CN1789125A - Small crystal grain molecular sieve preparation method - Google Patents
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- CN1789125A CN1789125A CN 200410098704 CN200410098704A CN1789125A CN 1789125 A CN1789125 A CN 1789125A CN 200410098704 CN200410098704 CN 200410098704 CN 200410098704 A CN200410098704 A CN 200410098704A CN 1789125 A CN1789125 A CN 1789125A
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Abstract
The invention discloses a method for preparing the NaY molecular screen of high alumina silica ratio and fine grain, firstly synthesizing NaY molecular screen guilding agent according to current technology, then producing gel with sodium silicate, guilding agent, acid aluminium salt and sodium metaaluminate, blooming the gei under the temperature of 50-100 Deg C for 0-70 hours, adding some silicon, then blooming continuously under temperature of 90-120 Deg C for 0.5-50 hours, finally filtering, washing and drying. The NaY molecular screen with the alumina silica ratio being 5.2-7.0, and fine grain being 100-400 nm can be prepared by using the method in this invention.
Description
Technical field
The invention relates to the preparation method of NaY molecular sieve.More particularly, be preparation method about the high silicon NaY of a kind of little crystal grain molecular sieve.
Background technology
As the core technology of petroleum refining industry, catalytic cracking and catalyzer thereof receive much attention.Along with the heaviness day by day of catalytically cracked material, mean sizes constantly increases at the proportion of macromole hydrocarbon in raw material more than the 2nm.As the Y zeolite of the main active component of catalytic cracking catalyst, its aperture has only 0.7nm, obviously has a large amount of raw molecules can not enter the duct reaction of Y zeolite.Although the macromole in the raw material can carry out presplittingization on catalyst substrates, diffusional effect still has remarkable influence to catalytic cracking reaction.Small crystal grain Y-shaped molecular sieve with flourishing outside surface can effectively solve this diffusion problem, and because its granularity is very little, can be distributed to equably in the matrix, also can contact with reactant more fully, thereby effectively improve catalytic efficiency, increase the light oil productive rate, reduce dry gas and coke yield.From improving the angle of heavy oil cracking, the crystal grain of Y zeolite the smaller the better (Ind.Eng.Chem.Res.1999,38,1350-1356).But along with reducing of zeolite crystal, its heat/hydrothermal stability will reduce, and catalyst activity will descend.As taking into account the stability of heavy oil cracking ability and molecular sieve, the Y zeolite about silica alumina ratio about 5.0, crystal grain 400nm is proper so.
From the synthetic angle, improve the heat/hydrothermal stability of Y zeolite and mainly can start with from two aspects: the one, the crystal grain of increase molecular sieve, the 2nd, the silica alumina ratio of raising molecular sieve.By above-mentioned discussion as can be known,, reduce coke and dry gas yied in order to increase the heavy oil cracking ability of catalyzer, should be when improving the molecular sieve silica alumina ratio as far as possible, appropriateness reduces the crystal grain of molecular sieve.
The method of present industrial production NaY molecular sieve all is the directing agent method that adopts U.S. Grace company to propose in US3639099 and US 3671191 basically.This method is to prepare to consist of (15～17) Na
2O: Al
2O
3: (14～16) SiO
2: (285～357) H
2O, nucleus particle diameter are generally less than 0.05 micron directed agents, this directed agents are mixed with water glass, sodium metaaluminate, Tai-Ace S 150 etc. to become to consist of (3～6) Na again
2O: Al
2O
3: (8～12) SiO
2: (120～200) H
2The reaction mixture of O, then with this mixture 100 ℃ of left and right sides crystallization.The method without the synthetic NaY molecular sieve of template of people's proposition after this is all similar with this method.Because be subjected to the restriction of electrochemical conditions in the building-up process, this method synthetic NaY framework of molecular sieve silica alumina ratio about 5.0, generally is lower than 5.2 usually, crystal grain is generally about 500～800nm.
