CN115974098A - Preparation method of ultra-small nano T-type zeolite molecular sieve - Google Patents
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- 239000010457 zeolite Substances 0.000 title claims abstract description 65
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 62
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 61
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000002425 crystallisation Methods 0.000 claims abstract description 35
- 230000008025 crystallization Effects 0.000 claims abstract description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 28
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 21
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- 239000012670 alkaline solution Substances 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 239000003517 fume Substances 0.000 claims description 6
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical group O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
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- 229910052782 aluminium Inorganic materials 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 abstract description 4
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- 238000010899 nucleation Methods 0.000 abstract description 2
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- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052663 cancrinite Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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Abstract
The invention provides a preparation method of an ultra-small nanometer T-shaped zeolite molecular sieve, belonging to the technical field of molecular sieve synthesis. The method uses aluminum powder as an aluminum source, gradually dissolves the aluminum powder into a sodium hydroxide solution at a high temperature, and stirs the aluminum powder until the aluminum powder is clear and is used as solution A; respectively dissolving an alkali source, TMAOH and a silicon source at low temperature, continuously and mechanically taking the solution A as a solution B, dropwise adding the solution A into the solution B, stirring, transferring the solution A into a water bath kettle, aging, and standing in a reaction kettle for crystallization; and washing with deionized water until the pH value is neutral, collecting solids, drying, grinding and calcining to obtain the T-type zeolite molecular sieve. The invention only uses a small amount of expensive organic template agent, thus greatly reducing the production cost; the sodium aluminate prepared by using the aluminum powder dissolved alkali liquor has better dispersibility, and the low-temperature crystallization is more favorable for controlling the uniform nucleation of the system, so that the size of the obtained T-shaped molecular sieve is more uniform.
Description
Technical Field
The invention belongs to the technical field of molecular sieve materials, and relates to a preparation method of an ultra-small nanometer T-type zeolite molecular sieve.
Background
Zeolite molecular sieves are a class of aluminosilicate structures having a regular pore structure TO share a T atom of TO 4 Tetrahedron is the basic unit of zeolite molecular sieve skeleton, and when T atoms are different, i.e. silicon atom, aluminum atom or phosphorus atom, the tetrahedron can form different structures through bridging connection of oxygen atomsThe basic units with different structures are connected through oxygen bridges to form multi-membered rings and cages with different structures, the multi-membered rings are secondary structural units, the cages are main structural units, and the same or different cage structural units are connected through oxygen atoms to form various zeolite molecular sieve structures. The zeolite molecular sieve has regular pore channels, unique ion exchange performance, adjustable adsorption performance, better hydrothermal and thermal stability and certain acidity, thereby being widely applied to the fields of petrochemical industry, fine chemical industry, pharmaceutical chemical industry, daily chemical industry, new energy and the like as an excellent catalytic material, an adsorption material and an ion exchange material.
The T-type zeolite is a symbiotic crystal formed by the intergrowth of offretite and erionite, wherein the content of the erionite is lower and is about 3-40%. The offretite and erionite are two kinds of different zeolites formed by different spatial interaction sequences of cancrinite cages and hexagonal prisms, and the difference of the spatial interaction sequences ensures that the framework structure of the offretite presents a pore channel consisting of eight-membered rings and twelve-membered rings, while the framework structure of the erionite consists of all eight-membered ring pore channels. The pore diameters of the twelve-membered ring and the eight-membered ring in the offretite are 0.67nm multiplied by 0.68nm and 0.36nm multiplied by 0.49nm respectively, and the pore diameter of the erionite is 0.36nm multiplied by 0.51nm. In the process of the intergrowth of the offretite and the erionite, the twisting growth of Mao Fei gabions causes the twelve-membered ring straight channels of the offretite to be blocked. The T-type zeolite has a shape selective effective pore size of 0.36nm × 0.51nm. The properties exhibited by type T zeolites are also similar to erionite. The silicon-aluminum ratio in the framework structure of the zeolite molecular sieve directly influences the hydrophilicity and hydrophobicity and the acid resistance of the zeolite, the silicon-aluminum ratio of the T-type zeolite molecular sieve is 3-4, the hydrophilicity and the acid resistance are considered, and the application range of the T-type zeolite molecular sieve is greatly widened.
