CN1286723C - Process for preparing NaY molecular sieve by using synthetic mother liquor - Google Patents
Process for preparing NaY molecular sieve by using synthetic mother liquor Download PDFInfo
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- CN1286723C CN1286723C CN 200310122462 CN200310122462A CN1286723C CN 1286723 C CN1286723 C CN 1286723C CN 200310122462 CN200310122462 CN 200310122462 CN 200310122462 A CN200310122462 A CN 200310122462A CN 1286723 C CN1286723 C CN 1286723C
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- China
- Prior art keywords
- crystallization
- sio
- silica gel
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- alumino silica
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- 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 45
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 44
- 239000012452 mother liquor Substances 0.000 title description 11
- 238000004519 manufacturing process Methods 0.000 title description 3
- 238000002425 crystallisation Methods 0.000 claims abstract description 134
- 230000008025 crystallization Effects 0.000 claims abstract description 126
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000000741 silica gel Substances 0.000 claims abstract description 47
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 47
- 239000000047 product Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000012065 filter cake Substances 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 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 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000012266 salt solution Substances 0.000 claims abstract description 10
- 239000000499 gel Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 65
- 239000011734 sodium Substances 0.000 claims description 42
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 31
- 238000002360 preparation method Methods 0.000 claims description 24
- 230000015572 biosynthetic process Effects 0.000 claims description 21
- 235000019353 potassium silicate Nutrition 0.000 claims description 21
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 21
- 238000003786 synthesis reaction Methods 0.000 claims description 21
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical group [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 20
- 229940037003 alum Drugs 0.000 claims description 15
- 239000004411 aluminium Substances 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 12
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 8
- 235000012976 tarts Nutrition 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 2
- 239000003637 basic solution Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 150000005837 radical ions Chemical class 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 25
- 239000011541 reaction mixture Substances 0.000 abstract description 9
- 159000000013 aluminium salts Chemical class 0.000 abstract description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract 2
- 239000010413 mother solution Substances 0.000 abstract 2
- 238000011084 recovery Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 22
- 229910021536 Zeolite Inorganic materials 0.000 description 17
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 17
- 239000010457 zeolite Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 16
- 239000000377 silicon dioxide Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011521 glass Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 230000032683 aging Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- -1 silicate ion Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000003483 aging Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- WAKTWVHWRCNIKU-UHFFFAOYSA-N S(=O)(=O)(O)O.[AlH3] Chemical compound S(=O)(=O)(O)O.[AlH3] WAKTWVHWRCNIKU-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention relates to a method using a synthesized mother solution to prepare NaY molecular sieves. The method comprises the steps: (1) precipitated silicon alumina gel is formed after aluminium salt solution is added into the synthesized mother solution, and filter cakes of the alumino silica gel are obtained by way of filtration and recovery; (2) the filter cakes of the alumino silica gel are uniformly mixed with soluble silicon resources, aluminum resources and guiding agents, pre-crystallization is carried out within the temperature interval from 30 to 100 DEG C for 0.5 to 30 hours; and (3) crystallized reaction mixture is formed after the pre-crystallized product is mixed with the soluble silicon resources and the aluminum resources, crystallization is carried out within the temperature range from 90 to 100 DEG C for 8 to 65 hours, and NaY molecular sieves with large crystal grains and large granules are obtained after the processes of filtration, washing and drying. The present invention overcomes the prejudices in the prior art, a pre-crystallization step is added before the conventional crystallization step, NaY molecular sieves with large crystal grains and large granules are prepared, and the problem of low filtration rate in after-treatment is solved.
Description
Technical field
The present invention relates to catalytic cracking catalyst, particularly the preparation method of NaY molecular sieve.
Background technology
NaY type molecular sieve is active component main in catalytic cracking catalyst source, the NaY molecular sieve consist of (0.9 ± 0.2) Na
2O: Al
2O
3: (3～6) SiO
2: xH
2O, wherein, the x value is generally 1～9.The directing agent method (US3639099, US 3671191) that the method for present industrial production Y zeolite adopts U.S. Grace company to propose basically.Be about to soluble silicon source, aluminium source by certain order of addition(of ingredients) with consist of (15～17) Na
2O: Al
2O
3: (14～16) SiO
2: (280～360) H
2The crystal grain of O mixes less than the directed agents of 0.1 μ m, and forming proportioning is (1.8～4) Na
2O: Al
2O
3: (7～12) SiO
2: (120～350) H
2The reaction mixture of O is then in about 100 ℃ of following crystallization.The shortcoming of these methods is: from the composition of reaction mixture and the composition of NaY molecular sieve, the SiO that reaction mixture provided
2, Na
2O is much larger than the needed amount of institute's synthetic Y zeolite.The NaY molecular sieve is separated from reaction mixture, and a large amount of SiO
2, Na
2O is excessive, along with synthesis mother liquid as sewage discharge, easily cause economic waste and problem of environmental pollution.
