CN1204969C - Process for preparing nano Y zeolite molecular sieve carried by kaolin microspheres - Google Patents
Process for preparing nano Y zeolite molecular sieve carried by kaolin microspheres Download PDFInfo
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- CN1204969C CN1204969C CN 01114194 CN01114194A CN1204969C CN 1204969 C CN1204969 C CN 1204969C CN 01114194 CN01114194 CN 01114194 CN 01114194 A CN01114194 A CN 01114194A CN 1204969 C CN1204969 C CN 1204969C
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- molecular sieve
- solution
- zeolite molecular
- kaolin
- microspheres
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Abstract
The present invention relates to a preparation method of nano zeolite molecular sieve Y supported by kaoline microspheres. The method comprises the following steps: (1)a guiding agent is prepared; (2) sodium citrates added with the guiding agent are magnetically stirred for 1.5 to 3 hours, and the weight ratio of the guiding agent to sodium citrates is 65 to 75: 2.5 to 3.5; (3) the solution of the step (2) added with the roasted kaoline microspheres are mechanically stirred, and the weight ratio of the additional quantity of the roasted kaoline microspheres to the solution is 65 to 75: 4 to 15; (4) a sulfuric acid solution is dripped into the mixed solution of the step (3) so that gelatin is obtained, wherein the dripping quantity of the sulfuric acid solution is from 23 to 32% of the mixed solution of the step (3), and the concentration of the sulfuric acid solution is from 28 to 32%; the gelatin is oscillated evenly and crystallized at a temperature of 90 to 110 DEG C; (5)the crystallized gelatin is separated so that a nano zeolite molecular sieve Y product supported by the kaoline microspheres is obtained. The product has good hydrothermal stability.
Description
The present invention relates to the synthetic nano Y zeolite molecular sieve crystal grain catalyst that supports of original position, specifically a kind of preparation method of nano Y zeolite molecular sieve carried by kaolin microspheres.
The catalyst of Y zeolite molecular sieve and kaolin mixed-forming has important application in catalytic cracking process.Nano Y zeolite molecular sieve is made catalyst can improve diesel yield, but hydrothermal stability remains to be improved.In the prior art, there is the separation difficulty problem in nano zeolite Y molecular sieve preparation process, is difficult to commercial Application; Nano zeolite Y molecular sieve hydrothermal stability difference also is a major reason of its application of restriction.After in the kaolin slurry, adding directed agents or crystal seed in addition, be spray dried to kaolin microsphere, in the system of synthesis zeolite Y, the synthetic product that obtains containing Y zeolite molecular sieve 40%.For example: the United States Patent (USP) (patent No. 4493902, January 15 1985 applying date) disclose a kind of on kaolin microsphere the method for in-situ crystallization synthesis zeolite Y crystal grain, be characterized in adding so-called crystal seed before the kaolin microsphere moulding, in-situ crystallization forms Y zeolite molecular sieve then.
The purpose of this invention is to provide a kind ofly separate easily, the preparation method of the nano Y zeolite molecular sieve carried by kaolin microspheres of good hydrothermal stability.
Technical scheme of the present invention is: the crystal grain of on kaolin microsphere, growing, and concrete steps are:
(1) preparation directed agents:
1) take by weighing the Ludox of 28～32% concentration, the weight ratio by 55～65: 15～25 adds NaOH, the vibration dissolving;
2) take by weighing water in addition, adding Al by weight 40～45: 10～15: 8～12
2(SO
4)
318H
2O and NaOH, stirring and dissolving; The Ludox of 28～32% concentration and Al
2(SO
4)
318H
2The weight ratio of O is 55～65: 10～15;
3) with step 2) described in solution add in the described solution of step 1), magnetic agitation 1～3 hour, aged at room temperature 1～15 day is made directed agents;
(2) get above-mentioned directed agents and add natrium citricum, magnetic agitation 1.5～3 hours; Wherein directed agents and natrium citricum weight ratio are 65～75: 2.5～3.5;
(3) kaolin microsphere after 600～650 ℃ of roastings is added in step (2) solution, mechanical agitation 5～8 hours, the weight ratio of addition and described solution are 4～15: 65～75;
(4) splash into sulfuric acid solution, the amount of splashing into is 23～32% of a solution weight described in the step (3), and concentration is 28～32%, obtains gel, vibration evenly the back in 90～110 ℃ of following crystallization 8～12 hours;
(5) take out that above-mentioned product separates, suction filtration, washing, drying, obtain containing the growth product of zeolite grain.
