CN1453212A - Prepn of superfine 4A zeolite - Google Patents
Prepn of superfine 4A zeolite Download PDFInfo
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- CN1453212A CN1453212A CN 03122334 CN03122334A CN1453212A CN 1453212 A CN1453212 A CN 1453212A CN 03122334 CN03122334 CN 03122334 CN 03122334 A CN03122334 A CN 03122334A CN 1453212 A CN1453212 A CN 1453212A
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Abstract
The process of preparing superfine 4A zeolite includes dissolving sodium silicate as silicon source in water or alkali solution to compound sodium silicate solution; dissolving sodium aluminate as aluminum source in alkali solution to compound sodium aluminate solution; mixing surfactant and sodium aluminate solution via stirring and adding sodium silicate solution; regulating pH value with alkali solution, crystallizing, filtering, washing and drying. The present invention has the advantages of small granularity, narrow granularity distribution, prefect crystal form, high crystallization degree and short crystallization time of the 4A zeolite product.
Description
Technical field:
The invention belongs to a kind of synthetic method of 4A zeolite, relate in particular to a kind of synthetic method of ultra-fine 4A zeolite.
Background technology:
Additive to the research work of the influence of zeolite crystallization speed and physical and chemical performance seldom.GScott, R.W. etc. be in zeolite magazine nineteen ninety, 10 volumes, and 44 pages " trolamine application in zeolite crystallization " reported the method (claim the Charnell method, promptly added trolamine in gel, granularity is reduced) that changes A type zeolite crystallization size; Wemer Stober etc. are in colloid and interfacial chemistry magazine nineteen sixty-eight, and 26 volumes have been reported for 62 pages to add the methods that ethanol reduces zeolite particle size in gel; Prabir K.Dutta etc. are zeolite magazine 1991,11 volumes, reported adding hexamethyl-phosphoramide and methyl-sulphoxide in 507 pages of " solvent is to synthetic A type and the influence of X type zeolite " literary compositions after, the method that synthetic A type and X type zeolite particle size are reduced.And the tensio-active agent adding does not appear in the newspapers as yet to the method that the 4A zeolite particle size reduces.
Summary of the invention:
The present invention provides a kind of method of synthesizing superfine particle 4A zeolite.
The present invention is achieved in that certain density sodium silicate solution, sodium aluminate solution and tensio-active agent by gelatinization reaction, the gel product crystallization that heats up again then, and washing and filtering, final drying gets ultra-fine grain 4A zeolite.
Synthetic method of the present invention comprises the steps:
It is 45-105g/l that the silicon source is configured to NaOH content in the water-soluble or alkali lye, and SiO2 content is the sodium silicate solution of 120-350g/l; The aluminium source is dissolved in that to be configured to Na2O content in the alkaline solution be 70-120g/l, and Al2O3 content is the sodium aluminate solution of 40-70g/l;
Tensio-active agent added behind the above-mentioned sodium aluminate solution fully stirs, add above-mentioned sodium silicate solution again, regulate pH value=10-12 with alkali lye after, the powerful 5-30min that stirs.
The colloid that the stirs crystallization device of packing into is warming up to 60-1000C, static or stir under carry out crystallization, residence time 10-80min.
Pass through the filtering and removing mother liquor after the crystallization, and utilize bright water washing pH value to 7-11;
Be dried to powder at 100-3000C at last and get ultra-fine 4A zeolite product.
The mol ratio of each component is in synthetic:
Al2O3/SiO2＝1-6
Al2O3/R=0.001-0.1 R refers to tensio-active agent.
Described silicon source is: water glass, water glass, silicon oxide particle, the silicon oxide water-sol or silica gel.
Described aluminium source is: aluminate, alumina gel, metallic aluminium salt.
Described alkali is: sodium hydroxide, potassium hydroxide, ammonia.
Described tensio-active agent is: nonionic, positively charged ion, negatively charged ion or amphoterics, as alkyl glycoside (APG), cocamidopropyl propyl amide sulphonic acid betaine (CHS-35), dodecylbenzyl ammonium chloride (1227), fatty acid methyl sulfonate (MES) etc.
