CN101337680A - Method for synthesizing 4A zeolite molecular sieve by adding guiding agent - Google Patents
Method for synthesizing 4A zeolite molecular sieve by adding guiding agent Download PDFInfo
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- CN101337680A CN101337680A CNA2008100729336A CN200810072933A CN101337680A CN 101337680 A CN101337680 A CN 101337680A CN A2008100729336 A CNA2008100729336 A CN A2008100729336A CN 200810072933 A CN200810072933 A CN 200810072933A CN 101337680 A CN101337680 A CN 101337680A
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Abstract
The invention relates to a method for synthesizing a 4A zeolite molecular sieve by adding a directing agent. The method comprises the steps of preparing the directing agent, preparing active silicon slag and preparing the 4A zeolite molecular sieve, and specifically comprises the steps of taking bentonite; obtaining active silicon slag through wet purification and acidification; alkalifying; adding the directing agent and aluminum needed to be added when the silicon slag is agitated to glue shape; crystallizing; filtering; washing; and drying to obtain the 4A zeolite molecular sieve. In the invention, the directing agent is added to shorten the crystallization time when synthesizing, and reduce the grain size of a product. The 4A zeolite molecular sieve product obtained through the method has small average particle size, and large ion exchange capacity, thereby obtaining product of better property and saving energy resource.
Description
Technical field
The present invention relates to a kind of method of the 4A of preparation zeolite molecular sieve, particularly a kind of is the method for feedstock production 4A zeolite molecular sieve with the wilkinite.
Technical background
Zeolite molecular sieve (claiming synthetic zeolite again) is an a kind of shape aluminosilicate, by [SiO
4] and [AlO
4] tetrahedron composition skeleton construction, have the broad cavity and the passage of broad.In the molecular sieve lattice, exist metallic cation (as Na, K, Ca etc.) with the balance tetrahedron in unnecessary electric charge.
A type molecular sieve belongs to tesseral system, unit cell parameters
Contain Na in the structure cell
96[Si
96Al
96O
384] 216H
2O is not if consider the difference of sial position, unit cell parameters
At this moment contain Na in the structure cell
12[Si
12Al
12O
48] 27H
2O.Its structure is that the β cage is arranged by the cubes mode and formed.Eight β cages are distributed on the top, cubical eight angles, connect by the formed cubes cage of tetra-atomic ring between two adjacent β hold together, and have so just formed the frame structure of A type molecular sieve.Eight β cages interconnect the back at big α cage of intermediate formation, and this α cage is the main hole of A type molecular sieve.Around the α cage eight β cages and 12 cubes cages are arranged, α cage and β cage are communicated with each other by six-ring, and α cage is connected with six α cages on every side by octatomic ring.The octatomic ring channel diameter of general sodium type is about
Claim the 4A molecular sieve; The octatomic ring channel diameter of calcium type is about
Claim the 5A molecular sieve; The aperture of potassium type has only
So claim the 3A molecular sieve.
The 4A zeolite molecular sieve is sorbent material, siccative, catalyzer and the solid support material of present widespread use.It is mainly used in industries such as chemical industry, petrochemical industry and washing composition, especially in washing composition is made, the 4A zeolite molecular sieve is nontoxic, environment is not produced pollution, and the calcium ions and magnesium ions in the water had adsorption preferably, thereby be considered to preferred material for phosphorus (tripoly phosphate sodium STPP) washing powder, washing composition.
The primary condition of synthesis zeolite is: the reactive behavior of (1) raw material wants high; (2) cationic structure choice is suitable; (3) reaction mixture helps to improve the gel degree of supersaturation, is beneficial to the formation of nucleus.At present, A type synthesis method of zeolite molecular sieve mainly contains following several: (1) hydrothermal method; (2) non-water system synthesis method; (3) vapor phase synthesis method; (4) high-temperature synthesis; (5) low temperature synthesis method; (6) microwave technology; (7) high pressure synthesis method.
Wherein, the most commonly used is hydrothermal synthesis method, investigates from the synthesis material source, and hydrothermal synthesis method can be divided into industrial chemicals synthesis method and natural mineral raw synthesis method.Though with purifying worker raw material synthesis zeolite technical maturity, technical parameter is controlled easily, sintetics quality height, but raw material sources difficulty, price is generally higher, had a strong impact on zeolite in extensive use,, thereby become tempting developing direction based on the zeolite synthetic of cheap raw mineral materials also because price factor has limited widening of Application Areas such as industries such as washing composition, fodder additives, agriculture chemical, coating, wastewater and exhaust gas purification processing.
