CN110844919B - Preparation method of NaY molecular sieve and NaY molecular sieve prepared by preparation method - Google Patents

Preparation method of NaY molecular sieve and NaY molecular sieve prepared by preparation method Download PDF

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CN110844919B
CN110844919B CN201810952266.4A CN201810952266A CN110844919B CN 110844919 B CN110844919 B CN 110844919B CN 201810952266 A CN201810952266 A CN 201810952266A CN 110844919 B CN110844919 B CN 110844919B
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sodium
molecular sieve
nay molecular
solution
aluminum
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CN110844919A (en
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杨为民
王闻年
高焕新
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/20—Faujasite type, e.g. type X or Y
    • C01B39/24—Type Y
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

Abstract

The invention relates to a preparation method of a NaY molecular sieve and the NaY molecular sieve prepared by the method. The method comprises the following steps: a) contacting an aluminum source with a sodium hydroxide solution to obtain a sodium aluminum solution; b) contacting a silicon source with a sodium hydroxide solution to obtain a sodium-silicon solution; c) contacting the sodium aluminum solution with the sodium silicon solution to obtain a mixture I; d) contacting the mixture I with an acidic aluminum source solution to obtain a gel; e) and crystallizing the gel to obtain the NaY molecular sieve. The method can be used for industrial production of NaY molecular sieves.

Description

Preparation method of NaY molecular sieve and NaY molecular sieve prepared by preparation method
Technical Field
The invention relates to a preparation method of a NaY molecular sieve and the NaY molecular sieve prepared by the method.
Background
The Y-type zeolite is the largest catalytic material currently used in the oil refining industry and has been a focus of attention and research by researchers. In 1974, the patent US3639099 was published by GRACE, usa, and a guiding agent method is proposed for synthesizing NaY molecular sieve, wherein the guiding agent is a mixture prepared by sodium silicate, sodium aluminate and water according to a certain molar ratio, and then a silicon source and an aluminum source are added to prepare NaY molecular sieve through crystallization at 100 ℃. The invention and the use of the guiding agent not only improve the silicon-aluminum ratio of the NaY molecular sieve, but also reduce the synthesis cost of the NaY molecular sieve, so that the guiding agent is a milestone in the synthesis history of the NaY molecular sieve. Therefore, the NaY molecular sieve is mainly synthesized by a guiding agent method in the industry at present, and in the subsequent development of the NaY molecular sieve, the majority of the method is the improvement of the process for preparing the NaY molecular sieve by the guiding agent method.
CN1266742A discloses a preparation method of NaY molecular sieve, which changes the adding mode of acidic aluminum salt on the basis of a guiding agent method, changes the one-time addition of aluminum salt into gel into the multi-time addition, so that the viscosity of the formed multi-time viscous point is lower than that of the one-time addition, and optimizes the process for preparing NaY molecular sieve. The method achieves the purpose of improving the yield of the NaY molecular sieve single kettle. CN104118884A is a solid silicon source, and the yield of the NaY molecular sieve single kettle is doubled by a guiding agent method. However, this method adds complexity to the feeding because the solid raw material is directly fed, and may cause solidification due to too fast feeding.
CN1683246A discloses a method for preparing a large-grain NaY molecular sieve, which is to prepare a guide gel with long-time activity by a guide agent method, and then mix the gel with a silica-alumina source for crystallization to prepare the NaY molecular sieve with the grain larger than 1000 nanometers. CN104773741A similarly, in addition to the guiding agent method, by changing the gel proportion, NaY molecular sieve with crystal grain of 3000nm is synthesized in a short time.
In the preparation of small-grain NaY molecular sieves, CN100586854A discloses a method for preparing small-grain NaY molecular sieves by adding crown ether into gel after the gel is formed by a guiding agent method. Similarly, CN105314651A is also prepared by the method, hexamethylenetetramine is added into the formed gel as an additive, and a high-dispersity small-crystal NaY molecular sieve is prepared by a sectional crystallization mode. CN106745045A also discloses the same method, and surfactant span-20 is added into the gel to prepare the nano NaY molecular sieve. CN103449469A is a NaY molecular sieve with high stability and small crystal grain obtained by adding a surfactant into a guiding agent.
