAOH 100SiO-in gel25200H2O, final mixture gel rubber system is crystallization 40h at 125 DEG C, and crystallization product is performing centrifugal separation on, deionized water wash, dry 12h under 120 DEG C of conditions, and under 550 DEG C of conditions, roasting 8h prepares Silicalite-2 silica zeolite, and specific surface area is 466m2/ g, relative crystallinity is 162%.
Embodiment 13
Configuration Silicalite-2 seed-solution: by ethanol water according to volume ratio be 10 100 be mixed to get alcoholic solution, according to the ratio that mass ratio is 4.5KBr 4.0PEG400 100 water, material added stirring 1h in alcoholic solution, then Silicalite-2 molecular sieve is ground to below 300 orders, according to the ratio that mass ratio is 5Silicalite-2 100 water, Silicalite-2 crystal seed is joined in above-mentioned solution, prepare Silicalite-2 seed-solution.
Preparation tetrabutylammonium hydroxide amine and the mixed solution of sodium hydroxide, (amount of seed accounts for SiO used with Silicalite-2 then to add Ludox and Silicalite-2 seed-solution in material2Mass percent be 2.5% calculating), airtight uniform stirring 1.5h, obtain mixture gel rubber system, each molar ratio of material 3.0NaOH 9.0TBAOH 100SiO-in gel25200H2O, final mixture gel rubber system is crystallization 40h at 125 DEG C, and crystallization product is performing centrifugal separation on, deionized water wash, dry 12h under 120 DEG C of conditions, and under 550 DEG C of conditions, roasting 8h prepares Silicalite-2 silica zeolite, and specific surface area is 481m2/ g, relative crystallinity is 167%.
Embodiment 14
Configuration Silicalite-2 seed-solution: by ethanol water according to volume ratio be 40 100 be mixed to get alcoholic solution, according to the ratio that mass ratio is 2KBr 1.2PEG400 100 water, material added stirring 1h in alcoholic solution, then Silicalite-2 molecular sieve is ground to below 300 orders, according to the ratio that mass ratio is 10Silicalite-2 100 water, Silicalite-2 crystal seed is joined in above-mentioned solution, prepare Silicalite-2 seed-solution.
Preparation tetrabutylammonium hydroxide amine and the mixed solution of sodium hydroxide, (amount of seed accounts for SiO used with Silicalite-2 then to add Ludox and Silicalite-2 seed-solution in material2Mass percent be 2.0% calculating), airtight uniform stirring 1.5 hours, obtain mixture gel rubber system, each molar ratio of material 3.0NaOH 9.0TBAOH 100SiO-in gel25200H2O, final mixture gel rubber system is crystallization 36h at 135 DEG C, and crystallization product is performing centrifugal separation on, deionized water wash, dry 10h under 100 DEG C of conditions, and under 600 DEG C of conditions, roasting 12h prepares Silicalite-2 silica zeolite, and specific surface area is 464m2/ g, relative crystallinity is 161%.
Comparative example 1
By the preparation method of patent CN101423225,9.56g tetraethyl orthosilicate and the tetrabutylammonium hydroxide amine aqueous solution that 32.44g mass concentration is 10% are added in the retort of politef, at 60 DEG C of heated and stirred 4.5h, keep the skin wet and make SiO in system2Mass concentration is 13%, 180 DEG C of airtight crystallization 2.5 days, and crystallization product is scrubbed, centrifugation, dry, roasting prepare Silicalite-2 silica zeolite, using this molecular sieve as reference, is used for calculating relative crystallinity.
Comparative example 2
Identical with embodiment 1, difference be described crystal seed not past pretreatment, for solid Silicalite-2 crystal seed, the relative crystallinity of gained Silicalite-2 silica zeolite is 121%.
Comparative example 1, comparative example 2 are compared known with embodiment 1, under identical crystallization condition, the degree of crystallinity of embodiment Silicalite-2 silica zeolite is generally higher than comparative example, in addition, the embodiment of the present invention adopts crystal seed induction synthesis silica zeolite, gel time is few, gel rubber system without heating, shorten generated time, reduce energy consumption.
