CN1417116A - Fast synthesis process of high-crystallinity zeolite molecular sieve - Google Patents
Fast synthesis process of high-crystallinity zeolite molecular sieve Download PDFInfo
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- CN1417116A CN1417116A CN 02155487 CN02155487A CN1417116A CN 1417116 A CN1417116 A CN 1417116A CN 02155487 CN02155487 CN 02155487 CN 02155487 A CN02155487 A CN 02155487A CN 1417116 A CN1417116 A CN 1417116A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 39
- 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 39
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 38
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000010457 zeolite Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000012065 filter cake Substances 0.000 claims abstract description 9
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000007789 sealing Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 150000008431 aliphatic amides Chemical class 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims 3
- 238000001035 drying Methods 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 4
- 230000032683 aging Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract 2
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 abstract 1
- 150000001412 amines Chemical class 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- 238000010792 warming Methods 0.000 description 12
- 239000013078 crystal Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000009415 formwork Methods 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- -1 tetrapropyl amine radical ion Chemical class 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
High-crystallinity H-type zeolite molecular sieve is synthesized through the fast process including: adding dropwise mixed solution B comprising Al2(SO4)3.18H2O, water and concentrated sulfuric acid to mixed solution A comprising water glass and deionized water while stirring drastically; adding fatty amine and inorganic ammonia solution to form gel mixture; sealing, ageing, crystallizing, cooling, solid-liquid separation, washing to filter cake pH value of 8-9, drying, calcining and HCl exchange. The process has the advantages of short synthesis period, high crystallinity, low organic template agent content in crystallized zeolite and low sodium ion content.
Description
Affiliated field:
The invention belongs to a kind of method of synthesis zeolite, relate to method specifically with a small amount of organic formwork agent and inorganic ammonia fast synthesis of ZSM-5-5 zeolite molecular sieve.
Background technology:
The main feature of zeolite molecular sieve is the solid material that it has regular pore passage structure.The uniqueness that itself had has determined zeolite molecular sieve to have purposes widely.As: (1) catalyzer, (2) washing composition, (3) sorbent material and siccative, (4) other (comprising sewage disposal etc.).And the economic and social benefit that zeolite catalyst produces is the most remarkable, and it not only can improve the productive rate and the quality of product in the petrochemical process, and shortened process reduces the technology cost significantly.
1972, United States Patent (USP) U.S.Patent 3,702,866 at first introduced the ZSM-5 zeolite molecular sieve preparation method, and the mol ratio of its oxide compound is: 0.9 ± 0.2M
2/nO: Al
2O
3: 5～100SiO
2: 0～40H
2O.
Wherein the M representative has n valency metallic cation, and as sodium ion and tetrapropyl amine radical ion, the optimum range of silica alumina ratio is 10～60, and adopting expensive tetrapropyl oxyammonia is template.At first, the synthesis condition of ZSM-5 zeolite molecular sieve be 120～200 ℃, boost under the power certainly, need about 5～7 days, template used dose mainly is tetrapropyl oxyammonia or tetrapropyl amine bromide.Simplify processing condition in order to reduce synthetic cost, researcher has carried out a large amount of research reports at the ZSM-5 zeolite molecular sieve, successively there is the patent documentation report can synthesize ZSM-5 type zeolite molecular sieve for template with primary amine, diamines, low-carbon alcohol etc., even under the situation without template, directly synthetic ZSM-5 zeolite molecular sieve.Generally speaking, aspect regularity, degree of crystallinity and the silica alumina ratio scope of crystal morphology, inorganic method synthetic molecular sieve is not as organic method synthetic molecular sieve.
The open report of United States Patent (USP) U.S.Patent 4,175,114 is directed agents with ethanol or can synthesizes ZSM-5 type zeolite molecular sieve with seed technology.But the author does not introduce the crystal morphology with this method synthetic ZSM-5 molecular sieve.In another piece patent U.S.Patent 4,891,199, Latourrette introduces a kind of ZSM-5 synthesis method of zeolite molecular sieve, without any template or directed agents, does not also add under the situation of crystal seed, directly synthesizes the ZSM-5 crystalline zeolite.It's a pity that the author does not provide the crystalline pattern yet.And in practical study work, we find that adopting alcohols is the template synthesis zeolite, obtain the zeolite molecular sieve of high purity high-crystallinity, must be just possible in narrower silica alumina ratio scope, and α-SiO appears easily
2With stray crystals such as mordenite mutually.Crystalline appearance irregularity, granular size is also inhomogeneous.There is such problem equally in direct method synthetic crystallization zeolite.
Summary of the invention:
The purpose of this invention is to provide a kind of activity that can make molecular sieve catalyst, synthetic method that stability is high, particularly be applicable to the reaction of MTG, aromizing and alkene oligomerization.
