CN1267345C - Preparation method of NaY molecular sieve - Google Patents
Preparation method of NaY molecular sieve Download PDFInfo
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- CN1267345C CN1267345C CN 200310115508 CN200310115508A CN1267345C CN 1267345 C CN1267345 C CN 1267345C CN 200310115508 CN200310115508 CN 200310115508 CN 200310115508 A CN200310115508 A CN 200310115508A CN 1267345 C CN1267345 C CN 1267345C
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- silicon
- sio
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- molecular sieve
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 49
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims description 21
- 238000000034 method Methods 0.000 claims abstract description 48
- 238000002425 crystallisation Methods 0.000 claims abstract description 44
- 230000008025 crystallization Effects 0.000 claims abstract description 43
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 19
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 51
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 26
- 239000000377 silicon dioxide Substances 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052710 silicon Inorganic materials 0.000 claims description 20
- 239000010703 silicon Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 13
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 159000000013 aluminium salts Chemical class 0.000 claims description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 229960001866 silicon dioxide Drugs 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 10
- 108010010803 Gelatin Proteins 0.000 abstract 4
- 229920000159 gelatin Polymers 0.000 abstract 4
- 239000008273 gelatin Substances 0.000 abstract 4
- 235000019322 gelatine Nutrition 0.000 abstract 4
- 235000011852 gelatine desserts Nutrition 0.000 abstract 4
- 230000002378 acidificating effect Effects 0.000 abstract 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- 150000004645 aluminates Chemical class 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 12
- 229910021536 Zeolite Inorganic materials 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 11
- 239000010457 zeolite Substances 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000007670 refining Methods 0.000 description 8
- 230000003068 static effect Effects 0.000 description 8
- 239000012013 faujasite Substances 0.000 description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229940037003 alum Drugs 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910002796 Si–Al Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 101000777220 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 3 Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 102100031287 Ubiquitin carboxyl-terminal hydrolase 3 Human genes 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Abstract
The present invention discloses a method for preparing NaY molecular sieves. The method comprises the steps: (1) a guiding agent is synthesized; (2) the guiding agent is uniformly mixed with water glass, acidic aluminum salt and aluminate, and gelatin is obtained; (3) the gelatin is crystallized; and (4) conventional procedures of filtration, washing and drying are carried out. The method is characterized in that silicon-contained substance is added after the gelatin prepared in step (2) is crystallized for 0.1 to 70 hours within the temperature of 80 to 120 DEG C through step (3), so that the molar ratio of the added silicon-contained substance (SiO2) to Al2O3 in the gelatin is from 0.1 to 10, and crystallization is continuously carried out for 1 to 50 hours. The method can shorten the time of crystallization, and can increase the silica-alumina ratio of NaY molecular sieves.
Description
Technical field
The present invention relates to the preparation method of NaY molecular sieve.
Background technology
Y zeolite with faujusite crystalline structure is the main raw material of preparation catalytic cracking catalyst.The method of present industrial production NaY molecular sieve all is to adopt U.S. Grace company at USP3 basically, 639,099 and USP 3,671,191 in the directing agent method that proposes.This method is to prepare to consist of (15～17) Na
2O: Al
2O
3: (14～16) SiO
2: (285～357) H
2O, the nucleus particle diameter is generally less than 0.05 micron directed agents, this directed agents is mixed with water glass, sodium aluminate, 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 aforesaid 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.
Because directly synthetic NaY framework of molecular sieve silica alumina ratio is lower, less stable.In the production process of FCC catalyzer, the NaY molecular sieve need pass through processes such as exchange, roasting and be converted into HY, causes the loss of partial crystallization degree.In the use of FCC catalyzer, the thermal and hydric environment in the revivifier can make the framework dealumination of Y zeolite, causes the catalyst activity poor stability.Like this, have good catalytic effect in order to make the FCC catalyzer, just needing increases the content of Y zeolite in catalyzer, and the result has improved the catalyzer cost.And the framework of molecular sieve silica alumina ratio links to each other closely with its hydrothermal stability, therefore, improve the silica alumina ratio of Y zeolite, for the quality product that improves the FCC catalyzer, reduce the consumption of Y zeolite in the FCC catalyzer, improve activity of such catalysts stability, significant.
The Y zeolite of high silica alumina ratio can obtain by back dealuminzation or dealumination complement silicon, and advantage is easy industrialization, and shortcoming is a complex process, and Y zeolite degree of crystallinity descends, and generates non-framework aluminum etc.
About adopting the method for template synthetic faujasites, the report of following document is arranged.
USP 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, and this molecular sieve has faujusite structure, SiO
2/ Al
2O
3Can be greater than 6.USP 4,965, and 059 discloses a kind of preparation method of the faujasite molecular sieve with tetra-alkyl ammonium hydroxide ECR-4 by name, this molecular sieve SiO
2/ Al
2O
3Be at least 6.USP 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.USP5,385,717 disclose a kind of is template with the polyglycol ether, prepares the faujasite molecular sieve method, the SiO of this molecular sieve
2/ Al
2O
3Can surpass 6.USP 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.