At present, the T-type zeolite molecular sieve is prepared by a hydrothermal method at the earliest time and is the most conventional and widely applied method at present. The hydrothermal method is to age the synthesis solution and then put the solution into a reaction kettle, and heat the solution to a required temperature through an oven, and the synthesis is usually completed under a static condition. In hydrothermal reactions, water plays an important role in promoting chemical reactions, transferring pressure, acting as a reaction medium, changing the physicochemical properties of reagents or products. The crystallization starting temperature and the reaction completion time of the T-type zeolite are the most critical parameters of a hydrothermal method, the nano-scale T-type zeolite molecular sieve can be successfully synthesized by the hydrothermal method, and the product yield is over eighty eight percent. The hydrothermal synthesis of the nano-sized T-type zeolite molecular sieve requires the use of a large amount of organic template, although the use of the template promotes the synthesis and development of zeolite materials, the industrial process of the zeolite molecular sieve is hindered, and the research on the synthesis of the zeolite molecular sieve by using the environment-friendly template and the development of a template-free synthesis method are of great significance for protecting the environment and promoting the industrial development of the molecular sieve. Therefore, the ultra-small nanometer T-shaped zeolite molecular sieve is prepared by adopting aluminum powder as an aluminum source, and the using amount of the template agent is reduced.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of an ultra-small nano T-type zeolite molecular sieve, which effectively reduces the usage amount of a template agent and greatly reduces the production cost. In order to optimize the molecular sieve in size, the preparation conditions are optimized to obtain the nano-scale T-type zeolite molecular sieve.
The technical scheme adopted by the invention is as follows:
a preparation method of an ultra-small nanometer T-type zeolite molecular sieve comprises the following steps:
step 1, preparing a solution A
Firstly, dispersing sodium hydroxide in deionized water to obtain an alkaline solution, heating the solution to 60-80 ℃ in a hydrothermal pot, then adding aluminum powder into an alkali liquor in batches, and stirring the solution until the solution is clear to obtain a solution A for later use.
The aluminum powder is used as an aluminum source and reacts with the alkali source to prepare the sodium aluminate, so that the sodium aluminate has better dispersibility and is beneficial to the subsequent preparation of the T-type zeolite molecular sieve synthetic fluid of a uniform nucleation system.
Step 2, preparing solution B
Dissolving an alkali source in deionized water in a low-temperature constant-temperature tank at 2-6 ℃ to obtain an alkali liquor, sequentially adding a template agent and a silicon source into the alkali liquor, and mechanically stirring and aging for 2-4h at 2-6 ℃ to prepare a gel liquid system serving as a solution B. The silicon source is silica sol, the alkali source is potassium hydroxide, and the template agent is TMAOH. The mass of the deionized water used in the step 2 is the same as that of the deionized water used in the step 1.
Step 3, mixing the solution A and the solution B
The clear solution a was added dropwise to solution B. Mechanically stirring the mixture in a low-temperature constant-temperature tank at the temperature of 2-6 ℃ to synthesize gel for 2-4h, then transferring the gel into a constant-temperature water bath kettle at the temperature of 20-30 ℃, stirring and aging for 12-24h to obtain stable SiO 2 -Al 2 O 3 -Na 2 O-K 2 O-TMAOH-H 2 O-gel liquid system. The low temperature condition in the invention is beneficial to inhibiting the polymerization of aluminate particles and silicate particles, obtaining more uniform precursor particles and being beneficial to preparing the T-type zeolite molecular sieve with smaller size.
The SiO 2 -Al 2 O 3 -Na 2 O-K 2 O-TMAOH-H 2 In the O gel liquid system, the molar ratio of each component is as follows: siO 2 2 ：Al 2 O 3 ：Na 2 O：K 2 O：TMAOH：H 2 O＝1：(0.065-0.095)：0.265：(0.072-0.09)：0.060：13.251。
Step 4, synthetic liquid crystallization
And (3) transferring the gel liquid system obtained in the step (3) into a reaction kettle, sealing, and performing crystallization reaction to obtain a synthetic liquid, wherein the crystallization temperature is 60-100 ℃, and the crystallization time is 48 hours.