The present invention has following advantage:
1. process is simple.The present invention uses high alkalinity directed agents and the Y zeolite molecular sieve crystal grain effect that supports, and can grow the Y zeolite molecular sieve crystal grain of 80～200 nanometers on kaolin microsphere.
2. good hydrothermal stability.Adopt the present invention to prepare the Y zeolite molecular sieve grain growth on kaolin microsphere, the good hydrothermal stability of the Y zeolite molecular sieve crystal grain that this supports is apparently higher than the non-hydrothermal stability (see figure 1) that is grown in the molecular sieve Y crystal grain on the kaolin microsphere.The non-degree of crystallinity that is grown in the molecular sieve Y molecular sieve after 650 ℃ of hydrothermal treatment consists on the kaolin microsphere is total loss almost, illustrates that major part is converted into unformed material, and its hydrothermal stability is poor; And the Y zeolite molecular sieve that supports changes not quite at 650 ℃ of hydrothermal treatment consists post crystallization degree.
3. separate easily.Because the present invention adopts directly nanometer Y grain growth measure on kaolin microsphere, has solved the problem that is difficult to filter in the industrial large-scale production nano molecular sieve.
Fig. 1 is Y molecular sieve crystallinity X-x ray diffraction (XRD) spectrogram of the embodiment of the invention 1.
Below in conjunction with embodiment and accompanying drawing in detail the present invention is described in detail.
Embodiment 1
The crystal grain of on kaolin microsphere, growing, concrete steps are:
(1) preparation directed agents:
The Ludox that claims 60.1g 30% adds 19.5g NaOH in 250ml round bottom beaker, vibration makes safe dissolving; Get small beaker, claim 42g water, add the Al of 12.5g
2(SO
4)
318H
2O, 9g NaOH stirs and makes dissolving fully; Then, join in the 250ml round bottom beaker of front magnetic agitation 1 hour, aged at room temperature 5 days;
(2) get the directed agents of 71.6g after aging, add the 2.8g natrium citricum, magnetic agitation 2 hours;
(3) the kaolin microsphere 6.0g after 600 ℃ of roastings is joined in step (2) beaker mechanical agitation 6 hours;
(4) splash into sulfuric acid solution (98% concentrated sulfuric acid 15.4g that has demarcated is diluted in the 35.6g water) 25.5g for preparing, with the vibration of the gel that obtains evenly, in 100 ℃ of following crystallization 10 hours;
(5) take out separation, suction filtration, washing, 120 ℃ of baking oven inner dryings obtain about 4 grams of powder (c) product of nano Y zeolite molecular sieve carried by kaolin microspheres, and it is about 20% to contain Y zeolite molecular sieve crystal grain, and grain size is 100～200nm; And the powder (a) of the nano Y zeolite molecular sieve of on kaolin microsphere, not growing.
As shown in Figure 1, the nanometer Y powder (a) that obtains among the embodiment 1 adopts the processing of 100% aqueous vapor to obtain nanometer Y powder (b) after 2 hours at 650 ℃.The carried by kaolin microspheres nanometer Y (c) of embodiment 1 in-situ crystallization preparation adopts the processing of 100% aqueous vapor to obtain carried by kaolin microspheres nanometer Y (d) after 2 hours at 650 ℃.Fig. 1 has compared the Y molecular sieve crystallinity change.As can be seen, the non-degree of crystallinity that is grown in the molecular sieve Y molecular sieve after 650 ℃ of hydrothermal treatment consists on the kaolin microsphere is total loss almost, illustrates that major part is converted into unformed material, and its hydrothermal stability is poor; And the Y zeolite molecular sieve that supports changes not quite at 650 ℃ of hydrothermal treatment consists post crystallization degree.Therefore, the good stability of the carried by kaolin microspheres nanometer Y ratio nano Y powder of in-situ crystallization preparation.
Embodiment 2
The crystal grain of on kaolin microsphere, growing, concrete steps are:
(1) preparation directed agents:
The Ludox that claims 57g 32% adds 25g NaOH in 250ml round bottom beaker, vibration makes safe dissolving; Get small beaker, claim 40g water, add the Al of 15g
2(SO
4)
318H
2O, 12g NaOH stirs and makes dissolving fully; Then, join in the 250ml round bottom beaker of front magnetic agitation 1 hour, aged at room temperature 15 days;
(2) get the directed agents of 65g after aging, add the 3.5g natrium citricum, magnetic agitation 3 hours;
(3) the kaolin microsphere 10.0g after 650 ℃ of roastings is joined in step (2) beaker mechanical agitation 8 hours;
(4) splash into sulfuric acid solution (32% concentration) 18g for preparing, with the vibration of the gel that obtains evenly, in 110 ℃ of following crystallization 8 hours;
(5) take out separation, suction filtration, washing, 120 ℃ of baking oven inner dryings obtain about 7 grams of powder product for the nano Y zeolite molecular sieve of growing on the kaolin microsphere, and it is about 20% to contain Y zeolite molecular sieve crystal grain, and grain size is 80～150nm.
