CN105712371A - USY-Y composite molecular sieve and preparation method thereof - Google Patents
USY-Y composite molecular sieve and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a USY-Y composite molecular sieve. The USY-Y composite molecular sieve uses a USY type molecular sieve as a core and a Y type molecular sieve as a shell, wherein the weight of the Y type molecular sieve in the composite molecular sieve is 10 to 90 wt%, the composite molecular sieve has a meso-microporous structure, the pore volume of meso pores is 15 to 50% of the total pore volume of the composite molecular sieve, a mol ratio of silicon oxide to alumina in the composite molecular sieve is 4.2 to 25, and the composite molecular sieve has a specific surface area of 450 to 900 m2/g, a pore volume of 0.33 to 0.62 ml/g and an average pore size of 1.5 to 4.0 nm. Since the composite molecular sieve has the obvious meso-microporous structure, the diffusion speeds of reactants and products can be improved, the possibility of secondary cracking of molecules is reduced, conditions are provided for reactions of large molecules, and the catalysis performance of the molecular sieve is improved.
Description
Technical field
The present invention relates to a kind of composite molecular screen and preparation method thereof, relate in particular to a kind of USY-Y composite molecular screen and preparation method thereof.
Background technology
Y type molecular sieve is mutually communicated along three crystalline axis direction by twelve-ring by octahedral molecular sieve cage and is formed, and is a kind of excellent catalyst activity component, and not only cracking activity is high, and selectivity is good.Therefore the discovery of Y type molecular sieve and be used in catalytic field there is epoch-making meaning.
Owing to the Y type molecular sieve (silicon oxide than the mol ratio of aluminium oxide between 3 ~ 4.5) of low silica-alumina ratio does not have good hydrothermal stability, therefore, research widely and general attention are not obtained in actual building-up process and in application.And high silica alumina ratio Y type molecular sieve (silicon oxide than the mol ratio of aluminium oxide more than 4.6) has good hydrothermal stability and absolute acid stability because of it, in the processes such as the modified catalytic cracking as a kind of catalysis material in PETROLEUM PROCESSING and hydrogenation cracking, playing irreplaceable effect.And the channel obtained of high-Si Y-type molecular sieve also has a variety of.Have by being directly synthesized and can obtain, but the silica alumina ratio (silicon oxide is than the mol ratio of aluminium oxide) of high-Si Y-type molecular sieve prepared by this method is often below 7.Traditional method preparing high silica alumina ratio Y type molecular sieve is mainly hydrothermal treatment consists dealuminzation and chemical dealuminization silicon reinsertion.
All the time, the extensive concern of numerous scientific research personnel is obtained about the modified work of Y type molecular sieve.The research of Y type molecular sieve, except carrying out the acid of routine, alkali and hydrothermal treatment consists and be modified, have also been obtained about the complex technique of high-Si Y-type molecular sieve and pays close attention to widely.CN200610048273.9 discloses a kind of composite molecular screen adopting high-Si Y-type molecular sieve to synthesize high silicon, this composite molecular screen organically combines the feature of high-Si Y-type molecular sieve and Beta zeolite, prepared composite not only has the good hydrothermal stability of high-Si Y-type molecular sieve and absolute acid stability, also there is the good heat of Beta zeolite and hydrothermal stability simultaneously, the acidity of appropriateness and absolute acid stability and hydrophobic properties, show the performance of excellence in the courses of reaction such as hydrogenation cracking.
And preparing currently without the attention causing vast researcher about Y-Y composite molecular screen, it is primarily due to the compound that its compound is a kind of zeolite type, its building-up process is similar to crystal seed method and prepares the process of molecular sieve, and the structure that the structure of this molecular sieve can not be two kinds different as Y-Beta composite molecular screen regulates mutually.Traditional Thinking is believed that this composite molecular screen is a kind of single molecular sieve.
And utilize the USY molecular sieve that Modified Zeolite Y obtains to prepare USY-Y composite molecular screen, it is possible to avoid above-mentioned phenomenon.But in actual fabrication process, owing to the structure of USY molecular sieve is in the building-up process of USY-Y composite molecular screen, standing the long-time crystallization of high temperature and high alkalinity, its structure cannot keep.Therefore, there is presently no researcher preparation and there is the USY-Y composite molecular screen of nucleocapsid different in kind.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of USY-Y composite molecular screen and preparation method thereof.Composite molecular screen prepared by the method has obvious mesoporous-microporous structure, it is possible to improves the diffusion velocity of reactant and product, reduces the chance of molecule generation second pyrolysis, provides condition for the reaction of macromole simultaneously, improves the catalytic performance of molecular sieve.
