CN102909065B - Synthetic method for Y-Beta composite molecular sieve having core-shell structures - Google Patents
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Abstract
The invention relates to a synthetic method for a Y-Beta composite molecular sieve having core-shell structures. An ion exchange method is employed to exchange a NaY type molecular sieve into a TEA-Y type molecular sieve; and a template guiding function is provided for the formation of a Beta molecular sieve shell in a second step. The obtained Y-Beta composite molecular sieve has no other mixed crystals; and all the Y type molecular sieves are coated by the Beta molecular sieve. In hydrocracking reactions, the Y-Beta composite molecular sieve reduces reaction temperature, increases coke-resistant capacity, increases medium oil selectivity and has far-reaching significance for the development of hydrocracking catalysts.
Description
Technical field
The present invention relates to a kind of synthetic technology with the Y-Beta composite molecular screen of nucleocapsid structure, specifically a kind of is core with Y zeolite, the synthetic method of the Y-Beta composite molecular screen of the nucleocapsid structure being shell with Beta molecular sieve.
Background technology
Y zeolite is mutually through and formed along three crystalline axis direction by twelve-ring by octahedral molecular sieve cage, and be a kind of excellent catalyst activity component, not only cracking activity is high, and selective good.Therefore Y zeolite discovery and be used in catalytic field there is epoch-making meaning.Because high silica alumina ratio Y zeolite has good hydrothermal stability and absolute acid stability, therefore it is widely used in chemical industry as a kind of catalysis material.
Beta molecular sieve is synthesized first in 1967 by Mobil company, and owing to failing to solve its structure determination problem for a long time, the synthesis of ZSM Series Molecules sieve and successful Application, therefore fail to cause the enough attention of people in addition.Until within 1988, disclose its distinctive Three Dimensions Structure, Beta molecular sieve causes again the interest of people, it has good heat and hydrothermal stability, the acidity of appropriateness and absolute acid stability and hydrophobicity, and be the macropore high-silica zeolite uniquely with intersection twelve-ring channel system, its catalytic applications shows the feature of hydrocarbon reaction not easily coking and long service life, in hydrocarbons hydrogenation cracking, hydroisomerization, alkane aromatization, the aspect such as alkylation and transalkylation reaction shows excellent catalytic performance, is very important catalysis material.
Y-Beta composite molecular screen has Y molecular sieve and Beta molecular sieve two kinds of crystalline phases simultaneously, integrates the advantage of two kinds of molecular sieves, at the mechanical impurity of its reactivity worth of some field apparently higher than two kinds of molecular sieves.Therefore Y-Beta composite molecular screen is comparatively extensive at Zeolite synthesis area research.
CN200710139691.3 reports a kind of preparation method of composite molecular screen of nucleocapsid structure, and its core preparation method is the Beta molecular sieve the prepared silicon source as synthesis mercerising molecular sieve.First, under certain proportioning, the gel of preparation synthesis Beta molecular sieve, at 120-140 DEG C of crystallization 6-13 days, obtains Beta molecular sieve.Then in the mixed liquor of the Beta molecular sieve obtained, add aluminium source, template and alkali, stir at 165-175 DEG C of crystallization 18-72 hour, obtain the binary composite molecular screen with nucleocapsid structure.The binary composite molecular screen prepared by the inventive method, prepares the catalyst of dimethyl ether after ammonium exchange is transformed into Hydrogen as methanol conversion.
Li Ruifeng in 2004 etc. have successfully prepared Y-Beta and Beta-Y composite molecular screen catalysis material, successively disclose two sections of patents, CN200410012333.2 and CN200410012336.6.CN200610048273.9 discloses a kind of composite molecular screen of the high silicon that adopted high-Si Y-type molecular sieve to synthesize, this composite molecular screen organically combines the feature of Y zeolite and Beta molecular sieve, prepared composite not only has the good hydrothermal stability of high-Si Y-type molecular sieve and absolute acid stability, simultaneously also there is the good heat of Beta molecular sieve and hydrothermal stability, the acidity of appropriateness and absolute acid stability and hydrophobic properties.