Embodiment 3
The crystal grain of on kaolin microsphere, growing, concrete steps are:
(1) preparation directed agents:
The Ludox that claims 65g 28% adds 15g NaOH in 250ml round bottom beaker, vibration makes safe dissolving; Get small beaker, claim 45g water, add the Al of 10g
2(SO
4)
318H
2O, 11g NaOH stirs and makes dissolving fully; Then, join in the 250ml round bottom beaker of front magnetic agitation 1 hour, aged at room temperature 8 days;
(2) get the directed agents of 75g after aging, add the 2.5g natrium citricum, magnetic agitation 1.5 hours;
(3) the kaolin microsphere 4.0g after 630 ℃ of roastings is joined in step (2) beaker mechanical agitation 5 hours;
(4) splash into sulfuric acid solution (concentration 28%) 22.4g for preparing, with the vibration of the gel that obtains evenly, in 90 ℃ of following crystallization 12 hours;
(5) take out separation, suction filtration, washing, 120 ℃ of baking oven inner dryings obtain about 3 grams of powder product for the nano Y zeolite molecular sieve of growing on the kaolin microsphere, and it is about 20% to contain Y zeolite molecular sieve crystal grain, and grain size is 100～200nm.
Claims (1)
1. the preparation method of a nano Y zeolite molecular sieve carried by kaolin microspheres is characterized in that: the crystal grain of on kaolin microsphere, growing, and concrete steps are:
(1) preparation directed agents:
1) take by weighing the Ludox of 28～32% concentration, the weight ratio by 55～65: 15～25 adds NaOH, the vibration dissolving;
2) take by weighing water in addition, adding Al by weight 40～45: 10～15: 8～12
2(SO
4)
318H
2O and NaOH, stirring and dissolving; The Ludox of 28～32% concentration and Al
2(SO
4)
318H
2The weight ratio of O is 55～65: 10～15;
3) with step 2) described in solution add in the described solution of step 1), magnetic agitation 1～3 hour, aged at room temperature 1～15 day is made directed agents;
(2) get above-mentioned directed agents and add natrium citricum, magnetic agitation 1.5～3 hours; Wherein directed agents and natrium citricum weight ratio are 65～75: 2.5～3.5;
(3) kaolin microsphere after 600～650 ℃ of roastings is added in step (2) solution, mechanical agitation 5～8 hours, the weight ratio of addition and described solution are 4～15: 65～75;
(4) splash into sulfuric acid solution, the amount of splashing into is 23～32% of a solution weight described in the step (3), and concentration is 28～32%, obtains gel, vibration evenly the back in 90～110 ℃ of following crystallization 8～12 hours;
(5) take out that above-mentioned product separates, suction filtration, washing, drying, obtain the nano Y zeolite molecular sieve carried by kaolin microspheres product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01114194 CN1204969C (en) | 2001-07-04 | 2001-07-04 | Process for preparing nano Y zeolite molecular sieve carried by kaolin microspheres |
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|---|---|---|---|
| CN 01114194 CN1204969C (en) | 2001-07-04 | 2001-07-04 | Process for preparing nano Y zeolite molecular sieve carried by kaolin microspheres |
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| CN1393402A CN1393402A (en) | 2003-01-29 |
| CN1204969C true CN1204969C (en) | 2005-06-08 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1275855C (en) | 2003-03-28 | 2006-09-20 | 中国石油化工股份有限公司 | Nano-grade Y type zeolite synthesized from kaolin and its preparation metod |
| CN1313207C (en) * | 2004-02-13 | 2007-05-02 | 中国石油天然气集团公司 | Method for preparing uniform nanometer molecular sieve material with high catalytic activity |
| CN102049278B (en) * | 2009-10-27 | 2012-08-29 | 中国石油化工股份有限公司 | Small-grain Y-type molecular sieve dispersing material |
| CN112642393B (en) * | 2019-10-10 | 2023-08-08 | 中国石油化工股份有限公司 | Y molecular sieve and preparation method thereof |
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