US 4164551 has proposed the method in the silicon source in the recycling NaY synthesis mother liquid, promptly in synthesis mother liquid, add aluminate and prepare sedimentary alumina silica hydrogel, remove by filter the water in the gel, with the silica-alumina gel that reclaims as a part of silicon and aluminum source, return once more in the Y zeolite synthesis procedure, reach the SiO that reclaims in the mother liquor
2The purpose (SiO in the mother liquor
2Exist with the multiple polymerized form of silicate ion).The shortcoming of aforesaid method is: institute's synthetic sieve particle is less, and in the subsequent disposal of molecular sieve such as ion-exchange, water washing process, filtering rate is slower, becomes the bottleneck in the production.
CN 1261554A proposes a kind of method of controlling molecular sieve granularity and size-grade distribution.Use the means of continuous synthetic molecular sieve, by the inter-stage back-mixing or regulate progression with control molecular sieve granularity.But this method mainly adopts the continous way operation.Though the sieve particle degree for preparing in this way is big, the zeolite crystal size does not change.For NaY molecular sieve synthetic, it is synthetic to carry out hydro-thermal under non-static condition, and the synthetic NaY of institute is prone to P type stray crystal.
Summary of the invention
The present invention has overcome the defective of prior art, increased pre-crystallization steps before the conventional crystallization steps in sieve synthesis procedure, solved in the process of the silicon source synthesis of molecular sieve in utilizing the NaY synthesis mother liquid, because zeolite crystal is little, particle is little, the slow problem of filtering rate when exchange is washed continuously, not only improve industrial production efficient, and can prepare big crystal grain, oarse-grained NaY molecular sieve.
Provided by the inventionly prepare the method for NaY molecular sieve, comprising with synthesis mother liquid:
(1) in synthesis mother liquid, adds aluminium salt, form sedimentary silica-alumina gel, and filtered and recycled obtains the alumino silica gel filter cake;
(2) alumino silica gel filter cake and soluble silicon source, aluminium source and directed agents is evenly mixed, pre-crystallization is 0.5～30 hour under 30～100 ℃.The SiO that synthesis mother liquid provided
2Account for SiO in the pre-crystallization mixture
2Mass percent be 10～90%, the Al in the directed agents
2O
3Account for total Al in the pre-crystallization mixture
2O
32～8% of amount.The mole of pre-crystallization mixture consists of (1.8～4) Na
2O: Al
2O
3: (7～12) SiO
2: (120～350) H
2O.
(3) pre-crystallization product and soluble silicon source, aluminium source is mixed, form the crystallization mixture, 90～100 ℃ of following crystallization 8～65 hours, filtration, washing, drying obtained big crystal grain, macrobead NaY molecular sieve.Wherein the mole of crystallization mixture consists of (1.8～4) Na
2O: Al
2O
3: (7～12) SiO
2: (120～350) H
2O, the SiO in the pre-crystallization product
2Account for the SiO in the crystallization mixture
2Mass percent be 10～90%.
Specifically, the synthesis mother liquid that usefulness provided by the invention is recovered to prepares the method for NaY molecular sieve, can carry out according to following steps:
1) preparation directed agents:
Prepare directed agents (can be with reference to US3639099, US 3671191) according to the method that is adopted in the conventional NaY molecular sieve preparation method, the directed agents mole consists of (15～17) Na
2O: Al
2O
3: (14～16) SiO
2: (280～360) H
2O.
2) preparation alumino silica gel:
In synthesis mother liquid, add aluminum salt solution, form SiO
2/ Al
2O
3=2～14 alumino silica gel slurries; With the alumino silica gel slurries 20～100 ℃ aging 0.5～12 hour down, preferred 1～10 hour, the alumino silica gel slurries are filtered dewater then, obtain the alumino silica gel filter cake.
Said synthesis mother liquid can be the NaY molecular sieve synthesis mother liquid, also can be other molecular sieve synthesis mother liquid, as A type, X type, type ZSM 5 molecular sieve synthesis mother liquid.The source of mother liquor can also be the waste liquid that contains soluble silicate.Silicate (the SiO that mainly contains different polymeric forms in the mother liquor
3 2-) ion, its content is (with SiO
2Meter) is 5～300g/L, also contains hydroxide ion (OH
-), its content is (with the Na among the NaOH of equivalent
2The O meter) be 2～160g/L.Can also contain other ion in the mother liquor, positively charged ion such as Na
+, K
+, NH
4 +, Ca
2+Deng, negatively charged ion such as SO
4 2-, PO
4 3-, HPO
4 2-, H
2PO
4 -, Cl
-Deng.