Claims (16)
1. a preparation method for Silicalite-2 silica zeolite, described preparation method comprises the steps:
(1) configuration Silicalite-2 seed-solution: first alcohol and water is mixed to get alcoholic solution, it is subsequently adding solvent orange 2 A and solvent B, stirring adds Silicalite-2 crystal seed to dissolving completely, Silicalite-2 seed-solution is obtained after stirring, wherein, described solvent orange 2 A is one or more in potassium bromide, sodium bromide, potassium chloride, sodium chloride, and described solvent B is one or more in Tween 80, PEG400～PEG2000；
(2) preparation solution containing alkali source, the pH value of solution is 9.0～14.0, it is preferred to 12.0～13.2；
(3) solution obtained to step (2) adds silicon source and Silicalite-2 seed-solution that step (1) obtains, wherein alkali source, silicon source, water mol ratio are 0.2～10:100:1000～10000, it is preferably 0.5～3.5:100:2500～6000, then mixed solution mix homogeneously in confined conditions is obtained gel；Then described gel is at 100 DEG C～180 DEG C, it is preferred to crystallization 10～120h at 150 DEG C～180 DEG C, it is preferable that 24～72h, and then separating, washing, drying, roasting prepare Silicalite-2 silica zeolite.
2. preparation method according to claim 1, it is characterized in that: the alcohols described in step (1) is one or more in methanol, ethanol, normal propyl alcohol, isopropanol, butanol, it is preferably one or more in ethanol, normal propyl alcohol, isopropanol, more preferably ethanol.
3. preparation method according to claim 1, it is characterised in that: in the alcoholic solution described in step (1), alcohol is 5～95:100 with the volume ratio of water, it is preferred to 10～80:100, more preferably 10～50:100.
4. preparation method according to claim 1, it is characterised in that: the solvent orange 2 A described in step (1) is one or more in potassium bromide, sodium bromide, it is preferred to potassium bromide.
5. preparation method according to claim 1, it is characterised in that: the mass ratio of the solvent orange 2 A described in step (1) and water is 0.5～20:100, it is preferred to 0.5～10:100, more preferably 0.5～5:100.
6. preparation method according to claim 1, it is characterised in that: the solvent B described in step (1) is one or more in PEG400～PEG2000, it is preferred to PEG400.
7. preparation method according to claim 1, it is characterised in that: the mass ratio of solvent B described in step (1) and water is 0.5～20:100, it is preferred to 0.5～10:100, more preferably 0.5～5:100.
8. preparation method according to claim 1, it is characterized in that: the Silicalite-2 crystal seed described in step (1) is the Silicalite-2 crystal seed being ground to below 300 orders, the mass ratio of Silicalite-2 crystal seed and water is 0.5～50:100, it is preferably 0.5～20:100, more preferably 5～20:100.
9. preparation method according to claim 1, it is characterized in that: the alkali source described in step (2) is one or more in ethamine, n-butylamine, sodium hydroxide, potassium hydroxide, it is preferably one or more in sodium hydroxide, potassium hydroxide, more preferably sodium hydroxid.
10. preparation method according to claim 1, it is characterised in that: the solution that step (2) described preparation contains alkali source adds template.
11. preparation method according to claim 10, it is characterized in that: described template is one or more in n-butylamine, hexamethylene diamine, 4-propyl bromide, TPAOH, tetraethyl ammonium hydroxide, tetrabutyl hydrogen-oxygen oxyammonia, Cetyltrimethylammonium bromide, it is preferably one or more in tetraethyl ammonium hydroxide, tetrabutylammonium hydroxide amine, more preferably tetrabutylammonium hydroxide amine.
12. preparation method according to claim 10, it is characterised in that: the mol ratio of described alkali source and template is 0.2～10:5.0～50, it is preferred to 0.5～3.5:3.0～15.
13. preparation method according to claim 1, it is characterised in that: the silicon source described in step (3) is one or more in tetraethyl orthosilicate, Ludox, white carbon, it is preferred to Ludox.
14. preparation method according to claim 1, it is characterised in that: the seed-solution described in step (3) accounts for SiO used with Silicalite-2 crystal seed contained in solution2Mass percent calculate, consumption is 0.1%～10%, it is preferred to 0.5%～5%, more preferably 2%～4%.
15. preparation method according to claim 1, it is characterised in that: step (3) is prepared gel and in a heated condition or is carried out under room temperature, it is preferable that carry out under normal temperature condition.
16. preparation method according to claim 1, it is characterised in that: step is separated into centrifugation described in (3)；Described washing is for using deionized water wash；Described drying as 6h ~ 12h dry under 100 DEG C～120 DEG C conditions, described roasting is roasting 8h ~ 12h under 500 DEG C～600 DEG C conditions.
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