In-situ synthesis of the catalytic cracking catalyst is also based on a guiding agent method, and CN102701232A discloses that the catalytic cracking catalyst meeting the requirements can be obtained by mixing microspheres roasted at different temperatures with a molecular sieve guiding agent and then carrying out hydrothermal crystallization. CN103058218A is also prepared by mixing the sprayed microsphere with guiding agent, silicon source and sodium hydroxide to obtain in-situ crystallized NaY molecular sieve microsphere.
Of course, there are many methods for preparing NaY molecular sieves by non-guiding agent methods. CN1951812A discloses that organic alkali or organic polymer is used as template agent to directly synthesize high-silicon faujasite under the conditions of less sodium consumption and no guiding agent, but the subsequent demoulding process caused by the use of organic template agent still causes environmental pollution. And US4436708 adds NaY molecular sieve seed crystals into a silicon source to be used as active species to finally synthesize the NaY molecular sieve.
As can be seen from the above, the preparation of the current NaY molecular sieve is not free from the guiding agent. The preparation of the directing agent usually requires a certain time and process, which actually increases the preparation time of the NaY molecular sieve. Even if the directing agent is not used, the aim of promoting crystallization is achieved by other ways, and the process for preparing the NaY molecular sieve is often complicated. The synthesis cost of the NaY molecular sieve is increased at the end.
Disclosure of Invention
The inventor of the invention finds a novel preparation method of the NaY molecular sieve through diligent research on the basis of the prior art. The method comprises the following steps: preparing a sodium-aluminum solution containing high-concentration sodium oxide and aluminum oxide; preparing a sodium silicon solution containing silicon oxide and sodium oxide, and treating the sodium silicon solution at a high temperature; mixing the sodium aluminum solution and the sodium silicon solution at low temperature; adding an acidic aluminum source; crystallizing at high temperature. It has at least an advantage of low synthesis cost as compared with the prior art, and the present invention has been completed based on this finding.
Specifically, the invention relates to a preparation method of a NaY molecular sieve. The method comprises the following steps:
a) contacting an aluminum source with a sodium hydroxide solution to obtain a sodium aluminum solution;
b) contacting a silicon source with a sodium hydroxide solution to obtain a sodium-silicon solution;
c) contacting the sodium aluminum solution with the sodium silicon solution to obtain a mixture I;
d) contacting the mixture I with an acidic aluminum source solution to obtain a gel;
e) and crystallizing the gel to obtain the NaY molecular sieve.
The invention also provides the NaY molecular sieve prepared by the method.
The invention also provides a NaY molecular sieve composition, which comprises the NaY molecular sieve prepared by the method or the NaY molecular sieve and a binder.
The invention also provides the application of the NaY molecular sieve prepared by the method.
The invention has the technical effects that:
according to the preparation method of the NaY molecular sieve, the NaY molecular sieve with the same property as that prepared by the guiding agent method can be finally obtained without depending on the conventional NaY guiding agent in the prior art.
According to the preparation method of the NaY molecular sieve, a guide agent method generally adopted in the prior art is omitted, and the NaY molecular sieve is prepared by mixing an alkali aluminum solution and a silicon-aluminum solution, gelling acid aluminum salt and directly crystallizing, so that the preparation process of the NaY molecular sieve is greatly simplified, the manufacture of the NaY molecular sieve is easier, and the industrialization prospect is wide.
According to the preparation method of the NaY molecular sieve, an organic template agent is not used. The addition of the template agent not only increases the crystallization time, but also has high price and complex structure. Furthermore, the templating agent present in the molecular sieve needs to be removed in a subsequent process in order not to interfere with the use of the molecular sieve, which tends to cause environmental pollution. Therefore, an organic template agent is not used, the production cost is reduced, meanwhile, the nitrogen-containing wastewater is greatly reduced, the post-treatment is easy, and the environment is green and friendly.
