CN104843736A - Y molecular sieve high in silica alumina ratio and abundant in secondary holes and preparation method therefor - Google Patents
Y molecular sieve high in silica alumina ratio and abundant in secondary holes and preparation method therefor Download PDFInfo
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Abstract
The invention provides a Y molecular sieve high in silica alumina ratio and abundant in secondary holes and a preparation method therefor. The preparation method comprises steps of: Y-type zeolite is processed for 1-5 hours at 300-600 DEG C to obtain dry Y-type zeolite, and calculated by SiO2 and Al2O3, the silica alumina mole ratio of the Y-type zeolite is (3-6):1;the temperature is lowered to 200-600 DEG C;in a waterless dry environment, dry air saturated by a dealuminated siliceous reinforcing agent is introduced to the dry Y-type zeolite to react for 0.5h-7h, or in a waterless dry environment, the temperature is raised to 500-700 DEG C at a constant speed, at the same time, the dry air saturated by a dealuminated siliceous reinforcing agent is introduced to the dry Y-type zeolite to react for 0.5h-7h, and a rough product is obtained; the rough product is subjected to alkali treatment for 10min-5h at 30-100 DEG C, solid-liquid mass ratio for the alkali treatment is (1-50):1, and a Y molecule sieve high in silica alumina ratio and abundant in secondary holes is obtained. The invention further provides the Y molecule sieve high in the silica alumina ratio and abundant in secondary holes, obtained by adopting the preparation method and has high silica aluminum ratio and abundant secondary hole structures.
Description
Technical field
The present invention relates to abundant Y molecular sieve of the high and second hole of a kind of silica alumina ratio and preparation method thereof, belong to technical field of molecular sieve preparation.
Background technology
Since the running of nineteen forty-two first set industrialization fluidized catalytic cracker, it has developed into the core complete processing in petroleum refining industry.And due to China self crude oil, the status of catalytic cracking process holds the balance especially, as the Y zeolite of cracking catalyst main active component, its importance is self-evident.
From Break successfully synthesizes Y zeolite, therefore the formation of world energy sources structure and chemical just changes, and has caused a revolution of petrochemical complex.Even to this day, through the transition of decades, although synthetic materials emerges in an endless stream, the monopoly position of Y molecular sieve is unmanned shakes.
The cracking activity of Y zeolite and selectivity directly affects the product slates of cracking reaction, and its degree of crystallinity, silica alumina ratio, pore structure and acid distribution etc. are on the research of catalytic performance impact always by people are paid close attention to, and the non-raising silica alumina ratio of the most important thing wherein does not belong to.High framework si-al ratio contributes to improving cracking/hydrogen transfer activity ratio, reduces the generation of catalysis Jiao, improves product slates; Improve hydrothermal stability and acid-resistant stability that silica alumina ratio can also significantly improve molecular sieve, thus enable molecular sieve bear reaction-regeneration condition harsh in catalytic cracking process; Improve silica alumina ratio simultaneously, also contribute to increasing yield of gasoline, improve octane value.Therefore, the Y zeolite of high silica alumina ratio is the target that heavy oil fluid catalytic cracking worker seek assiduously always.
Traditional method preparing high-Si Y-type molecular sieve can be divided into two kinds: direct synthesis technique and aftertreatment modification method.Direct synthesis technique many employings template prepares the Y zeolite of high silica alumina ratio, and such as application number is describe one in the Chinese patent application of 96108159.7 with quaternary ammonium hydroxide, quaternary ammonium salt for template, and obtained silica alumina ratio is the NaY molecular sieve of 10:1; Application number be 97196809.8 Chinese patent application disclose a kind of preparation method being raw material with a small amount of water and organism, the SiO of Y type octahedral molecular sieve that this preparation method generates
2/ Al
2o
3mol ratio can reach 6-10:1.But there is the shortcomings such as template is expensive, crystallization time is long in aforesaid method, the most important thing is that zeolite product silica alumina ratio increasing amount is limited, can't reach industrial application requirement.