A kind of USY-Y composite molecular screen, described composite molecular screen is with USY type molecular sieve for core, and with Y type sub-sieve for shell, in composite molecular screen, the weight content of Y type molecular sieve is 10wt% ~ 90wt%, it is preferable that 30wt% ~ 70wt%；Composite molecular screen has mesoporous-microporous structure, and mesoporous shared pore volume accounts for the 15% ~ 50% of the total pore volume of molecular sieve, it is preferable that 20% ~ 40%, and in composite molecular screen, silica/alumina molar ratio is 4.2 ~ 25, and specific surface area is 450 ~ 900m2/ g, pore volume is 0.33 ~ 0.62ml/g, and average pore size is 1.5 ~ 4.0nm；Preferential oxidation silicon/alumina molar ratio is 6 ~ 15, and specific surface area is 550 ~ 800m2/ g, pore volume is 0.35 ~ 0.50ml/g, and average pore size is 1.8 ~ 2.9nm.
The preparation method of a kind of USY-Y composite molecular screen, comprises the steps:
(1) ammonium salt is adopted to swap USY molecular sieve；
(2) according to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=15 ~ 20:1:15 ~ 22:320 ~ 420, are configured to mixed liquor by aluminum source, water, sodium hydroxide and waterglass, then ageing 0.5 ~ 2 day at 20 ~ 50 DEG C, prepare directed agents；
(3) according to the mol ratio of (USY molecular sieve that removing adds) each material in gel it isn(NaOH):n(Al2O3):n(SiO2):n(H2O)=14 ~ 18:1:9 ~ 20:320 ~ 760, it is preferable thatn(NaOH):n(Al2O3):n(SiO2):n(H2O)=14.5 ~ 16.5:1:11 ~ 18:400 ~ 650, by aluminum source, sodium hydroxide, water and waterglass are configured to mixed liquor, it is subsequently adding the directed agents that the USY molecular sieve after step (1) ammonium salt swaps and step (2) prepare, by gel thermostatic crystallization 12 ~ 72 hours under 85 ~ 120 DEG C of conditions after stirring, preferably in thermostatic crystallization 24 ~ 60 hours under 90 ~ 110 DEG C of conditions, then cooled, washing, sucking filtration, obtain after drying with USY molecular sieve for core and be shell with Y type molecular sieve USY-Y composite molecular screen, the quality of the USY molecular sieve wherein added accounts for 4 ~ 30wt% of gel rubber system gross mass, preferably 6 ~ 15wt%, the quality of the directed agents added accounts for 2 ~ 20wt% of gel rubber system gross mass, preferably 4 ~ 10wt%.
USY molecular sieve described in the inventive method step (1) is through modified Y type molecular sieve, is obtained by physics or chemical method dealuminzation, desiliconization or dealumination complement silicon.Wherein representative method of modifying is hydrothermal treatment consists dealuminzation and chemical method desiliconization, dealumination complement silicon.Modified Y type molecular sieve can be Hydrogen can also be sodium form.The silica/alumina molar ratio of USY molecular sieve is 4.2 ~ 35, and specific surface area is 450 ~ 850m2/ g；Preferential oxidation silicon/alumina molar ratio is 6 ~ 15, and specific surface area is 550 ~ 800m2/g。
The inventive method step (1) adopt ammonium salt to swap process as follows: to be added to the water by ammonium salt, be subsequently adding molecular sieve, after being stirred continuously 1 ~ 2 hour, sucking filtration, dry；The concentration of ammonium salt solution is 0.15mol/L ~ 0.5mol/L, it is preferable that 0.2mol/L ~ 0.3mol/L；The mass ratio of solution and molecular sieve is 6:1 ~ 20:1, it is preferable that 9:1 ~ 15:1.
Ammonium salt in the inventive method step (1) refers to various organic quaternary ammonium salt or long-chain organic cation type surfactant.The preferred tetraethyl ammonium radical ion of quaternary ammonium salt or tetrapropyl ammonium radical ion, the long-chain organic cation preferred cetyl trimethylammonium bromide of type surfactant, P123 or F127 etc..
In the inventive method step (2) and (3), described aluminum source includes one or more in aluminum chloride, aluminum sulfate, aluminum nitrate, sodium aluminate, it is preferable that sodium aluminate.
The inventive method is initially with based on USY, stable by utilizing cationic organic ammonium radical ion that USY molecular sieve structure is carried out, and then prepares Y type molecular sieve at USY molecular sieve outer layer, obtains USY-Y composite molecular screen.Present method be advantageous in that the composite molecular screen of preparation has typical mesoporous-microporous structure, shell has different physico-chemical properties from core simultaneously, in the modifying process of follow-up molecular sieve, the physico-chemical property of nucleocapsid and catalytic performance are also always be to maintain certain difference, it is possible to provide different reaction environments for reactant.