Use template synthetic faujasite-type molecular sieve, silica alumina ratio can be more than 6, can reach 12, its advantage is that product property is stable, has good hydrothermal stability, higher surface acid intensity, reduced the consumption of Y zeolite in the FCC catalyzer, shortcoming is the use of organic formwork agent, the production cost height, in the crystallization cycle long (7～15 days), can't satisfy industrial needs.
And exploitation is directly synthesized SiO without template
2/ Al
2O
3The method of the faujasite molecular sieve greater than 5.5 even 6, cost is lower, has very strong competitive power.
RU 2090902 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.USP 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, and synthesizing Si-Al is than the method that is 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.
Summary of the invention
The purpose of this invention is to provide a kind of the change basically under the prerequisite of conventional synthesis technique, improve the new preparation process of NaY zeolite product silica alumina ratio.
In the preparation method of NaY molecular sieve, 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 the silica alumina ratio height, nucleus forms difficulty, and crystallization is prolonged inductive phase greatly, causes the crystallization deadline to prolong greatly.In order to shorten crystallization time, need when feeding intake silica alumina ratio, increase increase the basicity that feeds intake, and can cause the increase of product NaY molecular sieve silica alumina ratio very little so again, in addition constant.
The inventor finds, earlier under the situation of the low silica alumina ratio that feeds intake, crystallization for some time, formed a large amount of nucleus in the crystallization system this moment, add a certain amount of silicon source then,, continue crystallization again to increase the silica alumina ratio of crystallization system, both crystallization time can be shortened, product NaY molecular sieve silica alumina ratio can be increased again.
Therefore, method provided by the invention comprises the steps:
(1) synthetic directed agents;
(2) directed agents and water glass, bialuminate and sodium aluminate mix and obtain gel;
(3) gel crystallization; With
(4) Chang Gui filtration, washing, drying step is characterized in that this method steps (3) is that the gel of preparation in the step (2) after 0.1～70 hour, is added silicon-containing material 80～120 ℃ of following crystallization, makes the silicon-containing material of adding with SiO
2Al in meter and the gel
2O
3Mol ratio be 0.1～10, continued crystallization 1～50 hour.
In the method provided by the invention, the directed agents of step (1) can prepare by the whole bag of tricks of preparation NaY molecular sieve guiding agent in the prior art, but preferably prepares according to the at present industrial generally ordinary method of the NaY directed agents of employing.For example, according to US3639099, the method disclosed in US3671191 and the US4166099 with the assurance constant product quality, and can keep technology and equipment not to do bigger change.Usually directed agents is with water glass, sodium aluminate, 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 after stirring, made in room temperature to 70 ℃ in aging 0.5～48 hour.
In the method provided by the invention, said bialuminate is one or more the mixture in Tai-Ace S 150, aluminum chloride or the aluminum nitrate in the step (2), wherein is preferably Tai-Ace S 150; The preferred sodium metaaluminate of said sodium aluminate.Aluminium in sodium aluminate and acid aluminium salt and the directed agents is together as the aluminium source of NaY molecular sieve compositions material; Silicon in water glass and the directed agents is together as the silicon source of NaY molecular sieve compositions material.The basicity that the sodium aluminate of bialuminate and alkalescence can be used to regulate total material, the two ratio requires to decide according to the basicity of total material.
In the method provided by the invention, step (2) is preferably according to (1.0～6.0) Na
2O: Al
2O
3: (5.5～16) SiO
2: (100～240) H
2O, more preferably (1.4～3.6) Na
2O: Al
2O
3: (6～10) SiO
2: (150～220) H
2The molar ratio of O mixes directed agents, water glass, acid aluminium salt and sodium aluminate and stir obtaining gel, wherein the Al in the directed agents
2O
3Account for Al
2O
30.1～10 heavy % of total amount, preferred 1～8 heavy %.
In the method provided by the invention, the gel of preparation in the step (2) 80～120 ℃ of following crystallization, and crystallization 0.1～70 hour, after preferred 0.5～40 hour, is added silicon-containing material,
Make SiO in the silicon-containing material of adding
2Amount and Al
2O
3The mol ratio of total amount is 0.1～10, preferred 0.2～7, more preferably 0.6～4, and make 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, preferred (1.8～3.5) Na
2O: Al
2O
3: (6.5～14) SiO
2: (160～230) H
2O continued crystallization 1～50 hour then, more after filtration, conventional steps such as washing, drying obtains NaY molecular sieve finished product.
Said silicon-containing material is selected from water glass, soft silica, silicon sol, also can be selected from the higher sial of silica alumina ratio to coagulate/siliceous compound such as colloidal sol and composition thereof.