And aftertreatment modification method prepares the topmost technique of high-Si Y-type molecular sieve at present, comprise hydrothermal dealumination method, chemical dealuminization method etc., wherein, SiCl
4gas phase dealumination complement silicon is the common method in chemical dealuminization route.
SiCl
4the reaction expression formula of NaY molecular sieve being carried out to dealumination complement silicon is:
Na
x(AlO
2)
x(SiO
2)
y+SiCl
4→Na
(x-1)(AlO
2)
(x-1)(SiO
2)
(y+1)+AlCl
3+NaCl
SiCl as can be seen here
4while removing framework aluminum, insert external silicon, complete dealumination complement silicon.The inevitable crystalline structure of such molecular sieve is complete, ensure that higher degree of crystallinity, but the molecular sieve that this method obtains lacks second hole.In catalytic cracking process, for crude oil, particularly heavy crude, great limitation is just there is in reactant molecule in the diffusion that Y zeolite is microporous mesoporous, nowadays the effect for micro porous molecular sieve intermediary hole is more and more paid attention to, the verified mesoporous existence of a lot of research can improve the rate of diffusion of reaction molecular and product molecule really, thus improves catalyzed reaction efficiency.
Current molecular sieve structure post-modification produces mesoporous mode and comprises dealuminzation or desiliconization.Dealuminzation can cause acidic site to lose, and same SiCl
4dealumination complement silicon route is overlapping, and alkaline purification desiliconization is made mesoporous technology and is tending towards ripe gradually, be commonly used by people for high-silica zeolite as ZSM-5, post-modification ((the Masaru O of Beta equimolecular sieve, Shin-yaS, JunkoT, et al.Alkali-treatment technique-new method for modification of structural andacid-catalytic properties of ZSM-5zeolites.Applied Catalysis A:General, 2001, 219:33-43.Effects of large pore zeolite additions in the catalyticpyrolysis catalyst on the light olefinsproduetion.Catalysis Today, 2007, 125:270-277.).In alkaline purification process, the silicon species on these high-silica zeolite skeletons is deviate from from framework of molecular sieve by selectivity, and the specific surface area of products molecule sieve increases, and forms skeleton secondary pore, and a large amount of microvoid structure is retained simultaneously.The cracking activity that the evaluation of isopropyl benzene catalytic cracking activity shows this material strengthens.Think that the secondary pore produced after alkali treatment modifying changes absorption and the diffusion of raw material and reaction product, thus cause the improvement of catalytic activity.
But there is an obvious limitation in alkaline purification technology, that is exactly the molecular sieve requirement of raw material being necessary for high silica alumina ratio, Here it is why disclosed data be mostly to make mesoporous with ZSM-5 or Beta equimolecular sieve for object carries out alkaline purification desiliconization, think that silica alumina ratio be 25-50:1 is the best sial scope of alkaline purification simultaneously.But synthesize the conventional Y zeolite obtained, silica alumina ratio is only about 3.0-6.0:1, not in this optimum range.
And CN101722022A discloses the method for Y zeolite being carried out to alkaline purification, the molecular sieve that the method obtains, compared with its parent Y molecular sieve, has higher N
2the advanced features such as adsorptive capacity, larger water absorption capacity, but this method does not produce mesoporous because of alkaline purification, but more play the effect of reaming, thus add follow-up hydrothermal dealuminzation and make mesoporous effect, visible high silica alumina ratio is that alkaline purification desiliconization produces a mesoporous prerequisite.Which greatly limits the raw material range of molecular sieve.
In sum, provide a kind of with the zeolite of low silica-alumina ratio for raw material, prepare high silica alumina ratio, mesoporous abundant Y molecular sieve is this area problem demanding prompt solution.
