CN110963502A - Preparation method of Y-type molecular sieve with high silica-alumina ratio - Google Patents
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Abstract
The invention belongs to the technical field of molecular sieve synthesis, and particularly relates to a preparation method of a Y-type molecular sieve with a high silica-alumina ratio. Dissolving two templates, and mixing a double-template solution with an aluminum source and an alkali source to obtain a first mixed solution; then mixing the first mixed solution with a silicon source and a seed crystal to obtain a second mixed solution; and finally, sequentially carrying out aging treatment and hydrothermal crystallization treatment on the second mixed solution to obtain the Y-type molecular sieve with the high silica-alumina ratio. The invention takes the high-silicon Y molecular sieve as the crystal seed to synthesize the high-silicon-aluminum-ratio Y molecular sieve in a double-template system, thereby realizing the one-step synthesis of SiO2/Al2O3The ratio of the Y molecular sieve to the Y molecular sieve is 6.00-21.352. In addition, the Y-type molecular sieve obtained by the preparation method has high crystallinity; the preparation method adopts cheap raw materials, and the synthesis method is simple and easy to operate and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of molecular sieve synthesis, and particularly relates to a preparation method of a Y-type molecular sieve with a high silica-alumina ratio.
Background
The Y molecular sieve is usually used as a catalyst and an adsorption separating agent in the petroleum catalytic cracking process. Currently, Y molecular sieves with FAU configuration are used in large numbers in petroleum conversion processes due to their oversized supercage structure and appropriate pore size. The silica-alumina ratio of the Y-type molecular sieve has important influence on the service life of the catalyst, the product distribution and the catalytic performance. The Y molecular sieve with high silica-alumina ratio has the advantages of high catalytic activity, good stability and the like.
The silicon-aluminum ratio of the Y-type molecular sieve is generally 3-5, when the SiO of the Y-type molecular sieve2/Al2O3When the molecular weight is more than 6, the molecular weight is called high-silicon Y molecular sieve, and the methods for improving the silicon-aluminum ratio of the Y molecular sieve in the prior art mainly comprise two methods, namely a secondary synthesis method and a direct synthesis method. The secondary synthesis method comprises the steps of firstly obtaining an initial Y molecular sieve through hydrothermal treatment, and then carrying out secondary dealumination on the initial Y molecular sieve, so that the framework silicon-aluminum ratio is improved. The dealumination of the Y molecular sieve can improve the silicon-aluminum ratio of a framework, but non-framework aluminum is generated in the dealumination process to cause the defect of the framework, a small amount of framework collapses to reduce the crystallinity of the molecular sieve, and in addition, the method has the disadvantages of complicated process, high energy consumption and great pollution.
The direct synthesis method can avoid complex post-treatment process, save manpower and material resources and reduce environmental pollution. Therefore, how to prepare the Y-type molecular sieve with high silica-alumina ratio by using the direct synthesis method becomes a hot spot.
In 1990, F.Delprat et al (Zeolite, 10(1990)546-552) use crown ether (such as 18-crown-6 and 15-crown-5) as a structure directing agent for the first time, and directly hydrothermally synthesize a high-silicon Y molecular sieve with silicon-aluminum molecules being 6-10, but the synthesis of the structure directing agent crown ether is complex, high in toxicity and expensive;
in the U.S. Pat. No. 4, 5385717A, Polyethylene Oxide (POE) is used as a structure directing agent to synthesize a high-silicon Y molecular sieve with the silicon-aluminum molecular ratio of more than 6, but the synthesis of the used structure directing agent is complicated;
patent No. CN105439168A discloses a method for preparing Y-type molecular sieve with high silica-alumina ratio, which comprises mixing deionized water, silicon source, aluminum source, alkali source and tetraalkylammonium cation source as template agent to obtain initial gel mixture, and mixing the initial gel mixture with quaternary ammonium cation sourceAging the gel mixture at a proper temperature, putting the gel mixture into a high-pressure synthesis kettle for crystallization, separating a solid product, and drying to obtain the Y-type molecular sieve with high silica-alumina ratio; SiO of the high-silicon aluminum Y-shaped molecular sieve prepared by the patent2/Al2O3Not less than 6, up to 7.2;
in the patent with the patent number of CN104692413A, short-chain alkyl imidazole ionic liquid (such as brominated 1-ethyl-3-methylimidazole and brominated 1-allyl-3-methylimidazole) is used as a structure directing agent to synthesize a high-silicon Y molecular sieve with the silicon-aluminum molecular ratio of 6-7.6;
patent No. CN109502604A discloses a method for synthesizing a high-silicon Y molecular sieve by using a template agent, wherein choline organic ammonium salts (such as choline chloride and choline hydroxide) are selected as structure directing agents to synthesize the high-silicon Y molecular sieve with the silicon-aluminum ratio of 6-7;
although the silicon-aluminum ratio of the existing Y-type molecular sieve prepared by a one-step synthesis method is improved to a certain extent, the existing Y-type molecular sieve has a large promotion space compared with the industrial requirement.