Accompanying drawing explanation
Fig. 1 is the composite molecular screen XRD diffraction pattern of the embodiment of the present invention 1 synthesis.
Fig. 2 is the adsorption isothermal curve of the composite molecular screen of synthesis in the present invention.
Fig. 3 is the graph of pore diameter distribution of the composite molecular screen of synthesis in the present invention.
Detailed description of the invention
Further illustrate the preparation process of the present invention below in conjunction with embodiment, but following example do not constitute the restriction to the inventive method.Preparation process all adopts and adds the USY type molecular sieve with following character: silica/alumina molar ratio is 9.2, and specific surface area is 650m2/ g, USY are the commodity USY bought.
Embodiment 1
(1) adopting tetraethylammonium bromide to swap USY molecular sieve, the pore passage structure making USY molecular sieve is stable.Concrete exchange process is as follows: be added to the water by tetraethylammonium bromide, then adds USY and enters molecular sieve, after being stirred continuously 1.5 hours, and sucking filtration, dry.The concentration of ammonium salt solution is 0.3mol/L, and the mass ratio of solution and molecular sieve is 8:1.
(2) according to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=16:1:18:360, under stirring, is sequentially added into sodium aluminate, water, sodium hydroxide and waterglass beaker and forms mixed liquor, then ageing 2 days at 25 DEG C, prepare directed agents.
(3) according to the mol ratio of (USY molecular sieve that removing adds) each material in gel it isn(NaOH):
n(Al2O3):n(SiO2):n(H2The condition of O)=15:1:16:450.When stirring, sodium aluminate, sodium hydroxide, water and waterglass are added sequentially in beaker and form mixed liquor, it is subsequently adding the directed agents that step (1) USY molecular sieve and step (2) prepare, by gel thermostatic crystallization 60 hours under 90 DEG C of conditions after stirring, then cooled, washing, sucking filtration, after drying obtain with USY molecular sieve for core and be shell with Y type molecular sieve USY-Y composite molecular screen, the quality of the USY molecular sieve wherein added accounts for the 8wt% of gel rubber system gross mass, and the quality of the directed agents of addition accounts for the 5wt% of gel rubber system gross mass.The character of composite molecular screen is as shown in table 1.
Embodiment 2
(1) adopt cetyl trimethylammonium bromide to swap USY molecular sieve, make molecular sieve structure stable.Cetyl trimethylammonium bromide is added to the water, then adds USY and enter molecular sieve, after being stirred continuously 1.5 hours, sucking filtration, dry.The concentration of ammonium salt solution is 0.2mol/L, and the mass ratio of solution and molecular sieve is 12:1.
(2) according to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=18:1:19:360, under stirring, is sequentially added into sodium aluminate, water, sodium hydroxide and waterglass beaker and forms mixed liquor, then ageing 1 day at 35 DEG C, prepare directed agents.
(3) according to the mol ratio of (USY molecular sieve that removing adds) each material in gel it isn(NaOH):
n(Al2O3):n(SiO2):n(H2The condition of O)=15.5:1:14:550.When stirring, aluminum sulfate, sodium hydroxide, water and waterglass are added sequentially in beaker and form mixed liquor, it is subsequently adding the directed agents that step (1) USY molecular sieve and step (2) prepare, by gel thermostatic crystallization 48 hours under 100 DEG C of conditions after stirring, then cooled, washing, sucking filtration, after drying obtain with USY molecular sieve for core and be shell with Y type molecular sieve USY-Y composite molecular screen, the quality of the USY molecular sieve wherein added accounts for the 10wt% of gel rubber system gross mass, and the quality of the directed agents of addition accounts for the 8wt% of gel rubber system gross mass.The character of composite molecular screen is as shown in table 1.
Embodiment 3
(1) adopt 4-propyl bromide to swap USY molecular sieve, make molecular sieve structure stable.4-propyl bromide is added to the water, then adds USY and enter molecular sieve, after being stirred continuously 1 hour, sucking filtration, dry.The concentration of ammonium salt solution is 0.35mol/L, and the mass ratio of solution and molecular sieve is 10:1.
(2) according to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=16:1:16:340, under stirring, is sequentially added into sodium aluminate, water, sodium hydroxide and waterglass beaker and forms mixed liquor, then ageing 1.5 days at 40 DEG C, prepare directed agents.