The present invention compared with prior art has following advantage:
The synthetic 4A zeolite of technology of the present invention has little, the narrower size-grade distribution of granularity, quite perfect crystalline form and high degree of crystallinity and short crystallization time.
Specific implementation method:
Embodiment 1
With the water glass sodium silicate solution (Na2O: 45g/l that is configured to soluble in water; SiO2: 120g/l), sodium aluminate solution is configured to sodium aluminate solution (Na2O: 90g/l in NaOH solution; Al2O3: 60g/l).Alkyl glycoside 1g is added after the above-mentioned sodium aluminate solution of 140ml fully stirs, add above-mentioned sodium silicate solution by Al2O3/SiO2=1.8 again, regulate pH value=powerful 10min of stirring in 10 backs with sodium hydroxide solution.The colloid that the stirs crystallization device of packing into is warming up to 750C, static or stir under carry out crystallization, residence time 30min.Remove mother liquor by the filtration washing device after the crystallization and utilize bright water washing pH value to 8, the mother liquor under filtering can be back to use in the preparation sodium aluminate solution and go.Be dried to powder through drying plant at 2000C at last and get ultra-fine 4A zeolite product.
Embodiment 2
With the water glass sodium silicate solution (Na2O: 60g/l that is configured to soluble in water; SiO2: 170g/l), sodium aluminate solution is configured to sodium aluminate solution (Na2O: 70g/l in NaOH solution; Al2O3: 40g/l).Cocamidopropyl propyl amide sulphonic acid betaine 1.2g is added after the above-mentioned sodium aluminate solution of 100ml fully stirs, add above-mentioned sodium silicate solution by Al2O3/SiO2=3 again, regulate pH value=powerful 30min of stirring in 11 backs with potassium hydroxide solution.The colloid that the stirs crystallization device of packing into is warming up to 600C, static or stir under carry out crystallization, residence time 30min.Remove mother liquor by the filtration washing device after the crystallization and utilize bright water washing pH value to 10.Be dried to powder through drying plant at 1000C at last and get ultra-fine 4A zeolite product.
Embodiment 3 is dissolved in the silicon oxide water-sol and is configured to sodium silicate solution (Na2O: 90g/l in the NaOH solution; SiO2: 200g/l), alumina gel is dissolved in and is configured to sodium aluminate solution (Na2O: 120g/l in the NaOH solution; Al2O3: 40g/l).Dodecylbenzyl ammonium chloride 0.11g is added after the above-mentioned sodium aluminate solution of 100ml fully stirs, add above-mentioned sodium silicate solution by Al2O3/SiO2=1 again, regulate pH value=powerful 15min of stirring in 12 backs with sodium hydroxide solution.The colloid that the stirs crystallization device of packing into is warming up to 950C, static or stir under carry out crystallization, residence time 15min.Remove mother liquor by the filtration washing device after the crystallization and utilize bright water washing pH value to 8, be dried to powder through drying plant at 1300C at last and get ultra-fine 4A zeolite product.
Embodiment 4
With the water glass sodium silicate solution (Na2O: 105g/l that is configured to soluble in water; SiO2: 350g/l), sodium aluminate solution is configured to sodium aluminate solution (Na2O: 140g/l in NaOH solution; Al2O3: 60g/l).Fatty acid methyl sulfonate 10g is added after the above-mentioned sodium aluminate solution of 150ml fully stirs, add above-mentioned sodium silicate solution by Al2O3/SiO2=4 again, regulate pH value=powerful 20min of stirring in 1 back with ammoniacal liquor.The colloid that the stirs crystallization device of packing into is warming up to 1000C, static or stir under carry out crystallization, residence time 80min.Remove mother liquor by the filtration washing device after the crystallization and utilize bright water washing pH value to 7, be dried to powder through drying plant at 1500C at last and get ultra-fine 4A zeolite product.