Disclosure of Invention
The invention aims to provide a method for preparing a Y-type molecular sieve with a high silica-alumina ratio, the preparation method provided by the invention is simple to operate and easy to realize, and the obtained Y-type molecular sieve has a high silica-alumina ratio.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a method for preparing a Y-type molecular sieve with a high silica-alumina ratio, which comprises the following steps:
1) mixing two organic templates with water to obtain a double-template solution, wherein the two organic templates are a first template and a second template respectively;
2) mixing the double-template agent solution obtained in the step 1) with an aluminum source and an alkali source to obtain a first mixed solution;
3) mixing the first mixed solution in the step 2) with a silicon source and a high-silicon Y molecular sieve seed crystal to obtain a second mixed solution, wherein the SiO of the high-silicon Y molecular sieve seed crystal2/Al2O3＞50；
4) Sequentially carrying out aging treatment and hydrothermal crystallization treatment on the second mixed solution in the step 3) to obtain the Y-type molecular sieve with the high silica-alumina ratio; the time of the hydrothermal crystallization treatment is 8-15 days, and the temperature of the hydrothermal crystallization treatment is 80-140 ℃.
Preferably, the first templating agent comprises tetramethylammonium hydroxide and the second templating agent comprises any tetraalkylammonium hydroxide other than tetramethylammonium hydroxide.
Preferably, the aluminum source is aluminum oxide, the alkali source is corresponding alkali metal oxide, the silicon source is silicon dioxide, and the molar ratio of the alkali metal oxide, the first template, the second template, the silicon dioxide, the aluminum oxide and the water in the second mixed solution is (0.5-6): (0.01-1): (0.5-4): 10: (0.01-1): (100-500).
Preferably, the silicon source is calculated by silicon dioxide, and the mass of the high-silicon Y molecular sieve seed crystal is 1-10% of the total mass of the silicon dioxide.
Preferably, the aging treatment is carried out under the condition of stirring, the stirring speed is 250-750 rpm, the stirring temperature is 10-30 ℃, and the time is 2-48 hours.
Preferably, the hydrothermal crystallization treatment comprises static crystallization or dynamic crystallization;
preferably, the dynamic crystallization is carried out in a rotary oven, the rotation speed of which is greater than 0 and equal to or less than 80 rpm.
Preferably, the aluminum source is one or more of sodium metaaluminate, aluminum hydroxide, aluminum sulfate and aluminum isopropoxide.
Preferably, the alkali source is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
Preferably, the silicon source is one or more of silica sol, tetraethoxysilane and gas-phase silica.