Synthetic method of the present invention comprises the steps:
(1) with water glass and deionized water SiO in molar ratio
2: H
2O=1: 10～40 are mixed into mixed liquor A;
(2) with Al
2(SO
4)
318H
2O, water and the vitriol oil be Al in molar ratio
2O
3: SO
4 2-: H
2O=1: 10～25: 500～3000 are mixed into mixed liquid B;
(3) under vigorous stirring, the B drips of solution is added in the A solution, stir; Adding aliphatic amide and concentration then is the inorganic ammonia solution of 5～7.9mol/L, mixes, and makes gel mixture;
(4) gel mixture is added in the synthesis reactor, sealing was worn out 10-24 hour down at 80～110 ℃ earlier, again at 170～190 ℃ of following crystallization 20-36 hours;
(5) after crystallization finished, cooling was carried out solid-liquid separation with reaction mixture, filter cake with deionized water wash to filter cake pH=8～9;
(6) filter cake is at 110 ± 10 ℃ of down dry 12～24h, and roasting is 2～3 hours in 540 ± 10 ℃ air atmosphere, under 90～110 ℃, exchanges 2～3 hours with the HCl of 0.3～0.5mol/L, promptly waits to obtain H type zeolite molecular sieve.
Wherein each component mol ratio consists of:
Inorganic ammonia: NaO
2: Al
2O
3: SiO
2: aliphatic amide=
0.09～0.25∶0.09～0.38∶0.01～0.25∶1∶0.05～0.12。Aforesaid inorganic ammonia is ammoniacal liquor and ammonium salt, as: ammonium nitrate, ammonium sulfate etc.Aforesaid aliphatic amide is a primary amine, and wherein alkyl comprises 2～6 carbon atoms.
The present invention compares with existing synthetic MFI type zeolite molecular sieve technology and has following advantage:
1. synthesis cycle of the present invention is short, and crystallization time only needed get final product in 24～48 hours, and the degree of crystallinity height
(＞90％)。
2. the present invention can synthesize the more regular zeolite molecular sieve of crystal morphology with a spot of organic formwork agent, and organic template agent content is low in the crystalline zeolite, and under 540 ℃, 2～3 hours can complete removed template method.
3. replace basic metal with inorganic ammonia, the content of sodium ion obviously reduces in the crystalline zeolite, is not higher than 0.15wt%.HCl exchange under 90～110 ℃ with 0.3～0.5mol/L can make the content of sodium ion drop to below the 0.01wt% in 2～3 hours.
Embodiment;
Embodiment 1
With 240g water glass (SiO
2: 30.56wt%, Na
2O: 10.4wt%) join in the 407g deionized water, mix and be solution A; With 11.7g Al
2(SO
4)
318H
2O, 462g water and the 31.5g vitriol oil (98wt%) mix and are solution B.
Batching is operation in the following order: under vigorous stirring, the B drips of solution is added in the A solution, stirs.Adding 7g n-Butyl Amine 99 and 18.3ml concentration then is the ammoniacal liquor of 7mol/L, regulates pH=10.5, stirs.At last the gel mixture for preparing is transferred in the synthesis reactor sealing.Each component mol ratio consists of:
14.6NH
3∶7.9Na
2O∶Al
2O
3∶69SiO
2∶5.45n-C
4H
9NH
2
Be warming up to 100 ℃ earlier, aging 20 hours.Continue to be warming up to 185 ℃ again, crystallization 28 hours.Cool off rapidly with frozen water, stop crystallization, the mixture in the synthesis reactor is shifted out.
Said mixture is carried out after the solid-liquid separation with deionized water wash to filter cake pH=9.Drying is 12 hours under 110 ℃, and roasting is 3 hours in 540 ℃ air atmosphere, under 100 ℃, uses the HCl of 0.5mol/L to exchange 2 hours, obtains H type zeolite molecular sieve.
X powder x ray diffractometer x (Japanese D/max-ra type x ray diffractometer x of science), tube voltage 40Kv, tube current 30mA, CuK are adopted in the crystalline phase analysis.Radiation, Ni filtering, 3～50 ° of sweep limits.XRD analysis as can be known, the X-ray diffraction analysis data of synthetic molecular sieve crystalline flour and patent U.S.Patent 3,702,866 data of giving conform to, relative crystallinity is that 98% (relative crystallinity is represented with the per-cent of the feature peak height sum of X-ray diffraction (XRD) figure of the feature peak height sum comparative sample of X-ray diffraction (XRD) figure of product, the contrast sample is that the method that provides according to patent U.S.Patent 3,702,866 is synthetic and come).Crystal morphology adopts the H-600-2 of Hitachi type scanning electron microscope (SEM) to analyze, and analyzes that the zeolite crystal size is more even as can be known, is shaped as the twin segment cylinder shape.