Preparation method provided by the invention, under identical proportioning raw materials, crystallization time shortens, silica alumina ratio is higher.For example, in embodiment 1 and the Comparative Examples 2, the feed molar proportioning is all 2.93Na
2O: Al
2O
3: 9SiO
2: 217H
2Under the situation of O, embodiment 1 adopts method provided by the invention, and total crystallization time is 23h and 15h sum, and the molecular sieve silica alumina ratio is 5.82, and the crystallization time of Comparative Examples 2 is 47h, and the molecular sieve silica alumina ratio is 5.33.
Embodiment
The following examples will the invention will be further described, but content not thereby limiting the invention.
Embodiment 1
Get 100ml water glass (Chang Ling oil-refining chemical factory catalyst plant product, proportion 1.26, SiO
2Content 255.8g/L, modulus 3.24) put into a 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), after mixing, 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 189ml deionized water, 86.6g directed agents, 130ml alum liquor (Chang Ling oil-refining chemical factory catalyst plant product, proportion 1.28, Al
2O
3Content 88.2g/L) and 100ml 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) be added in the 401ml water glass (specification is the same), add the back and continue violent stirring 30min, behind 100 ℃ of static crystallization 23h, add 32ml water glass (specification is the same) then, making total charge ratio is 2.93Na
2O: Al
2O
3: 9SiO
2: 217H
2O continues crystallization 15h, and it is 91% that product records the NaY molecular sieve crystallinity with x-ray diffraction method, SiO
2/ Al
2O
3Be 5.82.
Comparative Examples 1
The NaY molecular sieve synthesized gel rubber of preparation behind 100 ℃ of static crystallization 35h, stops crystallization in the example 1, and it is 91% that product records the NaY molecular sieve crystallinity with x-ray diffraction method, SiO
2/ Al
2O
3Be 5.15.
Comparative Examples 2
The NaY molecular sieve is according to 2.93Na
2O: Al
2O
3: 9SiO
2: 217H
2The proportioning of O is synthetic.Stir down, successively with 189ml deionized water, 86.6g directed agents (preparation among the embodiment 1), 130ml alum liquor (Chang Ling oil-refining chemical factory catalyst plant product, proportion 1.28, Al
2O
3Content 88.2g/L) and 100ml 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) be added in the 433ml water glass (specification is the same), add the back and continue violent stirring 30min, behind 100 ℃ of static crystallization 47h, stop crystallization then, it is 91% that product records the NaY molecular sieve crystallinity with x-ray diffraction method, SiO
2/ Al
2O
3Be 5.33.
Embodiment 2
The NaY molecular sieve synthesized gel rubber of preparation among the embodiment 1 behind 100 ℃ of static crystallization 10h, adds 78ml water glass (specification is the same) and continues crystallization 17h, and it is 97% that product records the NaY molecular sieve crystallinity with x-ray diffraction method, SiO
2/ Al
2O
3Be 5.92.
Embodiment 3
The NaY molecular sieve synthesized gel rubber of preparation among the embodiment 1 behind 100 ℃ of static crystallization 1h, adds 100ml water glass (specification is the same) and continues crystallization 17h, and it is 97% that product records the NaY molecular sieve crystallinity with x-ray diffraction method, SiO
2/ Al
2O
3Be 6.34.
Embodiment 4
The NaY molecular sieve synthesized gel rubber of preparation among the embodiment 1, behind 100 ℃ of static crystallization 15h, the silicon sol 45g that adds 30wt% continues crystallization 15h, and it is 97% that product records the NaY molecular sieve crystallinity with x-ray diffraction method, SiO
2/ Al
2O
3Be 6.17.
Embodiment 5
The NaY molecular sieve synthesized gel rubber of preparation among the embodiment 1 behind 90 ℃ of static crystallization 20h, behind the adding 14g silica gel, is warming up to 110 ℃ and continues crystallization 18h, and it is 94% that product records the NaY molecular sieve crystallinity with x-ray diffraction method, SiO
2/ Al
2O
3Be 6.20.
Embodiment 6
The NaY molecular sieve is according to 2.53Na
2O: Al
2O
3: 7SiO
2: 209H
2The proportioning of O is synthetic.Stir down, successively with the directed agents among 230ml deionized water, the 78.5g embodiment 1,107ml alum liquor (Chang Ling oil-refining chemical factory catalyst plant product, proportion 1.28, Al
2O
3Content 88.2g/L) and 100ml 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) be added in the 297.1ml water glass (specification is the same), add the back and continue violent stirring 30min, behind 100 ℃ of static crystallization 16h, add 190ml water glass then, making total charge ratio is 3.77Na
2O: Al
2O
3: 11SiO
2: 258H
2O continues crystallization 15h, and it is 98% that product records the NaY molecular sieve crystallinity with x-ray diffraction method, SiO
2/ Al
2O
3Be 6.12.