In order to improve the silica alumina ratio of synthetic NaY molecular sieve, the investigator has carried out many trials:
US 4,931, and 267 to disclose a kind of be the method for the molecular sieve of template preparation ECR-32 by name with TPAOH and/or TBAH.This molecular sieve has the faujusite structure, its SiO
2/ Al
2O
3Can be greater than 6.
US 4,965, and 059 to disclose a kind of be the method for the faujasite molecular sieve of template preparation ECR-4 by name with the tetra-alkyl ammonium hydroxide.This molecular sieve SiO
2/ Al
2O
3Be at least 6.
US 5,447, and 709 disclose a kind of is template with the crown ether, prepares SiO
2/ Al
2O
3Be at least 6 faujasite molecular sieve method.
US 5,385, and 717 to disclose a kind of be the method that template prepares faujasite molecular sieve with the polyglycol ether.The SiO of this molecular sieve
2/ Al
2O
3Can surpass 6.
US 5,637, and 287 to disclose a kind of be that template prepares SiO with the TPAOH that reclaims from mother liquor
2/ Al
2O
3The method of faujasite molecular sieve greater than 6.
In above-mentioned patent documentation, use the method for template can synthesize silica alumina ratio more than 6, even can reach 12 faujasite-type molecular sieve.Its advantage is that product property is stable, has good hydrothermal stability, and higher surface acid intensity has reduced the consumption of Y zeolite in the FCC catalyzer.Yet its shortcoming is to use organic formwork agent, and the production cost height in the crystallization cycle long (7～15 days), can't satisfy industrial needs.Therefore under without template, lower-cost situation, directly synthesize SiO
2/ Al
2O
3Greater than 5.5, even 6 faujasite molecular sieve has very strong competitive power.
RU2090902 discloses the amorphous Si O that adopts than higher polymeric form
2Perhaps silicon sol is the silicon source, directly synthesizes silica alumina ratio and be the method for 5.2～7.5 high silicon faujusite.
US 4,587, and 115 disclose elder generation prepares alumino silica gel with Tai-Ace S 150 and water glass, is raw material with this alumino silica gel again, synthesize silica alumina ratio and be the method for 5.5～6.3 high-Si Y-type molecular sieve.
JP 8-245216 discloses and has a kind ofly formed by changing directed agents, and synthesizing Si-Al is than more than 5, even can reach the method for 6 Y zeolite.
GB 2131597 discloses a kind of by reducing the basicity of synthesized gel rubber, and the preparation silica alumina ratio is the method for 5.3～6 Y zeolite.But this method significant prolongation crystallization time.
US H282 discloses a kind of by remove partial mother liquid before crystallization, and crystallization then is with the method for the silica alumina ratio that improves the NaY molecular sieve.
The existing a large amount of reports of the synthetic technology of little crystal grain faujusite.Processing condition and step when changing preparation can make little crystal grain faujusite:
Improving reaction batching Na as GB1223592
2O/Al
2O
3And SiO
2/ Al
2O
3Situation under, 0 ℃ of low temperature becomes glue, and ageing 0.2～5 hour under this temperature, makes the X type zeolite of particle diameter 100nm then 80～100 ℃ of crystallization.
Sdhoema etc. [J.Chem.Soc, Chem.Commun.1993:994-995] adopt the method for high basicity, high silica alumina ratio, have directly synthesized the NaY molecular sieve of grain-size less than 150nm from liquid phase.
Disclosed among the EP0435625A and in preparation process, adopted physical means, can make the X of particle diameter 100nm and the y-type zeolite of low silica-alumina ratio greater than the high-speed stirring of 3000rpm as adopting rotating speed.
Cheng Zhilin etc. (Acta PhySico-Chimica Sinica, 2003,19 (6): 487～491) find under the atmospheric pressure reflux microwave heating condition, can synthesize crystal grain less than 100nm, the NaY molecular sieve of silica alumina ratio about 5.2, and can significantly shorten crystallization time.