The invention provides a method for preparing a Y-type molecular sieve with a high silica-alumina ratio, which comprises the following steps: dissolving two organic templates to obtain a double-template solution; mixing the double template agent solution with an aluminum source and an alkali source to obtainTo the first mixed solution; mixing the first mixed solution with a silicon source and a high-silicon Y molecular sieve seed crystal to obtain a second mixed solution; sequentially carrying out aging treatment and hydrothermal crystallization treatment on the second mixed solution to obtain the Y-type molecular sieve with the high silica-alumina ratio; wherein SiO of the high-silicon Y molecular sieve crystal seed (Y molecular sieve crystal seed)2/Al2O3Is more than 50; the time of the hydrothermal crystallization treatment is 8-15 days, and the temperature of the hydrothermal crystallization treatment is 80-140 ℃. The invention takes the high-silicon Y molecular sieve as the crystal seed to synthesize the high-silicon-aluminum-ratio Y molecular sieve in a double-template system, thereby realizing the one-step synthesis of SiO2/Al2O3According to the Y molecular sieve with the ratio of 21.352, in the invention, a double-template system plays a role in filling space for a specific pore channel structure, wherein a longer molecular chain of a second template agent can occupy more pore channel space, so that the introduction amount of an aluminum source in a framework is reduced, the silicon-aluminum ratio of the molecular sieve is improved, meanwhile, a high-silicon Y molecular sieve crystal nucleus is provided for crystallization by a high-silicon Y molecular sieve crystal seed, the Y molecular sieve with the high silicon-aluminum ratio grows on the high-silicon Y molecular sieve crystal nucleus, and the silicon-aluminum ratio of the framework of the Y molecular sieve is improved under the synergistic effect of the double-template system and the crystal seed. In addition, the Y-type molecular sieve obtained by the preparation method has high crystallinity; the preparation method adopts cheap raw materials, and the synthesis method is simple and easy to operate and is suitable for large-scale industrial production.
Drawings
FIG. 1 is an X-ray diffraction diagram of the Y-type molecular sieve with high Si/Al ratio obtained in examples 1-3;
FIG. 2 is a schematic diagram of the Y-type molecular sieve with high Si/Al ratio obtained in example 329Si MAS NMR nuclear magnetic map;
FIG. 3 is a scanning electron micrograph of the Y-type molecular sieve with high Si/Al ratio in example 2;
FIG. 4 is a scanning electron microscope image of the Y-type molecular sieve with high Si/Al ratio in example 3;
FIG. 5 is an X-ray diffraction chart of the products obtained in comparative examples 1 to 6.
Detailed Description
The invention provides a method for preparing a Y-type molecular sieve with a high silica-alumina ratio, which comprises the following steps:
1) mixing two organic templates with water to obtain a double-template solution, wherein the two organic templates are a first template and a second template respectively;
2) mixing the double-template agent solution obtained in the step 1) with an aluminum source and an alkali source to obtain a first mixed solution;
3) mixing the first mixed solution in the step 2) with a silicon source and a high-silicon Y molecular sieve seed crystal to obtain a second mixed solution, wherein the SiO of the high-silicon Y molecular sieve seed crystal2/Al2O3＞50；
4) Sequentially carrying out aging treatment and hydrothermal crystallization treatment on the second mixed solution in the step 3) to obtain the Y-type molecular sieve with the high silica-alumina ratio; the time of the hydrothermal crystallization treatment is 8-15 days, and the temperature of the hydrothermal crystallization treatment is 80-140 ℃.
In the invention, two organic templates are mixed with water to obtain a double-template solution, wherein the first template preferably comprises tetramethylammonium hydroxide, and the mass percentage concentration of the first template in the double-template solution is preferably 0.01-8.34%, more preferably 0.036-6.6%, and even more preferably 1.42-2.18%; the second template preferably comprises any tetraalkylammonium hydroxide except tetramethylammonium hydroxide, more preferably comprises one or more of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and tetrapentylammonium hydroxide, and even more preferably comprises one of tetrapropylammonium hydroxide and tetrabutylammonium hydroxide, and the mass percentage concentration of the second template in the dual template solution is preferably 1.23-53.53%, even more preferably 5-45%, and even more preferably 12.2-25.97%. In the invention, the first template and the second template are selected from commercial products, the organic template is preferably mixed with deionized water, and the mixing mode is not particularly required as long as the organic template and the deionized water can be uniformly mixed.