The lower crystallization temperature in the invention can adjust the growth speed of the T-type zeolite molecular sieve, thereby regulating and controlling the size of the prepared T-type zeolite molecular sieve.
And adding deionized water into the synthetic liquid obtained by crystallization reaction, carrying out centrifugal washing until the synthetic liquid is neutral, drying and grinding the obtained product, and then placing the product in a muffle furnace to calcine and remove the template agent to finally obtain the T-type zeolite molecular sieve.
Further, in the step 1, the whole preparation process of the solution a needs to be carried out in a fume hood, after sodium hydroxide is dissolved in deionized water, the solution is heated to 60 ℃ to 80 ℃ in a water bath under stirring, then the weighed aluminum powder is added in a small amount in batches under the condition that the fume hood is operated, and the next batch can be added after the aluminum powder is completely dissolved.
Further, in the step 3, magnetic stirring is adopted in the aging process.
Further, in the step 4, the crystallization mode is microwave-assisted crystallization or standing hydrothermal crystallization, and preferably standing hydrothermal crystallization.
Further, in the step 5, the centrifugal washing process is to use a centrifuge to take the supernatant at a low rotation speed, and then take the precipitate from the supernatant at a high rotation speed; the obtained precipitate is placed in a muffle furnace after being centrifugally dried and ground, and is heated to 550 ℃ by program and calcined for 6h, and then the temperature is reduced to 25 ℃ by program so as to remove the template agent.
Further, in the step 5, the low rotating speed is 5000-6000r/min; the high rotating speed is 11000r/min. The heating/cooling rate is 1 ℃/min.
The invention has the beneficial effects that:
(1) The method uses aluminum powder as an aluminum source to prepare sodium aluminate with better dispersibility, and obtains the ultra-small nano T-type zeolite molecular sieve at a low crystallization temperature. The invention obtains more uniform precursor particles by utilizing low-temperature conditions. The invention avoids using a large amount of expensive organic template agent to control the size of the traditional method, greatly reduces the preparation cost of the zeolite molecular sieve, has high repetition rate and short preparation period, and has important industrial prospect and practical significance.
(2) The T-type zeolite molecular sieve prepared by the invention has small particle size and uniform particles, and is easy to form a uniform seed crystal layer with high density on a porous carrier, and the uniform zeolite molecular sieve film is synthesized by taking the seed crystal layer as an induction.
(3) The advantages of the T-type zeolite molecular sieve prepared by the invention in size enable the T-type zeolite molecular sieve to have stronger competitiveness in chemical processes such as catalysis, adsorption and the like.
(4) The T-type zeolite molecular sieve prepared by the invention is a pure-phase T-type zeolite molecular sieve and does not contain other crystal impurities.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of the ultra-small nano T-type zeolite molecular sieve synthesized in example 1;
FIG. 2 is the X-ray diffraction (XRD) pattern of the ultra-small nanometer zeolite T-type molecular sieve synthesized in example 1, wherein (a) is OFF characteristic peak and (b) is T-type zeolite molecular sieve characteristic peak;
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1
A preparation method of an ultra-small nanometer T-type zeolite molecular sieve comprises the following steps:
(1) Adding 3.25g of sodium hydroxide into a beaker, dispersing the sodium hydroxide in 9.74g of deionized water to obtain an alkaline solution, heating the alkaline solution to 80 ℃ in a hydrothermal pot, adding 0.55g of aluminum powder into an alkali liquor in batches, and stirring the solution until the solution is clear to obtain a solution A for later use, wherein the whole preparation process of the solution A needs to be carried out in a fume hood.
(2) Dissolving 2.12g of potassium hydroxide in 9.74g of deionized water in a low-temperature constant-temperature tank at 2 ℃ to obtain an alkali liquor, sequentially adding 4.64g of TMAOH and 23.20g of silica sol into the alkali liquor, and mechanically stirring and aging at 2 ℃ for 4 hours to prepare a solution B.