Embodiment 5
The silicon oxide water-sol is dissolved in is configured to sodium silicate solution (Na2O: 80g/l in the NaOH solution; SiO2: 300g/l), sodium aluminate solution in NaOH solution (in be configured to sodium aluminate solution (Na2O: 110g/l; Al2O3: 60g/l).Cocamidopropyl propyl amide sulphonic acid betaine 30g is added after the above-mentioned sodium aluminate solution of 200ml fully stirs, add above-mentioned sodium silicate solution by Al2O3/SiO2=6 again, regulate pH value=powerful 30min of stirring in 12 backs with sodium hydroxide solution.The colloid that the stirs crystallization device of packing into is warming up to 700C, static or stir under carry out crystallization, residence time 10min.Remove mother liquor by the filtration washing device after the crystallization and utilize bright water washing pH value to 10, be dried to powder through drying plant at 2000C at last and get ultra-fine 4A zeolite product.
Embodiment 6
With the silica gel sodium silicate solution (Na2O: 60g/l that is configured to soluble in water; SiO2: 180g/l), sodium aluminate solution is configured to sodium aluminate solution (Na2O: 90g/l in NaOH solution; Al2O3: 70g/l).Fatty acid methyl sulfonate 1g is added after the above-mentioned sodium aluminate solution of 100ml fully stirs, add above-mentioned sodium silicate solution by Al2O3/SiO2=2.8 again, regulate pH value=powerful 5min of stirring in 12 backs with potassium hydroxide solution.The colloid that the stirs crystallization device of packing into is warming up to 800C, static or stir under carry out crystallization, residence time 80min.Remove mother liquor by the filtration washing device after the crystallization and utilize bright water washing pH value to 9.Be dried to powder through drying plant at 1500C at last and get ultra-fine 4A zeolite product.
Embodiment 7
With the water glass sodium silicate solution (Na2O: 105g/l that is configured to soluble in water; SiO2: 300g/l), alumina gel is dissolved in and is configured to sodium aluminate solution (Na2O: 120g/l in the NaOH solution; Al2O3: 70g/l).Alkyl glycoside 10g is added after the above-mentioned sodium aluminate solution of 140ml fully stirs, add above-mentioned sodium silicate solution by Al2O3/SiO2=2 again, regulate pH value=powerful 20min of stirring in 10 backs with ammoniacal liquor.The colloid that the stirs crystallization device of packing into is warming up to 800C, static or stir under carry out crystallization, residence time 30min.Remove mother liquor by the filtration washing device after the crystallization and utilize bright water washing pH value to 11, be dried to powder through drying plant at 200 ℃ at last and get ultra-fine 4A zeolite product.
Claims (9)
1, a kind of method for preparing ultra-fine 4A zeolite is characterized in that comprising the steps:
(1) the silicon source being configured to NaOH content in the water-soluble or alkali lye is 45-105g/l, and SiO2 content is the sodium silicate solution of 120-350g/l; The aluminium source is dissolved in that to be configured to Na2O content in the alkaline solution be 70-120g/l, and Al2O3 content is the sodium aluminate solution of 40-70g/l;
Tensio-active agent fully stirs after adding above-mentioned sodium aluminate solution, adds above-mentioned sodium silicate solution again, regulate pH value=10-12 with alkali lye after, the powerful 5-30min that stirs;
(3) colloid that the stirs crystallization device of packing into is warming up to 60-1000C, static or stir under carry out crystallization, residence time 10-80min;
(4) change the back by the filtering and removing mother liquor, and utilize bright water washing pH value to 7-11;
(5) be dried to powder at 100-3000C at last and get ultra-fine 4A zeolite product;
The mol ratio of each component is in synthetic:
Al2O3/SiO2＝1-6
Al2O3/R=0.001-0.1 R refers to tensio-active agent.
2. a kind of method for preparing ultra-fine 4A zeolite as claimed in claim 1 is characterized in that described silicon source is water glass, water glass, silicon oxide particle, the silicon oxide water-sol or silica gel.
3. a kind of method for preparing ultra-fine 4A zeolite as claimed in claim 1 is characterized in that described aluminium source is aluminate, alumina gel or metallic aluminium salt.
4. a kind of method for preparing ultra-fine 4A zeolite as claimed in claim 1 is characterized in that described alkali is sodium hydroxide, potassium hydroxide or ammonia.
5. a kind of method for preparing ultra-fine 4A zeolite as claimed in claim 1 is characterized in that described tensio-active agent is nonionic, positively charged ion, negatively charged ion or amphoterics.