After the double template agent solution is obtained, the double template agent solution is mixed with an aluminum source and an alkali source to obtain a first mixed solution. In the present invention, the aluminum source preferably includes one or more of sodium metaaluminate, aluminum hydroxide, aluminum sulfate and aluminum isopropoxide, more preferably aluminum sulfate or aluminum isopropoxide, and still more preferably sodium metaaluminate. In the present invention, the alkali source preferably includes one or more of sodium hydroxide, potassium hydroxide, and lithium hydroxide, and more preferably sodium hydroxide.
The invention has no special requirement on the mixing mode of the double template agent solution, the aluminum source and the alkali source, and the preferred mixing mode is a stirring mode, so long as the alkali source and the aluminum source are completely dissolved and are uniformly mixed with the double template agent solution.
After the first mixed solution is obtained, the first mixed solution is mixed with a silicon source and high-silicon Y molecular sieve seed crystals to obtain a second mixed solution. In the present invention, the silicon source preferably includes one or more of silica sol, tetraethoxysilane and fumed silica, more preferably tetraethoxysilane or silica sol, and still more preferably silica sol. In the embodiment of the invention, the silicon source is a commercial product, and the silica sol is preferably LUDOX HS-40. When the silicon source is tetraethoxysilane or silica sol, the silicon source is preferably dropwise added into the first mixed solution in a dropwise adding mode, wherein the dropwise adding speed is preferably 1-2 drops per second, and is further preferably 1 drop per second; when the silicon source is fumed silica, the fumed silica is preferably poured directly into the first mixed solution. In the invention, when the silicon source is added into the first mixed solution, the solution is preferably stirred, and the stirring mode and speed of the invention have no special requirements as long as the aim of uniform mixing is achieved.
According to the invention, the silicon source and the first mixed solution are preferably uniformly mixed, and then the high-silicon Y molecular sieve seed crystal is added. In the invention, the SiO of the high-silicon Y molecular sieve seed crystal2/Al2O3Is more than 50; the mass of the high-silicon Y molecular sieve seed crystal is preferably 1 to 10% of the total mass of silicon dioxide (mass of a silicon source is converted to mass of silicon dioxide), more preferably 2 to 7%, and even more preferably 3 to 5%. In an embodiment of the invention, the high silicon Y molecular sieve seed is commercially available from Tosoh corporation of Japan as HSZ-385 HUA. In the invention, the high-silicon Y molecular sieve seed crystal provides crystal nucleus for hydrothermal crystallization treatment,the silicon source and the aluminum source in the solution grow by taking crystal nucleus of the high-silicon Y molecular sieve seed crystal as a substrate, so that the Y molecular sieve with high silicon-aluminum ratio is grown. In the invention, the silicon source, the aluminum source and the alkali source are respectively calculated by the amounts of silicon dioxide, aluminum oxide and corresponding alkali metal oxides, and the molar ratio of the alkali metal oxide, the first template agent, the second template agent, the silicon dioxide, the aluminum oxide and the water in the second mixed solution is preferably (0.5-6): (0.01-1): (0.5-4): 10: (0.01-1): (100-500).
After the second mixed solution is obtained, the second mixed solution is subjected to aging treatment and hydrothermal crystallization treatment in sequence. In the invention, the aging treatment is preferably carried out under the condition of stirring, the stirring speed is preferably 250-750 rpm, more preferably 300-560 rpm, the stirring temperature is preferably 10-30 ℃, more preferably 20-28 ℃, and the stirring time is preferably 2-48 hours, more preferably 8-9 hours, and even more preferably 12-20 hours. In the invention, the high-silicon Y molecular sieve seed crystal is dissolved and dispersed into smaller crystal nuclei in the aging treatment process, thereby providing a substrate for the growth of the high-silicon-aluminum ratio Y molecular sieve.
In the present invention, the hydrothermal crystallization treatment preferably includes static crystallization or dynamic crystallization. In the invention, the time of the hydrothermal crystallization treatment is 8-15 days, preferably 10-13 days; the temperature of the hydrothermal crystallization treatment is 80-140 ℃, preferably 90-130 ℃, and further preferably 110-120 ℃. In the present invention, the dynamic crystallization is preferably performed in a rotary oven, and the rotation speed of the rotary oven is preferably greater than 0 and equal to or less than 80rpm, more preferably 10 to 65rpm, and even more preferably 15 to 50 rpm.
