CN105366690B - A kind of y-type zeolite with transgranular multi-stage porous and preparation method and application - Google Patents
A kind of y-type zeolite with transgranular multi-stage porous and preparation method and application Download PDFInfo
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Abstract
The invention provides a kind of y-type zeolite with transgranular multi-stage porous and preparation method and application.This method includes：NaY zeolite containing boron, ammonium salt and water are mixed, obtain mixture, is stirred, is filtered, washing, obtains the Y zeolites containing boron of ammonium type；High-temperature water heat treatment is carried out to the Y zeolites containing boron of ammonium type, obtains the y-type zeolite with transgranular multi-stage porous.Y-type zeolite provided by the invention with transgranular multi-stage porous contains more rich hierarchical porous structure, and its preparation method is simple to operate.Present invention also offers application of the above-mentioned y-type zeolite with transgranular multi-stage porous as catalytic cracking catalyst and the active component of catalytic hydrogenation catalyst.
Description
Technical field
The present invention relates to a kind of y-type zeolite and preparation method and application, more particularly to a kind of Y with transgranular multi-stage porous
Type zeolite and preparation method and application, belong to zeolitic material and its preparing technical field.
Background technology
Catalytic cracking (FCC) is the most crucial heavy oil lighting means of petroleum refining industry, and the original that catalyst amount is maximum
Oily secondary processing process.In the development course of nearly 80 years, catalytic cracking catalyst is formed using sial as essential element,
What the micropore and carrier that its pore passage structure is mainly provided by Y type molecular sieve assigned a small amount of irregular mesoporous is formed.Chemical composition and
The determination of pore passage structure is restricted catalyst performance regulation and control, it is difficult to the raw materials requirement that adaptive character increasingly changes.Especially
Since the 1990s, the heaviness and in poor quality of world's crude oil are on the rise, and make colloid in catalytically cracked material, pitch
Matter and heavy metal components content are continuously increased, and peracid and high-alkali nitrogen raw material frequency are existing.Meanwhile the market demand of lighting oil product is continuous
Increase, quality control index is increasingly strict, reformulated gasoline in addition to unleaded and high-octane rating, added again vapour pressure, aromatic hydrocarbons and
The indexs such as content, sulfur content, oxygenatedchemicals and the olefin(e) centent of benzene.Raw material mix, the complexity of composition and the control of product refer to
The harshness FCC catalyst for causing structure-sensitive of target faces a severe challenge.
Existing catalyst is difficult to meet to the efficient light of different structure and quality heavy oil and cleans light oil
The demand of product production.FCC catalyst is in addition to the characteristic with conventional catalyst, it is necessary to possesses more preferable cracked fuel oil
The pore-size distribution of macromolecular, bigger specific surface area and pore volume and higher matrix-active and stronger anti-metallic contamination ability.
For this problem, there has been proposed different solution routes, for example, it is brilliant to prepare the molecular sieve with super large pore structure
Body (ITQ-21)；Material (MCM-41, SBA-15, FSM-16, MAS-5) of the synthesis with ordered mesopore structure, still, these roads
Line has significant limitation.For example, the molecular sieve with super big hole can effectively improve mass transfer rate, but these super larges
The molecular sieve crystal in hole needs high price and special organic template material, greatly limit extensive in petroleum refining process
Using；The mass transfer in reaction can be effectively improved using the ordered mesoporous material that surfactant micellar is templated synthesis, but
The hole wall for being due to the material is amorphous state, and hydrothermal stability and acidity are all weaker, it is impossible to are widely used in refining oil work
In industry.
At present, by post processing and the molecular sieve crystal catalysis material with certain meso-hole structure that obtains still widely
Applied in petroleum refining process, there is also declining by post-processing acidic zeolite, mesoporous, macropore volume is not abundant enough
The shortcomings that.Therefore, by straightforward procedure prepare the molecular sieve crystal catalysis material with hierarchical porous structure be still it is current very
Challenging research work, and the focus of molecular screen material synthesis at present.In addition, catalytic cracking, the skill such as being hydrocracked
Art etc. is still oil refining process main from now on, therefore y-type zeolite is still most important point in current and foreseeable future
Son sieve active component.
