CN1699173A - Synthesis method of fine grain ZSM-5 zeolite molecular sieve with high silicon aluminium ratio - Google Patents
Synthesis method of fine grain ZSM-5 zeolite molecular sieve with high silicon aluminium ratio Download PDFInfo
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- CN1699173A CN1699173A CN 200510200328 CN200510200328A CN1699173A CN 1699173 A CN1699173 A CN 1699173A CN 200510200328 CN200510200328 CN 200510200328 CN 200510200328 A CN200510200328 A CN 200510200328A CN 1699173 A CN1699173 A CN 1699173A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 58
- 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 58
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 18
- 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 18
- 239000010457 zeolite Substances 0.000 title claims abstract description 18
- 238000001308 synthesis method Methods 0.000 title claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract description 10
- 229910052710 silicon Inorganic materials 0.000 title abstract description 10
- 239000010703 silicon Substances 0.000 title abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 title abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title abstract description 6
- 239000004411 aluminium Substances 0.000 title abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000013078 crystal Substances 0.000 claims abstract description 43
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 22
- 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 21
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000011541 reaction mixture Substances 0.000 claims abstract description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 159000000013 aluminium salts Chemical class 0.000 claims abstract description 8
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims abstract description 8
- 238000007796 conventional method Methods 0.000 claims abstract description 3
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- 229910052681 coesite Inorganic materials 0.000 claims abstract 5
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract 5
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract 5
- 229910052682 stishovite Inorganic materials 0.000 claims abstract 5
- 229910052905 tridymite Inorganic materials 0.000 claims abstract 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910052593 corundum Inorganic materials 0.000 claims abstract 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910001868 water Inorganic materials 0.000 claims description 11
- 239000013543 active substance Substances 0.000 claims description 9
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical group CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 9
- 239000011707 mineral Substances 0.000 claims description 9
- 235000019353 potassium silicate Nutrition 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 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 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 13
- 230000008025 crystallization Effects 0.000 abstract description 13
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 239000004115 Sodium Silicate Substances 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 1
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 229910052911 sodium silicate Inorganic materials 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 14
- 238000003756 stirring Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000009415 formwork Methods 0.000 description 3
- 238000005304 joining Methods 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a synthesis method of fine grain ZSM-5 zeolite molecular sieve with high silicon aluminium ratio, which comprises using a surface active agent, charging it into acidified aluminium salt solution, then slowly dropping alkaline solution formed from sodium silicate, template agent and seed crystal into aluminium saline solution, the overall composition of the obtained reaction mixture being Na2O:Al2O3:SiO2:H2O=1.5-4.0:1:20-280:500-2000 by mol ratio, then subjecting the reaction mixture to thermal crystallization through the conventional method.
Description
Technical field
The invention belongs to the synthesis technical field of molecular sieve.Be particularly related to the synthetic method of the ZSM-5 molecular sieve with small crystal grains of high silica alumina ratio.
Background technology
The ZSM-5 molecular sieve (USP3702886,1972) of U.S. Mobil oil company invention has obtained using very widely in petrochemical process such as the type of the selecting cracking of hydro carbons, alkylation, isomerization, disproportionation, dewaxing, etherificate.The synthetic method of the ZSM-5 molecular sieve of reporting among the USP3702886 is with the silicon source.The aluminium source.Alkali, water and TPAOH organic formwork agent are mixed and made into reaction mixture, then with this reaction mixture in 100～175 ℃ of following crystallization 6 hours to 60 days (organic method).The improved afterwards synthetic method (inorganic method) of the ZSM-5 molecular sieve of organic formwork agent of not using also has a large amount of report (as EP0098641A2, CN85100463A etc.).In general the product degree of crystallinity of inorganic method and silica alumina ratio all are not so good as organic method, and specific surface also is starkly lower than organic product, but owing to do not use organic formwork agent, thereby cost reduces greatly.And do not have the pollution of organic amine, thereby the inorganic method of industrial general use is synthesized the ZSM-5 molecular sieve now to environment.The grain-size of the ZSM-5 molecular sieve of the above patent report is generally all more than several microns, because there are many unfavorable factors in big grain ZSM-5 molecular sieve.Weak points such as for example: the crystal grain of molecular sieve is big, and the duct is long, so the hand diffusional limitation is more serious, is unsuitable for macromolecular reaction and liquid reaction, and generates carbon deposit easily, and work-ing life is short.And small crystal grain molecular sieve has just in time remedied this deficiency, so, the present synthetic extensive concern that has caused domestic and international petrochemical complex boat field for ZSM-5 molecular sieve with small crystal grains.