Compared with the prior art, the preparation method of the NaY molecular sieve can obviously shorten the time for manufacturing the NaY molecular sieve. For example, while the prior art typically requires about 2-3 days for the same production of NaY molecular sieves, the present invention sometimes requires only 1-2 days or less. The whole time is shortened, namely the production period of the NaY molecular sieve is shortened, and the energy consumption is reduced.
According to the preparation method of the NaY molecular sieve, the NaY molecular sieve with large grains, such as the NaY molecular sieve with large grains of about 2000nm, can be prepared. The NaY molecular sieve with large crystal grains is more suitable for subsequent treatment and industrial application due to good stability, and the crystal grains are larger, so that the pore passage in the crystal is correspondingly lengthened, the retention time of reactant molecules in the molecular sieve crystal is prolonged, the intra-crystal reaction is increased, and the surface utilization rate of the molecular sieve is improved. Therefore, the preparation of the large-grain NaY molecular sieve has important significance.
Drawings
FIG. 1 shows XRD spectra of products prepared in examples 1 to 6 of the present invention and comparative examples 1 to 2. Wherein, the curves 1-6 are XRD spectrograms of the NaY molecular sieve prepared in [ examples 1-6 ]. From the XRD spectrum, the spectrum is the typical characteristic diffraction peak of the NaY molecular sieve, and no other crystal phase is seen. Curves 7 to 8 are XRD spectra of the products prepared in comparative examples 1 to 2. "Y standard" refers to the XRD spectrum of NaY molecular sieve prepared according to the guiding agent method provided in patent US 3639099.
FIGS. 2 to 7 are Scanning Electron Microscope (SEM) photographs of NaY molecular sieves prepared in the present invention [ examples 1 to 6 ], respectively.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or the like, to derive materials, substances, methods, procedures, devices, or components, etc., it is intended that the subject matter derived from the heading encompass those conventionally used in the art at the time of filing this application, but also include those that are not currently in use, but would become known in the art to be suitable for a similar purpose.
In the context of the present specification, the structure of NaY molecular sieves is determined by X-ray diffraction pattern (XRD) determined by X-ray powder diffractometry using a Cu-K α radiation source, K α 1 wavelength λ 1.5405980 angstroms
Figure BDA0001771811750000041
A nickel filter.
In the context of the present specification, the mean grain size of the NaY molecular sieve is determined by Scanning Electron Microscopy (SEM), using a Nova NanoSEM450 SEM from FEI, a fully dried sample is fixed on a sample tray with conductive gel, evacuated to 10 "4 Pa and then subjected to scanning testing.
In the context of the present specification, the term "relative crystallinity" refers to the crystallinity calculated by the method provided by petrochemical industry Standard SH/T0340-92 of the people's republic of China.
It should be noted that "Y standard" in FIG. 1 refers to NaY molecular sieve prepared by the guiding agent method provided in patent US 3639099.
It should be expressly understood that two or more of the aspects (or embodiments) disclosed in the context of this specification can be combined with each other as desired, and that such combined aspects (e.g., methods or systems) are incorporated in and constitute a part of this original disclosure, while remaining within the scope of the present invention.
Unless otherwise expressly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise not in accordance with the conventional knowledge of those skilled in the art.
According to one aspect of the invention, a method for preparing a NaY molecular sieve is provided. The method comprises the following steps:
a) contacting an aluminum source with a sodium hydroxide solution to obtain a sodium aluminum solution;
b) contacting a silicon source with a sodium hydroxide solution to obtain a sodium-silicon solution;
c) contacting the sodium aluminum solution with the sodium silicon solution to obtain a mixture I;
d) contacting the mixture I with an acidic aluminum source solution to obtain a gel;
e) and crystallizing the gel to obtain the NaY molecular sieve.
According to one aspect of the invention, the sodium aluminum solution contains not less than 20 wt% of sodium oxide, preferably 20-30 wt%; the content of alumina is 4 to 8 wt%.
According to one aspect of the invention, the contacting conditions of step a) of said aluminium source with said sodium hydroxide solution comprise: the contact temperature is 20-40 ℃, and the contact time is 0.1-3 hours.