In summary, aboundresources, low cost, environment-friendly multi-stage porous y-type zeolite catalysis material are once succeeded in developing
And industrialization is realized, the performance of oil refining catalyst will be greatly improved, drive the technological progress of oil refining catalyst, while will also bring
Huge Social benefit and economic benefit.Develop a kind of aboundresources, low cost, the catalysis of environment-friendly multi-stage porous y-type zeolite
Material is into a kind of needs.
The content of the invention
In order to solve the above problems, it is an object of the invention to provide a kind of y-type zeolite with multi-stage porous and its preparation
Method, abundant multi-stage porous should be contained with the y-type zeolite of multi-stage porous, and its preparation method is simple to operate.
In order to achieve the above object, should the invention provides a kind of preparation method of the y-type zeolite with transgranular multi-stage porous
Method comprises the following steps：
Step 1：NaY zeolite containing boron, ammonium salt and water are mixed, obtain mixture, is stirred, is filtered, washing, obtains ammonium
The NaY zeolite containing boron exchanged；
Step 2：High-temperature water heat treatment is carried out to the NaY zeolite containing boron that ammonium exchanges, obtains that there is transgranular multi-stage porous
Y-type zeolite.
In the preparation method of y-type zeolite provided by the invention with transgranular multi-stage porous, it is preferable that described containing boron
The mass ratio of NaY zeolite, ammonium salt and water is 1：0.1-2：2-30.Ammonium salt employed in ammonium exchange process preferably includes chlorination
One or more of combinations in ammonium, ammonium sulfate and ammonium nitrate etc..
In the preparation method of y-type zeolite provided by the invention with transgranular multi-stage porous, it is preferable that the temperature of the stirring
For 20-95 DEG C, the time of stirring is 0.5-4h, it is highly preferred that the pH that mixture is adjusted in whipping process is 1-7.Stirred
It is adjusted during the pH that mixture is adjusted in journey using the reagent of traditional regulation soda acid, such as the salt that concentration is 0.5mol/L
Acid solution.
Deionized water can be used to carry out when being washed after filtration, washed to neutrality.
In the preparation method of y-type zeolite provided by the invention with transgranular multi-stage porous, it is preferable that High-temperature water heat treatment exists
Carried out in 10-100% steam atmosphere, it is highly preferred that the temperature of High-temperature water heat treatment is 500-700 DEG C, at high temperature hydro-thermal
The time of reason is 0.5-4h.
In the preparation method of y-type zeolite provided by the invention with transgranular multi-stage porous, it is preferable that the NaY boilings containing boron
Stone is prepared using Direct Hydrothermal method, or is prepared using post-modification method；Wherein, Direct Hydrothermal method and post-modification method be conventionally
Operated, post-modification method includes ion-exchange, isomorphous replacement method etc..
In the preparation method of y-type zeolite provided by the invention with transgranular multi-stage porous, it is preferable that in the form of the oxide
Count, in the NaY zeolite containing boron of use, silicon (SiO2) and aluminium (Al2O3) mol ratio be 4-8：1.
In the preparation method of y-type zeolite provided by the invention with transgranular multi-stage porous, it is preferable that in the form of the oxide
Count, in the used NaY zeolite containing boron, boron (B2O3) and aluminium (Al2O3) mol ratio be 0.01-10:1；It is highly preferred that
Count in the form of the oxide, in the NaY zeolite containing boron of use, boron (B2O3) and aluminium (Al2O3) mol ratio be 0.01-2:
1。
, can be with specific operation process in the preparation method of y-type zeolite provided by the invention with transgranular multi-stage porous
Repeat step 1 according to actual conditions and step 2 is each one or many.
In the preparation method of y-type zeolite provided by the invention with transgranular multi-stage porous, it is preferable that the mixing in step 1
Thing is dried after filtering, washing, and dry temperature is 50-120 DEG C, and the dry time is 5-12h.
Present invention also offers a kind of y-type zeolite with transgranular multi-stage porous, and it is as made from above-mentioned preparation method.
Present invention also offers the related application of the above-mentioned y-type zeolite with transgranular multi-stage porous, it can split as catalysis
Change the active component of catalyst and catalytic hydrogenation catalyst.