But the report for ZSM-5 molecular sieve with small crystal grains is not a lot.
In 1975, United States Patent (USP) (USP3926782) has been reported with TPAOH and has been synthesized little crystal grain (5～100nm) ZSM-5 molecular sieve as structure directing agent, 1979, United States Patent (USP) (USP4151189) has disclosed the primary amine of 2-9 charcoal atom of usefulness as template synthesizing small crystal grain ZSM-5-5 molecular sieve, but its Si/Al=20.3.
1993, United States Patent (USP) (USP5240892) was reported a kind of method of inorganic method high-density synthesizing small crystal grain ZSM-5-5 molecular sieve, and water silicon ratio can be lower than 5 in its synthetic system.This method is earlier water-soluble silicate (as water glass) to be made non-water-soluble precipitation silica gel with mineral acid precipitation agent precipitation, precipitating silica gel with this then is the silicon source, be prepared into contain silicon source, aluminium source, alkali and water, solid content is at least the reaction mixture of 35 heavy %, then this reaction mixture is being kept stirring and temperature is lower than 250 ℃ condition crystallization.SiO in its reaction mixture
2/ Al
2O
3Mol ratio is 25～50, H
2O/SiO
2Less than 5.0, OH/SiO
2Greater than 0.11.Though colloid density is bigger in this method, thereby single-autoclave yield rate is higher, is the silicon source owing to adopt precipitation silica gel, the preparation process complexity, and also crystallization process needs vigorous stirring, and synthetic cost is higher.
Calendar year 2001, the CN1303816 patent report, method with directing agent method quickly synthesizing small crystal grain ZSM-5-5 molecular sieve, this method is earlier synthetic directed agents, replace the organic amine template with directed agents then in synthetic, this method need not add salt, and synthetic cost is lower, but must at first synthesize directed agents, synthesis cycle is longer like this.
United States Patent (USP) (USP6180550,2001) and United States Patent (USP) (USP6504075,2003) have successively been reported the synthetic method of ZSM-5 molecular sieve with small crystal grains.Raw material is a kind of unbodied silica-alumina material (being provided by WRGrace company), and its product has the crystal grain of 50wt% below 50nm, but its SiO
2/ Al
2O
3Less than 25.
The patent of above-mentioned several synthesizing small crystal grain ZSM-5-5 molecular sieve exists a common characteristic, is exactly SiO
2/ Al
2O
3Lower.Silica alumina ratio is low, and the thermostability of catalyzer and hydrothermal stability are just relatively poor, wants to improve the resistance toheat of catalyzer, just must be with adding some resistant to elevated temperatures materials in the ZSM-5 molecular sieve, as inertia silicon, metal oxide etc., troublesome poeration like this, and improved synthetic cost.
The silica alumina ratio that how to improve ZSM-5 molecular sieve with small crystal grains is an important topic, and in general, the silica alumina ratio that feeds intake is high more, and then the gained colloid is got over thickness during synthesis of molecular sieve, and the throwing water yield that needs is bigger, thereby single-autoclave yield rate reduces.In the prior art with water glass during for the synthetic ZSM-5 in silicon source, general product molecular sieve accounts for the ratio of weight of the water in the synthetic system less than 8%, feed intake the water aluminum ratio generally greater than 1500, water silicon is than greater than 30, otherwise become too thickness of colloid, occur stray crystals such as mordenite and quartz easily and can not get the ZSM-5 product of high-crystallinity.