Summary of the invention
In order to solve the problem, the object of the present invention is to provide a kind of with the y-type zeolite of low silica-alumina ratio for raw material, prepare and there is abundanter second hole, the stable and Y molecular sieve that silica alumina ratio is high.
In order to achieve the above object, the invention provides the preparation method of the Y molecular sieve that the high and second hole of a kind of silica alumina ratio enriches, this preparation method comprises the following steps:
By y-type zeolite pre-treatment 1-5h at 300 DEG C-600 DEG C, obtain dry y-type zeolite, wherein, with SiO
2and Al
2o
3meter, the silica alumina ratio of described y-type zeolite is 3-6:1;
After pre-treatment, be cooled to 200-600 DEG C;
In anhydrous dry environment, pass in the y-type zeolite of drying by the saturated dry gas of dealumination complement silicon agent, be 50mL/min by the speed that passes into of the saturated dry gas of dealumination complement silicon agent, contact reacts 0.5h-7h, obtain thick product, or, in anhydrous dry environment, pass in the y-type zeolite of drying by the saturated dry gas of dealumination complement silicon agent while temperature is at the uniform velocity risen to 500-700 DEG C, be 50mL/min by the speed that passes into of the saturated dry gas of dealumination complement silicon agent, contact reacts 0.5h-7h, obtains thick product;
Carry out alkaline purification to described thick product, its alkali purification temp is 30-100 DEG C, and the treatment time is 10min-5h, and the solid-liquid mass ratio of alkaline purification is 1-50:1, obtains the Y molecular sieve that the high and second hole of described silica alumina ratio is abundant.
In the preparation process in accordance with the present invention, preferably, the y-type zeolite of employing comprises NaY zeolite, NH
4y zeolite or HY zeolite.
In the preparation process in accordance with the present invention, preferably, the dealumination complement silicon agent of employing comprises SiCl
4and/or SiHCl
3.
In the preparation process in accordance with the present invention, preferably, the dry gas of employing comprises dry air, high pure nitrogen, high-purity argon gas or high-purity helium.
In the preparation process in accordance with the present invention, preferably, carry out the concentration of the basic solution of use during alkaline purification for 0.01mol/L-3mol/L, be more preferably 0.05mol/L-1mol/L.
In the preparation process in accordance with the present invention, preferably, the basic solution of employing comprises NaOH solution and/or KOH solution.
In the preparation process in accordance with the present invention, preferably, its alkali purification temp is 50-80 DEG C, and the treatment time is 30min-3h, and the solid-liquid mass ratio of alkaline purification is 5-30:1.
In the preparation process in accordance with the present invention, preferably, catalytic temperature rise rate be 0.5 DEG C/min-5 DEG C/min.
The preparation method of the Y molecular sieve that the high and second hole of silica alumina ratio provided by the invention enriches can comprise following concrete steps:
Y-type zeolite is placed in crystal reaction tube, passes into dry gas, be warming up to 300-600 DEG C of pre-treatment 1-5h, to remove the moisture in reaction tubes, pipeline and y-type zeolite, guarantee water-less environment;
Be cooled to 200-600 DEG C;
Pass in the y-type zeolite of drying by the saturated dry gas of dealumination complement silicon agent, reaction 0.5-7h is 50mL/min by the speed that passes into of the saturated dry gas of dealumination complement silicon agent; Or, pass in the y-type zeolite of drying by the saturated dry gas of dealumination complement silicon agent while temperature is raised to 500-700 DEG C with the speed of 0.5 DEG C/min-5 DEG C/min, be 50mL/min, contact reacts 0.5-7h by the speed that passes into of the saturated dry gas of dealumination complement silicon agent;
Reaction terminates rear maintenance temperature of reaction, stops passing into by the saturated dry gas of dealumination complement silicon agent, and dry gas continues to purge 1-5h, obtains thick product;
Thick product through washing, carry out alkaline purification after drying, also directly can carry out alkaline purification without washing, drying, preferably carry out alkaline purification after washing, drying, obtains the high and Y molecular sieve that second hole is abundant of described silica alumina ratio.