The above-mentioned y-type zeolite with transgranular multi-stage porous can be used as catalytic cracking catalyst, can also be used as catalytic hydrogenation
The activearm of catalyst is graded.Urged using the y-type zeolite provided by the invention with transgranular multi-stage porous as catalyst or conduct
The catalytic activity of catalyst can be significantly improved during the active component of agent.
The preparation method of y-type zeolite provided by the invention with transgranular multi-stage porous, using the special nature of boron element, lead to
Cross and use simple process directly NaY (B-NaY) zeolite of the synthesis containing boron and carried out using B-NaY zeolites as raw material one or many
Ammonium ion and High-temperature water heat treatment technique, obtain it is a kind of with the multi-stage porous more more rich than conventional y-type zeolite Y types boiling
Stone.
Y types (B-USY) zeolite provided by the invention with transgranular multi-stage porous is with higher silica alumina ratio, more flourishing more
Level hole.
Preparation method provided by the invention with transgranular multi-stage porous y-type zeolite, it is highly crystalline to be firstly introduced into hetero atom B synthesis
The B-NaY zeolites of degree, exchange, two processes of High-temperature water heat treatment (preferably alternate cycles progress), had then in conjunction with ammonium
The B-USY zeolites of transgranular multi-stage porous, B-USY zeolites are a kind of y-type zeolites with abundant multi-stage porous.
Reach more than 83 using y-type zeolite crystallinity made from preparation method provided by the invention, Jie-macropore volume accounts for always
40-60% of pore volume or so, compared with being not introduced into USY zeolite made from hetero atom B using same procedure, silica alumina ratio improves
More than 20%, Jie-macropore volume amplification is more than 40%.
Brief description of the drawings
Fig. 1 be embodiment 1 y-type zeolite and comparative example 1 zeolite USY1 XRD spectrum.
Fig. 2 be embodiment 2 y-type zeolite and comparative example 2 zeolite USY2 XRD spectrum.
Fig. 3 be embodiment 3 y-type zeolite and comparative example 3 zeolite USY3 XRD spectrum.
Fig. 4 be embodiment 4 y-type zeolite and comparative example 4 zeolite USY4 XRD spectrum.
Fig. 5 be embodiment 5 y-type zeolite and comparative example 5 zeolite USY5 XRD spectrum.
Embodiment
In order to which technical characteristic, purpose and the beneficial effect of the present invention is more clearly understood, now to the skill of the present invention
Art scheme carry out it is described further below, but it is not intended that to the present invention can practical range restriction.
In following embodiment, Jie-macropore volume of Y zeolites and the assay method of total pore volume are as follows：According to
RIPP151-90 standard methods《Petrochemical Engineering Analysis method》(RIPP test methods) (Yang Cui is waited and compiled surely, Science Press, and 1990
Year publish) total pore volume of zeolite is determined according to adsorption isotherm, then determine boiling from adsorption isotherm according to T graphing methods
The micro pore volume of stone, total pore volume is subtracted into micro pore volume and obtains Jie-macropore volume.
In each embodiment, measure BRUKER D8 ADVANCE (German Bruker) type X of relative crystallinity and silica alumina ratio is penetrated
Line diffractometer, experiment condition are：CuK α radiate (0.1541nm), tube voltage 40kV, tube current 40mA.The measure of relative crystallinity
Be according to SH/T 0340-92 standard methods (《Standard of chemical industry collects》, China Standards Press, publish within 2000) carry out
's.The measure of silica alumina ratio be according to SH/T 0339-92 standard methods (《Standard of chemical industry collects》, China Standards Press,
Publish within 2000) carry out, and after the lattice constant according to equation below calculating NaY zeolite, by Breck-Flanigen formula：
Si/Al=(25.858- α)/(α -24.191) is calculated.
Wherein, α is lattice constant,
λ is CuK α radiation wavelengths
h2+k2+l2For X-ray diffraction Miller index quadratic sum.
It is 040617 that the zeolite standard specimen as crystallinity standard used in embodiment and comparative example, which comes from numbering,
Industrial NaY references, the SiO of the zeolite is measured with x-ray diffraction method2/Al2O3For 5.1, and its crystallinity is set as 100%.