After the hydrothermal crystallization treatment, the obtained crystallization product is preferably washed and dried in sequence to obtain the Y-type molecular sieve with the high silica-alumina ratio. The invention has no special requirements for washing and drying. The crystallization product is preferably filtered before being washed, and the product obtained after filtration is preferably washed by water to remove impurities in the product. In the invention, the water washing preferably comprises soaking the crystallized product in deionized water, stirring and standing, and then centrifuging, wherein the stirring time is preferably 30-60 s, more preferably 45-60 s, and the number of water washing is preferably 3-5, specifically 3, 4, and 5.
The centrifugal drying method is used for drying the centrifuged solid, the drying temperature is preferably 50-90 ℃, more preferably 55-80 ℃, and the drying time is preferably 5-10 hours, more preferably 5-8 hours.
For further illustration of the present invention, the method for preparing the high silica alumina ratio Y-type molecular sieve provided by the present invention is described in detail below with reference to the accompanying drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1
6.495g of tetrabutylammonium hydroxide and 0.014g of tetramethylammonium hydroxide are added into 31.542g of deionized water and mixed uniformly to obtain a double template solution, wherein the mass percent concentration of the tetrabutylammonium hydroxide is 17.07%, and the mass percent concentration of the tetramethylammonium hydroxide is 0.037%. Adding 0.425g of sodium metaaluminate and 0.776g of sodium hydroxide into the double template agent solution, stirring and dissolving to obtain a first mixed solution, dropwise adding 7.510g of silica sol (content 40.0 wt.%) into the first mixed solution at a dropping speed of 1 drop/s, stirring uniformly, and finally adding 0.07g of Dongcao Y molecular Sieve (SiO)2/Al2O3115) as seed crystals to obtain a second mixed solution.
And stirring the second mixed solution at 25 ℃ for 15h, carrying out aging treatment, transferring the aged solution to a reaction kettle after the aging treatment is finished, putting the reaction kettle into a drying oven, and statically crystallizing at 100 ℃ for 8 d. Filtering the crystallized product after hydrothermal crystallization treatment, washing and centrifuging the filtered solid for 3 times, and drying at 80 ℃ for 8 hours to obtain the Y-type molecular sieve with high silica-alumina ratio.
Example 2
8.145g of tetrapropylammonium hydroxide and 0.685g of tetramethylammonium hydroxide are taken and added into 27.036g of deionized water, and the mixture is uniformly mixed to obtain a double template solution, wherein the mass percentage concentration of the tetrapropylammonium hydroxide is 22.71%, and the mass percentage concentration of the tetramethylammonium hydroxide is 1.91%. To the direction ofAdding aluminum sulfate 1.168g and potassium hydroxide 0.991g into the double template agent solution, stirring and dissolving to obtain a first mixed solution, adding fumed silica 3.004g into the first mixed solution, stirring uniformly, and finally adding 0.042g of Tosoh Y molecular Sieve (SiO)2/Al2O3115) as seed crystals to obtain a second mixed solution.
And stirring the second mixed solution at 25 ℃ for 8h, carrying out aging treatment, transferring the aged solution to a reaction kettle after the aging treatment is finished, putting the reaction kettle into a drying oven, and statically crystallizing at 120 ℃ for 10 d. Filtering the crystallized product after hydrothermal crystallization treatment, washing and centrifuging the filtered solid for 4 times, and drying at 60 ℃ for 10 hours to obtain the Y-type molecular sieve with high silica-alumina ratio.
Example 3
2.034g of tetrapropylammonium hydroxide and 0.237 g of tetramethylammonium hydroxide are added into 14.400g of deionized water and uniformly mixed to obtain a double-template solution, wherein the mass percentage concentration of the tetrapropylammonium hydroxide is 12.20%, and the mass percentage concentration of the tetramethylammonium hydroxide is 1.42%. Adding 0.340g of sodium metaaluminate and 0.460g of sodium hydroxide into the double template agent solution, stirring and dissolving to obtain a first mixed solution, dropwise adding 3.000g of silica sol (the content is 40.0 wt.%) into the first mixed solution at the dropping speed of 1 drop/s, stirring uniformly, and finally adding 0.070g of Dongcao Y molecular Sieve (SiO)2/Al2O3115) as seed crystals to obtain a second mixed solution.