Summary of the invention
The purpose of this invention is to provide a kind of method that adds the synthetic 4A zeolite molecular sieve of directed agents.Though with the wilkinite is the existing report of the synthetic 4A zeolite molecular sieve document of raw material, but the present invention is when synthesizing the 4A zeolite molecular sieve with wilkinite, shorten crystallization time when synthetic by adding directed agents, reduce the particle diameter of products obtained therefrom, thereby obtain the better product of performance and save the energy.
Described a kind of method that adds the synthetic 4A zeolite molecular sieve of directed agents of the present invention follows these steps to carry out:
The preparation directed agents:
A, get NaOH and be dissolved in the water, be heated to boiling, add Al (OH) when being cooled to 50 ℃ again
3Make solution, under constant temperature ebullient condition, add water glass while stirring, the adularescent flocks occurs during beginning, continue to stir, precipitation fades away, and is heated to 70 ℃, the constant temperature boiling is stirred 30min and is made gel, be divided into two parts then, difference ageing 24h and 48h under constant temperature, it is standby as crystallization director to get product;
Prepare active white residue:
B, being raw material with the wilkinite, the wilkinite raw ore is removed the bigger sand grains of granularity through wet purification, is sulfuric acid and the 300-400 purpose wilkinite of 30-40% with concentration, by 1: the solid-to-liquid ratio of 2-5 drops in the acidifying still, be warming up to 80-95 ℃, 4 hours after-filtration of acidification reaction get active white residue;
Preparation 4A zeolite molecular sieve:
C, measuring the sial content in the active white residue, is that 30% NaOH joins in the reactor that has agitator with concentration, or else disconnectedly adds active white residue in reactor, is heated to 60-70 ℃ simultaneously, alkalizes, and alkalization time is 1.5-2h;
Product after d, the alkalization is carried out to glue, and temperature is controlled at 20-50 ℃, and time 1h adds NaAlO when becoming glue
2Mend aluminium;
E, the reaction of one-tenth glue stop to stir after finishing, and add mass percent 3-15% step a directed agents, and temperature rises to 80-100 ℃ and carries out crystallization, and crystallization is filtered material, wash dealkalize, dehydrated after synthesizing 0.5-1h, promptly gets the 4A zeolite molecular sieve.
Described method, synthetic 4A zeolite reaction system ratio range should be controlled at Na
2O: Al
2O
3: SiO
2: H
2O=2-5: 1: 1.8-2.2: 70-180.
The add-on of NaOH NaOH: SiO in molar ratio among the step c
2Be 2.5-3: 1.
NaAlO in the steps d
2Add-on be that each component mol ratio of reaction system is determined.
A kind of method that adds the synthetic 4A zeolite molecular sieve of directed agents of the present invention, directed agents is the still uncompleted nucleus blank of crystallization in this method, has served as nucleation centre in synthetic system.Adding directed agents is in order to increase nucleus quantity, to reduce grain size number.It is generally acknowledged that it is active why directed agents has guiding, be because wherein containing atomic nucleus little, that have certain crystallographic structure exists, and its existence is to quicken the mushroom basic reason of crystal.Facts have proved that directed agents is the most effective means of control zeolite crystallization process.By in solution, introducing the directed agents of 3%-15% (mass percent), the crystallization time of zeolite is shortened more than 90%, and can improve the size-grade distribution and the reunion degree of product well.
A kind of method that adds the synthetic 4A zeolite molecular sieve of directed agents of the present invention is got the wilkinite of Toksun, Xinjiang, gets active white residue (SiO after the wet purification acidifying
2: 69.3%; Al
2O
3: 15.76%; Whiteness: 92.9), after alkalization, the aluminium that when stirring into glue, adds 5% directed agents and need add, crystallization 0.5h after-filtration, washing, the dry 4A zeolite molecular sieve that gets.With the 4A zeolite molecular sieve that obtains with do not add directed agents and prepare relatively seeing the following form of 4A zeolite:
As can be seen from the table: the 4A zeolite molecular sieve of gained of the present invention is compared with the 4A zeolite molecular sieve that does not add directed agents, the present invention has shortened crystallization time by adding directed agents, the 4A zeolite product mean particle size that obtains is little, and the calcium ion-exchanged capacity is big, better performances.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Below further specify the present invention by example.