CN1081425A disclose will not contain directed agents silica-alumina gel in the input orientation agent again in 1～10 hour of 80～180 ℃ of crystallization, it is complete up to crystallization to continue crystallization at 90～100 ℃ then.Can make the small crystal grain NaY molecular sieve of 0.1～0.5 μ m, silica alumina ratio is identical with the NaY molecular sieve that conventional method makes.
In the material system, add dispersion medium and also can prepare little crystal grain faujusite with some organism:
US 3,516, and 786 have proposed to add water-miscible organic solvent in a kind of reaction mixture, as methyl alcohol, dromisol etc., and the method for the X type zeolite of preparation particle diameter 100nm.
Reported among the EP0041338A that under 0 ℃ of gelatigenous prerequisite of low temperature add a certain amount of monose and disaccharide in the reaction mixture, having synthesized particle diameter is the X type zeolite of 30～60nm.
[Zeolites.1996 such as Linder, 16:196-206] studied a series of organic solvent as methyl ethyl diketone, Trisodium Citrate, Sodium Fluoride, sodium oxalate, trolamine and aminopolycanboxylic acid etc., discovery is except trolamine, and remaining solvent can both make the particle diameter of molecular sieve reduce.
[ACS 1989,398:98-10 for Zeolites synthesis, ACS Sym.Ser. for Dutta etc.; Zeolites, 1991,11:507-510] think, add alcohols, dimethyl sulfone and amine the crystal grain of molecular sieve is diminished.
(Industrial Catalysis such as Zhao Wenjiang, 2004,12 (4) 50～53) find when synthetic NaY molecular sieve a spot of Tween series of surfactants (Tween-20 of interpolation in synthetic system, Tween-40 Tween-60) can reduce the grain-size of molecular sieve significantly.
CN1354133A discloses a kind of at synthesizing Si-Al gel adding tensio-active agent, crystallization in the water-in-oil microemulsion liquid system, and synthetic crystal grain is less than the method for 400nm Y zeolite.
Disclosed among the CN1238305A in the synthetic system and to have added aluminum complexing agent as acetate, citric acid and ethylenediamine tetraacetic acid (EDTA), synthetic molecular sieve particle diameter is about 70nm.
Disclosed among the CN1238306A in synthesized gel rubber and to have added rare earth ion and can synthesize＜the NaY molecular sieve of 100nm.
Schoeman has reported in the presence of TMAOH, in the soliquid synthetic (Zeolites, 1994,14:110～116) of the y-type zeolite of particle diameter 150nm.
Also be usually used in preparing little crystal grain faujusite by composition and the preparation method who changes directed agents in addition:
All adopt transmittance to prepare the Y zeolite that granularity is about 200nm among CN1176848A and the CN1079444A greater than 75% transparent liquid phase directed agents.
Rolling has also been synthesized the Y zeolite (the 9th national catalysis academic meeting paper collection, 527～528) that granularity is about 90nm from win waiting by the method for adding rare earth element in directed agents.
CN1160676A, CN1296915A disclose in the directed agents for preparing, and add acidifying aluminium salt and be mixed with reaction gel, and then crystallization, the method for synthesizing small-grain NaY.
CN1285314A discloses in a kind of directed agents and has added organic dispersing agent, and then prepares the method for small crystal grain NaY molecular sieve.
CN1448338A discloses 0～10 ℃ of preparation directed agents and has become glue, thus the method for synthesizing small-grain NaX molecular sieve.
CN1354134A discloses a kind of 0～4 ℃ of preparation directed agents and become glue, thus the method for synthesizing small-grain NaX molecular sieve.
The method of above-mentioned synthesizing small-grain faujusite often can only be synthesized X type molecular sieve or SiO
2/ Al
2O
3＜5 Y zeolite than low silica-alumina ratio.