According to one aspect of the invention, the sodium silicon solution contains 6 to 12 wt% of sodium oxide and 18 to 25 wt% of silicon oxide.
According to one aspect of the invention, the contacting conditions of the silicon source with the sodium hydroxide solution of step b) comprise: the contact temperature is 20-40 ℃, and the contact time is 0.1-3 hours.
According to one aspect of the invention, in the step c), the sodium-silicon solution is treated at 80-110 ℃ for 0.5-3 hours and then contacted with the sodium-aluminum solution.
According to one aspect of the invention, the contacting conditions of the sodium aluminum solution and the sodium silicon solution in step c) comprise: the contact temperature is 20-65 ℃, and the contact time is 0.5-3 hours.
According to one aspect of the invention, the content of the alumina in the acidic aluminum source solution is 5-30 wt%.
According to one aspect of the invention, the contacting conditions of step d) of the mixture I with the acidic aluminum source solution comprise: the contact temperature is 20-65 ℃, and the contact time is 0.5-3 hours.
According to one aspect of the invention, the crystallization conditions of the gel comprise: the crystallization temperature is 90-120 ℃, and the crystallization time is 12-48 hours.
According to one aspect of the invention, the aluminum source is at least one selected from the group consisting of metallic aluminum, aluminum oxide, sodium metaaluminate, and aluminum hydroxide.
According to an aspect of the present invention, the silicon source is at least one selected from the group consisting of sol, water glass, solid silica gel, white carbon and sodium silicate.
According to one aspect of the invention, the source of acidic aluminium is selected from at least one of the group consisting of aluminium chloride, aluminium nitrate and aluminium sulphate.
According to one aspect of the invention, Na is added2O、Al2O3、SiO2And H2Calculated by O, the feeding molar ratio is Na2O:Al2O3:SiO2:H2O＝1.8～3.0:1:7.0～9.0:100～300。
According to one aspect of the invention, the sodium aluminum solution of step c) is contacted with the sodium silicon solution in a manner that: the sodium aluminum solution is added into the sodium silicon solution in a dropwise manner.
According to one aspect of the invention, the mixture I of step d) is contacted with the acidic aluminum source solution in a manner that: and adding the acidic aluminum source solution into the mixture I in a dropwise manner.
According to an aspect of the present invention, in the method for preparing the NaY molecular sieve, after the crystallization is completed, the NaY molecular sieve may be separated from the obtained reaction mixture as a product by any separation means conventionally known. The separation method includes, for example, a method of filtering, washing and drying the obtained reaction mixture.
According to an aspect of the present invention, in the preparation method of the NaY molecular sieve, the filtering, washing and drying may be performed in any manner conventionally known in the art. Specifically, for example, the reaction mixture obtained may be simply filtered by suction. Examples of the washing include washing with deionized water. The drying temperature is, for example, 40 to 250 ℃, preferably 60 to 150 ℃, and the drying time is, for example, 8 to 30 hours, preferably 10 to 20 hours. The drying may be carried out under normal pressure or under reduced pressure.
According to one aspect of the invention, the NaY molecular sieve is prepared according to the method for preparing the NaY molecular sieve.
According to one aspect of the invention, the average grain diameter of the NaY molecular sieve is 1000-3000 nanometers.
According to one aspect of the invention, the NaY molecular sieve may be in any physical form, such as a powder, a pellet, or a molded article (e.g., a bar, a trilobe, etc.). These physical forms can be obtained in any manner conventionally known in the art and are not particularly limited.
According to one aspect of the invention, the NaY molecular sieve may be used in combination with other materials, thereby obtaining a NaY molecular sieve composition. Examples of the other materials include active materials and inactive materials. Examples of the active material include synthetic zeolite and natural zeolite, and examples of the inactive material (generally referred to as a binder) include clay, silica gel, and alumina. These other materials may be used singly or in combination in any ratio. As the amount of the other materials, those conventionally used in the art can be directly referred to, and there is no particular limitation.