Embodiment 1
A kind of y-type zeolite with transgranular multi-stage porous is present embodiments provided, it is as made from following preparation method：
Ammonium exchange process：Boron aluminum ratio value is obtained (with B by hydrothermal synthesis method2O3, Al2O3Molar ratio computing) be respectively 0.1
With 0.2 B-NaY zeolites, then by mass ratio be 1：0.5：5 B-NaY zeolites, ammonium salt and water is well mixed, and is mixed
Thing, lasting stirring, the pH value of the hydrochloric acid solution for being 0.5mol/L with concentration regulation mixture is 2.3, is warming up to 30 DEG C, maintains pH
Be worth it is constant under conditions of stir 1h, filter, be washed with deionized to neutrality, dried at 120 DEG C, obtain containing for ammonium type
The Y zeolites of boron；
Hydrothermal treatment process：The Y zeolites containing boron of obtained ammonium type are put into hydrothermal device, are warming up to 500 DEG C, are led to
Enter 40% steam treatment 3h；
Repeat that above-mentioned ammonium exchanges, hydrothermal treatment process respectively once, obtains y-type zeolite, be designated as B-USY.
The X-ray diffraction thing phasor (XRD) of products therefrom as shown in figure 1, B-USY diffraction maximum (331), (511,333),
(440), (533), (642), (822,660), (555,751), eight characteristic diffraction peak peak shapes of (664) keep complete, without miscellaneous
Crystalline substance generation, the B-USY for showing the present embodiment is y-type zeolite structure.The structural parameters of y-type zeolite made from the present embodiment such as table 1
It is shown.
Table 1
Comparative example 1
Identical silica alumina ratio is handled according to the method in embodiment 1 but does not contain the NaY zeolite of boron, the sample obtained after processing
It is designated as USY1.
The X-ray diffraction thing phasor (XRD) of products therefrom as shown in figure 1, USY1 diffraction maximum (331), (511,333),
(440), (533), (642), (822,660), (555,751), eight characteristic diffraction peak peak shapes of (664) keep complete, without miscellaneous
Crystalline substance generation, show that obtained USY1 is y-type zeolite structure.The structural parameters of the USY1 zeolites are as shown in table 2.
Table 2
| USY1 | |
| Relative crystallinity, % | 79 |
| Framework si-al ratio | 11.7 |
| Specific surface area, m2/g | 563 |
| Total pore volume, mL/g | 0.36 |
| Micro pore volume, mL/g | 0.25 |
| Jie-macropore volume, mL/g | 0.11 |
| Jie-macropore volume/total pore volume, % | 30 |
It is can be seen that by comparative analysis table 1 with the content of table 2 compared with the zeolite (USY1) obtained by comparative example 1, it is real
Jie for applying the B-USY of the preparation of example 1-big level pore volume is in 0.23cm3·g-1More than, highest can reach 0.29cm3·g-1, together
When embodiment 1 the micro pore volumes of B-USY zeolites be not remarkably decreased, the micro pore volume of all B-USY zeolites all still maintains
In 0.20cm3·g-1More than even.As can be seen here, the y-type zeolite that prepared by embodiment 1 is a kind of Y types with abundant multi-stage porous
Zeolite.
Embodiment 2
Present embodiments providing one kind has transgranular multi-stage porous y-type zeolite, and it is as made from following preparation method：
Ammonium exchange process：Boron aluminum ratio value is obtained (with B by hydrothermal synthesis method2O3, Al2O3Molar ratio computing) be respectively 0.5
With 1 the NaY zeolite containing boron, then by mass ratio be 1：1：10 B-NaY zeolites, ammonium salt and water is well mixed, and is mixed
Compound, lasting stirring, the pH value of the hydrochloric acid solution for being 0.5mol/L with concentration regulation mixture is 3.3, is warming up to 50 DEG C, maintains
1.5h is stirred under conditions of pH value is constant, is filtered, is washed with deionized to neutrality, is dried at 120 DEG C, obtain ammonium type
Y zeolites containing boron；
Hydrothermal treatment process：The Y zeolites containing boron of obtained ammonium type are put into hydrothermal device, are warming up to 550 DEG C, are led to
Enter 80% steam treatment 2h；
Repeat that above-mentioned ammonium exchanges, hydrothermal treatment process respectively once, obtains y-type zeolite, be designated as B-USY.
