CN101704535A - Method for preparing Y-type zeolite - Google Patents
Method for preparing Y-type zeolite Download PDFInfo
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- CN101704535A CN101704535A CN200910198726A CN200910198726A CN101704535A CN 101704535 A CN101704535 A CN 101704535A CN 200910198726 A CN200910198726 A CN 200910198726A CN 200910198726 A CN200910198726 A CN 200910198726A CN 101704535 A CN101704535 A CN 101704535A
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Abstract
The invention provides a method for preparing Y-type zeolite. The method comprises: mixing an aluminum source, a silicon source and sodium hydroxide aqueous solution pro rata under a strong-stirring condition; adding Y-type zeolite directing agent of which the total addition amount is 5 to 15 percent of the volume of the mixture solution to the mixture solution in two steps after the gel formation of the mixture solution is completed, wherein the directing agent of which the addition amount is 1 to 5 percent of the volume of the mixture solution is added to the mixture solution for the first time after the aluminum source, the silicon source and the sodium hydroxide aqueous solution are strongly stirred and mixed to be gel, and after the mixture solution is stood fro 5 to 36 hours at 15 to 70 DEG C, the directing agent is added for the second time to the mixture solution in a stirring state in an addition amount 5 to 10 percent of the volume of the mixture solution; stirring for 5 to 10 minutes and performing crystallization for 12 to 36 hours at 90 to 110 DEG C; separating mother liquor; washing products till pH is less than 10; drying the obtained products at 100 to 110 DEG C; and obtaining Y-type zeolite products. As no organic template is used, the method has the advantages of effectively reducing production cost, reducing environmental pollution, shortening crystallization time and improving production efficiency.
Description
Technical field
The invention belongs to the inorganic porous material technical field, be specifically related to a kind of quick method for preparing y-type zeolite.
Background technology
Y-type zeolite is used industrial having obtained widely with its good catalytic activity and high-temperature stability.Zeolite catalyst replaces acid-treated clay and the amorphous silicon aluminium catalyzer increases substantially transformation efficiency, yield of gasoline and octane value in the catalytic cracking process, has reduced coke and gas yield simultaneously, causes the once technical revolution of petroleum refining industry.Particularly along with heaviness gradually, poor qualityization and the environmental protection restriction of crude oil are strict day by day, oil refining catalyst is higher to the specification of quality of zeolite, and demand also rises gradually, and the zeolite production cost just plays very important effect to the catalyzer cost.
The y-type zeolite directed agents is the essential condition that generates high-crystallinity and crystalline phase single Y type zeolite, and it plays structure-directing effect in zeolite synthesis.If system does not add directed agents, be difficult to synthesize the single y-type zeolite of crystalline phase; But when directed agents was used quantity not sufficient, the degree of crystallinity of zeolite was very low, and crystallization time is long, and the while product is with the generation of P type zeolite, so the consumption of directed agents plays a part very crucial in the crystallization process of product.The synthesis technique of y-type zeolite has industrial chemicals method and sticking dried mineral method at present.Industrial chemicals method good product performance, building-up process are easy to control, but production cost is higher; Clay mineral method (mainly being kaolin, wilkinite etc.) raw materials cost impurity low, that wherein contained can have certain influence to the performance of product, thus when selecting for use clay mineral to be raw material, select for use foreign matter content few, the raw material that grade is higher.
In the building-up process of y-type zeolite, adding organic formwork agent is the silica alumina ratio that improves synthetic zeolite, shorten one of method of crystallization time, but the use of organic formwork agent not only can increase production cost, pollutes but also can produce environment.
Chinese patent CN200510047508.8 has introduced a kind of synthetic method of faujusite, particularly the synthetic method of high silica alumina ratio faujusite.This invention faujusite building-up process is that hydrothermal crystallizing is synthetic under alkaline condition, and adopting lower molecular weight polyalcohols compound is template, does not need zeolite seed crystal, directly synthesizes the faujusite of high silica alumina ratio under hydrothermal condition.Under 90～130 ℃ of conditions under the reactor autogenous pressure hydrothermal crystallizing, its crystallization time length is 24～160 hours.