(3) according to the mol ratio of (USY molecular sieve that removing adds) each material in gel it isn(NaOH):
n(Al2O3):n(SiO2):n(H2The condition of O)=16:1:16:480.When stirring, sodium aluminate, sodium hydroxide, water and waterglass are added sequentially in beaker and form mixed liquor, it is subsequently adding the directed agents that step (1) USY molecular sieve and step (2) prepare, by gel thermostatic crystallization 48 hours under 95 DEG C of conditions after stirring, then cooled, washing, sucking filtration, after drying obtain with USY molecular sieve for core and be shell with Y type molecular sieve USY-Y composite molecular screen, the quality of the USY molecular sieve wherein added accounts for the 8wt% of gel rubber system gross mass, and the quality of the directed agents of addition accounts for the 6wt% of gel rubber system gross mass.The character of composite molecular screen is as shown in table 1.
Embodiment 4
(1) adopt cetyl trimethylammonium bromide to swap USY molecular sieve, make molecular sieve structure stable.Cetyl trimethylammonium bromide is added to the water, then adds USY and enter molecular sieve, after being stirred continuously 2 hours, sucking filtration, dry.The concentration of ammonium salt solution is 0.4mol/L, and the mass ratio of solution and molecular sieve is 9:1.
(2) according to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=16.5:1:19:330, under stirring, is sequentially added into sodium aluminate, water, sodium hydroxide and waterglass beaker and forms mixed liquor, then ageing 1 day at 35 DEG C, prepare directed agents.
(3) according to the mol ratio of (USY molecular sieve that removing adds) each material in gel it isn(NaOH):
n(Al2O3):n(SiO2):n(H2The condition of O)=16:1:17:450.When stirring, aluminum nitrate, sodium hydroxide, water and waterglass are added sequentially in beaker and form mixed liquor, it is subsequently adding the directed agents that step (1) USY molecular sieve and step (2) prepare, by gel thermostatic crystallization 24 hours under 110 DEG C of conditions after stirring, then cooled, washing, sucking filtration, after drying obtain with USY molecular sieve for core and be shell with Y type molecular sieve USY-Y composite molecular screen, the quality of the USY molecular sieve wherein added accounts for the 7wt% of gel rubber system gross mass, and the quality of the directed agents of addition accounts for the 5wt% of gel rubber system gross mass.The character of composite molecular screen is as shown in table 1.
Embodiment 5
(1) adopt cetyl trimethylammonium bromide to swap USY molecular sieve, make molecular sieve structure stable.Cetyl trimethylammonium bromide is added to the water, then adds USY and enter molecular sieve, after being stirred continuously 1.5 hours, sucking filtration, dry.The concentration of ammonium salt solution is 0.25mol/L, and the mass ratio of solution and molecular sieve is 15:1.
(2) according to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=17:1:20:400, under stirring, is sequentially added into sodium aluminate, water, sodium hydroxide and waterglass beaker and forms mixed liquor, then ageing 1 day at 35 DEG C, prepare directed agents.
(3) according to the mol ratio of (USY molecular sieve that removing adds) each material in gel it isn(NaOH):
n(Al2O3):n(SiO2):n(H2The condition of O)=15:1:16:480.When stirring, sodium aluminate, sodium hydroxide, water and waterglass are added sequentially in beaker and form mixed liquor, it is subsequently adding the directed agents that step (1) USY molecular sieve and step (2) prepare, by gel thermostatic crystallization 48 hours under 95 DEG C of conditions after stirring, then cooled, washing, sucking filtration, after drying obtain with USY molecular sieve for core and be shell with Y type molecular sieve USY-Y composite molecular screen, the quality of the USY molecular sieve wherein added accounts for the 12wt% of gel rubber system gross mass, and the quality of the directed agents of addition accounts for the 6wt% of gel rubber system gross mass.The character of composite molecular screen is as shown in table 1.
The partial materialization performance of the composite molecular screen of table 1 preparation
Characterization result shows, pore volume and the silica alumina ratio of the USY-Y composite molecular screen of preparation are all big than common Y type molecular sieve；Adsorption isothermal curve also indicates that the composite molecular screen of preparation has obvious hysteresis loop, illustrates have obvious mesoporous existence, is a kind of mesoporous-microporous composite molecular screen；Pore-size distribution result also indicates that the composite molecular screen of preparation has the mesoporous existence of an obvious 3-4nm simultaneously.