CN200710012675.8 reports a kind of preparation method of Y-Beta composite molecular screen of nucleocapsid structure, the Y-Beta composite molecular screen of the method nucleocapsid structure that utilized liquid concentration principle to synthesize.But having stray crystal to occur mutually in the composite molecular screen of synthesis, is not a kind of Y-Beta composite molecular screen of pure phase.Illustrate that the method is also immature, and the composite molecular screen nucleocapsid of synthesis breaks, and can not be bundled together completely.
The Y-Beta composite molecular screen of currently available technology synthesis does not have the nucleocapsid structure wrapped up completely, just a kind of parcel inlaying growth or part.Although the molecular sieve of the nucleocapsid structure that CN200710012675.8 obtains improves parcel degree, containing stray crystal phase.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method with the Y-Beta composite molecular screen of nucleocapsid structure, the composite molecular screen crystalline phase of the inventive method synthesis is pure, and parcel fully.
The synthetic method that the present invention has the Y-Beta composite molecular screen of nucleocapsid structure comprises following content:
(1) by NaOH and tetraethylammonium bromide soluble in water, selectively add ammoniacal liquor;
(2) Y zeolite powder adds in above-mentioned solution, preferably at 60 ~ 90 DEG C, processes 2 ~ 12 hours at 40 DEG C-100 DEG C;
(3) solution of step (2) is carried out filter, drying obtains the Y zeolite powder after processing;
(4) by NaOH, aluminium source, template, ammoniacal liquor and water mixing and stirring;
(5) the Y zeolite powder after process is joined the mixed solution that step (4) is prepared, after stirring, add silicon source, stir and obtain reaction mixture gel system, then carry out crystallization, finally reclaim and obtain composite molecular screen product.
In the inventive method said process, in Y zeolite powder-processed process, the concentration of NaOH is 0.2-1.0mol/L, and the concentration of tetraethylammonium bromide is 0.2-1.0mol/L, and the concentration of ammonia is 0.2-1.0mol/L, and liquid-solid ratio (ml/g) is 2.0-20.0.Dry temperature is 80 ~ 200 DEG C, and drying time is 2 ~ 20 hours.
In the inventive method said process, the silicon source described in synthesis material, aluminium source, ammoniacal liquor, template, NaOH and water in the mol ratio of following substances be:
Na
2o/SiO
2(moles/mole)=0.05 ~ 0.12
TEABr/SiO
2(moles/mole)=0.25 ~ 0.50
NH
4oH/SiO
2(moles/mole)=0.70 ~ 1.05
SiO
2/ Al
2o
3(moles/mole)=15 ~ 58
H
2o/SiO
2(moles/mole)=18 ~ 25
Wherein TEABr is tetraethylammonium bromide.Reactant mixture is crystallization 5.0-10.0 days at 135 DEG C-145 DEG C in confined conditions, obtains the Y-Beta composite molecular screen with nucleocapsid structure.
Above-mentioned composite molecular screen preparation method, NaY type molecular sieve processing procedure is carried out under 40 DEG C of-100 DEG C of conditions, and the molecular sieve obtained after process is TEA-Y.Described NaY type molecular sieve silica alumina ratio is 4.8-5.2(silica/alumina molecule mol ratio), the NaY type molecular sieve of commercial synthesis can be selected from.Described silicon source is Ludox, and template is tetraethylammonium bromide, and aluminium source is sodium aluminate.The weight ratio of the mixture that TEA-Y and silicon source, aluminium source, ammoniacal liquor, template, NaOH and water form is 1:5 ~ 1:20.
Preparation method of the present invention adopts NaOH and tetraethylammonium bromide and the selective ammoniacal liquor that adds to carry out pretreatment to NaY type molecular sieve under optimum conditions, then pretreated TEA-Y molecular sieve is added and first with containing sodium aluminate contact with the mixture of template, make the further modification of TEA-Y molecular sieve, finally add silicon source again, experiment shows that such processing procedure is conducive to being formed not containing the Y-Beta composite molecular screen of stray crystal, and the composite molecular screen of synthesis has perfect kernel shell structure.