Embodiment 2
With 165g water glass (SiO
2: 30.56wt%, Na
2O: 10.4wt%) join in the 380g deionized water, mix and be solution A; With 9.3g Al
2(SO
4)
318H
2O, 219g water and the 21.7g vitriol oil (98wt%) mix and are solution B.
Batching is operation in the following order: under vigorous stirring, the B drips of solution is added in the A solution, stirs.Adding 3.4g n-Butyl Amine 99 and 14.2ml concentration then is the ammoniacal liquor of 7mol/L, regulates pH=10.5, stirs.At last the gel mixture for preparing is transferred in the synthesis reactor sealing.Each component mol ratio consists of:
14.2NH
3∶6.6Na
2O∶Al
2O
3∶60SiO
2∶3.34?n-C
4H
9NH
2
Be warming up to 90 ℃ earlier, aging 22 hours.Continue to be warming up to 170 ℃ again, crystallization 36 hours.Cool off rapidly with frozen water, stop crystallization, the mixture in the synthesis reactor is shifted out.
Said mixture is carried out after the solid-liquid separation with deionized water wash to filter cake pH=9.Drying is 18 hours under 110 ℃, and roasting is 3 hours in 540 ℃ air atmosphere, under 100 ℃, uses the HCl of 0.5mol/L to exchange 2 hours, obtains H type zeolite molecular sieve.
Crystalline phase is analyzed with X powder x ray diffractometer x and scanning electron microscope (SEM), and the result shows that synthetic molecular sieve relative crystallinity is 101%, and grain size is more even, is shaped as the twin segment cylinder shape.
Embodiment 3
With l25g water glass (SiO
2: 30.56wt%, Na
2O: 10.4wt%) join in the 104g deionized water, mix and be solution A; With 10.5g Al
2(SO
4)
318H
2O, 362g water and the 15.8g vitriol oil (98wt%) mix and are solution B.
The batching order is with example 1, and the add-on of n-Butyl Amine 99 and ammoniacal liquor is respectively 2.7g and 13.4ml (7mol/L).Each component mol ratio consists of:
11.9NH
3∶4.34Na
2O∶Al
2O
3∶40SiO
2∶2.7n-C
4H
9NH
2
Be warming up to 90 ℃ earlier, kept constant temperature 24 hours.Continue to be warming up to 185 ℃ again, constant temperature can be finished in 28 hours.Cooling stops crystallization rapidly, and the mixture in the synthesis reactor is shifted out.
With said mixture by example 1 separate, washing, drying, get final product zeolite molecular sieve.Crystalline phase is analyzed with X powder x ray diffractometer x and scanning electron microscope (SEM), and the result shows that synthetic molecular sieve relative crystallinity is 97%, and grain size is more even, is shaped as the twin segment cylinder shape.
Embodiment 4
With 180g water glass (SiO
2: 30.56wt%, Na
2O: 10.4wt%) join in the 550g deionized water, mix and be solution A; With 12.2g Al
2(SO
4)
318H
2O, 204g water and the 25.4g vitriol oil (98wt%) mix and are solution B.
The batching order is with example 1, and the add-on of n-Butyl Amine 99 and ammoniacal liquor is respectively 5.3g and 15.2ml (7mol/L).Each component mol ratio consists of:
11.7NH
3∶4.30Na
2O∶Al
2O
3∶50SiO
2∶3.97n-C
4H
9NH
2
Be warming up to 100 ℃ earlier, kept constant temperature 22 hours.Continue to be warming up to 185 ℃ again, constant temperature can be finished in 28 hours.Cooling stops crystallization rapidly, and the mixture in the synthesis reactor is shifted out.
With said mixture by example 1 separate, washing, drying, get final product zeolite molecular sieve.Crystalline phase is analyzed with X powder x ray diffractometer x and scanning electron microscope (SEM), and the result shows that synthetic molecular sieve relative crystallinity is 101%, and grain size is more even, is shaped as the twin segment cylinder shape.
Embodiment 5
With 240g water glass (SiO
2: 30.56wt%, Na
2O: 10.4wt%) join in the 120g deionized water, mix and be solution A; With 9.7g Al
2(SO
4)
318H
2O, 754g water and the 31.5g vitriol oil (98wt%) mix and are solution B.
The batching order is with example 1, and the add-on of n-Butyl Amine 99 and ammoniacal liquor is respectively 11.0g and 20.1ml (7mol/L).Each component mol ratio consists of:
19.3NH
3∶9.85Na
2O∶Al
2O
3∶84SiO
2∶10.35n-C
4H
9NH
2
Be warming up to 90 ℃ earlier, kept constant temperature 24 hours.Continue to be warming up to 190 ℃ again, constant temperature can be finished in 34 hours.Cooling stops crystallization rapidly, and the mixture in the synthesis reactor is shifted out.
