CN112939008B - Rapid synthesis method of Beta molecular sieve with controllable particle size - Google Patents

Rapid synthesis method of Beta molecular sieve with controllable particle size Download PDF

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CN112939008B
CN112939008B CN201911169395.7A CN201911169395A CN112939008B CN 112939008 B CN112939008 B CN 112939008B CN 201911169395 A CN201911169395 A CN 201911169395A CN 112939008 B CN112939008 B CN 112939008B
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刘盛林
杨传禹
赵东璞
辛文杰
王新怡
朱向学
徐龙伢
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention provides a rapid synthesis method of a Beta molecular sieve with controllable particle size. The method comprises the steps of fully mixing a silicon source, an aluminum source, an inorganic base, a microporous template agent and a crystal particle size regulator R to obtain gel, and quickly preparing Beta molecular sieves with different particle sizes through short-time hydrothermal crystallization. The synthesis process is rapid, and the crystallization is directly carried out for 30-80 hours at a proper temperature. According to the invention, the Beta molecular sieves with different particle sizes are rapidly prepared by using a cheap crystal particle size regulating agent through a one-step method, and the particle size of the product is regulated and controlled by regulating the addition amount of the crystal particle size regulating agent, so that the method is an economic and rapid method for obtaining the Beta molecular sieves with different particle sizes. In addition, the method has simple and convenient synthesis steps, is easy to industrialize, has good sample crystallinity, can meet the requirements of different reactions on different particle sizes, and increases the application range of the Beta molecular sieve.

Description

Rapid synthesis method of Beta molecular sieve with controllable particle size
Technical Field
The invention belongs to the technical field of molecular sieve synthesis, and particularly relates to a rapid synthesis method of a Beta molecular sieve with a controllable particle size.
Background
The Beta molecular sieve is a medium-pore zeolite, has a unique cage-free three-dimensional twelve-membered ring large pore channel system, and has better catalytic stability, thermal stability and hydrothermal stability. Linear channels oriented along [100] and [010] with pore size of about 0.77 x 0.67 nm; along the [001] direction is a tortuous path through the straight path, with an aperture of about 0.56 x 0.56 nm. Beta molecular sieves have wide industrial applications, mainly in the catalytic conversion of hydrocarbons, such as: alkylation of benzene with olefins (production of ethylbenzene and cumene), transalkylation of heavy aromatics, cracking of hydrocarbons, hydroisomerization, and the like.
The size of Beta molecular sieve crystal grains is an important index for controlling shape-selective performance and catalytic performance of the Beta molecular sieve, and the small-crystal Beta molecular sieve has the advantages of large external surface area, short diffusion pore channels, more orifices, high catalytic activity, strong carbon deposition resistance and excellent catalytic performance in catalytic reaction with low requirement on shape-selective performance; the large-grain Beta molecular sieve active center is mainly positioned in a pore channel, has higher shape selectivity although the catalytic activity is lower, and is commonly used for shape-selective catalytic reaction.
CN200510028773.1 discloses a method for synthesizing small-grain Beta. The small-grain Beta molecular sieve is synthesized by adopting silica sol as a silicon source, aluminate or aluminum sulfate as an aluminum source and a mixture of tetraethylammonium cation and fluoride as a template agent.
CN201810119307.1 discloses a method for synthesizing a large-particle-size Beta molecular sieve, which comprises the steps of dissolving a template agent, an inorganic base, a silicon source, an aluminum source and water together, adding one or more of promoters dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate to react to obtain a gel, carrying out pre-crystallization on the gel under a negative pressure condition to obtain a pre-crystallized sample, and carrying out crystallization, roasting, ammonium exchange and separation on the sample to obtain the large-particle-size Beta molecular sieve. However, the method is complicated to operate, harsh in conditions and not beneficial to industrial production.
The molecular sieve synthesized by the currently reported Beta molecular sieve synthesis method has single particle size distribution, an uncontrollable particle size distribution interval, and no satisfaction for different reaction requirements on different crystal grain sizes, and the preparation process is complex and tedious, and is not beneficial to industrial production. Therefore, the rapid synthesis of the Beta molecular sieve with uniform particle size and controllable particle size distribution interval in a simple preparation process is urgently needed to be developed.