3) pre-crystallization steps:
At first the alumino silica gel filter cake is joined in the pre-crystallization jar of molecular sieve as part silicon source, aluminium source, add soluble silicon source, aluminium source and directed agents simultaneously, after brute force stirs, at 30～100 ℃, leave standstill heating 0.5～30 hour under preferred 40～98 ℃, preferred 1～20 hour, carry out pre-crystallization.Wherein, the Al in the directed agents
2O
3Account for total Al in the pre-crystallization mixture
2O
32～8%, preferred 3～7% of amount.The mole of pre-crystallization mixture consists of (1.8～4) Na
2O: Al
2O
3: (7～12) SiO
2: (120～350) H
2O, preferred (2.8～3.8) Na
2O: Al
2O
3: (9～10) SiO
2: (130～250) H
2O.The SiO that the alumino silica gel filter cake is provided
2Account for SiO in the pre-crystallization mixture
2Mass percent be 10～90%, preferred 20～80%.
Pre-crystallization steps can only be carried out once, also can carry out repeatedly, promptly the alumino silica gel filter cake can be joined to carry out once pre-crystallization in the pre-crystallization jar, also the SiO that for the first time pre-crystallization product can be provided according to for the first time pre-crystallization product
2Account for SiO in for the second time pre-crystallization thing
2Mass percent be 10～90% requirement, continue to replenish silicon source, aluminium source in pre-crystallization jar, carry out second time of crystallization in advance.Can carry out repeatedly pre-crystallization operation by that analogy, wherein before SiO in the once pre-crystallization product
2Account for the SiO in the pre-next time crystallization mixture
2Mass percent be 10～90%, numerical value each time can be the same or different.When carrying out pre-crystallization, all need powerful the stirring to make reaction mixture even at every turn.Pre-crystallization steps can be carried out in same pre-crystallization jar, also can carry out in different pre-crystallization jars.
4) crystallization steps:
In pre-crystallization product, replenish silicon source, aluminium source, make the SiO in the pre-crystallization product
2Account for the SiO in the crystallization mixture
2Mass percent be 1-90%, preferred 20～80%.The mole of crystallization mixture consists of (1.8～4) Na
2O: Al
2O
3: (7～12) SiO
2: (120～350) H
2O, preferred (2.8～3.8) Na
2O: Al
2O
3: (9～10) SiO
2: (130～250) H
2O.The crystallization mixture is formed with the mole of pre-crystallization mixture can be identical, also can be different.After brute force stirs, make reaction mixture under about 90～100 ℃, preferred 90～98 ℃ of following crystallization 8～65 hours, preferred 14～48 hours, filtration, washing, drying obtain silica alumina ratio and are about 5, grain size is that 1500～2000 , granular size are big crystal grain, the macrobead NaY molecular sieve of 0.4～1 μ m.
Crystallization steps can directly be carried out in pre-crystallization jar, also can carry out in molecular sieve crystallization jar separately.
Said aluminium source is sodium aluminate solution and aluminum salt solution.Wherein sodium aluminate solution is for containing Na
+, AlO
+, OH
-Basic solution, Na in the solution composition
2O is 100～350g/L, Al
2O
3Be 20～150g/L.Said aluminum salt solution can be alum liquor, liquor alumini chloridi, aluminum nitrate solution, also can be tart aluminium colloidal sol, tart alumina gel etc., the preferably sulfuric acid aluminum solutions.Aluminum salt solution concentration is (with Al
2O
3Meter) 5～350g/L.
Said soluble silicon source can be water glass solution, silicon sol, silicon gel.The preferably water glass solution, the modulus (SiO of water glass solution
2With Na
2The mol ratio of O) be 1～5, preferred 3～3.5.
Prior art thinks in the crystallization process of molecular sieve, disturbance must not be arranged, otherwise can influence the degree of crystallinity of Y zeolite, and generates with P type stray crystal.The present invention has overcome the prejudice of prior art, has increased pre-crystallization steps before conventional crystallization steps, prepares big crystal grain, oarse-grained NaY molecular sieve, and the slow problem of filtering rate when having solved aftertreatment.
Effect of the present invention: the present invention can make full use of resource, reduces discharging of waste liquid.The prepared NaY zeolite crystal size of the present invention is that 1500～2000 , granular size are 0.4～1 μ m.Compare with reclaiming mother liquor synthetic NaY molecular sieve with prior art, in the molecular sieve subsequent disposal, in ion-exchange, washing filtering process, fast 1～4 times of filtering rate helps improving NaY molecular sieve production efficiency.
Description of drawings
Fig. 1 is the sieve particle TEM figure of embodiment 3 preparations.
Fig. 2 is the sieve particle TEM figure of embodiment 4 preparations.
Fig. 3 is the sieve particle TEM figure of embodiment 5 preparations.
Fig. 4 is the sieve particle TEM figure of embodiment 7 preparations.
Fig. 5 is the sieve particle TEM figure of embodiment 8 preparations.
Fig. 6 is the sieve particle TEM figure of embodiment 9 preparations.
Fig. 7 is the sieve particle TEM figure of Comparative Examples 1 preparation.