Synthetic technology of the present invention is by destroying the complete structure on its surface to the pretreatment of NaY type molecular sieve, form a large amount of defective bit, in processing procedure, introduce template simultaneously, its blemish position is made to have carried out ion-exchange, such processing procedure is conducive to the composite molecular screen forming nucleocapsid structure, and does not produce stray crystal.The Y-Beta composite molecular screen of the inventive method synthesis is not containing stray crystal, and Y zeolite core is wrapped up completely by Beta molecular sieve shell.
The appearance of nucleocapsid structure have adjusted pore passage structure, acidity between them, improves the anti-carbon deposition ability of molecular sieve.Experiment shows, this Y-Beta composite molecular screen may be used for the petroleum refining process such as hydrocracking, catalytic cracking, also may be used for some petrochemical industry catalytic process, the serviceability of its some aspect is better than the Y-Beta composite molecular screen of other method synthesis and the serviceability of polytype molecular sieve physical mixed.
Accompanying drawing explanation
Fig. 1 is the composite molecular screen XRD diffraction pattern that the embodiment of the present invention 1 is synthesized, and can find out that sintetics belongs to Y-Beta composite molecular screen, not have other crystalline phase.
Fig. 2 is the graph of pore diameter distribution of the composite molecular screen that the embodiment of the present invention 1 is synthesized, and can find out that the Y-Beta composite molecular screen of synthesis has secondary pore structure.
Fig. 3 is the scanning electron microscope (SEM) photograph of composite molecular screen after high pressure breakage that the embodiment of the present invention 1 is synthesized, and can see the structure showing a kind of nucleocapsid parcel.
Detailed description of the invention
Preparation process of the present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
The first step, takes 2.0g NaOH and 10.5gTEABr is dissolved in 90.0ml deionized water, waits after being uniformly dissolved and adds 10.0m1 concentrated ammonia liquor again;
Second step, is placed in the water-bath of 80 DEG C by above-mentioned solution, add 10.0gY type molecule and be sieved in the solution of the first step under the condition stirred, and continues stirring 6 hours;
3rd step, carries out suction filtration by the solution of second step, drying obtains TEA-Y type molecular sieve powder;
4th step, at ambient temperature, by 0.90g NaOH, 1.67g sodium aluminate, 16g tetraethylammonium bromide and 50ml deionized water mixing and stirring, then adds 15ml ammoniacal liquor;
5th step, joins the mixed solution of step 4 preparation, after stirring, joins in solution by 50ml Ludox, stir 2 hours, obtain uniform reaction mixture gel system by the 10.0gTEA-Y type molecular sieve powder after the process obtained.Then mixture is moved on in airtight stainless steel cauldron.At 140 DEG C, crystallization 7 days, obtains composite molecular screen product, and through crystal phase analysis, synthetic product is pure Y-Beta composite molecular screen.(with oxide basis, not comprising the TEA-Y type molecular sieve added) proportioning: 3.0Na
2o:43SiO
2: Al
2o
3: 11TEABr:14NH
3oH:805H
2o.The mass ratio of the TEA-Y type molecular sieve added and NaOH, template, water, ammoniacal liquor, aluminium source and silicon source compositional system is 1:13.2.