Summary of the invention
The purpose of this invention is to provide a kind of under the prerequisite that does not change original NaY molecular sieve synthesis technique basically, the method for the NaY molecular sieve of synthesizing high-silicon aluminum ratio, little crystal grain.
The preparation method of the NaY molecular sieve of high silica alumina ratio provided by the invention, little crystal grain comprises:
(1) prepares directed agents: according to the method for synthetic NaY molecular sieve guiding agent in the prior art, with water glass, sodium metaaluminate, alkali lye and deionized water, according to (11～18) Na
2O: Al
2O
3: (10～17) SiO
2: (200～380) H
2The mixed in molar ratio of O is even, and ℃ down aging a 0.5～48h makes crystallization director in room temperature to 70.
(2) preparation gel: according to (1.0～6.0) Na
2O: Al
2O
3: (5.5～16) SiO
2: (100～240) H
2O, preferred (1.4～3.6) Na
2O: Al
2O
3.: (6～10) SiO
2: (150～220) H
2Total molar ratio of O adds directed agents, acid aluminium salt and the sodium metaaluminate that step (1) makes successively and mixes and makes gel in water glass.The Al in the directed agents wherein
2O
3Account for always feed intake in total Al
2O
30.1～20% of weight, preferred 5～15%.
(3) crystallization with mend silicon: at 50～100 ℃, preferred 60～80 ℃ of following crystallization 0～70h behind preferred 0.5～40h, add a certain amount of silicon source, make the mol ratio that finally feeds intake be (1.1～6.5) Na with the gel that makes in the step (2)
2O: Al
2O
3: (5.8～20) SiO
2: (120～300) H
2O, preferred (1.8～3.5) Na
2O: Al
2O
3: (6.5～14) SiO
2: (160～230) H
2O.Be warming up to 90～120 ℃ then, preferred 95～110 ℃ are continued crystallization 0.5～50h again, after crystallization is finished again after filtration, washing, drying obtain NaY molecular sieve finished product.
Directed agents in the step in the method provided by the present invention (1) can prepare by the whole bag of tricks of preparation faujusite directed agents in the prior art, but preferably prepares according to the at present industrial generally conventional preparation method of the NaY directed agents of employing.For example according to US 3,639, the preparation method who is proposed in 099, US 3,671,191 and US4,166,099 prepares, and guaranteeing constant product quality, and can keep technology and equipment not to do bigger change.
The said bialuminate of step in the method provided by the present invention (2) is Tai-Ace S 150, aluminum chloride or aluminum nitrate, wherein is preferably Tai-Ace S 150.Aluminium in sodium metaaluminate and acid aluminium salt and the directed agents is jointly as the aluminium source of NaY molecular sieve compositions material; Silicon in water glass and the directed agents is jointly as the silicon source of NaY molecular sieve compositions material.The basicity that the sodium metaaluminate of bialuminate and alkalescence can be used to regulate total material, the two ratio requires to decide according to the basicity of total material, should make the mixture that always feeds intake meet (1.0～6.0) Na
2O: Al
2O
3: (5.5～16) SiO
2: (100～240) H
2O, preferred (1.4～3.6) Na
2O: Al
2O
3: (6～10) SiO2: (150～220) H
2Total molar ratio of O.Na in the above-mentioned expression formula
2O represents the basicity of mixture, and it does not comprise the part that is neutralized by acid.In addition, also can be by adding acid or alkali is regulated basicity, but preferably adjust basicity according to the two ratio of the sodium metaaluminate of bialuminate and alkalescence.
The said silicon source of adding in crystallization process of step in the method provided by the present invention (3) can be water glass, amorphous silica gel, silicon sol, also can be siliceous compound such as higher silica-alumina gel of silica alumina ratio or colloidal sol and composition thereof.Add SiO in the silicon source
2Amount with feed intake in total Al
2O
3The mol ratio of amount is 0.1～10, preferred 0.2～7.