Fig. 8 is the sieve particle TEM figure of Comparative Examples 2 preparations.
Fig. 9 is the sieve particle TEM figure of Comparative Examples 3 preparations.
Embodiment
The grain size of molecular sieve (t) is measured by Scherrer (Scherrer) equation.
Wherein: λ: the characteristic X-ray wavelength; B: peak width at half height; θ: peak position
The sieve particle size is by transmissioning electric mirror determining.
Embodiment 1
Present embodiment is the preparation of directed agents.
Water intaking glass 126ml (proportion 1.278kg/L, SiO
2Content 287 grams per liters, modulus 3.3) put into beaker, slowly add 105ml sodium aluminate solution (Al
2O
3Content 38.7 grams per liters, Na
2O content 291 grams per liters, proportion 1233 grams per liters), mix under the room temperature, in 35 ℃ of following ageings 6 hours, making mole proportioning was 16.85Na
2O: Al
2O
3: 15.1SiO
2: 320.8H
2The directed agents of O.
Embodiment 2
Present embodiment is the preparation of alumino silica gel.
Get industrial NaY mother liquor 1500ml (Shandong catalyst plant, proportion 1.110, SiO
2Content 53.3 grams per liters, Na
2O content 26.6 grams per liters), when stirring mother liquor, slowly add alum liquor 154ml (Al with the rotating speed of 700r/min
2O
3Content 98 grams per liters, proportion 1.291), form the alumino silica gel slurries.After stirring the alumino silica gel slurries were put into 95 ℃ of water-bath heat agings 2 hours.The alumino silica gel slurries that take out after wearing out filter on the B of φ 200, and vacuum tightness is 0.05Mpa.Obtain the alumino silica gel filter cake.
Embodiment 3
Present embodiment is the preparation of big crystal grain macrobead NaY molecular sieve.
Pre-crystallization steps: water intaking glass 210ml (proportion 1.278kg/L, SiO
2Content 287 grams per liters, modulus 3.3) put into the 2L enamelled cup, add the alumino silica gel filter cake 1087g among the embodiment 2 when stirring water glass, the directed agents 88ml among the embodiment 1, alum liquor 33ml (Al
2O
3Content 98 grams per liters, proportion 1.291), sodium aluminate solution 77ml (Al
2O
3Content 102 grams per liters, Na
2O content 159 grams per liters, proportion 1.240), mix, under 95 ℃, carried out pre-crystallization 2 hours.Wherein, the SiO that provided of alumino silica gel filter cake
2Account for SiO in the pre-crystallization mixture
2Mass percent is 55%, the Al in the directed agents
2O
3Account for total Al in the pre-crystallization mixture
2O
35% of amount.
Crystallization steps: take out pre-crystallization product 800g, add water glass 122ml (proportion 1.278kg/L, SiO
2Content 287 grams per liters, modulus 3.3), alum liquor 27ml (Al
2O
3Content 98 grams per liters, proportion 1.291), sodium aluminate solution 36ml (Al
2O
3Content 102 grams per liters, Na
2O content 159 grams per liters, proportion 1.240).Wherein, the SiO in the pre-crystallization product
2Account for the SiO in the crystallization mixture
2Mass percent is 70%.The crystallization mixture is mixed, in 95 ℃ of following hydrothermal crystallizings 36 hours, after filtration, the washing drying obtains big crystal grain macrobead NaY zeolite product.Recording its silica alumina ratio is 5.3, and degree of crystallinity is 93.6%, and the physical and chemical performance data of product are listed in table 1.Measure the TEM picture of sieve particle size and see Fig. 1.
Embodiment 4
Present embodiment is the preparation of big crystal grain macrobead NaY molecular sieve.
Pre-crystallization steps: water intaking glass 210ml (proportion 1.278kg/L, SiO
2Content 287 grams per liters, modulus 3.3) put into the 2L enamelled cup, add the alumino silica gel filter cake 1087g among the embodiment 2 when stirring water glass, the directed agents 88ml among the embodiment 1, alum liquor 33ml (Al
2O
3Content 98 grams per liters, proportion 1.291), sodium aluminate solution 77ml (Al
2O
3Content 102 grams per liters, Na
2O content 159 grams per liters, proportion 1.240), mix.Under 98 ℃, carried out pre-crystallization 5 hours.Wherein, the SiO that provided of alumino silica gel filter cake
2Account for SiO in the pre-crystallization mixture
2Mass percent is 55%, the Al in the directed agents
2O
3Account for total Al in the pre-crystallization mixture
2O
35% of amount.
