CN1454842A - 4A zeolite, manufacture method and use thereof - Google Patents
4A zeolite, manufacture method and use thereof Download PDFInfo
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- CN1454842A CN1454842A CN 02118924 CN02118924A CN1454842A CN 1454842 A CN1454842 A CN 1454842A CN 02118924 CN02118924 CN 02118924 CN 02118924 A CN02118924 A CN 02118924A CN 1454842 A CN1454842 A CN 1454842A
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- zeolite
- sodium aluminate
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Abstract
The present invention discloses a method for preparing 4A zeolite. In the sodium aluminate solution containing sodium silicate the alumina content is 70-240 g/l, sodium oxide content is 80-200 g/l and silicon dioxide content is 2-15 g/l, said invention utilizes the additive of 4A zeolite crystal seed to obtain 4A zeolite. The calcium ion exchange capacity of 4A zeolite is 260-320 mg/g, and the water adsorptivity is 24-27 wt%. After the product 4A zeolite and sodium aluminate mother solution are separated, the residual silicon dioxide content in the mother solution is not greater than 2g/l.
Description
(1) technical field
The present invention relates to the manufacture method of a kind of synthetic 4A zeolite (or claim 4A molecular sieve), the zeolite that obtains by this method and the purposes of described zeolite.
(2) background technology
Synthetic 4A zeolite is a kind of multi-functional, broad-spectrum product.Utilize its ion exchanging function, the 4A zeolite can be used as detergent builder, prevents that the washing composition active constituent from combining with calcium ions and magnesium ions in the water and lose activity, and the active normal performance of protection washing composition is to prevent that bath water from polluting the important environmentfriendly products of rivers and lakes; Also can be used for removing heavy metal ion in the water,, purify water as lead, cadmium etc.The 4A zeolite has adsorptivity, and adsorbable molecular diameter as water molecules etc., carries out depth drying to air, oil gas, carbonic acid gas, organic solvent etc. less than the molecule of 4 dusts, is widely used in building, chemistry, chemical industry and the daily life.The 4A zeolite is again a raw material of making 3A, 5A zeolite.The multifunctionality of 4A zeolite makes the use range of 4A zeolite constantly obtain developing, and Application Areas is constantly developed.
The 4A zeolite is the reaction product of sodium aluminate, caustic soda and water glass.Common preparation method reacts under normal temperature condition for sodium aluminate solution and sodium silicate solution, generates colloid, improves temperature of reaction then, forms crystal 4 A zeolite.
The crystal component of 4A zeolite can be expressed as Na
2O.Al
2O
3.2SiO
2.xH
2O, wherein Al
2O
3With SiO
2The ratio of molecule number is 2; In the building-up reactions, the aluminum oxide in the solution approaches 2 reactions that help synthesizing the 4A zeolite more more with the ratio of silicon-dioxide.
In the reaction of 4A zeolite synthesis, the ratio of aluminum oxide in the solution and silicon-dioxide is usually between 1-3.
In order to improve reaction conditions or product quality, introduce crystal seed, the crystallisation process as inductor acceleration colloidal state sodium aluminium silicate forms the 4A zeolite crystal.The effect of introducing crystal seed is to introduce nucleus, makes the sodium aluminium silicate energy rapid crystallization of colloidal state, generates the 4A zeolite.This process is characterised in that nucleus is in the sodium aluminium silicate of colloidal state Al in the sodium aluminium silicate of colloidal state
2O
3With SiO
2The ratio of molecule number approaches 2, with the Al in the 4A zeolite crystal
2O
3With SiO
2The ratio of molecule number is close, and the effect of nucleus is to induce the sodium aluminium silicate generation hydro-thermal reaction of colloidal state, generates the 4A zeolite crystal.In this building-up process, if do not add crystal seed, the sodium aluminium silicate of colloidal state also can form the 4A zeolite, and just formation time prolongs to some extent, and crystallization purity may be lower.
(3) summary of the invention
The objective of the invention is, use the lower sodium aluminate solution of water glass content, after stir adding crystal seed 4A zeolite, the method that makes water glass in the solution and sodium aluminate generate a kind of crystallochemical reaction of 4A zeolite on the 4A zeolite seed crystal surface of adding is made the 4A zeolite.