Embodiment 1
The preparation directed agents:
A, get NaOH4g and be dissolved in the 146ml water, be heated to boiling, add Al (OH) when being cooled to 50 ℃ again
37.8g make solution, get this solution in beaker, add water glass 28.42g while stirring under constant temperature ebullient condition, the adularescent flocks occurs during beginning, continues to stir, precipitation fades away, be heated to 70 ℃, the constant temperature boiling is stirred 30min and is made gel, is divided into two parts then, difference ageing 24h and 48h under constant temperature, it is standby as crystallization director to get product;
Prepare active white residue:
B, the wilkinite of getting the Toksun, Xinjiang are raw material, the wilkinite raw ore is removed the bigger sand grains of granularity through wet purification, with concentration 30% sulfuric acid and 300 purpose wilkinites, pressing 1: 2 solid-to-liquid ratio of mass ratio drops in the acidifying still, be warming up to 80 ℃, 4 hours after-filtration of acidification reaction get active white residue (SiO
269.3%; Al
2O
315.76%; Whiteness 92.9);
Preparation 4A zeolite molecular sieve:
C, get the active white residue 10g of step b, measure the sial content in the active white residue, getting NaOH6.39g earlier, to be made into concentration be that the solution of 30% (mass concentration) joins in the reactor that has agitator, or else the disconnected active white residue 10g of step b that in reactor, adds, be heated to 60 ℃ simultaneously, alkalize, alkalization time is 1.5h.
Become the glue temperature to be controlled at 20 ℃, add the directed agents that embodiment 1 makes, 80 ℃ of following crystallization 1h, filtration, washing, drying had both got the 4A zeolite molecular sieve.
D, the product after will alkalizing add water 66ml, and temperature is controlled at 20 ℃ and is carried out to glue, and time 1h adds NaAlO when becoming glue
27.99g benefit aluminium, making the reaction system proportioning is 2Na
2O: 1Al
2O
3: 1.8SiO
2: 70H
2O;
E, the reaction of one-tenth glue stop to stir after finishing, the crystallization director that adds step a ageing 24h, the add-on of crystallization director is that 3% of reaction system total mass is 3.2g, temperature rises to 80 ℃ and carries out crystallization, behind the synthetic 0.5h of crystallization, material is filtered, washs dealkalize, dehydrates, promptly get the 4A zeolite molecular sieve.
Embodiment 2
The preparation directed agents:
A, get NaOH 4g and be dissolved in the 146ml water, be heated to boiling, add Al (OH) when being cooled to 50 ℃ again
37.8g make solution, get this solution in beaker, add water glass 28.42g while stirring under constant temperature ebullient condition, the adularescent flocks occurs during beginning, continues to stir, precipitation fades away, be heated to 70 ℃, the constant temperature boiling is stirred 30min and is made gel, is divided into two parts then, difference ageing 24h and 48h under constant temperature, it is standby as crystallization director to get product.
Prepare active white residue:
The wilkinite of b, Toksun, Xinjiang is a raw material, and the wilkinite raw ore is removed the bigger sand grains of granularity through wet purification, is 35% sulfuric acid and 350 purpose wilkinites with concentration, pressing 1: 3 solid-to-liquid ratio of mass ratio drops in the acidifying still, be warming up to 85 ℃, 4 hours after-filtration of acidification reaction get active white residue;
Preparation 4A zeolite molecular sieve:
C, get the active white residue 10g of step b, measure the sial content in the active white residue, getting NaOH10.48g earlier, to be made into concentration be that the solution of 30% (mass concentration) joins in the reactor that has agitator, or else the disconnected active white residue 10g of step b that in reactor, adds,, alkalize, alkalization time is 2h.
D, the product after will alkalizing add water 80ml, temperature is controlled at 30 ℃ and is carried out to glue, and time 1h adds NaAlO when becoming glue
26.93g benefit aluminium, making the reaction system proportioning is 3Na
2O: 1Al
2O
3: 2SiO
2: 100H
2O;
E, the reaction of one-tenth glue stop to stir after finishing, the crystallization director that adds step a ageing 48h, the add-on of crystallization director is that 5% of reaction system total mass is 6.57g, temperature rises to 85 ℃ and carries out crystallization, behind the synthetic 1h of crystallization, material is filtered, washs dealkalize, dehydrates, promptly get the 4A zeolite molecular sieve.
