CN1323031C - Process for preparing NaY molecular sieve - Google Patents
Process for preparing NaY molecular sieve Download PDFInfo
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- CN1323031C CN1323031C CNB2004100311863A CN200410031186A CN1323031C CN 1323031 C CN1323031 C CN 1323031C CN B2004100311863 A CNB2004100311863 A CN B2004100311863A CN 200410031186 A CN200410031186 A CN 200410031186A CN 1323031 C CN1323031 C CN 1323031C
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- Prior art keywords
- gel
- molecular sieve
- guiding
- nay molecular
- directed agents
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 55
- 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 53
- 238000004519 manufacturing process Methods 0.000 title 1
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- 239000011734 sodium Substances 0.000 claims abstract description 38
- 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
- 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 claims abstract description 15
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 22
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 159000000013 aluminium salts Chemical class 0.000 claims description 7
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- 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 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 34
- 239000013078 crystal Substances 0.000 abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 229910052681 coesite Inorganic materials 0.000 abstract description 3
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 229910052682 stishovite Inorganic materials 0.000 abstract description 3
- 229910052905 tridymite Inorganic materials 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 239000000499 gel Substances 0.000 abstract 5
- 230000002378 acidificating effect Effects 0.000 abstract 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- 238000007796 conventional method Methods 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 229910021536 Zeolite Inorganic materials 0.000 description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 13
- 239000010457 zeolite Substances 0.000 description 13
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 8
- 229910001388 sodium aluminate Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000003068 static effect Effects 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000013019 agitation Methods 0.000 description 7
- 229940037003 alum Drugs 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- -1 FCC olefin Chemical class 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
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Images
Abstract
The present invention relates to guiding gel capable of maintaining activity for a long time, and a method using the guiding gel to synthesize NaY molecular sieves with large crystal grains. Firstly, guiding agents are synthesized with conventional methods; then, the conventional guiding agents, acidic aluminum salt and sodium metaaluminate are added into water glass in sequence according to the total batch chargingmolar ratio of (1.0-6.0)Na2O to Al2O3 to (5.5-16)SiO2 to (100-240)H2O; and long-acting guiding gels are obtained when the mixture is crystallized within the temperature range from 80 to 120 DEG C. The guiding gel is crystallized within the temperature range of 80 to 120 DEG C after uniformly mixed with the water glass, the acidic aluminum salt and the sodium metaaluminate; and NaY molecular sieves with crystal grains larger than 1000 nm are obtained after steps of filtration, washing, drying and the like are carried out. The activity of the long-acting guiding gel is not reduced, after being preserved for 30 days at normal temperature.
Description
Technical field
The invention relates to a kind of preparation method of NaY molecular sieve.More particularly, be the preparation method that can keep active for a long time, be used for NaY molecular sieve synthetic guiding gel, and can synthesize the NaY molecular sieve of crystal grain greater than 1000nm with this gel that leads about a kind of.
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 the directing agent method that adopts U.S. Grace company to be proposed in US3639099 and US3671191 basically.This method at first 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 being consisted of (3～6) Na again with raw materials such as water glass, sodium metaaluminate, Tai-Ace S 150
2O:Al
2O
3: (8～12) SiO
2: (120～200) H
2The reacting material 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, the NaY zeolite crystal that this method synthesizes is generally about 300～800nm.
Before being used to make the FCC catalyzer, the NaY molecular sieve need pass through treating processess such as exchange, roasting.Grain size is the NaY molecular sieve of 300～800nm, because crystal grain is little, silica alumina ratio is low, less stable, thereby can cause the loss of partial crystallization degree in treating processes.In addition, in the use of FCC catalyzer, the thermal and hydric environment in the revivifier can also make the framework dealumination of Y zeolite, causes the decline of catalyst activity stability.For above-mentioned reasons, have good catalytic effect in order to make the FCC catalyzer, just needing increases the content of Y zeolite in catalyzer, has consequently improved the catalyzer cost.Therefore, the higher relatively big grain Y-molecular sieve of hydrothermal stability just become market requirement institute to.
On the other hand, FCC gasoline surpasses 80% in China's gasoline pool at present, and the FCC content of olefin in gasoline is up to 40-50 volume %.For satisfying the requirement of new gasoline standard, press for and reduce olefin(e) centent in the gasoline.In the FCC catalyzer, Y zeolite is along with the change of crystal grain is big, its inner ratio surface area will increase, external surface area will descend, the crystals duct also can be correspondingly elongated, and this can make reactant molecule prolong, increase intracrystalline reaction and hydrogen transfer reactions in the residence time of molecular sieve intracrystalline.Therefore, use the FCC catalyzer of big grain Y-molecular sieve can reduce the FCC olefin content in gasoline.