(3) Dropwise adding the clear solution A into the solution B, mechanically stirring at 2 deg.C in a low-temperature thermostatic bath to synthesize gel for 4h, and magnetically stirring and aging in a constant-temperature water bath at 20 deg.C for 12h to obtain stable SiO 2 -Al 2 O 3 -Na 2 O-K 2 O-TMAOH-H 2 O-gel liquid system. Wherein, siO 2 -Al 2 O 3 -Na 2 O-K 2 O-TMAOH-H 2 The O gel liquid system comprises the following components in a molar ratio: siO 2 2 ：Al 2 O 3 ：Na 2 O：K 2 O：TMAOH：H 2 O＝1：0.065：0.265：0.090：0.060：13.251。
(4) And (4) transferring the gel liquid system obtained in the step (3) into a reaction kettle, sealing, and then carrying out crystallization reaction to obtain a synthetic liquid, wherein the crystallization mode is standing hydrothermal crystallization, and the crystallization temperature is 60 ℃, and the crystallization time is 48 hours.
(5) Adding deionized water into the synthetic liquid obtained by crystallization, carrying out centrifugal washing until the synthetic liquid is neutral, drying and grinding the obtained product, then placing the product in a muffle furnace, heating from 25 ℃ to 550 ℃ at 1 ℃/min, calcining for 6h, cooling to 25 ℃ at 1 ℃/min, removing a template agent to obtain the T-type zeolite molecular sieve, wherein the centrifugal washing process is to use a centrifuge to obtain a supernatant at a low rotation speed of 5000r/min, and then taking a precipitate from the supernatant at a high rotation speed of 11000r/min.
As can be seen from fig. 1 and 2, the T-type zeolite molecular sieve can be prepared by using aluminum powder as an aluminum source, and the T-type zeolite molecular sieve prepared by using aluminum powder as an aluminum source has a weaker characteristic peak and a smaller size of about 20nm, which confirms the function of aluminum powder as an aluminum source in controlling the size of the zeolite molecular sieve.
Example 2
A preparation method of an ultra-small nanometer T-type zeolite molecular sieve comprises the following steps:
(1) Adding 2.60g of sodium hydroxide into a beaker, dispersing the sodium hydroxide in 7.75g of deionized water to obtain an alkaline solution, heating the alkaline solution to 70 ℃ in a hydrothermal pot, adding 0.55g of aluminum powder into an alkali liquor in batches, and stirring the solution until the solution is clear to obtain a solution A for later use, wherein the whole preparation process of the solution A needs to be carried out in a fume hood.
(2) In a low-temperature constant-temperature tank at 4 ℃, 1.43g of potassium hydroxide is firstly dissolved in 7.75g of deionized water to obtain an alkali liquor, then 3.71g of TMAOH and 18.56g of silica sol are sequentially added into the alkali liquor, and the mixture is mechanically stirred and aged for 3 hours at 4 ℃ to prepare a solution B.
(3) Dropwise adding the clear solution A into the solution B, mechanically stirring at 4 deg.C in a low-temperature thermostatic bath to synthesize gel liquid for 3h, transferring into a 25 deg.C thermostatic water bath, magnetically stirring and aging for 18h to obtain stable SiO 2 -Al 2 O 3 -Na 2 O-K 2 O-TMAOH-H 2 O-gel liquid system. Wherein, siO 2 -Al 2 O 3 -Na 2 O-K 2 O-TMAOH-H 2 Groups in O-gel liquid SystemThe molar ratio is as follows: siO 2 2 ：Al 2 O 3 ：Na 2 O：K 2 O：TMAOH：H 2 O＝1：0.085：0.265：0.082：0.060：13.251。
(4) And (4) transferring the gel liquid system obtained in the step (3) into a reaction kettle, sealing, and performing crystallization reaction to obtain a synthetic liquid, wherein the crystallization mode is standing hydrothermal crystallization, and the crystallization temperature is 80 ℃ and the crystallization time is 48 hours.