Embodiment 2
The first step, takes 2.5g NaOH and 8.5gTEABr is dissolved in 80.0ml deionized water, waits after being uniformly dissolved and adds 10.0m1 concentrated ammonia liquor again;
Second step, is placed in the water-bath of 60 DEG C by above-mentioned solution, add 10.0gY type molecule and be sieved in the solution of the first step under the condition constantly stirred, and continues stirring 8 hours;
3rd step, the solution of second step is carried out suction filtration, drying obtain process after Y zeolite powder;
4th step, at ambient temperature, by 0.90g NaOH, 1.67g sodium aluminate, 14g tetraethylammonium bromide and 50ml deionized water mixing and stirring, then adds 10ml ammoniacal liquor;
5th step, joins the mixed solution of step 4 preparation, after stirring, joins in solution by 45ml Ludox, airtight stirring 4 hours, obtain uniform reaction mixture gel system by the 10.0gY type molecular sieve powder after the process obtained.Then mixture is moved on in airtight stainless steel cauldron.At 140 DEG C, crystallization 6 days, obtains composite molecular screen product, and through crystal phase analysis, synthetic product is pure Y-Beta composite molecular screen.(with oxide basis, not comprising the TEA-Y type molecular sieve added) proportioning: 3.0Na
2o:39SiO
2: Al
2o
3: 9.5TEABr:9.3NH
3oH:745H
2o.The mass ratio of the TEA-Y type molecular sieve added and NaOH, template, water, ammoniacal liquor, aluminium source and silicon source compositional system is 1:13.0.
Embodiment 3
The first step, takes 1.5g NaOH and 12.5gTEABr is dissolved in 50.0ml deionized water, waits after being uniformly dissolved and adds 10.0m1 concentrated ammonia liquor again;
Second step, is placed in the water-bath of 90 DEG C by above-mentioned solution, add 10.0gY type molecule and be sieved in the solution of the first step under the condition constantly stirred, and continues stirring 4 hours;
3rd step, the solution of second step is carried out suction filtration, drying obtain process after Y zeolite powder;
4th step, at ambient temperature, by 0.90g NaOH, 1.67g sodium aluminate, 16g tetraethylammonium bromide and 50ml deionized water mixing and stirring, then adds 15ml ammoniacal liquor;
5th step, joins the mixed solution that step 4 obtains, after stirring, is joined slowly in solution by 45ml Ludox, airtight stirring 3 hours, obtain uniform reaction mixture gel system by the 15.0gY type molecular sieve powder after the process obtained.Then mixture is moved on in airtight stainless steel cauldron.At 138 DEG C, crystallization 8 days, obtains composite molecular screen product, and through crystal phase analysis, synthetic product is pure Y-Beta composite molecular screen.(with oxide basis, not comprising the TEA-Y type molecular sieve added) proportioning: 3.0Na
2o:39SiO
2: Al
2o
3: 11TEABr:14NH
3oH:770H
2o.The mass ratio of the TEA-Y type molecular sieve added and NaOH, template, water, ammoniacal liquor, aluminium source and silicon source compositional system is 1:9.1.
Embodiment 4
The first step, takes 2.0g NaOH and 15.5gTEABr is dissolved in 90.0ml deionized water, waits after being uniformly dissolved and adds 20.0m1 concentrated ammonia liquor again;
Second step, is placed in the water-bath of 60 DEG C by above-mentioned solution, add 10.0gY type molecule and be sieved in the solution of the first step under the condition constantly stirred, and continues stirring 8 hours;
3rd step, the solution of second step is carried out suction filtration, drying obtain process after Y zeolite powder;
4th step, at ambient temperature, by 0.85g NaOH, 1.67g sodium aluminate, 15g tetraethylammonium bromide and 55ml deionized water mixing and stirring, then adds 15ml ammoniacal liquor;
5th step, joins the mixed solution that step 4 obtains, after stirring, joins in solution by 40ml Ludox, airtight stirring 4 hours, obtain uniform reaction mixture gel system by the 15.0gY type molecular sieve powder after the process obtained.Then mixture is moved on in airtight stainless steel cauldron.At 140 DEG C, crystallization 8 days, obtains composite molecular screen product, and through crystal phase analysis, synthetic product is pure Y-Beta composite molecular screen.(with oxide basis, not comprising the TEA-Y type molecular sieve added) proportioning: 2.9Na
2o:34SiO
2: Al
2o
3: 10TEABr:14NH
3oH:778H
2o.The mass ratio of the TEA-Y type molecular sieve added and NaOH, template, water, ammoniacal liquor, aluminium source and silicon source compositional system is 1:8.9.
