CN104556122A - Molecular sieve supported nanocrystal Y-type molecular sieve and synthesis method thereof - Google Patents
Molecular sieve supported nanocrystal Y-type molecular sieve and synthesis method thereof Download PDFInfo
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- CN104556122A CN104556122A CN201310499215.8A CN201310499215A CN104556122A CN 104556122 A CN104556122 A CN 104556122A CN 201310499215 A CN201310499215 A CN 201310499215A CN 104556122 A CN104556122 A CN 104556122A
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Abstract
The invention discloses a preparation method for an in-situ crystallized Y-type molecular sieve. The preparation method comprises the following steps: (1) dissolving alkaline sodium salt, an aluminum compound and water glass with water and and mixing uniformly; (2) adding a deeply de-aluminized conventional Y-type molecular sieve powder matrix in the mixture obtained in the step (1), puling and ageing for 5-24 h; (3) crystallizing the material aged in the step (2) under a 80-120D EG C hydrothermal condition for 10-30 h, preferably 15-25 h, and filtering and washing after the crystallization to obtain the in-situ crystallized product. According to the preparation method, the natural kaolin material is replaced with the deeply treated conventional Y-type molecular sieve material which is used as the in-situ crystallization matrix, so that the in-situ crystallized Y-type molecular sieve which is small in crystalline grain and high in silica-alumina ratio is hydrothermally synthesized under an alkaline condition.
Description
Technical field
The present invention relates to a kind of method of load crystallization synthesis of faujasite, particularly with the conventional die Y zeolite of advanced treatment for matrix load crystallization synthesis loading type small-grain Y molecular sieve methods.
Technical background
Zeolite molecular sieve is extensively present in nature, and the realization of molecular sieve synthetic has then promoted the development of materials chemistry and Industrial Catalysis technology.Molecular sieve except being widely used in the processes such as catalysis, absorption, separation, and being constantly applied or having potential application foreground in micro laser, gas and liquid separating film, gas sensor, nonlinear optical material, fluorescent material, advanced low-k materials and impregnating material etc.At present, not lower thousand kinds, the molecular sieve of synthetic, obtain industrial application or cause industrial circle interest to only have about tens kinds, and first the obstacle affecting novel structure molecular sieve industrial application is exactly the maturity of its synthesis technique and the height of preparation cost, another one is exactly its good catalytic performance and unique catalysis feature.In the heavy oil deep process technology of petroleum refining process, landmark leap is exactly the heavy oit pyrolysis technological revolution that molecular sieve substitutes that natural clay and amorphous acidic silicic acid aluminium causes.
Molecular sieve fabricated in situ is exactly preparation method molecular sieve component be grown directly upon in certain matrix, and it is the same at the liquid phase synthesis of synthesis in essence with traditional, and difference is its single molecules of interest sieve product.It grows and is attached to the dispersion system of the zeolite crystal in matrix, says that it is a kind of matrix material in some sense.No matter be the fabricated in situ of what mode, there is requirement to matrix, require that it has the feature keeping original basic structure in synthetic environment in principle.Petrochemical process widely apply still based on micropore crystalline aluminium silicate molecular sieve, they nearly all synthesize under alkaline water heat condition.Therefore, common amorphous alkaline-earth oxide such as amorphous aluminum silicide is not suitable for doing matrix, because their major parts can dissolve or change into other alkali formula compound under alkali system.Therefore, existing fabricated in situ material all adopts natural inert material, as kaolin, clay, polynite etc., wherein kaolin has double-deck octahedra crystalline structure, surface has slightly acidic, also there is certain unreactiveness, therefore can as the matrix of fabricated in situ under alkaline water heat condition.Patent CN200810012205.6 with the kaolin of high-temperature roasting for matrix, in-situ crystallization synthetic faujasites is carried out by the mode in additional aluminium source, greatly can shorten crystallization time, and improve product property, the faujusite of synthesis can as the component of the catalyzer such as hydrocracking.
First Heden etc. disclose at US3391994 with kaolin is the NaY in-situ crystallization technology that raw material prepares active constituent and matrix symbiosis, and main consideration is applied on FCC catalyzer.In order to obtain the in-situ crystallization catalyzer of active good catalysis selection type excellence, there is particular requirement to substrate material, being raw material in-situ crystallization technology as EP0209332A2 discloses one with kaolin, using the metakaolin that 550-925 DEG C of roasting obtains.CN1549746A, CN1232862A, CN1334318A also relate to and adopt roasting kaolin to do matrix to carry out fabricated in situ and prepare Y molecular sieve.