Disclosure of Invention
The invention aims to provide a novel preparation method of a Beta molecular sieve with controllable particle size distribution, which has the characteristics of short crystallization time, low crystallization temperature, uniform particle size of the obtained product and controllable particle size distribution interval.
The invention mainly solves the technical problem by introducing a crystal grain size regulator into a Beta molecular sieve synthesis system.
A rapid synthesis method of a Beta molecular sieve with controllable particle size comprises the following specific steps:
silicon source, aluminum source, inorganic base and micropore template agent (TEA) + Aqueous solution), deionized water and crystal grain size regulator R are uniformly mixed, and the original molar composition isComprises the following steps: SiO 2 2 /Al 2 O 3 ＝10～1000，Na 2 O/SiO 2 ＝0.0～0.4，TEA + /SiO 2 ＝0.10～1.0，H 2 O/SiO 2 ＝5～40，R/SiO 2 0.1 to 10; the raw materials are directly crystallized at high temperature after being uniformly mixed; the product is a single crystal Beta molecular sieve with the grain diameter of 50 nm-3 um.
The high-temperature crystallization is as follows: static or dynamic crystallization is carried out at 95-150 ℃ for 20-80 h.
The dynamic crystallization treatment is carried out in a reactor of a rotary oven, and the rotating speed of the rotary oven is 10-100 revolutions per minute.
The selected silicon source is one or more of white carbon black, ethyl orthosilicate, water glass, silica sol, chromatographic silica gel and coarse-pore silica gel, and preferably, the white carbon black is the silicon source.
The aluminum source is one or more of sodium metaaluminate, aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum acetate, aluminum powder and pseudo-boehmite, and preferably, the sodium aluminate is the aluminum source;
the selected alkali source is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, and preferably, the sodium hydroxide is used as the alkali source;
the selected microporous template agent is one or more of tetraethyl ammonium hydroxide, tetraethyl ammonium bromide, tetraethyl ammonium chloride and tetraethyl ammonium fluoride, and tetraethyl ammonium hydroxide is preferred;
the alkalinity of the raw material mixture is adjusted by adding an inorganic base or a micropore template.
The selected crystal grain size regulating agent is one or more of imidazole, 2-methylimidazole, 2-chloroimidazole or 2-aminoimidazole, and the imidazole crystal grain size regulating agent is preferred. Wherein the molar ratio of the crystal grain size regulator R to the silicon source is 0.1-10: 1.
the invention can synthesize the single crystal Beta molecular sieve with the grain diameter of 50 nm-3 um by adjusting the raw material proportion and the crystallization condition, and the sample has the characteristics of short crystallization time, low crystallization temperature, high crystallinity, uniform grain diameter and controllable grain diameter distribution interval.
The invention preferably adopts the following technical scheme:
the raw materials are mixed by one of the following three methods:
1) the aluminum source, the inorganic base, the deionized water, the microporous template agent, the crystal grain size regulator and the silicon source are added into the reaction kettle slowly in turn under stirring to form a raw material mixture A, and the raw material mixture A is fully stirred to be uniformly mixed.
2) Preparing an aluminum source, partial inorganic alkali and a micropore template agent into a solution B 1 Preparing a silicon source, part of inorganic base, a micropore template agent and a crystal grain size regulator into a solution B 2 A 1 to B 1 Dropwise adding B 2 To form a solution B; fully stirring the mixture to uniformly mix the raw materials.
3) Preparing an aluminum source, partial inorganic alkali and a micropore template agent into a solution B 1 Preparing solution B from silicon source, part of inorganic alkali, micropore template agent and crystal grain size regulator 2 A 1 to B 2 Dropwise adding B 1 To form a solution C; fully stirring the mixture to uniformly mix the raw materials.