6. a kind of method for preparing ultra-fine 4A zeolite as claimed in claim 5 is characterized in that described nonionogenic tenside is an alkyl glycoside.
7. a kind of method for preparing ultra-fine 4A zeolite as claimed in claim 5 is characterized in that described amphoterics is the cocamidopropyl propyl amide sulphonic acid betaine.
8. a kind of method for preparing ultra-fine 4A zeolite as claimed in claim 5 is characterized in that described cats product is a dodecylbenzyl ammonium chloride.
9. a kind of method for preparing ultra-fine 4A zeolite as claimed in claim 5 is characterized in that described anion surfactant is a fatty acid methyl sulfonate.
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| CNB031223346A CN1305767C (en) | 2003-04-30 | 2003-04-30 | Prepn of superfine 4A zeolite |
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| CN1305767C CN1305767C (en) | 2007-03-21 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298627C (en) * | 2004-07-21 | 2007-02-07 | 中国日用化学工业研究院 | Method of quickly synthesizing super fine 4A zeolite |
| CN102070157A (en) * | 2010-12-02 | 2011-05-25 | 浙江大学 | Method for synthesizing A molecular sieve by semisolid phase |
| CN102502693A (en) * | 2011-10-27 | 2012-06-20 | 江苏奥石科技有限公司 | Method for synthesizing large-grain and highly-dispersed 4A zeolite |
| EP2471362A1 (en) * | 2009-08-28 | 2012-07-04 | FMC Foret S.A. | Strengthening composition that regulates transpiration and protects leaves and fruits, and use thereof |
| CN105860324A (en) * | 2016-04-18 | 2016-08-17 | 重庆理工大学 | Superfine zeolite and calcium zinc composite heat stabilizer |
| CN107720773A (en) * | 2017-10-30 | 2018-02-23 | 中海油天津化工研究设计院有限公司 | A kind of method for efficiently synthesizing the molecular sieves of B Al ZSM 5 |
| CN109678173A (en) * | 2019-02-26 | 2019-04-26 | 郑州雪山实业股份有限公司 | With the process of the sodium metaaluminate waste liquid synthesis 4A molecular sieve containing potassium |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1037166C (en) * | 1994-06-29 | 1998-01-28 | 中国石油化工总公司抚顺石油化工研究院 | Beta zeolite and preparing method thereof |
| CN1083399C (en) * | 1998-03-30 | 2002-04-24 | 中国石油化工总公司 | Synthesis of high-silicon mordenite |
-
2003
- 2003-04-30 CN CNB031223346A patent/CN1305767C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298627C (en) * | 2004-07-21 | 2007-02-07 | 中国日用化学工业研究院 | Method of quickly synthesizing super fine 4A zeolite |
| EP2471362A1 (en) * | 2009-08-28 | 2012-07-04 | FMC Foret S.A. | Strengthening composition that regulates transpiration and protects leaves and fruits, and use thereof |
| EP2471362A4 (en) * | 2009-08-28 | 2014-06-25 | Fmc Foret Sa | Strengthening composition that regulates transpiration and protects leaves and fruits, and use thereof |
| CN102070157A (en) * | 2010-12-02 | 2011-05-25 | 浙江大学 | Method for synthesizing A molecular sieve by semisolid phase |
| CN102502693A (en) * | 2011-10-27 | 2012-06-20 | 江苏奥石科技有限公司 | Method for synthesizing large-grain and highly-dispersed 4A zeolite |
| CN105860324A (en) * | 2016-04-18 | 2016-08-17 | 重庆理工大学 | Superfine zeolite and calcium zinc composite heat stabilizer |
| CN107720773A (en) * | 2017-10-30 | 2018-02-23 | 中海油天津化工研究设计院有限公司 | A kind of method for efficiently synthesizing the molecular sieves of B Al ZSM 5 |
| CN109678173A (en) * | 2019-02-26 | 2019-04-26 | 郑州雪山实业股份有限公司 | With the process of the sodium metaaluminate waste liquid synthesis 4A molecular sieve containing potassium |
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| CN1305767C (en) | 2007-03-21 |
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