In a word, increase the crystal grain of Y zeolite, for reduce the consumption of Y zeolite in the FCC catalyzer, improve activity of such catalysts stability, reduce FCC gasoline olefin(e) centent, to improve the FCC quality of gasoline all significant.
US6 discloses the synthetic method that a kind of grain size is the NaY molecular sieve of 1500～2000nm in 284,218.Wherein employed directed agents has following molecular ratio: Na
2O/SiO
2=0.5-2.0, SiO
2/ Al
2O
3=10-20, H
2O/Na
2O=10-40; The material composition of synthesis of molecular sieve has following molecular ratio: Na
2O/SiO
2=0.4-0.9, SiO
2/ Al
2O
3=7-13, H
2O/Na
2O=30-45; Synthetic the carrying out under 90-110 ℃ of this molecular sieve finished in 23-29 hour.
On the other hand, the directed agents of the above-mentioned United States Patent (USP) prescription of present industrial employing is because its basicity is very high, thereby its decay of activity is very fast, generally only can keep about 10～20 hours at normal temperatures.In order to prolong its work-ing life, need under lower temperature, preserve usually or in the directed agents gel, add water, with the concentration of dilution alkali (" (refining of petroleum ", 1978 11-12 phase 22～25 pages).
A kind of preparation method of high-temperature and long-efficiency directed agents is disclosed among the CN85102733.This directed agents has following mol ratio prescription: (13-16) Na
2O:Al
2O
3: (16.1～21) SiO
2: (250～800) H
2O, its preparation temperature are 0-45 ℃, preferred 10-40 ℃; Aging temperature is 20-60 ℃, preferred 30-40 ℃.The directed agents activity that this method makes can keep more than 40 hours at 40 ℃.Up to now, can keep active directed agents not appear in the newspapers as yet for more time.
Summary of the invention
The objective of the invention is on the basis of above-mentioned prior art, to provide a kind of preparation method that can keep active guiding gel for a long time, and synthesize the NaY molecular sieve of crystal grain greater than 1000nm with this gel that leads.
The synthetic method of long-acting guiding gel provided by the invention and big crystal NaY molecular sieve comprises the following steps:
(1) conventional directed agents is synthetic: 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 after stirring, at room temperature to 70 ℃ down aging 0.5～24h, promptly obtains directed agents.
(2) preparation of guiding 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 sodium metaaluminate that step (1) makes successively in water glass, the back that stirs promptly obtains the gel that leads at 80～120 ℃ of following crystallization 2～55h.Wherein the add-on of directed agents should make the Al in the directed agents
2O
3Account for the middle Al that always feeds intake
2O
30.1～10wt% of total amount, preferred 1～8wt%.
(3) the NaY molecular sieve is synthetic: 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 guiding gel, acid aluminium salt and sodium metaaluminate that step (2) makes successively in water glass, the back that stirs is at 80～120 ℃ of following crystallization 20～50h, more after filtration, washing, drying and other steps promptly obtain the NaY molecular sieve.The add-on of gel of wherein leading should make the Al in the guiding gel
2O
3Account for the middle Al that always feeds intake
2O
30.1～90wt% of total amount, preferred 1～80wt%.
Conventional directed agents in the step in the inventive method (1) can prepare by the various ordinary methods 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 US3,639,099, US3, disclosed preparation method prepares in 671,191 and US4,166,099, guaranteeing constant product quality, and can keep technology and equipment not to do bigger change.
Said bialuminate is optional from Tai-Ace S 150, aluminum chloride or aluminum nitrate in the step in the inventive method (2), wherein preferably sulfuric acid aluminium.Aluminium in sodium metaaluminate and acid aluminium salt and the directed agents is together as the aluminium source of synthesizing the guiding gel; Silicon in water glass and the directed agents is together as the silicon source of synthesizing the guiding gel.The sodium metaaluminate basicity that can be used to regulate total material of bialuminate and alkalescence, the two ratio requires to decide according to the basicity of total material, should make that the mol ratio of each component meets (1.0～6.0) Na in always feeding intake
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
2O.Na in the above-mentioned chemical formula
2O represents the basicity of each component mixture, and it does not comprise the part that is neutralized by acid.Certainly, also can be by adding acid or alkali is regulated basicity, but preferably adjust basicity in the methods of the invention according to the two ratio of the sodium metaaluminate of bialuminate and alkalescence.