Another object of the present invention is, is in the sodium aluminate solution of water glass of 2-15g/l at dioxide-containing silica, in the serious excessive solution environmental of sodium aluminate, stirs and adds crystal seed 4A zeolite in solution, makes a kind of method of 4A zeolite.
The present invention can make and contain the lower sodium aluminate solution of water glass and fully react, and generates the 4A zeolite.By stirring, generate the 4A zeolite at the 4A zeolite surface generation crystallochemical reaction that adds, the dioxide-containing silica of residual sodium silicate can be lower than 2.0g/l in the sodium aluminate liquor, and good be lower than 1.0g/l better can be lower than 0.6g/l slightly.
The 4A zeolite that the present invention generates, granularity are easy to control, can be at 0.5 micron-10 micron, and calcium ion exchange capacity is between 260-320mg/g, and the water adsorptive power is at 24-27wt.%.
Among the present invention, the Al in the sodium aluminate solution
2O
3Content is at 70-240g/l, and sodium oxide content is at 80-200g/l.
Among the present invention, the amount of the crystal seed 4A zeolite of interpolation is 5-100g/l.
Among the present invention, crystal seed 4A zeolite can an amount of at normal temperatures pre-the interpolation.
Among the present invention, the crystal seed 4A zeolite of interpolation can quicken the crystallochemical reaction of 4A zeolite after grinding.
Among the present invention, the crystal seed 4A zeolite sectional of interpolation adds.
Among the present invention, the crystal seed 4A zeolite of interpolation can be recycled.
The inventor thinks that the effect of the 4A zeolite of interpolation is: making aluminate in the solution and silicate ion is template with the active surface of 4A zeolite, carries out crystallochemical reaction, generates the 4A zeolite.In this process, if do not add the 4A zeolite, sodium aluminate in the solution and water glass can not form the 4A zeolite.
Contain in the sodium aluminate solution of water glass, alumina content 70-240g/l, sodium oxide content 80-200g/l, dioxide-containing silica 2-15g/l, under temperature 60-120 ℃, stir and add crystal seed 4A zeolite 5-100g/l, keep after 1.5-8 hour, liquid-solid separation after washing, drying, can make the 4A zeolite.
(4) embodiment
Measure the calcium switching performance of product with the following method, the water adsorptive power.
Measure the calcium ion-exchanged performance
Measure with the light industry standard QB1768-93 of the People's Republic of China (PRC).The calcium exchange capacity is at 285mg/gCaCO
3More than be salable product, calcium exchange capacity 295mg/gCaCO
3More than be first grade, calcium exchange energy 310mg/gCaCO
3More than be the top grade product.
Measure the water adsorptive power
With the BET determinator, the 4A zeolite is greater than 250 ℃, and vacuum tightness was less than activation under the 0.1mmHg condition 1.5 hours; At 25 ℃, under the 10mmHg water partial pressure, record the equilibrium moisture content percentage of 4A zeolite then.
Testing graininess
Use the Ma Erwen laser particle analyzer to measure granularity.
Embodiment 1
Contain in the sodium aluminate solution of water glass, alumina content 140g/l, sodium oxide content 140g/l, dioxide-containing silica 9g/l, under 95 ℃ of temperature, stir to add and be ground to the about 1 micron crystal seed 4A zeolite 40g/l of diameter, keep after 4 hours, liquid-solid separation after washing, drying, makes the 4A zeolite.
Product 4A zeolite calcium ion-exchanged rate 283mg/g, 1.5 microns of granularities, residual Si O in the sodium aluminate liquor of reaction back
2Amount 1.0g/l.
Embodiment 2
After the 4A zeolite of embodiment 1 gained is ground to about 1 micron of diameter, adopt the method for embodiment 1, make the 4A zeolite.
The 4A zeolite after grinding that repeatedly repeats to make by embodiment 1 is a crystal seed, repeats the test of embodiment 1, makes the 4A zeolite.
Product 4A zeolite calcium ion-exchanged rate 281mg/g, 1.5 microns of granularities, residual Si O in the mother liquor of reaction back
2Amount 1.0g/l.
Embodiment 3
Contain in the sodium aluminate solution of water glass, alumina content 200g/l, sodium oxide content 200g/l, dioxide-containing silica 5g/l are under 95 ℃ of temperature, stir and add crystal seed 4A zeolite 20g/l, keep after 5 hours liquid-solid separation, after washing, drying, make the 4A zeolite.