The molar composition of the raw material mixture is: SiO 2 2 /Al 2 O 3 ＝10～1000，Na 2 O/SiO 2 ＝0.0～0.4，TEA + /SiO 2 ＝0.10～1.0，H 2 O/SiO 2 ＝5～40，R/SiO 2 ＝0.1～10。
(II) hydrothermal crystallization
1) And (3) statically or dynamically crystallizing the A, B or C solution after being uniformly stirred at the temperature of 95-150 ℃ for 20-80 h, and synthesizing the Beta molecular sieve by hydrothermal crystallization, wherein the dynamic crystallization treatment is carried out in a reactor of a rotary oven, and the rotating speed of the rotary oven is 10-100 revolutions per minute.
2) Quenching the reaction kettle by using tap water, carrying out solid-liquid separation on the product, and filtering, washing and drying the solid product to obtain the Beta molecular sieve.
By adjusting the raw material proportion and the crystallization conditions, the Beta molecular sieve which has uniform particle size and is controllable within the range of 50 nm-3 um can be quickly synthesized. The Beta molecular sieve with uniform particle size and controllable particle size within the range of 50 nm-3 um is used for alkylation of benzene and olefin, transalkylation of heavy aromatic hydrocarbon, cracking of hydrocarbon, hydroisomerization and amination of isobutene.
Through ion exchange technology, other cations can be used for replacing sodium ions in the Beta molecular sieve synthesized by the method, so that hydrogen type, ammonium type, gallium type, zinc type and magnesium type Beta molecular sieves are obtained and are further applied to different catalytic reaction processes. The Beta molecular sieve synthesized by the method can be used for alkylation of benzene and olefin (production of ethylbenzene and cumene), transalkylation of heavy aromatics, cracking of hydrocarbons, hydroisomerization, amination of isobutene and the like.
The invention has the beneficial effects that:
according to the invention, one or more of cheap imidazole, 2-methylimidazole, 2-chloroimidazole or 2-aminoimidazole is/are used as a crystal grain size regulating agent, the Beta molecular sieve with uniform grain size and controllable grain size distribution interval is obtained through short-time hydrothermal crystallization, and the method is an economic, efficient and simple preparation method and is expected to realize large-scale commercial production.
Drawings
FIG. 1 is an SEM image of Beta molecular sieves samples prepared in examples 1, 2, 3 and comparative example 1.
FIG. 2 is an XRD spectrum of a Beta molecular sieve sample prepared in examples 1, 2, 3 and comparative example 1.
FIG. 3 is a graph showing the crystallization profiles of the Beta molecular sieves of example 1 and comparative example 1.
Detailed Description
The present invention will be further described with reference to the following examples, which are not intended to limit the scope of the present invention.
Example 1
Under stirring, 4.22g of white carbon black (95.0 wt.% SiO) 2 ，5.0wt.％H 2 O), 0.32g sodium metaaluminate (49.0 wt.% Al) 2 O 3 ，38.0wt.％Na 2 O，13.0wt.％H 2 O), 0.10g of sodium hydroxide (96.0 wt.% NaOH), 17.84g of tetraethylammonium hydroxide aqueous solution (TEAOH, purity not less than 35 wt.%), 2.29g of imidazole (IMD, not less than 99 wt.%), 7.37g of deionized water were added to the reaction kettle in the manner of mixing the raw materials of the above 1). The molar composition of the raw material mixture is: SiO 2 2 /Al 2 O 3 ＝43.5，Na 2 O/SiO 2 ＝0.048，TEA + /SiO 2 ＝0.636，IMD/SiO 2 ＝0.5，H 2 O/SiO 2 16. Stirring for 30min to mix thoroughly, and sealing the synthesis kettle. Directly carrying out static crystallization at 140 ℃ for 0-72 h. The reaction was quenched with tap water and centrifuged to obtain a solid product. Then washing with deionized water to neutrality. Drying at 120 ℃ overnight to obtain molecular sieve raw powder. The powder X-ray diffraction pattern of the molecular sieve raw powder obtained by crystallization for 72h is shown in figure 1. As can be seen from the figure, it is a pure phase Beta molecular sieve and has good crystallinity. The SEM image of the resulting Beta product is shown in FIG. 2, where it is seen that the sample is uniform in size, about 80 nm.