The X-ray diffraction thing phasor (XRD) of products therefrom as shown in Fig. 2 B-USY diffraction maximum (331), (511,333),
(440), (533), (642), (822,660), (555,751), eight characteristic diffraction peak peak shapes of (664) keep complete, without miscellaneous
Crystalline substance generation, the B-USY for showing the present embodiment is y-type zeolite structure.The structural parameters of the y-type zeolite of the present embodiment are as shown in table 3.
Table 3
Comparative example 2
Identical silica alumina ratio is handled according to the method in embodiment 2 but does not contain the NaY zeolite of boron, the sample obtained after processing
It is designated as USY2.
The X-ray diffraction thing phasor (XRD) of products therefrom as shown in Fig. 2 USY2 diffraction maximum (331), (511,333),
(440), (533), (642), (822,660), (555,751), eight characteristic diffraction peak peak shapes of (664) keep complete, without miscellaneous
Crystalline substance generation, show that obtained USY2 is y-type zeolite structure.The structural parameters of the USY2 zeolites are as shown in table 4.
Table 4
| USY2 | |
| Relative crystallinity, % | 77 |
| Framework si-al ratio | 11.4 |
| Specific surface area, m2/g | 589 |
| Total pore volume, mL/g | 0.39 |
| Micro pore volume, mL/g | 0.24 |
| Jie-macropore volume, mL/g | 0.15 |
| Jie-macropore volume/total pore volume, % | 38 |
The boiling prepared with comparative example 2 by hydrothermal dealumination method can be seen that by the content of comparative analysis table 3 and table 4
Stone (USY2) is compared, and B-USY prepared by embodiment 2 Jie-macropore volume is in 0.25cm3·g-1More than, highest can reach
0.27cm3·g-1, framework si-al ratio is more than 13.6, while the micro pore volume of B-USY zeolites is not remarkably decreased, all B-
The micro pore volume of USY zeolite all still maintains 0.22cm3·g-1More than even.As can be seen here, the Y types boiling that prepared by embodiment 2
Stone is a kind of y-type zeolite with abundant multi-stage porous.
Embodiment 3
Present embodiments provide one kind and contain transgranular multi-stage porous y-type zeolite, it is as made from following preparation method：
Ammonium exchange process：Boron aluminum ratio value is obtained (with B by hydrothermal synthesis method2O3, Al2O3Molar ratio computing) be respectively 0.8
With 1.2 the NaY zeolite containing boron, then by mass ratio be 1：1.5：15 B-NaY zeolites, ammonium salt and water is well mixed, and is obtained
To mixture, lasting stirring, the pH value of the hydrochloric acid solution for being 0.5mol/L with concentration regulation mixture is 4.3, is warming up to 70 DEG C,
Maintain to stir 2h under conditions of pH value is constant, filter, be washed with deionized to neutrality, dry, obtain under the conditions of 120 DEG C
The Y zeolites containing boron of ammonium type；
Hydrothermal treatment process：The Y zeolites containing boron of obtained ammonium type are put into hydrothermal device, are warming up to 650 DEG C, are led to
Enter 100% steam treatment 1h；
Repeat that above-mentioned ammonium exchanges, hydrothermal treatment process respectively once, obtains y-type zeolite, be designated as B-USY.
The X-ray diffraction thing phasor (XRD) of products therefrom as shown in figure 3, B-USY diffraction maximum (331), (511,333),
(440), (533), (642), (822,660), (555,751), eight characteristic diffraction peak peak shapes of (664) keep complete, without miscellaneous
Crystalline substance generation, the B-USY for showing the present embodiment is y-type zeolite structure.The structural parameters of the y-type zeolite of the present embodiment are as shown in table 5.
Table 5
Comparative example 3
Identical silica alumina ratio is handled according to the method in embodiment 3 but does not contain the NaY zeolite of boron, the sample obtained after processing
It is designated as USY3.