Chinese patent CN1951811 has reported a kind of synthetic method of faujusite, particularly the synthetic method of high silica alumina ratio faujusite.Building-up process is an alkaline condition, and adopting the high-molecular-weight poly alkylol cpd is template, does not need zeolite seed crystal, directly synthesizes the faujusite of high silica alumina ratio under hydrothermal condition.Under 90-130 ℃ of condition under the reactor autogenous pressure hydrothermal crystallizing 40～180 hours
Above-mentioned two kinds of methods not only increase cost, contaminate environment, and the crystallization cycle are long owing to use template, and combined coefficient is low.
Summary of the invention
The invention discloses a kind of method for preparing y-type zeolite, do not use organic formwork agent, can effectively overcome shortcomings such as the prior art crystallization time is long, preparation speed is slow, preparation cost is high, combined coefficient is low, and environmentally safe.
Method of the present invention is in the preparation process of y-type zeolite, a step added in the crystallization system and changes into after directed agents in the traditional technology finished by batching: do not changing on the basis that directed agents adds total amount, directed agents is added in two steps. directed agents mainly provides basic silicon-aluminum structure unit and structure-directing effect required in the y-type zeolite crystallization process, when adopting single stage method, directed agents becoming the glue stage to add fashionable, because at the initial stage of ageing process, the speed that the active silica-alumina structural unit forms in the mixed system is slower, so a plurality of highly active directed agents nucleus can be crosslinked together in ageing process, reduce the quantity of effective crystal seed. behind the ageing certain hour, add a part of directed agents again, because the sial composition in the system has formed gel, begun to take shape the basic structural unit that constitutes zeolite. simultaneously, initiate directed agents has higher structure-directing effect, better dispersed, thereby increased the relative populations of effective crystal seed, guaranteed the activity of nucleus, accelerated the formation of zeolite nucleus. as seen, when adopting directed agents two steps, addition method synthesizing y-type zeolite, the time that second step of control directed agents adds, can shorten crystallization time effectively, and synthesize the y-type zeolite of high-crystallinity.
A kind of method for preparing y-type zeolite is characterized in that: aluminium source, silicon source and aqueous sodium hydroxide solution are proportionally mixed obtaining mixed solution under violent stirring; Add directed agents in two steps in mixed solution, the directed agents total amount of twice adding is 5～15% of a mixed solution cumulative volume.Used directed agents proportioning is Na among the present invention
2O: Al
2O
3: SiO
2: H
2O=16: 1: 15: 320.
Concrete steps are as follows:
A) adding directed agents for the first time in mixed solution is after aluminium source, silicon source and aqueous sodium hydroxide solution violent stirring are mixed into glue, and the add-on of directed agents is 1～5% of total add-on for the first time;
B) after leaving standstill 5～36h under 15～70 ℃ the temperature, under whipped state, in mixed solution, add directed agents for the second time, the add-on of directed agents is 5～14% of total add-on for the second time;
C) stir after 5～10 minutes, under static condition under 90～110 ℃ temperature crystallization 12～36h;
D) after crystallization finishes mother liquor is separated, Recycling Mother Solution is used, and product makes the y-type zeolite product with the solid product oven dry then through being washed to the pH value less than 10 under 100～110 ℃ temperature.
After the directed agents adding was finished, the mol ratio of different components was in the described mixed solution: Na
2O: Al
2O
3: SiO
2: H
2O=1.6～4.5: 1: 4.4～18.6: 100～320.
Described aluminium source is sodium metaaluminate, aluminum nitrate, Tai-Ace S 150 or aluminum chloride.
Described silicon source is water glass, silicon sol.
Described aluminium source and silicon source also can be clay minerals such as kaolin, wilkinite.