Example 2
In example 1, the amount of imidazole added was changed to 13.74g so that the molar composition of the raw material mixture was: SiO 2 2 /Al 2 O 3 ＝43.5，Na 2 O/SiO 2 ＝0.048，TEA + /SiO 2 ＝0.636，IMD/SiO 2 ＝2.0，H 2 O/SiO 2 16. Other conditions were unchanged. The powder X-ray diffraction pattern of the molecular sieve raw powder obtained by crystallizing for 72h is shown in figure 1, and as can be seen from the pattern, the molecular sieve raw powder is a pure-phase Beta molecular sieve and has good crystallinity. The SEM image of the resulting Beta product is shown in FIG. 2, where it is seen that the sample is uniform in size, approximately 200 nm.
Example 3
In example 1, the amount of imidazole added was changed to 18.34g so that the molar composition of the raw material mixture was: SiO 2 2 /Al 2 O 3 ＝43.5，Na 2 O/SiO 2 ＝0.048，TEA + /SiO 2 ＝0.636，IMD/SiO 2 ＝4.0，H 2 O/SiO 2 16. Other conditions were unchanged. The powder X-ray diffraction pattern of the molecular sieve raw powder obtained by crystallizing for 72h is shown in figure 1, and as can be seen from the pattern, the molecular sieve raw powder is a pure-phase Beta molecular sieve and has good crystallinity. The SEM image of the resulting Beta product is shown in FIG. 2, where it is seen that the sample is uniform in particle size, about 500nm in size.
Comparative example 1
In example 1, no imidazole was added, so that the molar composition of the starting mixture was: siO 2 /Al 2 O 3 ＝43.5，Na 2 O/SiO 2 ＝0.048，TEA + /SiO 2 ＝0.636，H 2 O/SiO 2 Other conditions were unchanged at 16. Directly carrying out static crystallization at 140 ℃ for 0-160 h. The reaction was quenched with tap water and centrifuged to obtain a solid product. Then washing with deionized water to neutrality. Drying at 120 ℃ overnight to obtain molecular sieve raw powder. The change curve of the crystallinity of the crystallized product along with the crystallization time is shown in fig. 3, and the crystallization takes at least 112 hours for the complete crystallization, and compared with example 1, the crystallization speed is slower. The powder X-ray diffraction pattern of the molecular sieve raw powder obtained by crystallizing 120h is shown in figure 1, and as can be seen from the pattern, the molecular sieve raw powder is a pure-phase Beta molecular sieve and has good crystallinity. The SEM of the resulting Beta product is shown in FIG. 2, where it is seen that the sample has a particle size of about 300nm and is not uniform in size.
Example 4
Under the condition of stirring, 17.4g of tetraethoxysilane (more than or equal to 99 wt.%), 0.2g of aluminum chloride (more than or equal to 99 wt.%), 2.7g of sodium hydroxide, 24.5g of tetraethylammonium hydroxide aqueous solution and 6.8g of 2-methylimidazole (2-MI, more than or equal to 99 wt.%) are added into the reaction kettle according to the mixing mode of the raw materials of the type 2). The molar composition of the raw material mixture is: SiO 2 2 /Al 2 O 3 ＝200，Na 2 O/SiO 2 ＝0.4，TEA + /SiO 2 ＝0.7，2-MI/SiO 2 ＝1.0，H 2 O/SiO 2 30. Stirring for 30min to mix thoroughly, and sealing the synthesis kettle. Directly dynamically crystallizing at 120 ℃ (80 r/min) for 60 h. The reaction was quenched with tap water and centrifuged to obtain a solid product. Then washing with deionized water to neutrality. Drying at 80 ℃ overnight to obtain molecular sieve raw powder. The XRD spectrum of the Beta product is similar to that of figure 1, and the particle size of the sample is uniform and is about 40 nm.
Example 5
In example 4, the amount of 2-methylimidazole added was changed to 34g so that the molar composition of the raw material mixture was: SiO 2 2 /Al 2 O 3 ＝200，Na 2 O/SiO 2 ＝0.4，TEA + /SiO 2 ＝0.7，2-MI/SiO 2 ＝5.0，H 2 O/SiO 2 30. Other conditions were unchanged. The powder X-ray diffraction pattern of the molecular sieve raw powder obtained after 60 hours of crystallization is similar to that of figure 1, and the sample has uniform grain diameter of about 300 nm.