In NaY molecular sieve synthetic, under the constant situation of the basicity that feeds intake, increase the silica alumina ratio that feeds intake and can increase the product silica alumina ratio, but crystallization is prolonged inductive phase greatly, cause the crystallization deadline to prolong greatly.This is that nucleus forms difficulty because of the silica alumina ratio height.In order to shorten crystallization time, need when feeding intake silica alumina ratio, increase increase the basicity that feeds intake, and cause the increase of product NaY molecular sieve silica alumina ratio very little so again, in addition constant.Because when feeding intake silica alumina ratio, crystallization is short inductive phase low, nucleus generates easily, the inventor finds earlier under the situation of the low silica alumina ratio that feeds intake, low temperature aging for some time can produce a large amount of nucleus in the crystallization system, and the crystal grain of the crystallization that heats up again product NaY can significantly diminish; But low temperature aging causes the product silica alumina ratio significantly to reduce simultaneously, and synthetic NaY molecular sieve silica alumina ratio generally between 3～5, is difficult to surpass 5.If behind the low temperature aging, add a certain amount of silicon source,, continue crystallization to crystallization and finish to increase the silica alumina ratio of crystallization system.So both can effectively reduce the crystal grain of NaY molecular sieve, can increase product NaY molecular sieve silica alumina ratio again.
The silica alumina ratio that method provided by the invention can synthesize is 5.2～7.0, and crystal grain is at the NaY of 100～400nm molecular sieve.
Embodiment
The following examples will the present invention is further illustrated, but not thereby limiting the invention.
Comparative Examples 1
The situation of common prior art for preparing NaY molecular sieve is adopted in the explanation of this Comparative Examples.
Get 100ml water glass (Chang Ling oil-refining chemical factory catalyst plant product, proportion 1.26, SiO
2Content 255.8g/L, modulus 3.24, down together) and put into beaker, add the high sodium aluminate solution of 70.7g (Chang Ling oil-refining chemical factory catalyst plant product, proportion 1.33, Al
2O
3Content 41g/L, Na
2O content 280g/L, down together), mix the back in aged at room temperature 24h, promptly get required directed agents, its mole proportioning is 16Na
2O: Al
2O
3: 15SiO
2: 320H
2O.
The NaY molecular sieve is according to 2.76Na
2O: Al
2O
3: 8.4SiO
2: 209H
2The proportioning of O is synthetic.Stir down, successively with 450ml deionized water, 200.4g directed agents, 300ml alum liquor (Chang Ling oil-refining chemical factory catalyst plant product, proportion 1.28, Al
2O
3Content 88.2g/L, down together) and 243ml low sodium aluminate solution (Chang Ling oil-refining chemical factory catalyst plant product, proportion 1.23, Al
2O
3Content 102g/L, Na
2O content 151.9g/L, down together) be added in the 949ml water glass, add the back and continue violent stirring 30min, behind 100 ℃ of static aging 35h, stop crystallization and promptly get the NaY molecular sieve then.
The gained sample records its SiO with x-ray diffraction method
2/ Al
2O
3Be 5.15, and the degree of crystallinity that it records is decided to be 100%.The crystal grain that scanning electron microscope records is 700～1000nm.
Embodiment 1
The present embodiment explanation the invention provides the enforcement of method.
According to the Comparative Examples 1 described directed agents that makes.
The NaY molecular sieve is according to 2.76Na
2O: Al
2O
3: 8.4SiO
2: 209H
2The proportioning of O is synthetic.Stir down, successively the low sodium aluminate solution of 450ml deionized water, 200.4g directed agents, 300ml alum liquor and 243ml is added in the 949ml water glass, add the back and continue violent stirring 30min, then behind 60 ℃ of static aging 23h, add 248ml water glass, making total charge ratio is 3.37Na
2O: Al
2O
3: 10.4SiO
2: 233H
2O continues crystallization 15h and promptly gets the high silicon NaY of the little crystal grain molecular sieve that the inventive method makes.