And stirring the second mixed solution for 24 hours at 25 ℃, carrying out aging treatment, transferring the aged solution to a reaction kettle after the aging treatment is finished, putting the reaction kettle into a drying oven, and statically crystallizing for 9d at 140 ℃. Filtering the crystallized product after hydrothermal crystallization treatment, washing and centrifuging the filtered solid for 3 times, and drying at 65 ℃ for 9 hours to obtain the Y-type molecular sieve with high silica-alumina ratio.
The Y molecular sieve with high silica-alumina ratio obtained in the example is subjected to29Si MAS NMR analysis gave a nuclear magnetic spectrum as shown in FIG. 2, in which Q2Representing silicon and two silicon-oxygen tetrahedrons, two aluminum-oxygen tetrahedrons being joined Q3Representing silicon and three silicon-oxygen tetrahedronsA body, an alundum tetrahedron connected, Q4Representing the linkage of silicon to four silicon-oxygen tetrahedrons, the calculated silica-alumina ratio of the high silica-alumina ratio Y molecular sieve is 19.
Example 4
0.519g of tetrabutylammonium hydroxide and 0.164g of tetramethylammonium hydroxide are added into 1.8g of deionized water and mixed uniformly to obtain a double template agent solution, wherein the mass percent concentration of the tetrabutylammonium hydroxide is 20.90 percent and the mass percent concentration of the tetramethylammonium hydroxide is 6.6 percent. Adding 0.425g of sodium metaaluminate and 0.575g of sodium hydroxide into the double template agent solution, stirring and dissolving to obtain a first mixed solution, dropwise adding 3.000g of silica sol (the content is 40.0 wt.%) into the first mixed solution at the dropping speed of 2 drops/s, stirring uniformly, and finally adding 0.014g of Dongcao Y molecular Sieve (SiO)2/Al2O3115) as seed crystals to obtain a second mixed solution.
And stirring the second mixed solution for 24 hours at 25 ℃, carrying out aging treatment, transferring the aged solution to a reaction kettle after the aging treatment is finished, putting the reaction kettle into a rotary oven, and dynamically crystallizing for 8d at 140 ℃ and 60 rpm. Filtering the crystallized product after hydrothermal crystallization treatment, washing and centrifuging the filtered solid for 3 times, and drying at 80 ℃ for 8 hours to obtain the Y-type molecular sieve with high silica-alumina ratio.
Carrying out X-ray diffraction detection on the Y-type molecular sieve with the high silica-alumina ratio obtained in the embodiment 1-3 to obtain a figure 1;
scanning electron microscope detection is carried out on the Y-type molecular sieve with high silica-alumina ratio obtained in the example 2, and a graph 3 is obtained;
scanning electron microscope detection is performed on the Y-type molecular sieve with high silica-alumina ratio obtained in example 3, and fig. 4 is obtained.
The composition of the Y molecular sieve with high silicon-aluminum ratio is obtained by ICP determination examples 1-3, and the silicon-aluminum ratio is calculated; the crystallinity of the product obtained in examples 1 to 3 was obtained by analyzing the XRD spectrum using the product obtained in example 1 as a standard sample, and the specific results are shown in table 3.
Comparative examples 1 to 4 were carried out according to the method of example 1, and in comparative examples 1 to 4, the amounts of deionized water, a template agent, an aluminum source, an alkali source, a silicon source, and seed crystals were added according to the data in table 1.
TABLE 1 comparative examples 1-4 amounts of deionized water, template agent, aluminum source, alkali source, silicon source, and seed crystal
Comparative examples 1 to 4 the products prepared by the method of example 1 using the amounts of deionized water, templating agent, aluminum source, alkali source, silicon source, and seed crystal added in table 1 were in an amorphous state.