Crystallization steps: take out the product 400g after the pre-crystallization, add water glass 322ml (proportion 1.278kg/L, SiO
2Content 287 grams per liters, modulus 3.3), alum liquor 72ml (Al
2O
3Content 98 grams per liters, proportion 1.291), sodium aluminate solution 94ml (Al
2O
3Content 102 grams per liters, Na
2O content 159 grams per liters, proportion 1.240).Wherein, the SiO in the pre-crystallization product
2Account for the SiO in the crystallization mixture
2Mass percent is 30%.The crystallization mixture is mixed, in 95 ℃ of following hydrothermal crystallizings 40 hours, after filtration, the washing drying obtains big crystal grain macrobead NaY zeolite product.Recording its silica alumina ratio is 5.4, and degree of crystallinity is 93.6%, and the physical and chemical performance data of product are listed in table 1.Measure the TEM picture of sieve particle size and see Fig. 2.
Embodiment 5
Present embodiment is the preparation of big crystal grain macrobead NaY molecular sieve.
Pre-crystallization steps: water intaking glass 210ml (proportion 1.278kg/L, SiO2 content 287 grams per liters, modulus 3.3) put into the 2L enamelled cup, add the alumino silica gel filter cake 1087g among the embodiment 2 when stirring water glass, directed agents 88ml among the embodiment 1, alum liquor 33ml (Al
2O
3Content 98 grams per liters, proportion 1.291), sodium aluminate solution 77ml (Al
2O
3Content 102 grams per liters, Na
2O content 159 grams per liters, proportion 1.240), mix, under 50 ℃, carried out pre-crystallization 16 hours, wherein, the SiO that the alumino silica gel filter cake is provided
2Account for SiO in the pre-crystallization mixture
2Mass percent is 55%, the Al in the directed agents
2O
3Account for total Al in the pre-crystallization mixture
2O
35% of amount.
Crystallization steps: take out the product 700g after the pre-crystallization, add water glass 241ml (proportion 1.278kg/L, SiO
2Content 287 grams per liters, modulus 3.3), alum liquor 54ml (Al
2O
3Content 98 grams per liters, proportion 1.291), sodium aluminate solution 71ml (Al
2O
3Content 102 grams per liters, Na
2O content 159 grams per liters, proportion 1.240).Wherein, the SiO in the pre-crystallization product
2Account for the SiO in the crystallization mixture
2Mass percent is 50%.The crystallization mixture is mixed, in 95 ℃ of following hydrothermal crystallizings 37 hours, after filtration, the washing drying obtains big crystal grain macrobead NaY zeolite product.Recording its silica alumina ratio is 5.4, and degree of crystallinity is 93.8%, and the physical and chemical performance data of product are listed in table 1.Measure the TEM picture of sieve particle size and see Fig. 3.
Embodiment 6
Present embodiment is the preparation of alumino silica gel.
Get industrial NaY mother liquor 1700ml (Shandong catalyst plant, proportion 1.110, SiO
2Content 53.3 grams per liters, Na
2O content 26.6 grams per liters), when stirring mother liquor, slowly add alum liquor 174ml (Al with the rotating speed of 700r/min
2O
3Content 98 grams per liters, proportion 1.291), form the alumino silica gel slurries.After stirring the alumino silica gel slurries were put into 40 ℃ of water-bath heat agings 9 hours.The alumino silica gel slurries that take out after wearing out filter on the B of φ 200, and vacuum tightness is 0.05MPa.Obtain the alumino silica gel filter cake.
Embodiment 7
Present embodiment is the preparation of big crystal grain macrobead NaY molecular sieve.
Pre-crystallization steps: water intaking glass 98ml (proportion 1.278kg/L, SiO2 content 287 grams per liters, modulus 3.3) put into the 2L enamelled cup, add the alumino silica gel filter cake 1173g among the embodiment 6 when stirring water glass, directed agents 70ml among the embodiment 1, sodium aluminate solution 50ml (Al
2O
3Content 102 grams per liters, Na
2O content 159 grams per liters, proportion 1.240), mix.Under 90 ℃, carried out pre-crystallization 4.5 hours.Wherein, the SiO that provided of alumino silica gel filter cake
2Account for SiO in the pre-crystallization mixture
2Mass percent is 70%, the Al in the directed agents
2O
3Account for total Al in the pre-crystallization mixture
2O
35% of amount.
Crystallization steps: take out the product 800g after the pre-crystallization, add water glass 105ml (proportion 1.278kg/L, SiO
2Content 287 grams per liters, modulus 3.3), alum liquor 24ml (Al
2O
3Content 98 grams per liters, proportion 1.291), sodium aluminate solution 30ml (Al
2O
3Content 102 grams per liters, Na
2O content 159 grams per liters, proportion 1.240).Wherein, the SiO in the pre-crystallization product
2Account for the SiO in the crystallization mixture
2Mass percent is 70%.The crystallization mixture is mixed, in 95 ℃ of following hydrothermal crystallizings 30 hours, after filtration, the washing drying obtains big crystal grain macrobead NaY zeolite product.Recording its silica alumina ratio is 5.4, and degree of crystallinity is 93.3%, and the physical and chemical performance data of product are listed in table 1.Measure the TEM picture of sieve particle size and see Fig. 4.