Example 6
In example 4, the amount of 2-methylimidazole added was changed to 54g so that the molar composition of the raw material mixture was: SiO 2 2 /Al 2 O 3 ＝200，Na 2 O/SiO 2 ＝0.4，TEA + /SiO 2 ＝0.7，2-MI/SiO 2 ＝8.0，H 2 O/SiO 2 30. Other conditions were unchanged. The powder X-ray diffraction pattern of the molecular sieve raw powder obtained by crystallization for 60 hours is similar to that of figure 1, and the sample has uniform grain diameter of about 600nm
Comparative example 2
In example 4, 2-methylimidazole was not added, and the molar composition of the starting mixture was: SiO 2 2 /Al 2 O 3 ＝200，Na 2 O/SiO 2 ＝0.4，TEA + /SiO 2 ＝0.7，H 2 O/SiO 2 30. Other conditions were unchanged. The powder X-ray diffraction pattern of the molecular sieve raw powder obtained by crystallization for 130h is similar to that of FIG. 1, and the sample has a particle size of about 260nm and is not uniform in size.
Example 7
19.6g of silica sol (25.5 wt.% SiO) were mixed with stirring 2 ，74.5wt.％H 2 O), 2.9g of aluminum nitrate (more than or equal to 99 wt.%), 0.69g of sodium hydroxide, 5g of tetraethylammonium bromide 1.67(TEABr, purity more than or equal to 98 wt.%), 2.4g of 2-chloroimidazole (CMI, more than or equal to 99 wt.%), 34g of deionized water are added into the reaction kettle according to the raw material mixing mode of the 3 rd raw material. The molar composition of the raw material mixture is: SiO 2 2 /Al 2 O 3 ＝87，Na 2 O/SiO 2 ＝0.1，TEA + /SiO 2 ＝0.3，CMI/SiO 2 ＝0.1，H 2 O/SiO 2 40. Stirring for 30min to mix thoroughly, and sealing the synthesis kettle. Directly dynamically (10 r/min) crystallizing at 140 ℃ for 50 h. The reaction was quenched with tap water and centrifuged to obtain a solid product. Then washing with deionized water to neutrality. Drying at 80 ℃ overnight to obtain molecular sieve raw powder. XRD spectrogram and pattern of Beta productSimilar to 1, the sample has uniform particle size of about 200nm
Example 8
In example 7, the amount of 2-chloroimidazole added was changed to 24g so that the molar composition of the raw material mixture was: SiO 2 2 /Al 2 O 3 ＝87，Na 2 O/SiO 2 ＝0.1，TEA + /SiO 2 ＝0.1，CMI/SiO 2 ＝3.0，H 2 O/SiO 2 40. Other conditions were unchanged. The powder X-ray diffraction pattern of the molecular sieve raw powder obtained after 50h of crystallization is similar to that of figure 1, and the sample has uniform grain diameter which is about 900 nm.
Example 9
In example 7, the amount of 2-chloroimidazole added was changed to 48g so that the molar composition of the raw material mixture was: SiO 2 2 /Al 2 O 3 ＝87，Na 2 O/SiO 2 ＝0.1，TEA + /SiO 2 ＝0.1，CMI/SiO 2 ＝6.0，H 2 O/SiO 2 40. Other conditions were unchanged. The powder X-ray diffraction pattern of the molecular sieve raw powder obtained after 50h of crystallization is similar to that of figure 1, and the sample has uniform grain diameter which is about 2 um.
Comparative example 3
In example 7, 2-chloroimidazole was not added, so that the molar composition of the starting mixture was: SiO 2 2 /Al 2 O 3 ＝87，Na 2 O/SiO 2 ＝0.1，TEA + /SiO 2 ＝0.1，H 2 O/SiO 2 Other conditions were unchanged at 40. The powder X-ray diffraction pattern of the molecular sieve raw powder obtained by 100h crystallization is similar to that of FIG. 1, and the sample has a particle size of about 500nm and is not uniform in size.