From the XRD results of comparative examples 1 to 3 in fig. 5, it can be seen that Y molecular sieve crystals cannot be obtained without adding a template or with adding only one template when seed crystals are added. From the XRD results of comparative example 4 in fig. 5, it can be seen that Y molecular sieve crystals can not be obtained either by adding the bimodal template but not adding the seed crystals during the preparation process.
Comparative examples 5 and 6 the process of example 1 was followed except that the hydrothermal crystallization temperature in comparative example 5 was 100 ℃ and the hydrothermal crystallization time was 4 d; in comparative example 6, the crystallization temperature was 160 ℃ and the crystallization time was 16 d.
From the XRD results of comparative examples 5 and 6 in fig. 5, it can be seen that the product obtained in comparative example 5 is amorphous powder, and the product obtained in comparative example 6 is a heterogeneous phase, which indicates that the crystallization time and crystallization temperature affect the structure of the molecular sieve crystals, and the Y molecular sieve with high silica-alumina ratio can be obtained within the crystallization time and crystallization temperature of the present invention.
TABLE 3 Performance parameters of examples 1-3 high silica to alumina ratio Y-type molecular sieves
According to the invention, a high-silicon Y-type molecular sieve is added under a dual-template system to serve as a seed crystal, the hydrothermal crystallization temperature is limited to 80-140 ℃, the hydrothermal crystallization time is 8-15 days, the silicon-aluminum ratio of the prepared high-silicon-aluminum ratio Y-type molecular sieve is 6-21.352, and the crystallinity is high.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. A method for preparing a Y-type molecular sieve with high silica-alumina ratio comprises the following steps:
1) mixing two organic templates with water to obtain a double-template solution, wherein the two organic templates are a first template and a second template respectively;
2) mixing the double-template agent solution obtained in the step 1) with an aluminum source and an alkali source to obtain a first mixed solution;
3) mixing the first mixed solution in the step 2) with a silicon source and a high-silicon Y molecular sieve seed crystal to obtain a second mixed solution, wherein the SiO of the high-silicon Y molecular sieve seed crystal2/Al2O3＞50；
4) Sequentially carrying out aging treatment and hydrothermal crystallization treatment on the second mixed solution in the step 3) to obtain the Y-type molecular sieve with the high silica-alumina ratio; the time of the hydrothermal crystallization treatment is 8-15 days, and the temperature of the hydrothermal crystallization treatment is 80-140 ℃.
2. The method of claim 1, wherein the first template comprises tetramethylammonium hydroxide and the second template comprises any tetraalkylammonium hydroxide other than tetramethylammonium hydroxide.
3. The method for preparing the Y-type molecular sieve with high silica-alumina ratio as claimed in claim 1 or 2, wherein the aluminum source is aluminum oxide, the alkali source is corresponding alkali metal oxide, the silicon source is silicon dioxide, and the molar ratio of the alkali metal oxide, the first template agent, the second template agent, the silicon dioxide, the aluminum oxide and the water in the second mixed solution is (0.5-6): (0.01-1): (0.5-4): 10: (0.01-1): (100-500).
4. The method for preparing the Y-type molecular sieve with high silica-alumina ratio according to claim 1, wherein the mass of the high-silica Y-type molecular sieve seed crystal is 1-10% of the total mass of the silica, calculated by silica as the silicon source.
5. The method for preparing the Y-type molecular sieve with high silica-alumina ratio according to claim 1, wherein the aging treatment is carried out under the condition of stirring, the stirring speed is 250-750 rpm, the stirring temperature is 10-30 ℃, and the stirring time is 2-48 h.
6. The method for preparing the Y-type molecular sieve with high Si/Al ratio as claimed in claim 1, wherein the hydrothermal crystallization treatment comprises static crystallization or dynamic crystallization.
7. The method for preparing the Y-type molecular sieve with high silica-alumina ratio according to claim 6, wherein the dynamic crystallization is carried out in a rotary oven, and the rotation speed of the rotary oven is more than 0 and less than or equal to 80 rpm.
8. The method for preparing the high silica to alumina ratio Y-type molecular sieve according to claim 3, wherein the aluminum source is one or more of sodium metaaluminate, aluminum hydroxide, aluminum sulfate and aluminum isopropoxide.