It is 97% that the gained sample records its relative crystallinity with x-ray diffraction method, SiO
2/ Al
2O
3Be 5.90.The crystal grain that scanning electron microscope records is 100～300nm.
Comparative Examples 2
The situation of common prior art for preparing NaY molecular sieve is adopted in the explanation of this Comparative Examples.
According to the NaY molecular sieve synthesized gel rubber of preparing among the embodiment 1, behind 60 ℃ of static crystallization 23h, be warming up to 100 ℃ and continue crystallization 18h, stop crystallization and promptly get the NaY molecular sieve.
It is 95% that the gained sample records its relative crystallinity with x-ray diffraction method, SiO
2/ Al
2O
3Be 4.92.The crystal grain that scanning electron microscope records is 100～400nm.
Comparative Examples 3
The situation of common prior art for preparing NaY molecular sieve is adopted in the explanation of this Comparative Examples.
The NaY molecular sieve is according to 3.37Na
2O: Al
2O
3: 10.4SiO
2: 233H
2The proportioning of O is synthetic.Stir down, successively 450ml deionized water, 200.4g directed agents (preparation in the Comparative Examples 1), 300ml alum liquor and the low sodium aluminate solution of 243ml are added in the 1197ml water glass, add the back and continue violent stirring 30min, behind 100 ℃ of static crystallization 47h, stop crystallization and promptly get the NaY molecular sieve then.
It is 98% that the gained sample records its relative crystallinity with x-ray diffraction method, SiO
2/ Al
2O
3Be 5.34.The crystal grain that scanning electron microscope records is 600～1000nm.
Embodiment 2
The present embodiment explanation the invention provides the enforcement of method.
According to the NaY molecular sieve synthesized gel rubber of preparing among the embodiment 1, behind 80 ℃ of static aging 20h, add 74ml water glass, be warming up to 100 ℃ of continuation crystallization 15h and promptly get the high silicon NaY of the little crystal grain molecular sieve that the inventive method makes.
It is 102% that the gained sample records its relative crystallinity with x-ray diffraction method, SiO
2/ Al
2O
3Be 5.72, the crystal grain that scanning electron microscope records is 100～200nm.
Embodiment 3
The present embodiment explanation the invention provides the enforcement of method.
According to the NaY molecular sieve synthesized gel rubber of preparing among the embodiment 1, behind 70 ℃ of static aging 6h, add 320ml water glass, be warming up to 100 ℃ of continuation crystallization 25h and promptly get the high silicon NaY of the little crystal grain molecular sieve that the inventive method makes.
It is 108% that the gained sample records its relative crystallinity with x-ray diffraction method, SiO
2/ Al
2O
3Be 6.10, the crystal grain that scanning electron microscope records is 300～600nm.
Embodiment 4
The present embodiment explanation the invention provides the enforcement of method.
According to the NaY molecular sieve synthesized gel rubber of preparing among the embodiment 1, behind 50 ℃ of static aging 21h, add silicon sol (Chang Ling catalyst plant product, the SiO of 30wt%
2Content is 30wt%) 130g, be warming up to 100 ℃ of continuation crystallization 25h and promptly get the high silicon NaY of the little crystal grain molecular sieve that the inventive method makes.
It is 103% that the gained sample records its relative crystallinity with x-ray diffraction method, SiO
2/ Al
2O
3Be 6.30.The crystal grain that scanning electron microscope records is 200～400nm.
Embodiment 5
The present embodiment explanation the invention provides the enforcement of method.
According to the NaY molecular sieve synthesized gel rubber of preparing among the embodiment 1, behind 65 ℃ of static aging 15h, add 52g silica gel (Qingdao Marine Chemical Co., Ltd.'s product, silochrom), be warming up to 110 ℃ of continuation crystallization 18h and promptly get the high silicon NaY of the little crystal grain molecular sieve that the inventive method makes.