With said mixture by example 1 separate, washing, drying, get final product zeolite molecular sieve.Crystalline phase is analyzed with X powder x ray diffractometer x and scanning electron microscope (SEM), and the result shows that synthetic molecular sieve relative crystallinity is 93%, and grain size is more even, is shaped as the twin segment cylinder shape.
Embodiment 6
With 165g water glass (SiO
2: 30.56wt%, Na
2O: 10.4wt%) join in the 280g deionized water, mix and be solution A; With 7.3g Al
2(SO
4)
318H
2O, 319g water and the 23.4g vitriol oil (98wt%) mix and are solution B.
The batching order is with example 1, and the add-on of n-Butyl Amine 99 and ammoniacal liquor is respectively 3.4g and 9.2ml (7mol/L).Each component mol ratio consists of:
10.7NH
3∶6.51Na
2O∶Al
2O
3∶70SiO
2∶6.16n-C
4H
9NH
2
Be warming up to 90 ℃ earlier, kept constant temperature 22 hours.Continue to be warming up to 190 ℃ again, constant temperature can be finished in 36 hours.Cooling stops crystallization rapidly, and the mixture in the synthesis reactor is shifted out.
With said mixture by example 1 separate, washing, drying, get final product zeolite molecular sieve.Crystalline phase is analyzed with X powder art x ray diffractometer x and scanning electron microscope (SEM), and the result shows that synthetic molecular sieve relative crystallinity is 95%, and grain size is more even, is shaped as the twin segment cylinder shape.
Claims (5)
1. the method for a fast synthetic high-crystallinity zeolite molecular sieve is characterized in that synthetic method comprises the steps:
(1) with water glass and deionized water SiO in molar ratio
2: H
2O=1: 10～40 are mixed into mixed liquor A;
(2) with Al
2(SO
4)
318H
2O, water and the vitriol oil be Al in molar ratio
2O
3: SO
4 2-: H
2O=1: 10～25: 500～3000 are mixed into mixed liquid B;
(3) under vigorous stirring, the B drips of solution is added in the A solution, stir; Adding aliphatic amide and concentration then is the inorganic ammonia solution of 5～7.9mol/L, mixes, and makes gel mixture;
(4) gel mixture is added in the synthesis reactor, sealing was worn out 10-24 hour down at 80～110 ℃ earlier, again at 170～190 ℃ of following crystallization 20-36 hours;
(5) after crystallization finished, cooling was carried out solid-liquid separation with reaction mixture, filter cake with deionized water wash to filter cake pH=8～9;
(6) filter cake is at 110 ± 10 ℃ of down dry 12～24h, in 540 ± 10 ℃ air atmosphere roasting 2～3 little, under 90～110 ℃, exchange 2～3 hours with the HCl of 0.3～0.5mol/L, promptly wait to obtain H type zeolite molecular sieve.
Wherein each component mol ratio consists of:
Inorganic ammonia: NaO
2: Al
2O
3: SiO
2: aliphatic amide=
0.09～0.25∶0.09～0.38∶0.01～0.25∶1∶0.05～0.12。
2. the method for a kind of fast synthetic high-crystallinity zeolite molecular sieve as claimed in claim 1 is characterized in that described inorganic ammonia is ammoniacal liquor and ammonium salt, as: ammonium nitrate, ammonium sulfate etc.
3. the method for a kind of fast synthetic high-crystallinity zeolite molecular sieve as claimed in claim 2 is characterized in that described ammonium salt is ammonium nitrate or ammonium sulfate.
4. the method for a kind of fast synthetic high-crystallinity zeolite molecular sieve as claimed in claim 1 is characterized in that described aliphatic amide is a primary amine, and wherein alkyl comprises 2～6 carbon atoms.
5. the method for a kind of fast synthetic high-crystallinity zeolite molecular sieve as claimed in claim 4 is characterized in that described primary amine is the primary amine that alkyl comprises 2～6 carbon atoms.
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|---|---|---|---|
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|---|---|---|---|
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| Publication Number | Publication Date |
|---|---|
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| CN1176849C CN1176849C (en) | 2004-11-24 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113620312A (en) * | 2021-08-24 | 2021-11-09 | 常州工学院 | Preparation method of SAPO-20 zeolite molecular sieve with high crystallinity |
-
2002
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113620312A (en) * | 2021-08-24 | 2021-11-09 | 常州工学院 | Preparation method of SAPO-20 zeolite molecular sieve with high crystallinity |
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| Publication number | Publication date |
|---|---|
| CN1176849C (en) | 2004-11-24 |
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