Embodiment 3
The preparation directed agents:
A, get NaOH 4g and be dissolved in the 146ml water, be heated to boiling, add Al (OH) when being cooled to 50 ℃ again
37.8g make solution, get this solution in beaker, add water glass 28.42g while stirring under constant temperature ebullient condition, the adularescent flocks occurs during beginning, continues to stir, precipitation fades away, be heated to 70 ℃, the constant temperature boiling is stirred 30min and is made gel, is divided into two parts then, difference ageing 24h and 48h under constant temperature, it is standby as crystallization director to get product.
Prepare active white residue:
B, the wilkinite of getting the Toksun, Xinjiang are raw material, the wilkinite raw ore is removed the bigger sand grains of granularity through wet purification, with concentration 38% sulfuric acid and 350 purpose wilkinites, pressing 1: 5 solid-to-liquid ratio of mass ratio drops in the acidifying still, be warming up to 95 ℃, 4 hours after-filtration of acidification reaction get active white residue;
Preparation 4A zeolite molecular sieve:
C, get the active white residue 10g of step b, measure the sial content in the active white residue, getting NaOH15.1g earlier, to be made into concentration be that the solution of 30% (mass concentration) joins in the reactor that has agitator, or else the disconnected active white residue 10g of step b that in reactor, adds, add water 156ml, be heated to 70 ℃ simultaneously, alkalize, alkalization time is 2h.
D, the product after will alkalizing add water 121ml, and temperature is controlled at 50 ℃ and is carried out to glue, and time 1h adds NaAlO when becoming glue
26.93g benefit aluminium, making the reaction system proportioning is 4Na
2O: 1Al
2O
3: 2SiO
2: 150H
2O;
E, the reaction of one-tenth glue stop to stir after finishing, the crystallization director that adds step a ageing 24h, the add-on of crystallization director is that 10% of reaction system total mass is 18.8g, temperature rises to 100 ℃ and carries out crystallization, behind the synthetic 1h of crystallization, material is filtered, washs dealkalize, dehydrates, promptly get the 4A zeolite molecular sieve.
Embodiment 4
The preparation directed agents:
A, get NaOH and be dissolved in the water, be heated to boiling, add Al (OH) when being cooled to 50 ℃ again
3Make solution, under constant temperature ebullient condition, add water glass while stirring, the adularescent flocks occurs during beginning, continue to stir, precipitation fades away, and is heated to 70 ℃, the constant temperature boiling is stirred 30min and is made gel, be divided into two parts then, difference ageing 24h and 48h under constant temperature, it is standby as crystallization director to get product;
Prepare active white residue:
B, the wilkinite of getting the Toksun, Xinjiang are raw material, the wilkinite raw ore is removed the bigger sand grains of granularity through wet purification, with concentration 30% sulfuric acid and 400 purpose wilkinites, pressing 1: 4 solid-to-liquid ratio of mass ratio drops in the acidifying still, be warming up to 85 ℃, 4 hours after-filtration of acidification reaction get active white residue;
Preparation 4A zeolite molecular sieve:
C, get the active white residue 10g of step b, measure the sial content in the active white residue, getting NaOH18.04g earlier, to be made into concentration be that the solution of 30% (mass concentration) joins in the reactor that has agitator, or else the disconnected active white residue 10g of step b that in reactor, adds, alkalize, alkalization time is 1.5h.
D, the product after will alkalizing add water 128ml, and temperature is controlled at 50 ℃ and is carried out to glue, and time 1h adds NaAlO when becoming glue
26.08g benefit aluminium, making the reaction system proportioning is 5Na
2O: 1Al
2O
3: 2.2SiO
2: 180H
2O;
E, the reaction of one-tenth glue stop to stir after finishing, the crystallization director that adds step a ageing 48h, the add-on of crystallization director is that 15% of reaction system total mass is 30.62g, temperature rises to 98 ℃ and carries out crystallization, behind the synthetic 0.5h of crystallization, material is filtered, washs dealkalize, dehydrates, promptly get the 4A zeolite molecular sieve.