Embodiment 5
The first step, takes 2.0g NaOH and 10.5gTEABr is dissolved in 50.0ml deionized water, waits after being uniformly dissolved and adds 20.0m1 concentrated ammonia liquor again;
Second step, is placed in the water-bath of 80 DEG C by above-mentioned solution, add 10.0gY type molecule and be sieved in the solution of the first step under the condition constantly stirred, and continues stirring 6 hours;
3rd step, the solution of second step is carried out suction filtration, drying obtain process after Y zeolite powder;
4th step, at ambient temperature, by 0.90g NaOH, 1.67g sodium aluminate, 16g tetraethylammonium bromide and 50ml deionized water mixing and stirring, then adds 15ml ammoniacal liquor;
5th step, the 12.0gY type molecular sieve powder after the process obtained is joined the mixed solution that step 4 obtains, after stirring, join in solution by 50ml Ludox, airtight stirring 2-4 hour, obtains uniform reaction mixture gel system.Then mixture is moved on in airtight stainless steel cauldron.At 140 DEG C, crystallization 9 days, obtains composite molecular screen product, and through crystal phase analysis, synthetic product is pure Y-Beta composite molecular screen.(with oxide basis, not comprising the TEA-Y type molecular sieve added) proportioning: 3.0Na
2o:43SiO
2: Al
2o
3: 11TEABr:14NH
3oH:750H
2o.The mass ratio of the TEA-Y type molecular sieve added and NaOH, template, water, ammoniacal liquor, aluminium source and silicon source compositional system is 1:11.8.
Embodiment 6
The first step, takes 1.0g NaOH and 15.5gTEABr is dissolved in 60.0ml deionized water, waits after being uniformly dissolved and adds 10.0m1 concentrated ammonia liquor again;
Second step, is placed in the water-bath of 50 DEG C by above-mentioned solution, add 10.0gY type molecule and be sieved in the solution of the first step under the condition constantly stirred, and continues stirring 8 hours;
3rd step, the solution of second step is carried out suction filtration, drying obtain process after Y zeolite powder;
4th step, at ambient temperature, by 0.90g NaOH, 1.67g sodium aluminate, 16g tetraethylammonium bromide and 50ml deionized water mixing and stirring, then adds 10ml ammoniacal liquor;
5th step, joins the mixed solution that step 4 obtains, after stirring, is joined slowly in solution by 40ml Ludox, airtight stirring 4 hours, obtain uniform reaction mixture gel system by the 12.0gY type molecular sieve powder after the process obtained.Then mixture is moved on in airtight stainless steel cauldron.At 140 DEG C, crystallization 5 days, obtains composite molecular screen product, and through crystal phase analysis, synthetic product is pure Y-Beta composite molecular screen.(with oxide basis, not comprising the TEA-Y type molecular sieve added) proportioning: 3.0Na
2o:34SiO
2: Al
2o
3: 11TEABr:9.3NH
3oH:750H
2o.The mass ratio of the TEA-Y type molecular sieve added and NaOH, template, water, ammoniacal liquor, aluminium source and silicon source compositional system is 1:10.5.
Comparative example 1
The composite molecular screen that CN200710012675.8 embodiment 1 method obtains, can find out wherein containing ZSM-12 crystalline phase from its XRD figure.The composite molecular screen that CN200710012675.8 embodiment 3 method obtains, can find out wherein containing ZSM-12 crystalline phase, and the composite molecular screen in stereoscan photograph comes out completely, does not wrap up completely from its XRD figure.
Comparative example 2
By the method described in embodiment 1, by NaY after alkali treatment, directly mix with required all synthesis materials, then synthesize under the same conditions.Result shows, although composite molecular screen product does not have stray crystal to occur, parcel degree is poor, there is the Y zeolite particle much do not wrapped up.