According to one aspect of the invention, the NaY molecular sieve or NaY molecular sieve composition may be used as an adsorbent, for example to separate at least one component from a mixture of components in a gas or liquid phase. Thus, at least one component may be partially or substantially completely separated from a mixture of the various components by contacting the mixture with the NaY molecular sieve or the NaY molecular sieve composition to selectively adsorb that component.
According to one aspect of the invention, the NaY molecular sieve or the NaY molecular sieve composition may also be used as a catalyst (or as a catalytically active component thereof) either directly or after having been subjected to the necessary treatments or conversions (such as ion exchange, etc.) conventionally performed in the art for NaY molecular sieves. To this end, according to one aspect of the present invention, it is possible, for example, to subject a reactant (such as a hydrocarbon) to a predetermined reaction in the presence of the catalyst, and thereby obtain a target product.
The invention is further illustrated by the following specific examples.
[ example 1 ]
The feeding molar ratio is Na2O:Al2O3:SiO2:H2O ═ 2.5:1:7.5: 173. In particular, the method comprises the following steps of,
preparing a sodium-aluminum solution: 200g of water is taken, 41.9g of sodium metaaluminate is added, and stirring is carried out until complete dissolution. Then adding 101.3g of sodium hydroxide, and stirring until the sodium hydroxide is completely dissolved to obtain the sodium-aluminum solution. The preparation process maintained the solution temperature at 35 ℃. In the prepared sodium-aluminum solution, the content of sodium oxide is 25 percent, and the content of aluminum oxide is 5 percent.
84g of water was taken, 23.1g of sodium hydroxide was added thereto, and stirred until completely dissolved, and then 107.1g of 40 wt% silica sol was added dropwise thereto and stirred for 0.5 hour to form a uniform solution. And then heating to 90 ℃ for treatment for 10min to obtain the sodium-silicon solution. In the prepared sodium-silicon solution, the content of sodium oxide is 8 percent, and the content of silicon oxide is 20 percent.
94.15g of sodium silicon solution is taken, 19.68g of sodium aluminum solution is added dropwise at 35 ℃, and the mixture is stirred for 30 minutes until the mixture is uniformly mixed to form a mixture I.
65.52g of a 5 wt% aluminum sulfate solution were slowly added dropwise to the mixture I to obtain a gel. Stirring was continued for 1 hour until complete and uniform mixing.
And transferring the gel into a hydrothermal crystallization kettle, and crystallizing for 32 hours at 100 ℃. Washing the crystallized product with deionized water until the filtrate is nearly neutral, and drying the filter cake at 120 ℃ for 5 hours to obtain the required NaY molecular sieve product.
The XRD spectrum of the product is shown as curve 1 in figure 1. The spectrum shows that it is a pure phase NaY molecular sieve with a relative crystallinity of 100%.
Fig. 2 is a Scanning Electron Microscope (SEM) photograph of the product. The average grain diameter was 2000 nm.
[ example 2 ]
The same as [ example 1 ] except that the silicon source was solid silica gel.
The XRD spectrum of the product is shown as curve 2 in figure 1. The spectrum shows that it is a pure phase NaY molecular sieve with a relative crystallinity of 91%.
Fig. 3 is a Scanning Electron Microscope (SEM) photograph of the product. The average grain diameter was 2000 nm.
[ example 3 ]
The same as [ example 1 ], except that the aluminum source is metallic aluminum.
The XRD spectrum of the product is shown as curve 3 in figure 1. The spectrum shows that it is a pure phase NaY molecular sieve with a relative crystallinity of 85%.
Fig. 4 is a Scanning Electron Microscope (SEM) photograph of the product. The average grain diameter was 2000 nm.
[ example 4 ]
As in example 1, except that the source of acidic aluminum was aluminum nitrate.
The XRD spectrum of the product is shown as curve 4 in figure 1. The spectrum shows that it is a pure phase NaY molecular sieve with a relative crystallinity of 100%.
Fig. 5 is a Scanning Electron Microscope (SEM) photograph of the product. The average grain diameter was 2000 nm.