At employing natural mineral, as kaolin, polynite, clay, carry out in fabricated in situ Y zeolite process as matrix, natural mineral demonstrates good stability and adaptability, the severe condition such as high temperature high alkalinity environment can be resisted, meet the requirement of in-situ crystallization reaction to matrix.But the character of matrix is in-situ crystallization reaction process key influence factor.Due to the difference that natural mineral raw at source exists with storage in form, and natural mineral foreign matter content is far from each other, causes natural mineral character to there is larger difference, even if the mineral being derived from same mineral reserve also also exist larger performance difference.Difference in these performances directly will have influence on the stability of in-situ crystallization compound experiment and repeatability, sometimes directly has influence on some Key Performance Indicator of object product.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of matrix of conventional Y zeolite material substitution natural kaolin material as in-situ crystallization adopting advanced treatment, Hydrothermal Synthesis goes out the in-situ crystallization Y zeolite of little crystal grain, high silica alumina ratio in the basic conditions.
A preparation method for in-situ crystallization Y zeolite, comprises the steps:
(1) alkaline sodium salt, aluminum contained compound, water glass are dissolved in water and are mixed;
(2) in step (1), the conventional Y zeolite powdered substrate making beating through deep sealumination modified process is added and aging 5 ~ 24h;
(3) step (2) aging after material crystallization under 80 ~ 120 DEG C of hydrothermal conditions, crystallization time is 10 ~ 30 hours, be preferably 15 ~ 25 hours, crystallization terminates rear filtration washing and obtains in-situ crystallization product.
The inventive method, the alkaline sodium salt described in step (1) comprises one or more mixing of sodium carbonate, sodium hydroxide and sodium aluminate.The additional silicon source that described water glass (main component is water glass) is building-up process.Described aluminum contained compound is additional aluminium source, comprises one or more mixing of aluminum oxide or aluminate compound.Aluminate comprises one or more mixtures of Tai-Ace S 150, aluminum chloride, aluminum nitrate and sodium aluminate, and aluminum oxide is generally inverse boehmite.
The inventive method, the conventional Y zeolite in step (2) can be the commercially available or homemade conventional die molecular sieve such as HY, low sodium ammonium Y, SSY, USY and USSY.Lattice constant is generally 2.440 ~ 24.74, and degree of crystallinity is generally 80% ~ 120%.
In the inventive method, the deep sealumination modified process in step (2) adopts hydrothermal treatment consists and making beating to process the mode combined.Hydrothermal treatment consists temperature is 500 ~ 900 DEG C, pressure is 0.05 ~ 1.0MPa, and the treatment time is 0.5 ~ 6h.During making beating process, the concentration of acid solution or alkali lye is 0.2mol/L ~ 4.0mol/L, and solid-to-liquid ratio is 1:2 ~ 1:10, and beating time is 20 ~ 200min, making beating temperature 35 ~ 95 DEG C.
The inventive method is 6 ~ 40:1 preferably through the silica alumina ratio after degree of depth modification in step (2), best 9 ~ 30:1, and lattice constant is 24.25 ~ 24.38, and the best is 24.28 ~ 24.33; Degree of crystallinity is 70% ~ 100%, and the best is the Y zeolite of 50% ~ 80%.
The inventive method, the weathering process in step (2) is carried out under hyperacoustic effect, preferred composite ultraphonic ripple.Composite ultraphonic ripple is made up of low frequency and high frequency, and low-frequency ultrasonic waves frequency control is 20 ~ 60KHz, and power is 2 ~ 6W/mL; It is 100 ~ 200KHz that high-frequency ultrasonic controls power, and power is 10 ~ 20W/mL; The mode of action can be act on simultaneously, also can be alternating action.By controlling the weathering process of double-frequency ultrasound wave frequency and energy level, being conducive to small crystal grain molecular sieve and growing uniformly on the conventional Y zeolite through deep sealumination modified modification.
The inventive method, the Y zeolite added in step (2) and water glass weight ratio are 0.1:1 ~ 1:1.Material mol ratio time aging is (3 ~ 12) Na
2o:Al
2o
3: (10 ~ 25) SiO
2: (80 ~ 400) H
2o, reaches necessary requirement by the silica alumina ratio of the add-on controlling crystallizing synthesis material adjusting aluminium salt or aluminum oxide.
The present invention adopts the Y zeolite of conventional die size through deep sealumination modified modified, substantially increase its chemical stability, overbasic molecular sieve water heat building-up process can be stood, meet the requirement as the molecular sieve carried matrix of in-situ crystallization, simultaneously large Y molecular sieve crystal grain, also as the carrier of newly-generated nano-class molecular sieve particle, forms the core shell structure of the Y-Y molecular sieve compound of nanometer-size die shell and micron order kernel.