Claims (11)
1. there is a synthetic method for the Y-Beta composite molecular screen of nucleocapsid structure, it is characterized in that comprising following content:
(1) solution is obtained by soluble in water to NaOH, tetraethylammonium bromide and ammoniacal liquor;
(2) Y zeolite powder adds in above-mentioned solution, at 40 DEG C-100 DEG C, process 2 ~ 12 hours;
(3) solution of step (2) is carried out filter, drying obtains the Y zeolite powder after processing;
(4) NaOH, aluminium source, tetraethylammonium bromide, ammoniacal liquor and water mixing and stirring are obtained mixed solution;
(5) the Y zeolite powder after process is joined in the mixed solution that step (4) prepares, after stirring, add silicon source, stir and obtain reaction mixture gel system, then carry out crystallization, finally reclaim and obtain composite molecular screen product.
2. in accordance with the method for claim 1, it is characterized in that: the temperature described in step (2) is 60 ~ 90 DEG C.
3. in accordance with the method for claim 1, it is characterized in that: in step (1) described ammoniacal liquor, the concentration of ammonia is 0.2-1.0mol/L.
4. in accordance with the method for claim 1, it is characterized in that: the naoh concentration described in step (1) is 0.2-1.0mol/L, the concentration of tetraethylammonium bromide is 0.2-1.0mol/L, and in step (2), in Y type molecular sieve powder processing procedure, liquid-solid ratio (ml liquid/g solid) is 2.0-20.0.
5. in accordance with the method for claim 1, it is characterized in that: the silicon source of synthesis material, aluminium source, ammoniacal liquor, tetraethylammonium bromide, NaOH and water in the mol ratio of following substances be:
Na
2O/SiO
2=0.05～0.12
TEABr?/SiO
2=0.25～0.50
NH
4OH?/SiO
2=0.70～1.05
SiO
2/Al
2O
3=15～58
H
2O/SiO
2=18～25
Wherein, the silicon source of synthesis material, aluminium source are with oxide basis, and do not comprise the TEA-Y type molecular sieve added, described TEABr is tetraethylammonium bromide.
6. in accordance with the method for claim 1, it is characterized in that: the crystallization crystallization 5.0-10.0 days at 135 DEG C-145 DEG C in confined conditions of step (5), obtains the Y-Beta composite molecular screen with nucleocapsid structure.
7. in accordance with the method for claim 1, it is characterized in that: the Y zeolite in step (2) is NaY type molecular sieve, and silica/alumina molecule mol ratio is 4.8-5.2.
8. in accordance with the method for claim 1, it is characterized in that: the aluminium source described in step (4) is sodium aluminate.
9. in accordance with the method for claim 1, it is characterized in that: the silicon source described in step (5) is Ludox.
10. according to the method described in claim 1 or 5, it is characterized in that: the weight ratio of the mixture that the Y zeolite powder after process and silicon source, aluminium source, ammoniacal liquor, tetraethylammonium bromide, NaOH and water form is 1:5 ~ 1:20.
The Y-Beta composite molecular screen that described in 11. 1 kinds of arbitrary claims of claim 1 to 10 prepared by method, Y-Beta composite molecular screen is not containing stray crystal, and Y zeolite core is wrapped up completely by Beta molecular sieve shell.
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| CN104556095B (en) * | 2013-10-22 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of preparation method of Y/Silicalite-1 composite molecular screen |
| CN104556094B (en) * | 2013-10-22 | 2016-06-22 | 中国石油化工股份有限公司 | A kind of Y/Silicalite-1 composite molecular screen and preparation method thereof |
| CN106587093B (en) * | 2015-10-15 | 2018-09-14 | 中国石油化工股份有限公司 | The preparation method of Y-Beta composite molecular screens |
| CN106986353B (en) * | 2017-04-28 | 2019-01-11 | 长乐净能新材料科技有限公司 | A kind of nanometer of Pr, Ce-Y/Beta modified molecular screen and its application |
| CN115504483B (en) * | 2021-06-23 | 2024-02-02 | 中国石油化工股份有限公司 | Mesoporous Beta-USY type composite molecular sieve and preparation method and application thereof |
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