Present invention also offers the Y molecular sieve that the high and second hole of a kind of silica alumina ratio is abundant, it is prepared by above-mentioned preparation method.
According to specific embodiment of the invention scheme, preferably, the degree of crystallinity of this molecular sieve is greater than 85%, and second hole volume accounts for the 30%-50% of total pore volume, with SiO
2and Al
2o
3meter, the silica alumina ratio of this molecular sieve is 10-50:1.
Silica alumina ratio provided by the invention is high, the preparation method of the Y molecular sieve that second hole enriches, operation steps is simple, reagent cost is low, low to the requirement of processing unit, there is very strong applicability, and it is wider that alkaline purification technology can be adopted to carry out the silica alumina ratio scope of the molecular sieve processed, can be that the y-type zeolite of 3-6 carries out gas method dealumination complement silicon and makes the thick product that silica alumina ratio is 10-50 by silica alumina ratio, can prepare high silica alumina ratio and there is the Y molecular sieve of abundant second hole structure, compare the zeolite that existing alkaline purification technical requirements raw material is necessary for high silica alumina ratio (silica alumina ratio is more than 50), method of the present invention has widened the material choice scope utilizing alkaline purification technology to prepare molecular sieve greatly.
The silica alumina ratio of the Y molecular sieve obtained by preparation method provided by the invention is 10-50:1, and adjustable in 10-50:1.
The Y molecular sieve that the preparation method of the Y molecular sieve that high and second hole enriches obtains by silica alumina ratio provided by the invention compares the simple molecular sieve using gas phase dealumination complement silicon obtained, there is more abundant second hole structure, and the degree of crystallinity of this molecular sieve is very high, be greater than 85%, part can reach more than 90%.
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
In each embodiment, the secondary pore volume of obtained Y molecular sieve and the measuring method of total pore volume as follows:
According to RIPP 151-90 standard method (" Petrochemical Engineering Analysis method (RIPP test method) ", the Yang Cui volume such as surely, Science Press, nineteen ninety publishes) total pore volume of molecular sieve is determined according to adsorption isothermal line, then determine the micro pore volume of molecular sieve from adsorption isothermal line according to T graphing method, total pore volume is deducted micro pore volume and obtain second hole volume.The mensuration of relative crystallinity and silica alumina ratio all adopts x-ray powder diffraction instrument, test condition is: CuK α radiation, Ni filtering, tube voltage 30kV, tube current 40Ma, walk wide by 0.02, adopt area sum (comparing with NaY molecular sieve standard specimen) the calculation sample degree of crystallinity (relative crystallinity) at (331), (511,333), (440), (533), (642), (822,660), (555,751), (664) totally eight peaks.The measuring method of silica alumina ratio according to SH/T0339-92 standard method (see " standard of chemical industry compilation ", China Standards Press, publishes for 2000), and calculates lattice constant according to following formula:
In formula: α is lattice constant
λ is u-K α
1wavelength
(h
2+ k
2+ l
2) be X-ray diffraction index sum of squares.
According to Breck-Flanigen formulae discovery Y zeolite silica alumina ratio: Si/Al=(25.858-a)/(a-24.191), SiO
2/ Al
2o
3=2 × (Si/Al).