[ example 5 ]
The feeding molar ratio is Na2O:Al2O3:SiO2:H2O ═ 1.85:1:7.3: 156. In particular, the method comprises the following steps of,
preparing a sodium-aluminum solution: 200g of water is taken, 51.7g of sodium metaaluminate is added, and stirring is carried out until complete dissolution. Then adding 101.3g of sodium hydroxide, and stirring until the sodium hydroxide is completely dissolved to obtain the sodium-aluminum solution. The preparation process maintained the solution temperature at 35 ℃. In the prepared sodium-aluminum solution, the content of sodium oxide is 25 percent, and the content of aluminum oxide is 6 percent.
84g of water was taken, 23.1g of sodium hydroxide was added thereto, and stirred until completely dissolved, and then 137.5g of 40 wt% silica sol was added dropwise thereto and stirred for 0.5 hour to form a uniform solution. And then heating to 90 ℃ for treatment for 10min to obtain the sodium-silicon solution. In the prepared sodium-silicon solution, the content of sodium oxide is 7 percent, and the content of silicon oxide is 22.5 percent.
400.1g of sodium-silicon solution is added dropwise with 93.8g of sodium-aluminum solution at 35 ℃ and stirred for 30 minutes until the mixture is uniformly mixed to form a mixture I.
218.4g of a 7% by weight aluminum sulfate solution are slowly added dropwise to the mixture I to give a gel. Stirring was continued for 1 hour until complete and uniform mixing.
And transferring the gel into a hydrothermal crystallization kettle, and crystallizing for 32 hours at 100 ℃. Washing the crystallized product with deionized water until the filtrate is nearly neutral, and drying the filter cake at 120 ℃ for 5 hours to obtain the required NaY molecular sieve product.
The XRD spectrum of the product is shown as curve 5 in figure 1. The spectrum shows that it is a pure phase NaY molecular sieve with a relative crystallinity of 99%.
Fig. 6 is a Scanning Electron Microscope (SEM) photograph of the product. The average grain diameter was 2000 nm.
[ example 6 ]
The feeding molar ratio is Na2O:Al2O3:SiO2:H2O2.5: 1:8.75: 171. In particular, the method comprises the following steps of,
preparing a sodium-aluminum solution: 200g of water is taken, 51.7g of sodium metaaluminate is added, and stirring is carried out until complete dissolution. Then adding 101.3g of sodium hydroxide, and stirring until the sodium hydroxide is completely dissolved to obtain the sodium-aluminum solution. The preparation process maintained the solution temperature at 35 ℃. In the prepared sodium-aluminum solution, the content of sodium oxide is 25 percent, and the content of aluminum oxide is 6 percent.
84g of water was taken, 23.1g of sodium hydroxide was added thereto, and stirred until completely dissolved, and then 137.5g of 40 wt% silica sol was added dropwise thereto and stirred for 0.5 hour to form a uniform solution. And then heating to 90 ℃ for treatment for 10min to obtain the sodium-silicon solution. In the prepared sodium-silicon solution, the content of sodium oxide is 7 percent, and the content of silicon oxide is 22.5 percent.
380.2g of sodium-silicon solution is taken, 80.0g of sodium-aluminum solution is added dropwise at 35 ℃, and the mixture is stirred for 30 minutes until the mixture is mixed uniformly to form a mixture I.
168g of a 7 wt% aluminum sulfate solution were slowly added dropwise to the mixture I to obtain a gel. Stirring was continued for 1 hour until complete and uniform mixing.
And transferring the gel into a hydrothermal crystallization kettle, and crystallizing for 32 hours at 100 ℃. Washing the crystallized product with deionized water until the filtrate is nearly neutral, and drying the filter cake at 120 ℃ for 5 hours to obtain the required NaY molecular sieve product.
The XRD spectrum of the product is shown as curve 6 in figure 1. The spectrum shows that it is a pure phase NaY molecular sieve with a relative crystallinity of 101%.
Fig. 7 is a Scanning Electron Microscope (SEM) photograph of the product. The average grain diameter was 2000 nm.