The X-ray diffraction thing phasor (XRD) of products therefrom as shown in figure 3, USY3 diffraction maximum (331), (511,333),
(440), (533), (642), (822,660), (555,751), eight characteristic diffraction peak peak shapes of (664) keep complete, without miscellaneous
Crystalline substance generation, show that obtained USY3 is y-type zeolite structure.Gained zeolite USY3 structural parameters are as shown in table 6.
Table 6
| USY3 | |
| Relative crystallinity, % | 80 |
| Framework si-al ratio | 12.2 |
| Specific surface area, m2/g | 591.9 |
| Total pore volume, mL/g | 0.38 |
| Micro pore volume, mL/g | 0.23 |
| Two level pore volume, mL/g | 0.15 |
| Two level pore volume/total pore volume, % | 39 |
As can be seen that the zeolite prepared with the hydrothermal dealumination method that comparative example 3 provides from the comparative analysis of table 5 and table 6
(USY3) compare, Jie-macropore volume for the B-USY that embodiment 3 is prepared is in 0.28cm3·g-1More than, highest can reach
0.29cm3·g-1, framework si-al ratio is more than 15.7, while the micro pore volume of B-USY zeolites is not remarkably decreased, all B-
The micro pore volume of USY zeolite all still maintains 0.24cm3·g-1More than even.As can be seen here, the Y types boiling that prepared by embodiment 3
Stone is a kind of y-type zeolite with abundant multi-stage porous.
Embodiment 4
Present embodiments provide one kind and contain transgranular multi-stage porous y-type zeolite, it is as made from following preparation method：
Ammonium exchange process：Boron aluminum ratio value is obtained (with B by hydrothermal synthesis method2O3, Al2O3Molar ratio computing) be respectively 1.3
With 1.6 the NaY zeolite containing boron, then by mass ratio be 1：1.5：20 B-NaY zeolites, ammonium salt and water is well mixed, and is obtained
To mixture, lasting stirring, the pH value of the hydrochloric acid solution for being 0.5mol/L with concentration regulation mixture is 5.3, is warming up to 90 DEG C,
Maintain to stir 3h under conditions of pH value is constant, filter, be washed with deionized to neutrality, dry, obtain under the conditions of 120 DEG C
The Y zeolites containing boron of ammonium type；
Hydrothermal treatment process：The Y zeolites containing boron of obtained ammonium type are put into hydrothermal device, are warming up to 650 DEG C, are led to
Enter 100% steam treatment 2h；
Repeat that above-mentioned ammonium exchanges, hydrothermal treatment process respectively once, obtains y-type zeolite, be designated as B-USY.
The X-ray diffraction thing phasor (XRD) of products therefrom as shown in figure 4, B-USY diffraction maximum (331), (511,333),
(440), (533), (642), (822,660), (555,751), eight characteristic diffraction peak peak shapes of (664) keep complete, without miscellaneous
Crystalline substance generation, the B-USY for showing the present embodiment is y-type zeolite structure.The structural parameters of the y-type zeolite of the present embodiment are as shown in table 7.
Comparative example 4
Identical silica alumina ratio is handled according to the method in embodiment 4 but does not contain the NaY zeolite of boron, the sample obtained after processing
It is designated as USY4.
The X-ray diffraction thing phasor (XRD) of products therefrom as shown in figure 4, USY4 diffraction maximum (331), (511,333),
(440), (533), (642), (822,660), (555,751), eight characteristic diffraction peak peak shapes of (664) keep complete, without miscellaneous
Crystalline substance generation, it is y-type zeolite structure to show USY4.The structural parameters of the USY4 zeolites are as shown in table 8.
Table 7
Table 8
| USY4 | |
| Relative crystallinity, % | 79 |
| Framework si-al ratio | 13.1 |
| Specific surface area, m2/g | 625.3 |
| Total pore volume, mL/g | 0.37 |
| Micro pore volume, mL/g | 0.22 |
| Two level pore volume, mL/g | 0.15 |
| Two level pore volume/total pore volume, % | 40 |
The boiling prepared with comparative example 4 using hydrothermal dealumination method can be seen that by the content of comparative analysis table 7 and table 8
Stone (USY4) is compared, and Jie-macropore volume for the B-USY that embodiment 4 is prepared is in 0.24cm3·g-1More than, highest can reach
To 0.29cm3·g-1, framework si-al ratio is more than 18.6, while the micro pore volume of B-USY zeolites is not remarkably decreased, and owns
The micro pore volume of B-USY zeolites all still maintains 0.23cm3·g-1More than even.As can be seen here, the Y types that prepared by embodiment 4
Zeolite is a kind of y-type zeolite with abundant multi-stage porous.