Example 10
Under stirring, 5.1g of chromatography silica gel (98.0 wt.% SiO) 2 ，2.0wt.％H 2 O), 0.03g of pseudoboehmite (69 wt.% SiO) 2 ，31wt.％H 2 O), 2.3g potassium carbonate (more than or equal to 98 wt.%), 4.4g tetraethyl ammonium fluoride (more than or equal to 98 wt.%), 3.2g 2-aminoimidazole (AMI, more than or equal to 99 wt.%), and 15g deionized water are added into the reaction kettle according to the mixing mode of the raw materials of the type 1). The molar composition of the raw material mixture is: SiO 2 2 /Al 2 O 3 ＝400，K 2 CO 3 /SiO 2 ＝0.2，TEA + /SiO 2 ＝0.3，AMI/SiO 2 ＝0.3，H 2 O/SiO 2 10. Stirring for 30min to mix thoroughly, and sealing the synthesis kettle. Directly carrying out dynamic crystallization (20 r/min) at 150 ℃ for 48 h. The reaction was quenched with tap water and centrifuged to obtain a solid product. Then washing with deionized water to neutrality. Drying at 80 ℃ overnight to obtain molecular sieve raw powder. The XRD spectrum of the Beta product is similar to that of figure 1, and the sample has uniform grain diameter of about 60 nm.
Example 11
In example 10, the amount of 2-aminoimidazole added was changed to 19.2g so that the molar composition of the raw material mixture was: SiO 2 2 /Al 2 O 3 ＝400，K 2 CO 3 /SiO 2 ＝0.2，TEA + /SiO 2 ＝0.3，AMI/SiO 2 ＝3.0，H 2 O/SiO 2 10. Other conditions were unchanged. The powder X-ray diffraction pattern of the molecular sieve raw powder obtained by crystallization for 48 hours is similar to that of figure 1, and the sample has uniform grain diameter of about 500 nm.
Example 12
In example 10, the amount of 2-aminoimidazole added was changed to 32g so that the molar composition of the raw material mixture was: SiO 2 2 /Al 2 O 3 ＝400，K 2 CO 3 /SiO 2 ＝0.2，TEA + /SiO 2 ＝0.3，AMI/SiO 2 ＝5.0，H 2 O/SiO 2 10. Other conditions were unchanged. The powder X-ray diffraction pattern of the molecular sieve raw powder obtained by crystallization for 48 hours is similar to that of figure 1, and the sample has uniform grain diameter which is about 1 um.
Comparative example 4
In example 10, 2-aminoimidazole was not added, so that the molar composition of the starting mixture was: SiO 2 2 /Al 2 O 3 ＝400，K 2 CO 3 /SiO 2 ＝0.2，TEA + /SiO 2 ＝0.3，H 2 O/SiO 2 10. Other conditions were not changed. The powder X-ray diffraction pattern of the molecular sieve raw powder obtained by crystallization for 110h is similar to that of FIG. 1, and the sample has a particle size of about 200nm and is not uniform in size.

Claims (4)

1. A method for quickly synthesizing a Beta molecular sieve with a controllable particle size is characterized by comprising the following steps: uniformly mixing raw materials including a silicon source, an aluminum source, inorganic base, a microporous template agent, deionized water and a crystal particle size regulator R, wherein the raw materials comprise the following raw materials in mole: SiO 2 2 /Al 2 O 3 =10~1000，Na 2 O/SiO 2 =0.0~0.4，TEA + /SiO 2 =0.10~1.0，H 2 O/SiO 2 =5~40，R/SiO 2 = 0.1-10; the raw materials are directly crystallized at high temperature after being uniformly mixed; carrying out solid-liquid separation on the product, and filtering, washing and drying the solid product to obtain the single crystal Beta molecular sieve with the particle size of 50 nm-3 um; the selected crystal particle size regulating agent R is one or more of imidazole, 2-methylimidazole, 2-chloroimidazole or 2-aminoimidazole, wherein the molar ratio of the crystal particle size regulating agent R to the silicon source is 0.1-10: 1, high-temperature crystallization: 95 to 150 g o And C, performing dynamic or static crystallization for 20-80 h, wherein the dynamic crystallization treatment is performed in a reactor of a rotary oven, and the rotating speed of the rotary oven is 10-100 r/min.