Claims (4)
1, a kind of preparation method of NaY molecular sieve, its step comprises:
(1) with water glass, sodium aluminate, alkali lye and deionized water, according to Na
2O: Al
2O
3: SiO
2: H
2The mole proportioning of O=11～18: 1: 10～17: 200～380 is mixed, after stirring, in room temperature to 70 ℃ aging 0.5～48 hour synthetic directed agents that obtains;
(2) directed agents and water glass, acid aluminium salt and sodium aluminate mix and obtain gel, and material mole proportioning is Na in the said gel
2O: Al
2O
3: SiO
2: H
2O=1.0～6.0: 1: 5.5～16: 100～240, wherein, the Al of directed agents
2O
3Account for Al
2O
30.1～10 heavy % of total amount;
(3) gel crystallization; With
(4) Chang Gui filtration, washing, drying;
It is characterized in that this method steps (3) be will step (2) in the gel of preparation 80～120 ℃ of following crystallization after 0.1～70 hour, add silicon-containing material, said silicon-containing material is selected from one of water glass, indefiniteness silicon-dioxide, silicon sol, silica-alumina gel, silicon-aluminum sol or their mixture, makes the silicon-containing material of adding with SiO
2Al in meter and the gel
2O
3Mol ratio be 0.1～10, and to make the mol ratio that finally feeds intake be Na
2O: Al
2O
3: SiO
2: H
2Crystallization was continued 1～50 hour in O=1.1～6.5: 1: 5.8～20: 120～300.
2, according to the method for claim 1, material mole proportioning is Na in the said gel
2O: Al
2O
3: SiO
2: H
2O=1.4～3.6: 1: 6～10: 150～220, wherein, the Al of directed agents
2O
3Account for Al
2O
31～8 heavy % of total amount.
3,, it is characterized in that silicon-containing material that step (3) added is with SiO according to the method for claim 1
2Al in meter and the gel
2O
3Mol ratio be 0.2～7.
4, according to the method for claim 3, said silicon-containing material is with SiO
2Al in meter and the gel
2O
3Mol ratio be 0.6～4.
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|---|---|---|---|
| CN 200310115508 CN1267345C (en) | 2003-11-28 | 2003-11-28 | Preparation method of NaY molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310115508 CN1267345C (en) | 2003-11-28 | 2003-11-28 | Preparation method of NaY molecular sieve |
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| CN101722023B (en) * | 2008-10-28 | 2012-05-30 | 中国石油化工股份有限公司 | NaY-type molecular sieves and preparation method thereof |
| CN104118884B (en) * | 2013-04-23 | 2016-05-11 | 中国石油大学(北京) | A kind of preparation method of NaY molecular sieve |
| CN104118885B (en) * | 2013-04-23 | 2016-05-11 | 中国石油天然气股份有限公司 | A kind of synthetic method of high silica alumina ratio NaY zeolite |
| CN104229822A (en) * | 2013-06-13 | 2014-12-24 | 天津神能科技有限公司 | Preparation method for small-crystal-grain Y molecular sieve with high specific surface area and high silicon-aluminium ratio |
| CN106268919B (en) * | 2015-06-29 | 2018-11-13 | 中国石油化工股份有限公司 | A kind of Modified Zeolite Y catalyst containing rare earth and phosphorus |
| CN111825105B (en) * | 2019-04-18 | 2022-08-19 | 中国科学院大连化学物理研究所 | Preparation of Y molecular sieve with FAU structure by guide agent method |
| CN114534774A (en) * | 2020-11-25 | 2022-05-27 | 中国石油化工股份有限公司 | Composite material, catalytic cracking catalyst and preparation method thereof |
| CN114471693A (en) * | 2020-11-13 | 2022-05-13 | 中国石油化工股份有限公司 | Heavy metal pollution resistant catalyst and preparation method thereof |
| CN113830775A (en) * | 2020-06-23 | 2021-12-24 | 中国石油化工股份有限公司 | Silicon-aluminum material, preparation thereof and low-coke-formation high-activity heavy oil conversion catalytic cracking catalyst |
| CN113828350A (en) * | 2020-06-23 | 2021-12-24 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| JP2023531740A (en) * | 2020-06-23 | 2023-07-25 | 中国石油化工股▲ふん▼有限公司 | Catalytic cracking catalyst and its preparation method |
| CN114426307B (en) * | 2020-10-09 | 2024-04-02 | 中国石油化工股份有限公司 | Zirconium sol, preparation method thereof and heavy oil catalytic cracking catalyst |
| TW202235371A (en) * | 2021-01-07 | 2022-09-16 | 大陸商中國石油化工科技開發有限公司 | Y-type molecular sieve and synthesis method therefor |
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