Summary of the invention
Purpose of the present invention just provides that a kind of to carry synthetic cost low, and method is simple, the small-grain ZSM-5 synthesis method of zeolite molecular sieve of the even-grained silica alumina ratio of ZSM-5 zeolite molecular sieve.
Technical solution of the present invention is that a kind of small-grain ZSM-5 synthesis method of zeolite molecular sieve of high silica alumina ratio comprises:
A. with aluminium salt with deionized water dissolving after, use the mineral acid acidifying again, add salt then, after treating to dissolve fully, add and to use water-soluble tensio-active agent; Aluminium salt is Tai-Ace S 150, aluminum chloride or aluminum nitrate; Mineral acid is sulfuric acid, phosphoric acid, nitric acid or hydrochloric acid; Said tensio-active agent is Virahol, propyl carbinol, the trimethyl carbinol or isopropylcarbinol;
B. water glass, deionized water, template are mixed; Said template is n-Butyl Amine 99, quadrol or tripropyl amine;
C. aluminum salt solution is added drop-wise in the water glass solution at leisure, makes that the mol ratio of total composition of mixture is Na
2O: Al
2O
3: SiO
2: H
2O=1.5-4.0: 1: 20-280: 500-2000, wherein Na
2O represents the basicity of mixture;
D. in mixture, can add the molecular sieve crystal seed, the add-on of molecular sieve crystal seed by weight percentage, butt crystal seed weight/SiO
2=0-15%, SiO in the crystal seed
2And Al
2O
3Be not counted in the total composition of said mixture; The crystal seed of said molecular sieve is ZSM-5 molecular sieve or y-type zeolite;
E. with reaction mixture hydrothermal crystallizing according to a conventional method; The hydrothermal crystallizing temperature is 100-180 ℃.
Aluminium salt is industrial aluminum sulphate.
Mineral acid is a sulfuric acid.
The add-on of molecular sieve crystal seed by weight percentage, butt crystal seed weight/SiO
2=0-10%.
The crystal seed of said molecular sieve is the ZSM-5 molecular sieve.
Said template is a n-Butyl Amine 99.
Said tensio-active agent is a Virahol.
Said tensio-active agent is the trimethyl carbinol.
The said aluminium salt of step a can be one or more in Tai-Ace S 150, aluminum chloride or the aluminum nitrate in the method provided by the present invention; Industrial aluminum sulphate preferably.Said mineral acid is a kind of or mixture among them that is selected from sulfuric acid, phosphoric acid, nitric acid or the hydrochloric acid, and preferably mineral acid is a sulfuric acid.The crystal seed of said molecular sieve is ZSM-5 molecular sieve or y-type zeolite, preferably the ZSM-5 molecular sieve.Said template is a kind of or mixture among them that is selected from n-Butyl Amine 99, quadrol or the tripropyl amine; N-Butyl Amine 99 preferably.Said tensio-active agent is Virahol, propyl carbinol, the trimethyl carbinol, isopropylcarbinol is a kind of or the mixture among them; The preferably Virahol and the trimethyl carbinol.Can add the molecular sieve crystal seed in mixture, the add-on of crystal seed is pressed crystal seed weight (butt)/SiO
2=0～15% calculates SiO in the crystal seed
2And Al
2O
3Be not counted in the total composition of said mixture.(butt)/SiO preferably
2=0～10 heavy % calculate.
Said crystallization is carried out according to the conventional crystallization condition of ZSM-5 molecular sieve in the method provided by the present invention, is under 120-170 ℃, crystallization 20-80 hour.
The beneficial effect that the present invention reached is, under the prerequisite that does not change original ZSM-5 preparation of molecular sieve, improves the silica alumina ratio of ZSM-5 molecular sieve with small crystal grains, and synthetic cost is lower, and method is simple, easily row.By this method synthetic ZSM-5 zeolite molecular sieve epigranular.