Embodiment 8
Present embodiment is the preparation of big crystal grain macrobead NaY molecular sieve.
Pre-crystallization steps: water intaking glass 98ml (proportion 1.278kg/L, SiO2 content 287 grams per liters, modulus 3.3) put into the 2L enamelled cup, add the alumino silica gel filter cake 1173g among the embodiment 6 when stirring water glass, directed agents 70ml among the embodiment 1, sodium aluminate solution 50ml (Al
2O
3Content 102 grams per liters, Na
2O content 159 grams per liters, proportion 1.240), mix.Under 95 ℃, carried out pre-crystallization 2 hours.Wherein, the SiO that provided of alumino silica gel filter cake
2Account for SiO in the pre-crystallization mixture
2Mass percent is 70%, the Al in the directed agents
2O
3Account for total Al in the pre-crystallization mixture
2O
35% of amount.
Crystallization steps: take out the colloid 700g after the pre-crystallization, add water glass 214ml (proportion 1.278kg/L, SiO
2Content 287 grams per liters, modulus 3.3), alum liquor 47ml (Al
2O
3Content 98 grams per liters, proportion 1.291), sodium aluminate solution 64ml (Al
2O
3Content 102 grams per liters, Na
2O content 159 grams per liters, proportion 1.240), wherein, the SiO in the pre-crystallization product
2Account for the SiO in the crystallization mixture
2Mass percent is 50%.The crystallization mixture is mixed, in 95 ℃ of following hydrothermal crystallizings 47 hours, after filtration, the washing drying obtains big crystal grain macrobead NaY zeolite product.Recording its silica alumina ratio is 5.4, and degree of crystallinity is 92.2%, and the physical and chemical performance data of product are listed in table 1.Measure the TEM picture of sieve particle size and see Fig. 5.
Embodiment 9
Present embodiment is the preparation of big crystal grain macrobead NaY molecular sieve.
Pre-crystallization steps: water intaking glass 98ml (proportion 1.278kg/L, SiO
2Content 287 grams per liters, modulus 3.3) put into the 2L enamelled cup, add the alumino silica gel filter cake 1173g among the embodiment 2 when stirring water glass, the directed agents 70ml among the embodiment 1, sodium aluminate solution 50ml (Al
2O
3Content 102 grams per liters, Na
2O content 159 grams per liters, proportion 1.240), mix.Under 95 ℃, carried out pre-crystallization 8 hours.Wherein, the SiO that provided of alumino silica gel filter cake
2Account for SiO in the pre-crystallization mixture
2Mass percent is 70%, the Al in the directed agents
2O
3Account for total Al in the pre-crystallization mixture
2O
35% of amount.
Crystallization steps: take out the colloid 800g after the pre-crystallization, add water glass 322ml (proportion 1.278kg/L, SiO
2Content 287 grams per liters, modulus 3.3), alum liquor 71ml (Al
2O
3Content 98 grams per liters, proportion 1.291), sodium aluminate solution 95ml (Al
2O
3Content 102 grams per liters, Na
2O content 159 grams per liters, proportion 1.240), wherein, the SiO in the pre-crystallization product
2Account for the SiO in the crystallization mixture
2Mass percent is 30%.The crystallization mixture is mixed, in 95 ℃ of following hydrothermal crystallizings 42 hours, after filtration, the washing drying obtains big crystal grain macrobead NaY zeolite product.Recording its silica alumina ratio is 5.4, and degree of crystallinity is 90%, and the physical and chemical performance data of product are listed in table 1.Measure the TEM picture of sieve particle size and see Fig. 6.
Comparative Examples 1
This Comparative Examples prepares the NaY molecular sieve according to the US3639099 method.
Water intaking glass 344ml (proportion 1.278kg/L, SiO
2Content 287 grams per liters, modulus 3.3) put into the 2L enamelled cup, add the directed agents 58ml among the embodiment 1 when stirring water glass, alum liquor 100ml (Al
2O
3Content 98 grams per liters, proportion 1.291), sodium aluminate solution 84ml (Al
2O
3Content 102 grams per liters, Na
2O content 159 grams per liters, proportion 1.240), distilled water 71g mixes.In 95 ℃ of following hydrothermal crystallizings 24 hours, after filtration, the washing drying obtains the NaY zeolite product.Recording its silica alumina ratio is 5.3, and degree of crystallinity is 91.6%, and the physical and chemical performance data of product are listed in table 1.Measure the TEM picture of sieve particle size and see Fig. 7.
Comparative Examples 2
This Comparative Examples prepares the NaY molecular sieve according to the US4164551 method.