Said bialuminate is selected from Tai-Ace S 150, aluminum chloride or aluminum nitrate in the step in the inventive method (3), wherein preferably sulfuric acid aluminium.Aluminium in sodium metaaluminate and acid aluminium salt and the guiding gel is together as the aluminium source of synthesizing the NaY molecular sieve; Silicon in water glass and the guiding gel is together as the silicon source of synthesizing the NaY molecular sieve.The sodium metaaluminate basicity that can be used to regulate total material of bialuminate and alkalescence, the two ratio requires to decide according to the basicity of total material, should make that the mol ratio of each component meets (1.0～6.0) Na in always feeding intake
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
2O.Na in the above-mentioned chemical formula
2The O representative is equipped with the basicity of component mixture, and it does not comprise the part that is neutralized by acid.Certainly, also can be by adding acid or alkali is regulated basicity, but preferably adjust basicity in the methods of the invention according to the two ratio of the sodium metaaluminate of bialuminate and alkalescence.
The guiding gel of preparing with the inventive method can preserve at normal temperatures 30 days and the activity that leads does not subtract, and can synthesize the NaY molecular sieve of crystal grain greater than 1000nm with this guiding gel.
Description of drawings
Fig. 1 is the stereoscan photograph of the NaY molecular sieve prepared of embodiment 1, magnification 2000;
Fig. 2 is the stereoscan photograph of the NaY molecular sieve prepared of embodiment 2, magnification 2000;
Fig. 3 is the stereoscan photograph of the NaY molecular sieve prepared of embodiment 4, magnification 10000.
Embodiment
The following examples will be made further instruction to method provided by the invention, but not thereby limiting the invention.
Embodiment 1
The explanation of this example prepares long-acting guiding gel and big crystal NaY molecular sieve with the method for the invention provides.
(1) preparation of directed agents: 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 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,, promptly get directed agents in aged at room temperature 24 hours.Its mole consists of 16Na
2O:Al
2O
3: 15SiO
2: 320H
2O.
(2) preparation of guiding gel: the under agitation directed agents that successively 189ml deionized water, 86.6g above-mentioned steps is made, 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) is added in the 401ml water glass (specification is the same), adds the back and continued violent stirring 30 minutes, in 80 ℃ of static wearing out 55 hours, promptly get the gel that leads then.Its mole consists of 2.76Na
2O:Al
2O
3: 8.4SiO
2: 209H
2O.
(3) the NaY molecular sieve is synthetic: under agitation the low sodium aluminate solution (specification is the same) of the guiding gel that successively 160ml deionized water, 20g above-mentioned steps is made, 82ml alum liquor (specification is the same) and 100ml is added in the 336ml water glass (specification is the same), add the back and continued violent stirring 30 minutes, this moment, the mole of this reactant consisted of 2.76Na
2O:Al
2O
3: 8.4SiO
2: 209H
2O in 100 ℃ of static crystallization 38 hours, promptly gets the NaY molecular sieve then.
The degree of crystallinity that records this NaY molecular sieve with x-ray diffraction method is 95%; Recording this zeolite crystal size with scanning electron microscope is 2000～5000nm, as shown in Figure 1.
Embodiment 2
The explanation of this example still can synthesize the NaY molecular sieve of big crystal grain after placing 10 days with the long-acting guiding gel that the invention provides the method preparation.
(1) and (2) prepares directed agents and guiding gel successively according to the embodiment the steps described in Example 1, and the gel that will lead was at room temperature placed 10 days.
According to the synthetic NaY molecular sieve of example 1 described method, but in the reaction mixture of step (3), add the guiding gel that 200g at room temperature placed 10 days again, after stirring,, promptly get the NaY molecular sieve in 100 ℃ of static crystallization 32 hours.
The degree of crystallinity that records this NaY molecular sieve with x-ray diffraction method is 97%; Recording this zeolite crystal size with scanning electron microscope is 1000～3000nm, as shown in Figure 2.
Embodiment 3
The explanation of this example still can synthesize the NaY molecular sieve of big crystal grain after high temperature is placed 15 days with the long-acting guiding gel that the invention provides the method preparation.
(1) prepares directed agents according to the embodiment the steps described in Example 1.