Claims (4)
1, a kind of method that adds the synthetic 4A zeolite molecular sieve of directed agents is characterized in that following these steps to carrying out:
The preparation directed agents:
A, get NaOH and be dissolved in the water, be heated to boiling, add Al (OH) when being cooled to 50 ℃ again
3Make solution, under the azeotropic condition, add water glass while stirring, the adularescent flocks occurs during beginning, continue to stir, precipitation fades away, and is heated to 70 ℃, the constant temperature boiling is stirred 30min and is made gel, be divided into two parts then, difference ageing 24h and 48h under constant temperature, it is standby as crystallization director to get product;
Prepare active white residue:
B, be raw material with the wilkinite, the wilkinite raw ore is removed the bigger sand grains of granularity through wet purification, with concentration is sulfuric acid and the 300-400 purpose wilkinite of 30-40%, the solid-to-liquid ratio of pressing mass ratio 1: 2-5 drops in the acidifying still, be warming up to 80-95 ℃, 4 hours after-filtration of acidification reaction get active white residue;
Preparation 4A zeolite molecular sieve:
C, measuring the sial content in the active white residue, is that 30% NaOH joins in the reactor that has agitator with concentration, or else disconnectedly adds active white residue in reactor, is heated to 60-70 ℃ simultaneously, alkalizes, and alkalization time is 1.5-2h;
D, the product after will alkalizing are carried out to glue, and temperature is controlled at 20-50 ℃, and time 1h adds NaAlO when becoming glue
2Mend aluminium;
E, the reaction of one-tenth glue stop to stir after finishing, and add mass percent 3-15% step a directed agents, and temperature rises to 80-100 ℃ and carries out crystallization, and crystallization is filtered material, wash dealkalize, dehydrated after synthesizing 0.5-1h, promptly gets the 4A zeolite molecular sieve.
2. method according to claim 1 is characterized in that synthetic 4A zeolite reaction system ratio range should be controlled at mol ratio Na
2O: Al
2O
3: SiO
2: H
2O=2-5: 1: 1.8-2.2: 70-180.
3. method according to claim 1, the add-on that it is characterized in that step cNaOH is NaOH: SiO in molar ratio
2Be 2.5-3: 1.
4. according to claims 1 and 2 described methods, it is characterized in that steps d NaAlO
2Add-on be that each component mol ratio of reaction system is determined.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103303974A (en) * | 2013-06-20 | 2013-09-18 | 淄博广通化工有限责任公司 | Method for recycling waste silicon slag discharged in production of zirconyl chloride |
| CN103318913A (en) * | 2013-04-09 | 2013-09-25 | 洛阳市建龙化工有限公司 | Preparation method for small-grain A-type molecular sieve primary powder |
| CN106190643A (en) * | 2015-05-04 | 2016-12-07 | 蒋华 | A kind of method of attapulgite clay synthesizing washing adjuvant |
| 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 |
| CN107673368A (en) * | 2017-10-25 | 2018-02-09 | 常州大学盱眙凹土研发中心 | A kind of method for synthesizing 5A molecular sieves using directed agents for raw material with recessed soil |
| CN109928406A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | A kind of analcime and its synthetic method |
| CN115417421A (en) * | 2022-08-16 | 2022-12-02 | 陇东学院 | Loess-based 4A type molecular sieve and preparation method and application thereof |
-
2008
- 2008-08-07 CN CNA2008100729336A patent/CN101337680A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103318913A (en) * | 2013-04-09 | 2013-09-25 | 洛阳市建龙化工有限公司 | Preparation method for small-grain A-type molecular sieve primary powder |
| CN103318913B (en) * | 2013-04-09 | 2015-05-06 | 洛阳市建龙化工有限公司 | Preparation method for small-grain A-type molecular sieve primary powder |
| CN103303974A (en) * | 2013-06-20 | 2013-09-18 | 淄博广通化工有限责任公司 | Method for recycling waste silicon slag discharged in production of zirconyl chloride |
| CN103303974B (en) * | 2013-06-20 | 2014-09-10 | 淄博广通化工有限责任公司 | Method for recycling waste silicon slag discharged in production of zirconyl chloride |
| CN106190643A (en) * | 2015-05-04 | 2016-12-07 | 蒋华 | A kind of method of attapulgite clay synthesizing washing adjuvant |
| 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 |
| CN107673368A (en) * | 2017-10-25 | 2018-02-09 | 常州大学盱眙凹土研发中心 | A kind of method for synthesizing 5A molecular sieves using directed agents for raw material with recessed soil |
| CN109928406A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | A kind of analcime and its synthetic method |
| CN115417421A (en) * | 2022-08-16 | 2022-12-02 | 陇东学院 | Loess-based 4A type molecular sieve and preparation method and application thereof |
| CN115417421B (en) * | 2022-08-16 | 2023-12-05 | 陇东学院 | Loess-based 4A type molecular sieve and preparation method and application thereof |
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