Feedstock property, by adding the matrix of deep sealumination modified Y type molecular sieve as fabricated in situ molecular sieve, effectively realizes controlled, eliminates the impact that material property change brings Zeolite synthesis, improve the stability of Zeolite synthesis by the inventive method; Use the synthetic material of large pore volume bigger serface to substitute almost without the natural mineral such as kaolin of internal surface area simultaneously, substantially improve synthesis Molecular Sieve Pore afterwards.
The present invention adopts Y zeolite as the matrix of fabricated in situ, undersized zeolite crystal can in the surface growth of advanced treatment Y zeolite under hydrothermal conditions, generate conventional die and small crystal grain Y-shaped molecular sieve two kinds of size Y zeolite matrix materials, not only can solve the stability of small crystal grain molecular sieve, the Y zeolite novel material in compound duct can also be obtained.In addition the more important thing is and adopt Y zeolite as matrix, in building-up process, it can play the effect of guiding crystal growth, therefore can cancel adding of directed agents.
Accompanying drawing explanation
Fig. 1, Fig. 2, Fig. 3 are respectively the SEM figure of embodiment 2, embodiment 3 and comparative example 1.
embodiment:
The preparation method of in-situ crystallization Y molecular sieve of the present invention, specifically comprises the steps:
(1) successively join in deionized water by the alkaline sodium salt of metering, aluminum contained compound, water glass, unlatching is uniformly mixed;
(2) temperature of learning from else's experience is 500 ~ 1000 DEG C, pressure 0.05 ~ 1.0MPa Water Under thermal treatment and be 0.2mol/L ~ 4.0mol/L strong acid or highly basic making beating Combined Processing Y zeolite through concentration, add slurry system, continue to stir, aging 5 ~ 24h, preferably carries out aging under hyperacoustic effect;
(3) said mixture is proceeded to reactor and under 80 ~ 120 DEG C of hydrothermal conditions crystallization, crystallization time is less than 30 hours, is generally 10 ~ 30 hours, be preferably 15 ~ 25 hours; Filter washing and obtain in-situ crystallization product.
Following examples further illustrate essence of the present invention and effect, are not construed as limiting the invention, and the composition percentage composition related to is weight percentage.
eXAMPLE l
Get commercially available SSY and be placed in hydrothermal treatment consists stove, vapour pressure 0.1MPa, 600 DEG C of process 2h, then with 1.5mol/L salpeter solution making beating process 60min, temperature 65 DEG C, solid-to-liquid ratio 1:4, solid-liquid separation, dry.Then 5 liters of beakers are got, add 145.6g Tai-Ace S 150 and the 600g dissolving that adds water, get in addition 56.3g solid sodium hydroxide add water 171g dissolve, under agitation the former is slowly added the latter, then the water glass 992g of silica content 28% is added, finally add the above-mentioned Modified Zeolite Y of metering ratio, aging 4h, time aging, material mole consists of 7.6Na
2o:Al
2o
3: 12.1SiO
2: 210H
2o, proceed to reactor after aging end and under l10 DEG C of hydrothermal condition crystallization 20h, filter washing obtain in-situ crystallization product, be numbered 1.
embodiment 2
Example 1 Middle molecule sieve hydrothermal treatment consists temperature is increased to 800 DEG C, and nitric acid changes the caustic solution of same concentrations into, and time aging, material mole consists of 10.1Na
2o:Al
2o
3: 17.4SiO
2: 300H
2o, other prepares crystallization product numbering 2 with example 1.
embodiment 3
Change SSY in example 1 into HY, add the conventional Y zeolite directed agents of 50mL before crystallization, directed agents proportioning: 8Na
2o:Al
2o
3: 20SiO
2: 240H
2o, other prepares crystallization product numbering 3 with example 1.
embodiment 4
Weathering process is carried out under the effect of composite ultraphonic ripple, and frequency is respectively 40KHz and 120KHz, and power is respectively 3W/mL and 15W/mL, and ultrasonic wave is opened simultaneously, and other prepares crystallization product numbering 4 with example 1.
comparison example 1
Molecular sieve matrix in example 1 is changed to the kaolin (roasting 2h) of 900 DEG C of high-temperature roastings, other is with example 1, numbering BJY-1.
comparison example 2
Adding not treated Y zeolite is matrix, and other is with example 1, obtains products nr BJY-2.