Embodiment 5
A kind of y-type zeolite with transgranular multi-stage porous is present embodiments provided, it is as made from following preparation method：
Ammonium exchange process：Boron aluminum ratio value is obtained (with B by isomorphous substitution method2O3, Al2O3Molar ratio computing) be respectively
0.08 and 0.16 B-NaY zeolites, it is then 1 by mass ratio：1：10 B-NaY zeolites, ammonium salt and water is well mixed, and is mixed
Compound, lasting stirring, the pH value of the hydrochloric acid solution for being 0.5mol/L with concentration regulation mixture is 2.3, is warming up to 90 DEG C, maintains
1h is stirred under conditions of pH value is constant, is filtered, is washed with deionized to neutrality, is dried at 120 DEG C, obtain containing for ammonium type
There are the Y zeolites of boron；
Hydrothermal treatment process：The Y zeolites containing boron of obtained ammonium type are put into hydrothermal device, are warming up to 500 DEG C, are led to
Enter 40% steam treatment 4h；
Repeat that above-mentioned ammonium exchanges, hydrothermal treatment process respectively once, obtains y-type zeolite, be designated as B-USY.
The X-ray diffraction thing phasor (XRD) of products therefrom as shown in figure 5, B-USY diffraction maximum (331), (511,333),
(440), (533), (642), (822,660), (555,751), eight characteristic diffraction peak peak shapes of (664) keep complete, without miscellaneous
Crystalline substance generation, the B-USY for showing the present embodiment is y-type zeolite structure.The structural parameters of y-type zeolite made from the present embodiment such as table 9
It is shown.
Table 9
Comparative example 5
Identical silica alumina ratio is handled according to the method in embodiment 5 but does not contain the NaY zeolite of boron, the sample obtained after processing
It is designated as USY5.
The X-ray diffraction thing phasor (XRD) of products therefrom as shown in figure 5, USY5 diffraction maximum (331), (511,333),
(440), (533), (642), (822,660), (555,751), eight characteristic diffraction peak peak shapes of (664) keep complete, without miscellaneous
Crystalline substance generation, show that obtained USY1 is y-type zeolite structure.The structural parameters of the USY5 zeolites are as shown in table 10.
It is can be seen that by comparative analysis table 9 with the content of table 10 compared with the zeolite (USY5) obtained by comparative example 5,
B-USY prepared by embodiment 5 Jie-big level pore volume is in 0.21cm3·g-1More than, highest can reach 0.29cm3·g-1,
The micro pore volume of the B-USY zeolites of embodiment 5 is not remarkably decreased simultaneously, and the micro pore volume of all B-USY zeolites is all still tieed up
Hold in 0.22cm3·g-1More than even.As can be seen here, the y-type zeolite that prepared by embodiment 5 is a kind of Y with abundant multi-stage porous
Type zeolite.
Table 10
| USY5 | |
| Relative crystallinity, % | 77 |
| Framework si-al ratio | 11.6 |
| Specific surface area, m2/g | 571 |
| Total pore volume, mL/g | 0.38 |
| Micro pore volume, mL/g | 0.24 |
| Jie-macropore volume, mL/g | 0.14 |
| Jie-macropore volume/total pore volume, % | 37 |
In summary, there is higher silica alumina ratio, more flourishing using B-USY zeolites made from the preparation method of the present invention
Hierarchical porous structure.