The method of a kind of fast synthetic y-type zeolite that the present invention proposes, its advantage and positively effect are: owing to do not use organic formwork agent, can effectively reduce cost, save energy also reduces environmental pollution, has shortened crystallization time greatly simultaneously, has improved production efficiency.
Embodiment
Below by specific embodiment technical scheme of the present invention is further described, but present embodiment is not limited to the present invention, every employing the inventive method and similar variation thereof all should be listed protection scope of the present invention in.
Embodiment 1: used directed agents proportioning is Na among the present invention
2O: Al
2O
3: SiO
2: H
2O=16: 1: 15: 320.With water glass is the silicon source, and sodium metaaluminate is the aluminium source.Sodium metaaluminate, water glass and aqueous sodium hydroxide solution are disposed in proportion, after adding twice directed agents, make the material proportion of total system be: Na
2O: Al
2O
3: SiO
2: H
2O=3: 1: 8.6: 240.Concrete steps are as follows:
A) adding directed agents for the first time in mixed solution is after sodium metaaluminate, water glass and aqueous sodium hydroxide solution violent stirring are mixed into glue, and the amount that adds directed agents is 1.2% of total directed agents add-on;
B) dwell temperature is 70 ℃, time of repose 24 hours; The amount that adds for the second time directed agents is 10% of a directed agents adding total amount;
C) stir after 5～10 minutes, under static condition in 100 ℃ of following crystallization 16 hours;
D) after crystallization finishes mother liquor is separated, Recycling Mother Solution is used, and product makes the y-type zeolite product A with the solid product oven dry then through being washed to the pH value less than 10 under 100～110 ℃ temperature.
In order to guarantee the comparability of experimental example, in following experimental example, after guarantee adding directed agents mixed liquefied on the identical basis of the proportioning of each component, only change the adding mode of directed agents, other processes are identical.
Embodiment 2: as different from Example 1: the amount that adds directed agents for the first time is 5% of total directed agents add-on.Dwell temperature is 15 ℃, time of repose 36 hours; The amount that adds for the second time directed agents is 5% of a directed agents adding total amount.Reaction mixture is following 90 ℃ of following crystallization 36 hours, product B.
Embodiment 3: as different from Example 1: be the silicon source with water glass, Tai-Ace S 150 is the aluminium source.The amount that adds for the first time directed agents is 5% of total directed agents add-on.Dwell temperature is 70 ℃, time of repose 6 hours; The amount that adds for the second time directed agents is 10% of a directed agents adding total amount.Reaction mixture is following 110 ℃ of following crystallization 12 hours, products C.
Embodiment 4: as different from Example 1: be the silicon source with water glass, aluminum nitrate is the aluminium source.The amount that adds for the first time directed agents is 2.5% of total directed agents add-on.Dwell temperature is 45 ℃, time of repose 18 hours; The amount that adds for the second time directed agents is 10% of a directed agents adding total amount.Reaction mixture is following 100 ℃ of following crystallization 16 hours, product D.
Embodiment 5: as different from Example 1: be the silicon source with the silicon sol, sodium metaaluminate is the aluminium source.The amount that adds for the first time directed agents is 5% of total directed agents add-on.Dwell temperature is 50 ℃, time of repose 12 hours; The amount that adds for the second time directed agents is 10% of a directed agents adding total amount.Reaction mixture is following 100 ℃ of following crystallization 16 hours, product E.
Embodiment 6: as different from Example 1: be the silicon source with the silicon sol, sodium metaaluminate is the aluminium source.The amount that adds for the first time directed agents is 4.5% of total directed agents add-on.Dwell temperature is 30 ℃, time of repose 24 hours; The amount that adds for the second time directed agents is 10% of a directed agents adding total amount.Reaction mixture is following 100 ℃ of following crystallization 16 hours, product F.