(5) Adding deionized water into the synthetic liquid obtained by crystallization, carrying out centrifugal washing to neutrality, drying and grinding the obtained product, then placing the product in a muffle furnace, heating from 25 ℃ to 550 ℃ at 1 ℃/min, calcining for 6h, then cooling to 25 ℃ at 1 ℃/min, removing a template agent to obtain the T-type zeolite molecular sieve, wherein the centrifugal washing process is to obtain a supernatant at a low rotating speed of 5500r/min by using a centrifugal machine, and then taking a precipitate at a high rotating speed of 11000r/min from the supernatant.
XRD (X-ray diffraction) characterization shows that the prepared T-type zeolite molecular sieve is a pure-phase T-type zeolite molecular sieve.
Example 3
A preparation method of an ultra-small nanometer T-type zeolite molecular sieve comprises the following steps:
(1) Adding 2.16g of sodium hydroxide into a beaker, dispersing the sodium hydroxide in 6.45g of deionized water to obtain an alkaline solution, heating the alkaline solution to 60 ℃ in a hydrothermal pot, then adding 0.55g of aluminum powder into an alkali liquor in batches, and stirring the solution until the solution is clear to obtain a solution A for later use, wherein the whole preparation process of the solution A needs to be carried out in a fume hood.
(2) In a low-temperature constant-temperature tank at 6 ℃, 1.23g of potassium hydroxide is firstly dissolved in 6.45g of deionized water, then 3.09g of TMAOH and 15.40g of silica sol are sequentially added into alkali liquor, and the solution B is prepared by mechanical stirring and aging for 2h at 6 ℃.
(3) Dropwise adding the clear solution A into the solution B, mechanically stirring at 6 deg.C in a low-temperature thermostatic bath to synthesize gel liquid for 2h, transferring into 30 deg.C thermostatic water bath, magnetically stirring and aging for 24h to obtain stable SiO 2 -Al 2 O 3 -Na 2 O-K 2 O-TMAOH-H 2 Coagulation of OAnd (4) a glue solution system. Wherein, siO 2 -Al 2 O 3 -Na 2 O-K 2 O-TMAOH-H 2 The O gel liquid system comprises the following components in a molar ratio: siO 2 2 ：Al 2 O 3 ：Na 2 O：K 2 O：TMAOH：H 2 O＝1：0.095：0.265：0.072：0.060：13.251。
(4) And (4) transferring the gel liquid system obtained in the step (3) into a reaction kettle, sealing, and performing crystallization reaction to obtain a synthetic liquid, wherein the crystallization mode is microwave-assisted crystallization, and the crystallization temperature is 100 ℃, and the crystallization time is 48 hours.
(5) Adding deionized water into the synthetic liquid obtained by crystallization, then carrying out centrifugal washing to neutrality, drying and grinding the obtained product, then placing the product in a muffle furnace, heating from 25 ℃ to 550 ℃ at 1 ℃/min, calcining for 6h, then cooling to 25 ℃ at 1 ℃/min, removing a template agent, and obtaining a T-type zeolite molecular sieve; the centrifugal washing process is to use a centrifugal machine to take supernatant liquid at a low rotating speed of 6000r/min, and then take sediment from the supernatant liquid at a high rotating speed of 11000r/min.
XRD (X-ray diffraction) characterization shows that the prepared T-type zeolite molecular sieve is a pure-phase T-type zeolite molecular sieve.
The above-mentioned embodiments only express the embodiments of the present invention, but not should be understood as the limitation of the scope of the invention patent, it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the concept of the present invention, and these all fall into the protection scope of the present invention.