The property list 1 of above-described embodiment and the molecular sieve prepared by comparative example, sample segment scanning electron microscope (SEM) photograph is shown in accompanying drawing 1,2 and 3.
the character of table 1 embodiment and comparative example gained molecular sieve
Fig. 1 ~ Fig. 3 gives the SEM contrast images of embodiment and comparative example, can clearly find out from contrast images, it is matrix that embodiment is larger crystal molecular sieve, the Y-Y composite molecular screen of the good nucleocapsid structure of secondary crystal effect, and comparative example is macrobead kaolin grows the poor in-situ crystallization molecular sieve of homogeneity.
Claims (15)
1. a preparation method for in-situ crystallization Y zeolite, is characterized in that: comprise the steps: that alkaline sodium salt, aluminum contained compound, water glass are dissolved in water and are mixed by (1); (2) in step (1), the conventional Y zeolite powdered substrate making beating through deep sealumination modified process is added and aging 5 ~ 24h; (3) step (3) aging after material crystallization under 80 ~ 120 DEG C of hydrothermal conditions, crystallization time is 10 ~ 30 hours, be preferably 15 ~ 25 hours, crystallization terminates rear filtration washing and obtains in-situ crystallization product.
2. method according to claim 1, is characterized in that: the alkaline sodium salt described in step (1) comprises one or more mixing of sodium carbonate, sodium hydroxide and sodium aluminate.
3. method according to claim 1, is characterized in that: the aluminum contained compound described in step (1) is additional aluminium source, comprises one or more mixing of aluminum oxide or aluminate compound.
4. method according to claim 3, is characterized in that: aluminate comprises one or more mixing of Tai-Ace S 150, aluminum chloride, aluminum nitrate and sodium aluminate, and aluminum oxide is inverse boehmite.
5. method according to claim 1, is characterized in that: the conventional Y zeolite in step (2) comprises HY, low sodium ammonium Y, SSY, USY and USSY.
6. method according to claim 1 or 5, it is characterized in that: molecular sieve lattice constant is 2.440 ~ 24.74, degree of crystallinity is 80% ~ 120%.
7. method according to claim 1, is characterized in that: the deep sealumination modified process in step (2) adopts hydrothermal treatment consists and making beating to process the mode combined.
8. method according to claim 7, is characterized in that: hydrothermal treatment consists temperature is 500 ~ 900 DEG C, pressure is 0.05 ~ 1.0MPa, and the treatment time is 0.5 ~ 6h.
9. method according to claim 7, is characterized in that: during making beating process, the concentration of acid solution or alkali lye is 0.2mol/L ~ 4.0mol/L, and solid-to-liquid ratio is 1:2 ~ 1:10, and beating time is 20 ~ 200min, making beating temperature 35 ~ 95 DEG C.
10. method according to claim 1, is characterized in that: the conventional Y zeolite silica alumina ratio in step (2) after degree of depth modification is 6 ~ 40:1, and lattice constant is 24.25 ~ 24.38; Degree of crystallinity is 70% ~ 100%.
11. methods according to claim 11, is characterized in that: sieve silica alumina ratio is 9 ~ 30:1, and lattice constant is 24.28 ~ 24.33; Degree of crystallinity is 50% ~ 80%.
12. methods according to claim 1, is characterized in that: the weathering process in step (2) is carried out under hyperacoustic effect.
13. methods according to claim 12, is characterized in that: weathering process is carried out under the effect of composite ultraphonic ripple, and composite ultraphonic ripple is made up of low frequency and high frequency, and low-frequency ultrasonic waves frequency control is 20 ~ 60KHz, and power is 2 ~ 6W/mL; It is 100 ~ 200KHz that high-frequency ultrasonic controls power, and power is 10 ~ 20W/mL; The mode of action can be act on simultaneously, also can be alternating action.
14. methods according to claim 1, is characterized in that: the Y zeolite added in step (2) and water glass weight ratio are 0.1:1 ~ 1:1.
15. methods according to claim 1, is characterized in that: material mol ratio time aging in step (2) is (3 ~ 12) Na
2o:Al
2o
3: (10 ~ 25) SiO
2: (80 ~ 400) H
2o.
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| CN108946758A (en) * | 2018-08-22 | 2018-12-07 | 太原理工大学 | A kind of high-silicon Y-Zeolite and preparation method thereof |
| CN112717981A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
| CN116062764A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Y-Y composite molecular sieve with core-shell structure, and preparation method and application thereof |
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| CN112717981B (en) * | 2019-10-28 | 2022-04-08 | 中国石油化工股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
| CN116062764A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Y-Y composite molecular sieve with core-shell structure, and preparation method and application thereof |
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