[ COMPARATIVE EXAMPLE 1 ]
The procedure is as in [ example 1 ] except that the molar ratio of the feed is Na2O:Al2O3:SiO2:H2O ═ 2.5:1:7.5: 173. The content of alumina in the sodium-aluminum solution was 3%.
As a result: no NaY product is obtained.
The XRD spectrum of the product is shown as curve 7 in figure 1. The spectrum showed it to be an amorphous material.
[ COMPARATIVE EXAMPLE 2 ]
The procedure is as in [ example 1 ] except that the sodium-silicon solution is not subjected to a high temperature treatment at 90 ℃.
The XRD spectrum of the product is shown as curve 8 in figure 1. The spectrum shows that it is a pure phase NaY molecular sieve with a relative crystallinity of 37%.
As a result: the crystallization time was 72 hours.

Claims (11)

1. A preparation method of NaY molecular sieve comprises the following steps:
a) contacting an aluminum source with a sodium hydroxide solution to obtain a sodium aluminum solution;
b) contacting a silicon source with a sodium hydroxide solution to obtain a sodium-silicon solution;
c) treating the sodium-silicon solution at 80-110 ℃ for 0.5-3 hours, and then contacting the sodium-silicon solution with the sodium-aluminum solution to obtain a mixture I;
d) contacting the mixture I with an acidic aluminum source solution to obtain a gel;
e) crystallizing the gel to obtain the NaY molecular sieve;
the content of alumina in the sodium-aluminum solution is 4-8 wt%.
2. The method of claim 1, wherein the sodium aluminum solution contains no less than 20 wt% sodium oxide.
3. The method for preparing the NaY molecular sieve of claim 1, wherein the sodium aluminum solution contains not less than 20-30 wt% of sodium oxide.
4. The method for preparing NaY molecular sieve of claim 1, wherein the contacting conditions of the aluminum source and the sodium hydroxide solution in step a) comprise: the contact temperature is 20-40 ℃, and the contact time is 0.1-3 hours.
5. The method for preparing the NaY molecular sieve of claim 1, wherein the sodium-silicon solution contains 6-12 wt% of sodium oxide and 18-25 wt% of silicon oxide.
6. The method for preparing NaY molecular sieve of claim 1, wherein the contacting conditions of step b), the silicon source and the sodium hydroxide solution comprise: the contact temperature is 20-40 ℃, and the contact time is 0.1-3 hours.
7. The method for preparing the NaY molecular sieve of claim 1, wherein the contacting conditions of the sodium aluminum solution and the sodium silicon solution in step c) comprise: the contact temperature is 20-65 ℃, and the contact time is 0.5-3 hours.
8. The method for preparing NaY molecular sieve of claim 1, wherein the content of alumina in the acidic aluminum source solution is 5-30 wt%.
9. The method for preparing NaY molecular sieve of claim 1, wherein the contacting conditions of the mixture I and the acidic aluminum source solution in step d) comprise: the contact temperature is 20-65 ℃, and the contact time is 0.5-3 hours.
10. The method for preparing NaY molecular sieve of claim 1, wherein the crystallization conditions of the gel comprise: the crystallization temperature is 90-120 ℃, and the crystallization time is 12-48 hours.
11. The method for preparing NaY molecular sieve according to claim 1,
the aluminum source is at least one selected from the group consisting of metallic aluminum, aluminum oxide, sodium metaaluminate, and aluminum hydroxide;
the silicon source is at least one selected from the group consisting of sol, water glass, solid silica gel, white carbon black and sodium silicate;
the acidic aluminum source is at least one selected from the group consisting of aluminum chloride, aluminum nitrate, and aluminum sulfate;
with Na2O、Al2O3、SiO2And H2Calculated by O, the feeding molar ratio is Na2O∶Al2O3∶SiO2∶H2O＝1.8～3.0∶1∶7.0～9.0∶100～300。
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* Cited by examiner, † Cited by third party
Title
纳米NaY分子筛的合成优化;常彦斌等;《石油学报（石油加工）》;20160630;第32卷(第3期);477-485页 *

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