Embodiment 1
Present embodiments provide the Y molecular sieve that a kind of silica alumina ratio is high, second hole is abundant, it is prepared by following steps:
The NaY zeolite sample weighing 20.0g dried overnight is placed in crystal reaction tube, pass into nitrogen, carry out leak detection work, after ready, setting nitrogen purging speed 50mL/min (glass rotameter), setting Reaktionsofen heating schedule: keep 120min by starting temperature 30 DEG C after 100min is warming up to 500 DEG C, now stop heating, when temperature Temperature fall is to 270 DEG C, pass into by SiCl
4saturated N
2, be warmed up to 430 DEG C, after having reacted with the temperature rise rate 40min of 4 DEG C/min simultaneously, stop passing into by SiCl
4saturated N
2, N
2continue to purge 120min, stop heating Temperature fall afterwards, take out sample and obtain thick product through washing drying;
Get thick product 10g, joining 200mL concentration is in the sodium hydroxide solution of 0.1mol/L, water-bath 70 DEG C heating, rapid stirring 1h simultaneously, take out suction filtration to pH value weakly acidic pH, 120 DEG C of oven for drying are spent the night, and finally obtain the Y molecular sieve that silica alumina ratio is high, second hole is abundant.
The test that the Y molecular sieve that the silica alumina ratio obtained the present embodiment is high, second hole enriches is correlated with characterizes, and it the results are shown in table 1.
Comparative example 1
Prepare contrast molecular sieve by the preparation method of embodiment 1, difference is do not carrying out alkaline purification after preparing thick product.
The test that the Y molecular sieve obtained this comparative example is correlated with characterizes, and it the results are shown in table 1.
Embodiment 2
Present embodiments provide the Y molecular sieve that a kind of silica alumina ratio is high, second hole is abundant, it is prepared by following steps:
The NaY zeolite sample weighing 20.0g dried overnight is placed in crystal reaction tube, pass into nitrogen, carry out leak detection work, after ready, setting nitrogen purging speed 50mL/min (glass rotameter), setting Reaktionsofen heating schedule: keep 120min by starting temperature 30 DEG C after 100min is warming up to 500 DEG C, now stop heating, when temperature Temperature fall is to 270 DEG C, pass into by SiCl
4saturated N
2, be warmed up to 510 DEG C, after having reacted with the temperature rise rate 1h of 4 DEG C/min simultaneously, stop passing into by SiCl
4saturated N
2, independent N
2continue to purge 120min, stop heating Temperature fall afterwards, take out sample and obtain thick product through washing drying;
Get thick product 10g, join in the sodium hydroxide solution (concentration is 0.15mol/L) of 200g, water-bath 70 DEG C heating, rapid stirring 1h simultaneously, take out suction filtration to pH value weakly acidic pH, 120 DEG C of oven for drying are spent the night, and finally obtain the Y molecular sieve that silica alumina ratio is high, second hole is abundant.
The test that the Y molecular sieve that the silica alumina ratio obtained the present embodiment is high, second hole enriches is correlated with characterizes, and it the results are shown in table 1.
Comparative example 2
Prepare contrast molecular sieve by the preparation method of embodiment 2, difference is do not carrying out alkaline purification after preparing thick product.
The test that the Y molecular sieve obtained this comparative example is correlated with characterizes, and it the results are shown in table 1.
Embodiment 3
Present embodiments provide the Y molecular sieve that a kind of silica alumina ratio is high, second hole is abundant, it is prepared by following steps:
The NaY zeolite sample weighing 20.0g dried overnight is placed in crystal reaction tube, pass into nitrogen, carry out leak detection work, after ready, setting nitrogen purging speed 50mL/min (glass rotameter), setting Reaktionsofen heating schedule: keep 120min by starting temperature 30 DEG C after 100min is warming up to 500 DEG C, now stop heating, when temperature Temperature fall is to 270 DEG C, pass into by SiCl
4saturated N
2, be warmed up to 510 DEG C, after having reacted with the temperature rise rate 80min of 3 DEG C/min simultaneously, stop passing into by SiCl
4saturated N
2, N
2continue to purge 120min, stop heating Temperature fall afterwards, take out sample and obtain thick product through washing drying;
Get thick product 10g, join in the sodium hydroxide solution (concentration is 0.2mol/L) of 200g, water-bath 80 DEG C heating, rapid stirring 1h simultaneously, take out suction filtration to pH value weakly acidic pH, 120 DEG C of oven for drying are spent the night, and finally obtain the Y molecular sieve that silica alumina ratio is high, second hole is abundant.