Embodiment
The present invention is described further below in conjunction with embodiment.
Embodiment 1
Take by weighing industrial aluminum sulphate (Al
2O
3Content be 15.8wt%) 8.6 the gram, to wherein add 230 the gram distilled water make its dissolving, (concentration is 26wt%, d to add sulfuric acid then
4 20=1.192) 28 grams, the basicity of regulator solution is adding sodium-chlor 10 grams, after constantly stirring is dissolved it fully, adds Virahol (production of Tianjin Milky Way chemical reagent factory) 1.5 grams again, forms A solution.With 100 gram water dissolution, 517 gram water glass (27.6wt%SiO
2, 8.8wt%Na
2O, 63.6wt%H
2O), add homemade ZSM-5 crystal seed 2.5 grams then, constantly carry out mechanical stirring in the reinforced process, behind the adding n-Butyl Amine 99 slowly, form B solution,, used mulser emulsification then 15 minutes B solution joining in the middle of the A solution slowly under constantly stirring, then this reaction mixture is installed in the reactor, stir crystallization 24 hours at 100 ℃, be warming up to 170 ℃ then, crystallization 24 hours, products therefrom after filtration, after the washing, drying, ZSM-5 product 170 grams (butt).Average crystal grain diameter 40nm, SiO
2/ Al
2O
3Be 90.
Embodiment 2
Take by weighing industrial aluminum sulphate (Al
2O
3Content be 15.8wt%) 8.6 the gram, to wherein add 300 the gram distilled water make its dissolving, (concentration is 26wt%, d to add sulfuric acid then
4 20=1.192) 40 grams, the basicity of regulator solution at adding sodium-chlor 10 grams, after constantly stirring is dissolved it fully, adds isopropylcarbinol (chemical reagent work of connection chemical reagent factory produces in Beijing) 2.0 grams, formation A solution again.With 100 gram water dissolution, 560 gram water glass (27.6wt%SiO
2, 8.8wt%Na
2O, 63.6wt%H
2O), add homemade ZSM-5 crystal seed 2.0 grams then, constantly carry out mechanical stirring in the reinforced process, behind the adding n-Butyl Amine 99 slowly, form B solution,, used mulser emulsification then 15 minutes B solution joining in the middle of the A solution slowly under constantly stirring, then this reaction mixture is installed in the reactor, stir crystallization 24 hours at 100 ℃, be warming up to 160 ℃ then, crystallization 28 hours, products therefrom after filtration, after the washing, drying, ZSM-5 product 171 grams (butt).Average crystal grain diameter 70nm, SiO
2/ Al
2O
3Be 95.
Embodiment 3
Take by weighing industrial aluminum sulphate (Al
2O
3Content be 15.8wt%) 8.6 the gram, to wherein add 200 the gram distilled water make its dissolving, (concentration is 26wt%, d to add sulfuric acid then
4 20=1.192) 50.2 grams, the basicity of regulator solution is adding sodium-chlor 10 grams, after constantly stirring is dissolved it fully, adds the trimethyl carbinol (Military Medical Science Institute medical supply station) 2.6 grams again, forms A solution.With 100 gram water dissolution, 500.4 gram water glass (27.6wt%SiO
2, 8.8wt%Na
2O, 63.6wt%H
2O), add homemade ZSM-5 crystal seed 3.0 grams then, constantly carry out mechanical stirring in the reinforced process, behind the adding n-Butyl Amine 99 slowly, form B solution,, used mulser emulsification then 15 minutes B solution joining in the middle of the A solution slowly under constantly stirring, then this reaction mixture is installed in the reactor, stir crystallization 24 hours at 100 ℃, be warming up to 150 ℃ then, crystallization 34 hours, products therefrom after filtration, after the washing, drying, ZSM-5 product 165 grams (butt).Average crystal grain diameter 60nm, SiO
2/ Al
2O
3Be 90
Claims (8)
1. the small-grain ZSM-5 synthesis method of zeolite molecular sieve of a high silica alumina ratio is characterized in that, this method comprises:
A. with aluminium salt with deionized water dissolving after, use the mineral acid acidifying again, add salt then, after treating to dissolve fully, add and to use water-soluble tensio-active agent; Aluminium salt is Tai-Ace S 150, aluminum chloride or aluminum nitrate; Mineral acid is sulfuric acid, phosphoric acid, nitric acid or hydrochloric acid; Said tensio-active agent is Virahol, propyl carbinol, the trimethyl carbinol or isopropylcarbinol;
B. with water glass, deionized water, template is mixed; Said template is n-Butyl Amine 99, quadrol or tripropyl amine;
C. aluminum salt solution is added drop-wise in the water glass solution at leisure, makes that the mol ratio of total composition of mixture is Na2O: Al2O3: SiO2: H2O=1.5-4.0: 1: 20-280: 500-2000, wherein Na2O represents the basicity of mixture;
D. in mixture, can add the molecular sieve crystal seed, the add-on of molecular sieve crystal seed by weight percentage, butt crystal seed weight/SiO2=0-15% is during SiO2 and Al2O3 are not counted in that said mixture is total and form in the crystal seed; The crystal seed of said molecular sieve is ZSM-5 molecular sieve or y-type zeolite;
E. with reaction mixture hydrothermal crystallizing according to a conventional method; The hydrothermal crystallizing temperature is 100-180 ℃, and the time is 20-80 hour
2. the small-grain ZSM-5 synthesis method of zeolite molecular sieve of a kind of high silica alumina ratio according to claim 1 is characterized in that, aluminium salt is industrial aluminum sulphate.
3. the small-grain ZSM-5 synthesis method of zeolite molecular sieve of a kind of high silica alumina ratio according to claim 1 is characterized in that, mineral acid is a sulfuric acid.
4. the small-grain ZSM-5 synthesis method of zeolite molecular sieve of a kind of high silica alumina ratio according to claim 1 is characterized in that, the add-on of molecular sieve crystal seed by weight percentage, butt crystal seed weight/SiO2=0-10%
5. the small-grain ZSM-5 synthesis method of zeolite molecular sieve of a kind of high silica alumina ratio according to claim 1 is characterized in that, the crystal seed of said molecular sieve is the ZSM-5 molecular sieve.
6. the small-grain ZSM-5 synthesis method of zeolite molecular sieve of a kind of high silica alumina ratio according to claim 1 is characterized in that, said template is a n-Butyl Amine 99.
7. the small-grain ZSM-5 synthesis method of zeolite molecular sieve of a kind of high silica alumina ratio according to claim 1 is characterized in that, said tensio-active agent is a Virahol.
8. the small-grain ZSM-5 synthesis method of zeolite molecular sieve of a kind of high silica alumina ratio according to claim 1 is characterized in that, said tensio-active agent is the trimethyl carbinol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005102003289A CN100364890C (en) | 2005-06-14 | 2005-06-14 | Synthesis method of fine grain ZSM-5 zeolite molecular sieve with high silicon aluminium ratio |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005102003289A CN100364890C (en) | 2005-06-14 | 2005-06-14 | Synthesis method of fine grain ZSM-5 zeolite molecular sieve with high silicon aluminium ratio |
Publications (2)
| Publication Number | Publication Date |
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| CN1699173A true CN1699173A (en) | 2005-11-23 |
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| CN100455511C (en) * | 2006-11-10 | 2009-01-28 | 南京工业大学 | Method for synthesizing small-grain ZSM-5 zeolite molecular sieve |
| CN101837298A (en) * | 2010-05-14 | 2010-09-22 | 广西壮族自治区化工研究院 | Small-grain ZSM-5 molecular sieve catalyst used for preparing ethylene from bioethanol and preparation method thereof |
| CN101723401B (en) * | 2008-10-28 | 2011-07-20 | 中国石油化工股份有限公司 | ZSM-5/ZSM-5 core-shell type zeolite molecular sieve |
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