Water intaking glass 210ml (proportion 1.278kg/L, SiO
2Content 287 grams per liters, modulus 3.3) put into the 2L enamelled cup, add the alumino silica gel filter cake 1087g among the embodiment 2 when stirring water glass, the directed agents 88ml among the embodiment 1, alum liquor 33ml (Al
2O
3Content 98 grams per liters, proportion 1.291), sodium aluminate solution 77ml (Al
2O
3Content 102 grams per liters, Na
2O content 159 grams per liters, proportion 1.240), mix.Wherein, the SiO that provided of alumino silica gel filter cake
2Account for SiO in the crystallization mixture
2Mass percent is 55%.Reaction mixture is in 95 ℃ of following hydrothermal crystallizings 28 hours, after filtration, the washing drying obtains the NaY zeolite product.Recording its silica alumina ratio is 5.4, and degree of crystallinity is 90%, and the physical and chemical performance data of product are listed in table 1.Measure the TEM picture of sieve particle size and see Fig. 8.
Comparative Examples 3
This Comparative Examples prepares the NaY molecular sieve according to the US4164551 method.
Water intaking glass 98ml (proportion 1.278kg/L, SiO
2Content 287 grams per liters, modulus 3.3) put into the 2L enamelled cup, add the alumino silica gel filter cake 1173g among the embodiment 2 when stirring water glass, the directed agents 70ml among the embodiment 1, sodium aluminate solution 50ml (Al
2O
3Content 102 grams per liters, Na
2O content 159 grams per liters, proportion 1.240), mix.Wherein, the Si0 that provided of alumino silica gel filter cake
2Account for SiO in the crystallization mixture
2Mass percent is 70%.Reaction mixture is in 95 ℃ of following hydrothermal crystallizings 28 hours, after filtration, the washing drying obtains the NaY zeolite product.Recording its silica alumina ratio is 5.3, and degree of crystallinity is 91.6%, and the physical and chemical performance data of product are listed in table 1.Measure the TEM picture of sieve particle size and see Fig. 9.
Table 1
| Product performance | Degree of crystallinity % | Lattice constant | The silica alumina ratio of molecular sieve | Temperature failure temperature ℃ | BET specific surface area m 2/g | Zeolite crystal size |
| Embodiment 3 | 93.6 | 24.65 | 5.3 | 921 | 762 | 1719 |
| Embodiment 4 | 93.6 | 24.64 | 5.4 | 910 | 735 | 1719 |
| Embodiment 5 | 93.8 | 24.64 | 5.4 | 910 | 754 | 1600 |
| Embodiment 7 | 93.3 | 24.64 | 5.4 | 927 | 752 | 1750 |
| Embodiment 8 | 92.2 | 24.64 | 5.4 | 910 | 710 | 1781 |
| Embodiment 9 | 90 | 24.64 | 5.4 | 907 | 730 | 1750 |
| Comparative Examples 1 | 91.6 | 24.65 | 5.3 | 921 | 766 | 1140 |
| Comparative Examples 2 | 92.9 | 24.64 | 5.4 | 910 | 738 | 1420 |
| Comparative Examples 3 | 91.6 | 24.65 | 5.3 | 908 | 747 | 1550 |
Claims (13)
1. prepare the method for NaY molecular sieve with synthesis mother liquid, comprising:
(1) in synthesis mother liquid, add aluminum salt solution, form sedimentary silica-alumina gel, and filtered and recycled obtains the alumino silica gel filter cake;
(2) alumino silica gel filter cake and soluble silicon source, aluminium source and directed agents is evenly mixed, pre-crystallization is 0.5～30 hour under 30～100 ℃, and wherein the mole of pre-crystallization mixture consists of (1.8～4) Na
2O: Al
2O
3: (7～12) SiO
2: (120～350) H
2O, the SiO that the alumino silica gel filter cake is provided
2Account for SiO in the pre-crystallization mixture
2Mass percent be 10～90%, the Al in the directed agents
2O
3Account for total Al in the pre-crystallization mixture
2O
32～8% of amount, the mole of directed agents consists of (15～17) Na
2O: Al
2O
3: (14～16) SiO
2: (280～360) H
2O;
(3) pre-crystallization product and soluble silicon source, aluminium source is mixed, form the crystallization mixture, in 90～100 ℃ of following crystallization 8～65 hours, filtration, washing, drying, wherein the mole of crystallization mixture consists of (1.8～4) Na
2O: Al
2O
3: (7～12) SiO
2: (120～350) H
2O, the SiO in the pre-crystallization product
2Account for the SiO in the crystallization mixture
2Mass percent be 10～90%.
2. in accordance with the method for claim 1, it is characterized in that the preparation method of alumino silica gel filter cake comprises: in synthesis mother liquid, add aluminum salt solution, form SiO
2/ Al
2O
3=2～14 alumino silica gel slurries wear out the alumino silica gel slurries 0.5～12 hour down at 20～100 ℃, the alumino silica gel slurries are filtered to dewater then, obtain the alumino silica gel filter cake.