The preparation of guiding gel: under agitation the low sodium aluminate solution (specification is the same) of the directed agents that successively 189ml deionized water, 86.6g above-mentioned steps is made, 130ml alum liquor (specification is the same) and 100ml is added in the 401ml water glass (specification is the same), add the back and continued violent stirring 30 minutes, in 100 ℃ of static wearing out 5 hours, promptly get the gel that leads then.Its mole consists of 2.76Na
2O:Al
2O
3: 8.4SiO
2: 209H
2O.The gel that should lead was placed 15 days down at 60 ℃.
Under agitation successively 160ml deionized water, 500g are added in the 336ml water glass in 60 ℃ of low sodium aluminate solutions (specification is the same) of guiding gel, 82ml alum liquor (specification is the same) and 100ml of placing 15 days, add the back and continued violent stirring 30 minutes, this moment, the mole of this reactant consisted of 2.76Na
2O:Al
2O
3: 8.4SiO2:209H
2O in 100 ℃ of static crystallization 42 hours, promptly gets the NaY molecular sieve then.
Recording this NaY molecular sieve crystallinity with x-ray diffraction method is 89%, and recording this zeolite crystal size with scanning electron microscope is 1000～3000nm.
Embodiment 4
The explanation of this example still can synthesize the NaY molecular sieve of big crystal grain after placing 25 days with the long-acting guiding gel that the invention provides the method preparation.
(1) and (2) prepares directed agents and guiding gel successively according to the embodiment the steps described in Example 1, and the gel that will lead was at room temperature placed 25 days.
The low sodium aluminate solution of under agitation successively 100ml deionized water, 1000g at room temperature being placed 25 days (specification is the same) of guiding gel, 90ml alum liquor (specification is the same) and 100ml is added in the 336ml water glass (specification is the same), add the back and continued violent stirring 30 minutes, this moment, the mole of this reactant consisted of 3.10Na
2O:Al
2O
3: 10SiO
2: 210H
2O in 103 ℃ of static crystallization 28 hours, promptly gets the NaY molecular sieve then.
Recording this NaY molecular sieve crystallinity with x-ray diffraction method is 98%, and recording this zeolite crystal size with scanning electron microscope is 800～1200nm, as shown in Figure 3.
Embodiment 5
The explanation of this example prepares big crystal NaY molecular sieve with the method for the invention provides.
(1) prepares directed agents according to the embodiment the steps described in Example 1.
(2) prepare the guiding gel according to the embodiment the steps described in Example 3.
Under agitation successively 160ml deionized water, 4000g guiding gel and 500g are added in the 336ml water glass in 60 ℃ of low sodium aluminate solutions (specification is the same) of guiding gel, 82ml alum liquor (specification is the same) and 100ml of placing 15 days, add the back and continued violent stirring 30 minutes, in 95 ℃ of static crystallization 30 hours, promptly get the NaY molecular sieve then.
Recording this NaY molecular sieve crystallinity with x-ray diffraction method is 94%, and recording this zeolite crystal size with scanning electron microscope is 800～1200nm.
Comparative Examples 1
The explanation of this Comparative Examples prepares the situation of NaY molecular sieve according to prior art synthetic directed agents.
According to US6, the embodiment 1 in 284,218 prepares directed agents.In room temperature it was placed 30 hours again.
Under agitation successively the low sodium aluminate solution (specification is the same) of 190ml deionized water, the above-mentioned directed agents of 75.2g, 100ml alum liquor (specification is the same) and 100ml is added in the 329ml water glass (specification is the same), add the back and continue violent stirring 30min, this moment, the mole of this reactant consisted of 2.76Na
2O:Al
2O
3: 8.4SiO
2: 209H
2O, then in 100 ℃ of static crystallization 45 hours, the NaY molecular sieve that promptly handy prior art makes.
Recording this NaY molecular sieve crystallinity with x-ray diffraction method is 75%, and recording this zeolite crystal size with scanning electron microscope is about 1000nm.
Comparative Examples 2
The explanation of this Comparative Examples is according to the less stable of prior art synthetic directed agents.
According to US6, the embodiment 1 in 284,218 prepares directed agents, in room temperature it is placed 60 hours again.
Prepare the NaY molecular sieve according to Comparative Examples 1 described method.
Recording this NaY molecular sieve crystallinity with x-ray diffraction method is 45%, has a small amount of P type molecular sieve stray crystal to generate simultaneously.