Product 4A zeolite water adsorptive capacity 24.3wt%, residual Si O in the sodium aluminate liquor of reaction back
2Amount 2.0g/l.
Embodiment 4
Contain in the sodium aluminate solution of water glass, alumina content 90g/l, sodium oxide content 100g/l, dioxide-containing silica 15g/l, under 95 ℃ of temperature, stir and add the about 2 microns crystal seed 4A zeolite 45g/l of particle diameter, keep after 3 hours, stir and add the about 2 microns crystal seed 4A zeolite 25g/l of particle diameter, keep after 2 hours, liquid-solid separation after washing, drying, makes the 4A zeolite.
Product 4A zeolite calcium ion-exchanged rate 302mg/g, 2.4 microns of particle diameters, water adsorption amount 26.0wt%
Embodiment 5
Contain in the sodium aluminate solution of water glass, alumina content 105g/l, sodium oxide content 110g/l, dioxide-containing silica 5g/l are under 95 ℃ of temperature, stir and add crystal seed 4A zeolite 40g/l, keep after 4.5 hours liquid-solid separation, after washing, drying, make the 4A zeolite.
Product 4A zeolite water adsorptive capacity 25.7wt%, residual Si O in the sodium aluminate liquor of reaction back
2Amount 0.60g/l.
Embodiment 6
Contain in the sodium aluminate solution of water glass, alumina content 130g/l, sodium oxide content 110g/l, dioxide-containing silica 9g/l, temperature 35-50 ℃, add crystal seed 26g/l, kept 30 minutes, be warming up to 105 ℃, stir and add crystal seed 4A zeolite 14g/l, keep after 2 hours liquid-solid separation, after washing, drying, make the 4A zeolite.
Product 4A zeolite calcium ion-exchanged rate 310mg/g, water adsorption amount 27.0wt%, residual Si O in the sodium aluminate liquor of reaction back
2Amount 0.70g/l.
Claims (20)
1. one kind is used the lower sodium aluminate solution of water glass content, add crystal seed 4A zeolite after, make water glass in the solution and sodium aluminate generate the method for the crystallochemical reaction of 4A zeolite at the 4A zeolite surface that adds, make the 4A zeolite.
2. a dioxide-containing silica is in the sodium aluminate solution of the water glass of 2-15g/l, in the serious excessive solution environmental of sodium aluminate, stirs and adds crystal seed 4A zeolite in solution, makes the method for 4A zeolite.
3. the manufacture method of a 4A zeolite, it is included in the sodium aluminate solution that contains water glass, alumina content 70-240g/l, sodium oxide content 80-200g/l, dioxide-containing silica 2-15g/l, under temperature 60-120 ℃, stir and add crystal seed 4A zeolite 5-100g/l, keep after 1.5-8 hour liquid-solid separation, after washing, drying, make the 4A zeolite.
4. method as claimed in claim 3 is characterized in that under 30-50 ℃ of condition, adds the 30-80% that adds 4A zeolite seed crystal total amount, 10-120 minute in advance to the sodium aluminate solution that contains water glass; All the other crystal seeds add when temperature reaches 80-115 ℃.
5. method as claimed in claim 4 is characterized in that under 30-50 ℃ of condition, adds the 40-70% that adds 4A zeolite seed crystal total amount, 10-90 minute in advance to the sodium aluminate solution that contains water glass; All the other crystal seeds add when temperature reaches 95-115 ℃.
6. as the described method of claim 3,4 or 5, make the water glass reaction in the sodium aluminate solution, generate the 4A zeolite, after the liquid-solid separation, the silicon-dioxide of residual sodium silicate is not more than 2.0g/ in the sodium aluminate liquor.
7. the 4A zeolite that makes as the described method of claim 3,4 or 5, its calcium ion exchange capacity 260-320mg/g, water adsorptive power 24-27wt.%
8. as claim 3 or 4 described methods, it is characterized in that in containing the sodium aluminate solution of water glass, alumina content 90-180g/l, sodium oxide content 100-180g/l, dioxide-containing silica 2-10g/l, temperature 80-115 ℃, crystal seed 4A zeolite adds total amount 20-80g/l, time 1.5-6 hour.
9. method as claimed in claim 8 makes the water glass reaction in the sodium aluminate solution, generates the 4A zeolite, and after the liquid-solid separation, the silicon in the sodium aluminate liquor is not more than 1.0g/l.