3. in accordance with the method for claim 1, it is characterized in that the content of said synthesis mother liquid mesosilicic acid radical ion is 5～300g/L, the content of hydroxide ion is 2～160g/L.
4. according to the described preparation method of claim 1, it is characterized in that pre-crystallization temperature is 40～98 ℃, pre-crystallization time is 1～20 hour.
5. in accordance with the method for claim 1, it is characterized in that, in pre-crystallization steps, the Al in the directed agents
2O
3Account for total Al in the pre-crystallization mixture
2O
33～7% of amount, the mole of pre-crystallization mixture consists of (2.8～3.8) Na
2O: Al
2O
3: (9～10) SiO
2: (130～250) H
2O, the SiO that the alumino silica gel filter cake is provided
2Account for SiO in the pre-crystallization mixture
2Mass percent be 20～80%.
6. according to claim 1,4 or 5 described methods, it is characterized in that pre-crystallization is carried out repeatedly, the SiO in the preceding once pre-crystallization product
2Account for the SiO in the pre-next time crystallization mixture
2Mass percent be 10～90%.
7. in accordance with the method for claim 1, it is characterized in that crystallization temperature is 90～98 ℃, crystallization time is 14～48 hours.
8. in accordance with the method for claim 1, it is characterized in that, in crystallization steps, in pre-crystallization product, replenish silicon source, aluminium source, make the SiO in the pre-crystallization product
2Account for the SiO in the crystallization mixture
2Mass percent be 20～80%, the mole of crystallization mixture consists of (2.8～3.8) Na
2O: Al
2O
3: (9～10) SiO
2: (130～250) H
2O.
9. in accordance with the method for claim 1, it is characterized in that said aluminium source is sodium aluminate solution or aluminum salt solution.
10. in accordance with the method for claim 9, it is characterized in that sodium aluminate solution is for containing Na
+, AlO
+, OH
-Basic solution, Na in the solution composition
2O is 100～350g/L, Al
2O
3Be 20～150g/L.
11. in accordance with the method for claim 9, it is characterized in that said aluminum salt solution is alum liquor, liquor alumini chloridi, aluminum nitrate solution, or tart aluminium colloidal sol, tart alumina gel, aluminum salt solution concentration is 5～350g/L.
12. in accordance with the method for claim 1, it is characterized in that said soluble silicon source is water glass solution, silicon sol or silicon gel.
13. in accordance with the method for claim 12, it is characterized in that said soluble silicon source is a water glass solution, the modulus of water glass solution is 1～5.
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| CN101250428B (en) * | 2008-04-07 | 2015-11-25 | 华东理工大学 | A kind of in-situ crystallization cracking catalyst and preparation method thereof |
| CN102775026B (en) * | 2012-08-13 | 2014-04-30 | 四川理工学院 | Method for treating biogas slurry by using modified fly ash |
| CN102765996B (en) * | 2012-08-21 | 2014-03-26 | 四川理工学院 | Method of recycling ammonia nitrogen in biogas slurry |
| CN104591213B (en) * | 2013-11-03 | 2017-02-15 | 中国石油化工股份有限公司 | Preparation method of small-grain NaY-type molecular sieve |
| 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 |
| CN104692421A (en) * | 2015-01-29 | 2015-06-10 | 安徽同丰橡塑工业有限公司 | Recovery treatment technique of alumino silica gel waste liquid |
| CN106673031B (en) * | 2015-11-09 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of NaY molecular sieve and alumina compound and preparation method thereof |
| CN105858682A (en) * | 2016-06-15 | 2016-08-17 | 山东齐鲁华信高科有限公司 | Method for utilizing ZSM-11 molecular sieve synthesizing mother liquor |
| CN109516473B (en) * | 2017-09-20 | 2020-11-13 | 中国石油化工股份有限公司 | Production method of NaY molecular sieve |
| CN110092393B (en) * | 2018-01-30 | 2022-12-13 | 中国石油化工股份有限公司 | Method for preparing small-grain NaY molecular sieve by using NaY molecular sieve synthesis mother liquor |
| CN111320184A (en) * | 2018-12-13 | 2020-06-23 | 湖北赛因化工有限公司 | Method for preparing NaY molecular sieve by recycling NaY mother liquor |
| CN110194467A (en) * | 2019-07-04 | 2019-09-03 | 青岛惠城环保科技股份有限公司 | A method of 13X molecular sieve is prepared by NaY mother liquor |
| CN113880105A (en) * | 2020-07-02 | 2022-01-04 | 中国石油化工股份有限公司 | Treatment method of NaY molecular sieve waste liquid, application of NaY molecular sieve waste liquid and NaY molecular sieve |
| CN112694098A (en) * | 2020-12-31 | 2021-04-23 | 山东齐鲁华信实业股份有限公司 | Method for recovering and synthesizing molecular sieve ZSM-5X from silicon-containing sewage |
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