The test that the Y molecular sieve that the silica alumina ratio obtained the present embodiment is high, second hole enriches is correlated with characterizes, and it the results are shown in table 1.
Comparative example 3
Prepare contrast molecular sieve by the preparation method of embodiment 3, difference is do not carrying out alkaline purification after preparing thick product.
The test that the Y molecular sieve obtained this comparative example is correlated with characterizes, and it the results are shown in table 1.
Embodiment 4
Present embodiments provide the Y molecular sieve that a kind of silica alumina ratio is high, second hole is abundant, it is prepared by following steps:
The NaY zeolite sample weighing 20.0g dried overnight is placed in crystal reaction tube, pass into nitrogen, carry out leak detection work, after ready, setting nitrogen purging speed 50mL/min (glass rotameter), setting Reaktionsofen heating schedule: keep 120min after 100min is warming up to 500 DEG C, Temperature fall to 450 DEG C by starting temperature 30 DEG C, pass into by SiCl afterwards
4saturated N
2, contact reacts 2h, stops passing into by SiCl afterwards
4saturated N
2, N
2continue to purge 120min, stop heating Temperature fall, take out sample and obtain thick product through washing drying;
Get thick product 10g, join in the sodium hydroxide solution (concentration is 0.25mol/L) of 200g, water-bath 85 DEG C heating, rapid stirring 1h simultaneously, take out suction filtration to pH value weakly acidic pH, 120 DEG C of oven for drying are spent the night, and finally obtain the Y molecular sieve that silica alumina ratio is high, second hole is abundant.
The test that the Y molecular sieve that the silica alumina ratio obtained the present embodiment is high, second hole enriches is correlated with characterizes, and it the results are shown in table 1.
Comparative example 4
Prepare contrast molecular sieve by the preparation method of embodiment 4, difference is do not carrying out alkaline purification after preparing thick product.
The test that the Y molecular sieve obtained this comparative example is correlated with characterizes, and it the results are shown in table 1.
The chemical composition and structure parameter of each embodiment of table 1 and comparative example gained sample
Embodiment 5
Present embodiments provide the Y molecular sieve that a kind of silica alumina ratio is high, second hole is abundant, it is prepared by following steps:
The NaY zeolite sample weighing 20.0g dried overnight is placed in crystal reaction tube, pass into helium, carry out leak detection work, after ready, setting nitrogen purging speed 50mL/min (glass rotameter), setting Reaktionsofen heating schedule: keep 120min by starting temperature 30 DEG C after 150min is warming up to 600 DEG C, now stop heating, when temperature Temperature fall is to 570 DEG C, pass into by SiCl
4with saturated He, reaction 5h, after having reacted, stops passing into by SiCl
4saturated He, He continue to purge 120min, stop heating Temperature fall afterwards, take out sample and obtain thick product through washing drying;
Get thick product 10g, join in the sodium hydroxide solution (concentration is 0.4mol/L) of 200g, water-bath 75 DEG C heating, rapid stirring 1h simultaneously, take out suction filtration to pH value weakly acidic pH, 120 DEG C of oven for drying are spent the night, and finally obtain the Y molecular sieve that silica alumina ratio is high, second hole is abundant.
The test that the Y molecular sieve that the silica alumina ratio obtained the present embodiment is high, second hole enriches is correlated with characterizes, and it the results are shown in table 1.
Comparative example 5
Prepare contrast molecular sieve by the preparation method of embodiment 5, difference is do not carrying out alkaline purification after preparing thick product.
The test that the Y molecular sieve obtained this comparative example is correlated with characterizes, and it the results are shown in table 1.
Above embodiment illustrates, the degree of crystallinity of the Y molecular sieve that the silica alumina ratio utilizing preparation method of the present invention to obtain is high is high, and has abundant second hole structure.