Claims (7)
1. A preparation method of an ultra-small nanometer T-shaped zeolite molecular sieve is characterized by comprising the following steps:
step 1, preparing a solution A
Dispersing sodium hydroxide in deionized water at room temperature to obtain an alkaline solution, heating to 60-80 ℃, adding aluminum powder in batches, and stirring until the solution is clear to obtain a solution A for later use;
step 2, preparing solution B
Dissolving an alkali source in deionized water in a low-temperature constant-temperature tank at 2-6 ℃ to obtain an alkali liquor, sequentially adding a template agent and a silicon source into the alkali liquor, and mechanically stirring and aging for 2-4h at 2-6 ℃ to prepare a gel liquid system serving as a solution B; the silicon source is silica sol, the alkali source is potassium hydroxide, and the template agent is TMAOH; the mass of the deionized water used in the step 2 is the same as that of the deionized water in the step 1;
step 3, mixing the solution A and the solution B
Dropwise adding the clear solution A into the solution B, stirring at 2-6 deg.C in a low-temperature thermostatic bath to synthesize gel for 2-4h, and aging in a constant-temperature water bath at 20-30 deg.C for 12-24h to obtain stable SiO 2 -Al 2 O 3 -Na 2 O-K 2 O-TMAOH-H 2 An O-gel liquid system;
the SiO 2 -Al 2 O 3 -Na 2 O-K 2 O-TMAOH-H 2 In the O gel liquid system, the molar ratio of each component is as follows: siO 2 2 ：Al 2 O 3 ：Na 2 O：K 2 O：TMAOH：H 2 O＝1：(0.065-0.95)：0.265：(0.072-0.9)：0.060：13.251；
Step 4, crystallizing the gel liquid system
Transferring the gel liquid system obtained in the step 3 into a reaction kettle, sealing and then carrying out crystallization reaction to obtain a synthetic liquid, wherein the crystallization temperature is 60-100 ℃, and the crystallization time is 48 hours;
step 5, collecting the product after post-treatment
And adding deionized water into the synthetic liquid obtained by crystallization reaction, carrying out centrifugal washing to neutrality, drying and grinding the obtained product, and then placing the product in a muffle furnace to calcine and remove the template agent to finally obtain the T-type zeolite molecular sieve.
2. The method as claimed in claim 1, wherein the preparation of the ultra-small nanometer T-type zeolite molecular sieve in step 1 is carried out in a fume hood, the aluminum powder is added in small amount in batches, and the next batch can be added after the aluminum powder is completely dissolved.
3. The method for preparing ultra-small nanometer T-type zeolite molecular sieve as claimed in claim 1, wherein in said step 3, magnetic stirring is adopted during aging.
4. The method for preparing ultra-small nanometer T-shaped zeolite molecular sieve of claim 1, wherein in the step 4, the crystallization mode is microwave-assisted crystallization or standing hydrothermal crystallization.
5. The method for preparing ultra-small nanometer T-shaped zeolite molecular sieve of claim 4, wherein in the step 4, the crystallization mode is static hydrothermal crystallization.
6. The method for preparing an ultra-small nanometer T-type zeolite molecular sieve of claim 1, wherein in the step 5, the centrifugal washing process is to use a centrifuge to take a supernatant at a low rotation speed, and then take a precipitate from the supernatant at a high rotation speed; the obtained precipitate is placed in a muffle furnace after being centrifugally dried and ground, and is heated to 550 ℃ by program and calcined for 6h, and then the temperature is reduced to 25 ℃ by program so as to remove the template agent.
7. The method for preparing the ultra-small nanometer T-type zeolite molecular sieve of claim 6, wherein in the step 5, the low rotation speed is 5000-6000r/min; the high rotating speed is 11000r/min; the heating/cooling rate is 1 ℃/min.
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| CN101164883A (en) * | 2007-09-27 | 2008-04-23 | 江西师范大学 | Preparation method for nano T-type molecular sieve |
| CN104030313A (en) * | 2014-05-26 | 2014-09-10 | 中国海洋石油总公司 | Method of synthesizing submicron T-type molecular sieve |
| CN111760467A (en) * | 2020-07-27 | 2020-10-13 | 明光市飞洲新材料有限公司 | Preparation method of T-type zeolite molecular sieve membrane |
| CN115245838A (en) * | 2022-06-16 | 2022-10-28 | 天津大学 | T molecular sieve rapid synthesis method, catalyst and application |
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| CN101164883A (en) * | 2007-09-27 | 2008-04-23 | 江西师范大学 | Preparation method for nano T-type molecular sieve |
| CN104030313A (en) * | 2014-05-26 | 2014-09-10 | 中国海洋石油总公司 | Method of synthesizing submicron T-type molecular sieve |
| CN111760467A (en) * | 2020-07-27 | 2020-10-13 | 明光市飞洲新材料有限公司 | Preparation method of T-type zeolite molecular sieve membrane |
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