2. The method for rapidly synthesizing the Beta molecular sieve with controllable particle size according to claim 1, wherein the method comprises the following steps: the silicon source is one or more of white carbon black, ethyl orthosilicate, water glass, silica sol, chromatographic silica gel or coarse-pore silica gel;
the aluminum source is one or more of sodium metaaluminate, aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum acetate, aluminum powder or pseudo-boehmite;
the inorganic alkali source is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.
3. The method for rapidly synthesizing the Beta molecular sieve with controllable particle size according to claim 1, wherein the method comprises the following steps: the selected microporous template agent is one or more of tetraethylammonium hydroxide, tetraethylammonium bromide, tetraethylammonium chloride or tetraethylammonium fluoride.
4. The method for rapidly synthesizing the Beta molecular sieve with controllable particle size according to claim 1, wherein the method comprises the following steps: the raw materials are uniformly mixed by adopting one of the following three methods:
1) slowly adding an aluminum source, inorganic base, deionized water, a microporous template agent, a crystal particle size regulator and a silicon source into a reaction kettle in sequence under stirring to form a raw material mixture A, and fully stirring to uniformly mix the raw material mixture A;
2) preparing an aluminum source, part of inorganic base and a micropore template agent into a solution B1, preparing a silicon source, part of inorganic base, a micropore template agent and a crystal particle size regulator into a solution B2, and dropwise adding B1 into B2 to form a solution B; fully stirring to uniformly mix the raw materials;
3) preparing an aluminum source, part of inorganic base and a micropore template agent into a solution B1, preparing a silicon source, part of inorganic base, a micropore template agent and a crystal particle size regulator into a solution B2, and dropwise adding B2 into B1 to form a solution C; fully stirring the mixture to uniformly mix the raw materials.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005537229A (en) * 2002-05-03 2005-12-08 アベンティス・ファーマ・ドイチユラント・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング Optically active β-aminoketone, optically active 1,3-aminoalcohol, and production method thereof
CN104261423A (en) * 2014-09-29 2015-01-07 吉林大学 Preparation method of single crystal hierarchical porous Beta molecular sieve
CN108217675A (en) * 2018-01-26 2018-06-29 中国科学院大连化学物理研究所 A kind of preparation method of hollow monocrystalline Beta molecular sieves
CN108217684A (en) * 2018-02-11 2018-06-29 中国科学院大连化学物理研究所 A kind of method for promoting Beta Zeolite synthesis
CN109759127A (en) * 2019-02-27 2019-05-17 中国科学院大连化学物理研究所 A kind of preparation method for isobutene and the hollow monocrystalline Beta molecular sieve catalyst of benzene liquid-phase alkylation
CN110372003A (en) * 2019-08-22 2019-10-25 正大能源材料(大连)有限公司 A kind of preparation method of big partial size Beta molecular sieve

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005537229A (en) * 2002-05-03 2005-12-08 アベンティス・ファーマ・ドイチユラント・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング Optically active β-aminoketone, optically active 1,3-aminoalcohol, and production method thereof
CN104261423A (en) * 2014-09-29 2015-01-07 吉林大学 Preparation method of single crystal hierarchical porous Beta molecular sieve
CN108217675A (en) * 2018-01-26 2018-06-29 中国科学院大连化学物理研究所 A kind of preparation method of hollow monocrystalline Beta molecular sieves
CN108217684A (en) * 2018-02-11 2018-06-29 中国科学院大连化学物理研究所 A kind of method for promoting Beta Zeolite synthesis
CN109759127A (en) * 2019-02-27 2019-05-17 中国科学院大连化学物理研究所 A kind of preparation method for isobutene and the hollow monocrystalline Beta molecular sieve catalyst of benzene liquid-phase alkylation
CN110372003A (en) * 2019-08-22 2019-10-25 正大能源材料(大连)有限公司 A kind of preparation method of big partial size Beta molecular sieve

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