Claims (11)
1. a USY-Y composite molecular screen, it is characterised in that: described composite molecular screen is with USY type molecular sieve for core, and with Y type sub-sieve for shell, in composite molecular screen, the weight content of Y type molecular sieve is 10wt% ~ 90wt%；Composite molecular screen has mesoporous-microporous structure, and mesoporous shared pore volume accounts for the 15% ~ 50% of the total pore volume of molecular sieve；In composite molecular screen, silica/alumina molar ratio is 4.2 ~ 25, and specific surface area is 450 ~ 900m2/ g, pore volume is 0.33 ~ 0.62ml/g, and average pore size is 1.5 ~ 4.0nm.
2. molecular sieve according to claim 1, it is characterised in that: in composite molecular screen, the weight content of Y type molecular sieve is 30wt% ~ 70wt%；Mesoporous shared pore volume accounts for the 20% ~ 40% of the total pore volume of molecular sieve；In composite molecular screen, silica/alumina molar ratio is 6 ~ 15, and specific surface area is 550 ~ 800m2/ g, pore volume is 0.35 ~ 0.50ml/g, and average pore size is 1.8 ~ 2.9nm.
3. the preparation method of USY-Y composite molecular screen described in claim 1 or 2, it is characterised in that: comprise the steps:
(1) ammonium salt is adopted to swap USY molecular sieve；
(2) according to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=15 ~ 20:1:15 ~ 22:320 ~ 420, are configured to mixed liquor by aluminum source, water, sodium hydroxide and waterglass, then ageing 0.5 ~ 2 day at 20 ~ 50 DEG C, prepare directed agents；
(3) according to the mol ratio of material each in gel it isn(NaOH):n(Al2O3):n(SiO2):n(H2O)=14 ~ 18:1:9 ~ 20:320 ~ 760, by aluminum source, sodium hydroxide, water and waterglass are configured to mixed liquor, it is subsequently adding the directed agents that the USY molecular sieve after step (1) ammonium salt swaps and step (2) prepare, thermostatic crystallization 12 ~ 72 hours under 85 ~ 120 DEG C of conditions, then cooled, washing, sucking filtration, obtain after drying with USY molecular sieve for core and be shell with Y type molecular sieve USY-Y composite molecular screen, the quality of the USY molecular sieve wherein added accounts for 4 ~ 30wt% of gel rubber system gross mass, the quality of the directed agents added accounts for 2 ~ 20wt% of gel rubber system gross mass.
4. method according to claim 3, it is characterised in that: USY molecular sieve described in step (1) is through modified Y type molecular sieve, is obtained by physics or chemical method dealuminzation, desiliconization or dealumination complement silicon.
5. method according to claim 3, it is characterised in that: described in step (1), the silica/alumina molar ratio of USY molecular sieve is 4.2 ~ 35, and specific surface area is 450 ~ 850m2/g。
6. method according to claim 5, it is characterised in that: silica/alumina molar ratio is 6 ~ 15, and specific surface area is 550 ~ 800m2/g。
7. method according to claim 3, it is characterised in that: step (1) adopt ammonium salt to swap process as follows: to be added to the water by ammonium salt, be subsequently adding molecular sieve, after being stirred continuously 1 ~ 2 hour, sucking filtration, dry；The concentration of ammonium salt solution is 0.15mol/L ~ 0.5mol/L；The mass ratio of solution and molecular sieve is 6:1 ~ 20:1.
8. method according to claim 3, it is characterised in that: in step (1), ammonium salt refers to various organic quaternary ammonium salt or long-chain organic cation type surfactant.
9. method according to claim 8, it is characterised in that: quaternary ammonium salt is tetraethyl ammonium radical ion or tetrapropyl ammonium radical ion, and long-chain organic cation type surfactant is cetyl trimethylammonium bromide, P123 or F127.
10. method according to claim 3, it is characterised in that: in step (2) and (3), described aluminum source includes one or more in aluminum chloride, aluminum sulfate, aluminum nitrate, sodium aluminate.
11. method according to claim 3, it is characterised in that: step (3) according to the mol ratio of material each in gel isn(NaOH):n(Al2O3):n(SiO2):n(H2O)=14.5 ~ 16.5:1:11 ~ 18:400 ~ 650, aluminum source, sodium hydroxide, water and waterglass are configured to mixed liquor, by gel thermostatic crystallization 24 ~ 60 hours under 90 ~ 110 DEG C of conditions after stirring, the quality of the USY molecular sieve added accounts for 6 ~ 15wt% of gel rubber system gross mass, and the quality of the directed agents of addition accounts for 4 ~ 10wt% of gel rubber system gross mass.
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| CN110871104A (en) * | 2018-08-29 | 2020-03-10 | 中国石油化工股份有限公司 | Porous catalytic material and preparation method thereof |
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| RU2744166C1 (en) * | 2019-12-09 | 2021-03-03 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) | Type mor zeolite and a method for production thereof |
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