Claims (12)
1. a kind of preparation method of the y-type zeolite with transgranular multi-stage porous, this method comprise the following steps：
Step 1：NaY zeolite containing boron, ammonium salt and water are mixed, obtain mixture, is stirred, is filtered, washing, obtains ammonium type
Y zeolites containing boron；
Step 2：High-temperature water heat treatment is carried out to the Y zeolites containing boron of ammonium type, obtains the y-type zeolite with transgranular multi-stage porous；
The High-temperature water heat treatment is carried out in 10-100% steam atmosphere, and the temperature of High-temperature water heat treatment is 500-700 DEG C, high
The time of warm water heat treatment is 0.5-4h.
2. preparation method according to claim 1, wherein, the mass ratio of the NaY zeolite containing boron, ammonium salt and water is
1：0.1-2：2-30.
3. preparation method according to claim 1, wherein, the ammonium salt is included in ammonium chloride, ammonium sulfate and ammonium nitrate
One or more of combinations.
4. preparation method according to claim 1, wherein, the temperature of the stirring is 20-95 DEG C, and the time of stirring is
0.5-4h。
5. preparation method according to claim 4, wherein, the pH that mixture is adjusted in whipping process is 1-7.
6. preparation method according to claim 1, wherein, the NaY zeolite containing boron is prepared using Direct Hydrothermal method
Or prepared using post-modification method.
7. according to the preparation method described in claim 1,2 or 6, wherein, count in the form of the oxide, the NaY containing boron
In zeolite, the mol ratio of silicon and aluminium is 4-8：1.
8. according to the preparation method described in claim 1,2 or 6, wherein, count in the form of the oxide, the NaY containing boron
In zeolite, the mol ratio of boron and aluminium is 0.01-10:1.
9. preparation method according to claim 8, wherein, count in the form of the oxide, the NaY zeolite containing boron
In, the mol ratio of boron and aluminium is 0.01-2:1.
10. preparation method according to claim 1, wherein, the mixture in step 1 is done after filtering, washing
Dry, dry temperature is 50-120 DEG C, and the dry time is 5-12h.
11. a kind of y-type zeolite with transgranular multi-stage porous, it is made as the preparation method described in claim any one of 1-10
's.
12. the application of the y-type zeolite with transgranular multi-stage porous described in claim 11, the Y types should with transgranular multi-stage porous boil
Masonry is the active component of catalytic cracking catalyst and catalytic hydrogenation catalyst.
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| CN107777697B (en) * | 2016-08-30 | 2020-11-03 | 中国石油化工股份有限公司 | Y-type molecular sieve and preparation method thereof |
| CN108238613B (en) * | 2016-12-27 | 2020-04-10 | 中国石油天然气集团公司 | Small mesoporous ultrastable Y-type zeolite and preparation method and application thereof |
| WO2019010700A1 (en) * | 2017-07-14 | 2019-01-17 | 北京大学深圳研究生院 | Multi-pore zeolite having layered structure and preparation method therefor |
| CN109928404A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | A kind of synthetic method of zeolite molecular sieve |
| CN111689504A (en) * | 2019-03-12 | 2020-09-22 | 中国石油天然气股份有限公司 | Preparation method of mesoporous-microporous Y-type zeolite molecular sieve |
| CN111689505A (en) * | 2019-03-12 | 2020-09-22 | 中国石油天然气股份有限公司 | Preparation method of ZSM-5 molecular sieve with mesoporous-microporous hierarchical structure |
| CN111072045B (en) * | 2019-12-26 | 2022-12-20 | 闽南师范大学 | Hierarchical pore molecular sieve material and preparation method thereof |
| CN111672534B (en) * | 2020-06-10 | 2023-10-03 | 中国石油天然气集团有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
| CN111686787B (en) * | 2020-06-10 | 2023-10-03 | 中国石油天然气集团有限公司 | Hydrocracking catalyst carrier, and preparation method and application thereof |
| CN114604876A (en) * | 2022-03-10 | 2022-06-10 | 中国石油大学(北京) | Ultrastable Y-type zeolite and its preparing process and application |
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| CN1042523A (en) * | 1989-06-15 | 1990-05-30 | 中国石油化工总公司兰州炼油化工总厂 | A kind of method for preparing high-silicon Y-Zeolite |
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| CN1042523A (en) * | 1989-06-15 | 1990-05-30 | 中国石油化工总公司兰州炼油化工总厂 | A kind of method for preparing high-silicon Y-Zeolite |
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