10. the 4A zeolite that makes as method as described in the claim 8, its calcium ion exchange capacity 260-315mg/g, water adsorptive power 24-27wt.%
11. as claim 3 or 4 described methods, it is characterized in that in containing the sodium aluminate solution of water glass, alumina content 100-160g/l, sodium oxide content 100-160g/l, dioxide-containing silica 3-8g/l, temperature 95-110 ℃, crystal seed 4A zeolite adds total amount 20-60g/l, time 1.5-4 hour.
12. method as claimed in claim 11 makes the water glass reaction in the sodium aluminate solution, generates the 4A zeolite, after the liquid-solid separation, the silicon in the sodium aluminate liquor is not more than 0.6g/l.
13. as the 4A zeolite that method as described in the claim 11 makes, calcium ion exchange capacity 260-305mg/g, water adsorptive power 24-26wt.%
14. as claim 3, the 4A zeolite that 4,5,8 or 11 described methods make, its size range is at 0.5 micron-10 microns.
15. 4A zeolite as claimed in claim 14, its size range is at 1 micron-7 microns.
16. as claim 3,6,9 described 4A zeolites, size range is at 1 micron-4 microns.
17., it is characterized in that adding the 4A zeolite seed crystal after the grinding as the arbitrary described method of claim 1-16.
18., it is characterized in that segmentation interpolation 4A zeolite seed crystal as the arbitrary described method of claim 1-16.
19., it is characterized in that the 4A zeolite seed crystal that adds recycles as the arbitrary described product of claim 1-16.
20. the purposes of 4A zeolite as claimed in claim 11 in ion-exchanger or sorbent material.
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|---|---|---|---|
| CN 02118924 CN1289398C (en) | 2002-04-30 | 2002-04-30 | 4A zeolite, manufacture method and use thereof |
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|---|---|---|---|
| CN 02118924 CN1289398C (en) | 2002-04-30 | 2002-04-30 | 4A zeolite, manufacture method and use thereof |
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|---|---|
| CN1454842A true CN1454842A (en) | 2003-11-12 |
| CN1289398C CN1289398C (en) | 2006-12-13 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348487C (en) * | 2004-11-12 | 2007-11-14 | 山东铝业股份有限公司 | Guiding agent for preparing 4A zeolite |
| CN103635426A (en) * | 2011-03-11 | 2014-03-12 | 日立化成株式会社 | Aluminum silicate, metal ion adsorbent, and method for producing same |
| CN106892438A (en) * | 2017-02-10 | 2017-06-27 | 山东鲁北企业集团总公司 | A kind of preparation method of 4A zeolites |
| CN109922872A (en) * | 2016-09-01 | 2019-06-21 | 埃克森美孚上游研究公司 | Use the zeolite structured variation adsorption treatment for removing water of 3A |
| CN113603111A (en) * | 2021-08-23 | 2021-11-05 | 中国科学院宁波材料技术与工程研究所 | 4A zeolite with adjustable oxygen vacancy content and preparation method and application thereof |
-
2002
- 2002-04-30 CN CN 02118924 patent/CN1289398C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348487C (en) * | 2004-11-12 | 2007-11-14 | 山东铝业股份有限公司 | Guiding agent for preparing 4A zeolite |
| CN103635426A (en) * | 2011-03-11 | 2014-03-12 | 日立化成株式会社 | Aluminum silicate, metal ion adsorbent, and method for producing same |
| CN103635426B (en) * | 2011-03-11 | 2017-03-01 | 日立化成株式会社 | Aluminosilicate, metal ion adsorbent and their manufacture method |
| CN109922872A (en) * | 2016-09-01 | 2019-06-21 | 埃克森美孚上游研究公司 | Use the zeolite structured variation adsorption treatment for removing water of 3A |
| CN106892438A (en) * | 2017-02-10 | 2017-06-27 | 山东鲁北企业集团总公司 | A kind of preparation method of 4A zeolites |
| CN113603111A (en) * | 2021-08-23 | 2021-11-05 | 中国科学院宁波材料技术与工程研究所 | 4A zeolite with adjustable oxygen vacancy content and preparation method and application thereof |
| CN113603111B (en) * | 2021-08-23 | 2022-01-04 | 中国科学院宁波材料技术与工程研究所 | 4A zeolite with adjustable oxygen vacancy content and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1289398C (en) | 2006-12-13 |
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