9. The method for preparing the Y-type molecular sieve with high silica-alumina ratio according to claim 3, wherein the alkali source is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
10. The method for preparing the Y-type molecular sieve with high silica-alumina ratio according to claim 1 or 4, wherein the silicon source is one or more of silica sol, tetraethoxysilane and gas-phase silica.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113233474A (en) * | 2021-05-31 | 2021-08-10 | 吉林大学 | Preparation method of GME molecular sieve with high silica-alumina ratio |
| CN113979444A (en) * | 2020-07-27 | 2022-01-28 | 中国石油化工股份有限公司 | Preparation method of molecular sieve with FER structure and molecular sieve with FER structure |
| CN114426285A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Direct synthesis method of Y molecular sieve with high silica-alumina ratio |
| FR3127416A1 (en) | 2021-09-29 | 2023-03-31 | IFP Energies Nouvelles | Dissolution and recrystallization process of FAU zeolite with a high Si/Al ratio |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2151739C1 (en) * | 1998-06-03 | 2000-06-27 | ООО Компания Катахим | Method of preparing high modulus type y zeolite |
| JP2003137538A (en) * | 2001-11-01 | 2003-05-14 | Catalysts & Chem Ind Co Ltd | NaY-TYPE ZEOLITE |
| US6756029B2 (en) * | 1999-08-11 | 2004-06-29 | Petroleo Brasileiro S.A.-Petrobras | Molecular sieves of faujasite structure |
| KR100809074B1 (en) * | 2006-11-08 | 2008-03-03 | 한국전력공사 | Method and apparatus for synthesizing of zeolite y with high purity by microwave heating source |
| CN101190417A (en) * | 2006-11-21 | 2008-06-04 | 中国石油化工股份有限公司 | Catalyst for preparing ethylene and propylene by catalytic cracking method |
| CN101376505A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Preparation of composite double microporous material |
-
2019
- 2019-12-31 CN CN201911420547.6A patent/CN110963502B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2151739C1 (en) * | 1998-06-03 | 2000-06-27 | ООО Компания Катахим | Method of preparing high modulus type y zeolite |
| US6756029B2 (en) * | 1999-08-11 | 2004-06-29 | Petroleo Brasileiro S.A.-Petrobras | Molecular sieves of faujasite structure |
| JP2003137538A (en) * | 2001-11-01 | 2003-05-14 | Catalysts & Chem Ind Co Ltd | NaY-TYPE ZEOLITE |
| KR100809074B1 (en) * | 2006-11-08 | 2008-03-03 | 한국전력공사 | Method and apparatus for synthesizing of zeolite y with high purity by microwave heating source |
| CN101190417A (en) * | 2006-11-21 | 2008-06-04 | 中国石油化工股份有限公司 | Catalyst for preparing ethylene and propylene by catalytic cracking method |
| CN101376505A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Preparation of composite double microporous material |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113979444A (en) * | 2020-07-27 | 2022-01-28 | 中国石油化工股份有限公司 | Preparation method of molecular sieve with FER structure and molecular sieve with FER structure |
| CN113979444B (en) * | 2020-07-27 | 2023-11-24 | 中国石油化工股份有限公司 | Preparation method of molecular sieve with FER structure and molecular sieve with FER structure |
| CN114426285A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Direct synthesis method of Y molecular sieve with high silica-alumina ratio |
| CN114426285B (en) * | 2020-10-13 | 2023-08-29 | 中国石油化工股份有限公司 | Direct synthesis method of high silicon-aluminum ratio Y molecular sieve |
| CN113233474A (en) * | 2021-05-31 | 2021-08-10 | 吉林大学 | Preparation method of GME molecular sieve with high silica-alumina ratio |
| CN113233474B (en) * | 2021-05-31 | 2022-10-28 | 吉林大学 | Preparation method of GME molecular sieve with high silica-alumina ratio |
| FR3127416A1 (en) | 2021-09-29 | 2023-03-31 | IFP Energies Nouvelles | Dissolution and recrystallization process of FAU zeolite with a high Si/Al ratio |
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