It is 100% that the gained sample records its relative crystallinity with x-ray diffraction method, SiO
2/ Al
2O
3Be 6.20.The crystal grain that scanning electron microscope records is 200～400nm.
Claims (8)
1, the preparation method of the NaY molecular sieve of a kind of high silica alumina ratio, little crystal grain comprises:
(1) prepares directed agents: according to the method for synthetic NaY molecular sieve guiding agent in the prior art, with water glass, sodium metaaluminate, alkali lye and deionized water, according to (11～18) Na
2O: Al
2O
3: (10～17) SiO
2: (200～380) H
2The mixed in molar ratio of O is even, and ℃ down aging a 0.5～48h makes crystallization director in room temperature to 70;
(2) preparation gel: according to (1.0～6.0) Na
2O: Al
2O
3: (5.5～16) SiO
2: (100～240) H
2Total molar ratio of O adds directed agents, acid aluminium salt and the sodium metaaluminate that step (1) makes successively and mixes and makes gel in water glass, wherein the Al in the directed agents
2O
3Account for always feed intake in total Al
2O
3Weight O.1～20%;
(3) crystallization with mend silicon: the gel that makes in the step (2) behind 50～100 ℃ of following crystallization 0～70h, is added a certain amount of silicon source, makes the mol ratio that finally feeds intake be (1.1～6.5) Na
2O: Al
2O
3: (5.8～20) SiO
2: (120～300) H
2O is warming up to 90～120 ℃ then and continues crystallization 0.5～50h again, after crystallization is finished again after filtration, washing, drying.
2, according to the said method of claim 1, wherein total molar ratio of preparation gel is (1.4～3.6) Na in the step (2)
2O: Al
2O
3: (6～10) SiO
2: (150～220) H
2O, the wherein Al in the directed agents
2O
3Account for always feed intake in total Al
2O
35～15% of weight.
3, according to the said method of claim 1, wherein the said bialuminate of step (2) is selected from one of Tai-Ace S 150, aluminum chloride and aluminum nitrate.
4, according to the said method of claim 3, wherein the said bialuminate of step (2) is a Tai-Ace S 150.
5,, wherein add before the silicon source crystallization of gel in the step (3) and under 60～80 ℃, carry out 0.5～40h according to the said method of claim 1.
6, according to the said method of claim 1, wherein the silicon source of adding in the step (3) is selected from water glass, amorphous silica gel, silicon sol, perhaps higher silica-alumina gel or the colloidal sol of silica alumina ratio.
7,, wherein add in the step (3) and make behind the silicon source mol ratio that finally feeds intake be (1.8～3.5) Na according to the said method of claim 1
2O: Al
2O
3: (6.5～14) SiO
2: (160～230) H
2O.
8, according to the said method of claim 1, the crystallization of wherein adding in the step (3) behind the silicon source is carried out 0.5～50h under 95～110 ℃.
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| CN101767799B (en) * | 2008-12-31 | 2012-05-30 | 中国石油化工股份有限公司 | Method for synthesizing high-silicon small grain NaY molecular sieve |
| CN101723400B (en) * | 2008-10-29 | 2013-01-09 | 中国石油化工股份有限公司 | Small crystal grain Y-shaped molecular sieve and preparation method thereof |
| CN103449469A (en) * | 2012-06-01 | 2013-12-18 | 中国石油天然气股份有限公司 | Preparation method of NaY molecular sieve with enhanced stability |
| CN103449470A (en) * | 2012-06-01 | 2013-12-18 | 中国石油天然气股份有限公司 | Highly-stable small-grain NaY molecular sieve |
| CN103449468A (en) * | 2012-05-28 | 2013-12-18 | 中国石油天然气股份有限公司 | Synthesis method of NaY molecular sieve |
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