Embodiment 7: as different from Example 1: be the silicon source with the silicon sol, sodium metaaluminate is the aluminium source.The amount that adds for the first time directed agents is 5% of total directed agents add-on.Dwell temperature is 30 ℃, time of repose 24 hours; The amount that adds for the second time directed agents is 10% of a directed agents adding total amount.Reaction mixture is following 100 ℃ of following crystallization 16 hours, product G.
More than the physical properties of each routine prepared y-type zeolite list in the table 1.
Table 1 adopts different methods to prepare the physical properties of product
| Sample number into spectrum | ??A | ??B | ??C | ??D | ??E | ??F | ??G |
| Pore volume (ml/g) | ??0.363 | ??0.339 | ??0.352 | ??0.366 | ??0.347 | ??0.358 | ??0.344 |
| Specific surface area (m 2/g) | ??760 | ??742 | ??759 | ??777 | ??729 | ??756 | ??757 |
| Silica alumina ratio | ??5.12 | ??5.07 | ??5.05 | ??5.20 | ??5.18 | ??5.22 | ??5.07 |
Claims (4)
1. a method for preparing y-type zeolite is characterized in that: aluminium source, silicon source and aqueous sodium hydroxide solution are proportionally mixed obtaining mixed solution under violent stirring; Add directed agents in two steps in mixed solution, the directed agents total amount of twice adding is 5～15% of a mixed solution cumulative volume, and concrete steps are as follows:
A) adding directed agents for the first time in mixed solution is after aluminium source, silicon source and aqueous sodium hydroxide solution violent stirring are mixed into glue, and add-on is 1～5% of a mixeding liquid volume;
B) after leaving standstill 5～36h under 15～70 ℃ the temperature, in mixed solution, add directed agents for the second time, add-on is 5～10% of a mixeding liquid volume, and stirs 5～10 minutes;
C) stir end back crystallization 12～36h under 90～110 ℃ temperature;
D) after crystallization finishes mother liquor is separated, Recycling Mother Solution is used, and product is through being washed to the pH value less than 10, and oven dry makes the y-type zeolite product under 100～110 ℃ temperature then.
2. a kind of method for preparing y-type zeolite according to claim 1 is characterized in that: the mol ratio that adds different components in the described mixed solution in back in directed agents in two steps is: Na
2O: Al
2O
3: SiO
2: H
2O=1.6～4.5: 1: 4.4～18.6: 100～320.
3. a kind of method for preparing y-type zeolite according to claim 1 is characterized in that: described aluminium source is sodium metaaluminate, aluminum nitrate, Tai-Ace S 150 or aluminum chloride.
4. a kind of method for preparing y-type zeolite according to claim 1 is characterized in that: described silicon source is water glass, silicon sol.
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| CN200910198726A CN101704535A (en) | 2009-11-13 | 2009-11-13 | Method for preparing Y-type zeolite |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK201600157A1 (en) * | 2016-03-14 | 2017-10-02 | Haldor Topsoe As | Zeolite (Y) and process for the production thereof |
| CN111410206A (en) * | 2020-04-13 | 2020-07-14 | 邹凌峰 | Preparation method of Y-type molecular sieve with high silica-alumina ratio |
| CN111825105A (en) * | 2019-04-18 | 2020-10-27 | 中国科学院大连化学物理研究所 | Preparation of Y molecular sieve with FAU structure by guide agent method |
-
2009
- 2009-11-13 CN CN200910198726A patent/CN101704535A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK201600157A1 (en) * | 2016-03-14 | 2017-10-02 | Haldor Topsoe As | Zeolite (Y) and process for the production thereof |
| CN111825105A (en) * | 2019-04-18 | 2020-10-27 | 中国科学院大连化学物理研究所 | Preparation of Y molecular sieve with FAU structure by guide agent method |
| CN111410206A (en) * | 2020-04-13 | 2020-07-14 | 邹凌峰 | Preparation method of Y-type molecular sieve with high silica-alumina ratio |
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Open date: 20100512 |