Claims (10)
1. the preparation method of Y molecular sieve that enriches of the high and second hole of silica alumina ratio, this preparation method comprises the following steps:
By y-type zeolite pre-treatment 1-5h at 300 DEG C-600 DEG C, obtain dry y-type zeolite, wherein, with SiO
2and Al
2o
3meter, the silica alumina ratio of described y-type zeolite is 3-6:1;
After pre-treatment, be cooled to 200-600 DEG C;
In anhydrous dry environment, pass in the y-type zeolite of drying by the saturated dry gas of dealumination complement silicon agent, be 50mL/min by the speed that passes into of the saturated dry gas of dealumination complement silicon agent, contact reacts 0.5h-7h, obtain thick product, or, in anhydrous dry environment, pass in the y-type zeolite of drying by the saturated dry gas of dealumination complement silicon agent while temperature is at the uniform velocity risen to 500-700 DEG C, be 50mL/min by the speed that passes into of the saturated dry gas of dealumination complement silicon agent, contact reacts 0.5h-7h, obtains thick product;
Carry out alkaline purification to described thick product, its alkali purification temp is 30-100 DEG C, and the treatment time is 10min-5h, and the solid-liquid mass ratio of alkaline purification is 1-50:1, obtains the Y molecular sieve that the high and second hole of described silica alumina ratio is abundant.
2. preparation method according to claim 1, wherein, described y-type zeolite comprises NaY zeolite, NH
4y zeolite or HY zeolite.
3. preparation method according to claim 1, wherein, described dealumination complement silicon agent comprises SiCl
4or SiHCl
3.
4. preparation method according to claim 1, wherein, described dry gas comprises dry air, high pure nitrogen, high-purity argon gas or high-purity helium.
5. preparation method according to claim 1, wherein, the concentration of the basic solution that described alkaline purification uses is 0.01mol/L-3mol/L, is preferably 0.05mol/L-1mol/L.
6. preparation method according to claim 5, wherein, described basic solution comprises NaOH solution and/or KOH solution.
7. preparation method according to claim 1, wherein, its alkali purification temp is 50-80 DEG C, and the treatment time is 30min-3h, and the solid-liquid mass ratio of alkaline purification is 5-30:1.
8. preparation method according to claim 1, wherein, described catalytic temperature rise rate is 0.5 DEG C/min-5 DEG C/min.
9. the Y molecular sieve that the high and second hole of silica alumina ratio is abundant, it is prepared by the preparation method described in any one of claim 1-8.
10. the Y molecular sieve that the high and second hole of silica alumina ratio according to claim 9 is abundant, wherein, the degree of crystallinity of this molecular sieve is greater than 85%, and second hole volume accounts for the 30%-60% of total pore volume, with SiO
2and Al
2o
3meter, the silica alumina ratio of described molecular sieve is 10-50:1.
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| CN108698842A (en) * | 2016-02-29 | 2018-10-23 | 勒芬天主教大学 | To the controlled alkali process of molecular sieve |
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| CN114988428A (en) * | 2022-07-11 | 2022-09-02 | 吉林大学 | Y-type molecular sieve with high silica-alumina ratio and preparation method and application thereof |
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| CN107344106B (en) * | 2016-05-05 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and preparation method thereof |
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| CN107758684B (en) * | 2016-08-23 | 2019-05-31 | 中国石油天然气集团公司 | A kind of high mesoporous amount y-type zeolite and preparation method thereof |
| CN110127716A (en) * | 2019-06-11 | 2019-08-16 | 太原大成环能化工技术有限公司 | A kind of preparation method of multistage pore canal Y molecular sieve |
| CN114988428A (en) * | 2022-07-11 | 2022-09-02 | 吉林大学 | Y-type molecular sieve with high silica-alumina ratio and preparation method and application thereof |
| CN114988428B (en) * | 2022-07-11 | 2023-10-24 | 吉林大学 | Y-type molecular sieve with high silicon-aluminum ratio and preparation method and application thereof |
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