Claims (4)
1, a kind of preparation method of NaY molecular sieve comprises the following steps:
(1) conventional directed agents is synthetic: 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 after stirring, at room temperature to 70 ℃ down aging 0.5～24h;
(2) preparation of guiding 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 sodium metaaluminate that step (1) makes successively in water glass, the back that stirs promptly obtains the gel that leads at 80～120 ℃ of following crystallization 2～55h; Wherein the add-on of directed agents should make the Al in the directed agents
2O
3Account for the middle Al that always feeds intake
2O
30.1～10wt% of total amount;
(3) the NaY molecular sieve is synthetic: 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 guiding gel, acid aluminium salt and sodium metaaluminate that step (2) makes successively in water glass, the back that stirs is at 80～120 ℃ of following crystallization 20～50h, more after filtration, wash, be drying to obtain the NaY molecular sieve; The add-on of gel of wherein leading should make the Al in the guiding gel
2O
3Account for the middle Al that always feeds intake
2O
30.1～90wt% of total amount.
2, according to the preparation method of claim 1, wherein total molar ratio of guiding gel is (1.4～3.6) Na in the step (2)
2O: Al
2O
3: (6～10) SiO
2: (150～220) H
2O, wherein the add-on of directed agents should make the Al in the directed agents
2O
3Account for the middle Al that always feeds intake
2O
31～8wt% of total amount.
3, according to the preparation method of claim 1, wherein total molar ratio of NaY molecular sieve is (1.4～3.6) Na in the step (3)
2O: Al
2O
3: (6～10) SiO
2: (150～220) H
2O, the add-on of the gel that wherein leads should make the Al in the guiding gel
2O
3Account for the middle Al that always feeds intake
2O
31～80wt% of total amount.
4, according to the preparation method of claim 1, wherein said acid aluminium salt is selected from Tai-Ace S 150, aluminum chloride or aluminum nitrate.
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| CN100575258C (en) * | 2006-11-21 | 2009-12-30 | 中国石油大学(北京) | Adopt solid phase to transform the method for preparing the NaY molecular sieve |
| CN102050468B (en) * | 2009-10-27 | 2012-10-24 | 中国石油化工股份有限公司 | Method for preparing NaY molecular sieve by using crystallized mother liquor of molecular sieve |
| 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 |
| CN105712368B (en) * | 2014-12-01 | 2018-08-21 | 中国石油化工股份有限公司 | A kind of Y type molecular sieve and preparation method thereof |
| CN105709799B (en) * | 2014-12-01 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of catalyst for hydro-upgrading and preparation method thereof |
| CN105709848B (en) * | 2014-12-01 | 2018-03-16 | 中国石油化工股份有限公司 | A kind of carrier of hydrocracking catalyst and preparation method thereof |
| US10265687B2 (en) | 2014-12-01 | 2019-04-23 | China Petroleum & Chemical Corporation | Na—Y molecular sieve, H—Y molecular sieve, and preparation methods thereof, hydrocracking catalyst, and hydrocracking method |
| CN105709819B (en) * | 2014-12-01 | 2018-04-10 | 中国石油化工股份有限公司 | Hydrocracking catalyst and its preparation method |
| CN105709845B (en) * | 2014-12-01 | 2018-02-09 | 中国石油化工股份有限公司 | Carrier of hydrocracking catalyst and preparation method thereof |
| CN105709847B (en) * | 2014-12-01 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of carrier of hydrocracking catalyst and its preparation method |
| CN105709797B (en) * | 2014-12-01 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and preparation method thereof |
| CN105709798B (en) * | 2014-12-01 | 2018-01-16 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and its preparation method |
| CN105618125B (en) * | 2014-12-01 | 2018-01-16 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN105709844B (en) * | 2014-12-01 | 2018-04-10 | 中国石油化工股份有限公司 | Carrier of hydrocracking catalyst and its preparation method |
| CN105709846B (en) * | 2014-12-01 | 2018-02-09 | 中国石油化工股份有限公司 | A kind of catalyst for hydro-upgrading carrier and preparation method thereof |
| CN105621449B (en) * | 2014-12-01 | 2017-12-15 | 中国石油化工股份有限公司 | A kind of NaY types molecular sieve and preparation method thereof |
| CN114735716A (en) * | 2021-01-07 | 2022-07-12 | 中国石油化工股份有限公司 | Y-type molecular sieve and synthesis method thereof |
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