CN118026198A - Synthesis method of super-hydrophilic molecular sieve for hydrogen purification device - Google Patents
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 156
- 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 156
- 239000001257 hydrogen Substances 0.000 title claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000000746 purification Methods 0.000 title claims abstract description 19
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 19
- 238000002425 crystallisation Methods 0.000 claims abstract description 18
- 230000008025 crystallization Effects 0.000 claims abstract description 18
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 17
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010457 zeolite Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000005342 ion exchange Methods 0.000 claims abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- -1 methyl modified silicon Chemical class 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 17
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 239000004115 Sodium Silicate Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 12
- 238000004090 dissolution Methods 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000003463 adsorbent Substances 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 239000010703 silicon Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000006698 induction Effects 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 125000005372 silanol group Chemical group 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a synthesis method of a super-hydrophilic molecular sieve for a hydrogen purification device, which comprises the following steps: preparing molecular sieve seed crystals; preparing a methyl modified silicon source species; adding seed crystal, silicon source and aluminum source into alkali liquor to hydrothermally synthesize an A-type molecular sieve; carrying out high-temperature treatment on the A-type molecular sieve to obtain an A-type zeolite molecular sieve rich in hydroxyl; ion exchange is carried out on the A-type zeolite molecular sieve to obtain the ion modified A-type molecular sieve. The invention has simple synthesis steps, shortens crystallization induction period by using the seed crystal, accelerates the crystallization process of the molecular sieve, and has high crystallinity and uniform particle size of the synthesized molecular sieve. In addition, silanol groups are introduced into the molecular sieve framework, so that the hydrophilicity of the molecular sieve is effectively improved, and the hydrophilicity of the molecular sieve is further improved by ion exchange. The super-hydrophilic molecular sieve prepared by the invention has a hydrophilic contact angle of 23-26 degrees.
Description
Technical Field
The invention relates to the technical field of inorganic chemical synthesis, in particular to a method for synthesizing a super-hydrophilic molecular sieve for a hydrogen purification device, and specifically relates to a surface modified hydrophilic zeolite molecular sieve, a preparation method thereof and a hydrogen purification device based on the molecular sieve.
Background
The type A molecular sieve is an alkali metal aluminosilicate mineral with a regular pore system. The A-type molecular sieve has various excellent performances such as innocuity, high porosity, large specific surface area, good thermal stability, high-efficiency cation exchange capacity, environmental friendliness and the like, and has wide potential application value in various fields such as hard water softeners, catalysts, adsorbents, ion exchangers, novel functional materials and the like.
The hydrogen purification process is to remove impurities in the hydrogen and improve the purity of the hydrogen so as to meet specific industrial requirements and applications. In many industrial applications, high purity hydrogen is required to perform properly, such as hydrogen fuel cells, semiconductor manufacturing, petroleum processing, and the like. Through the purification process, impurities in the hydrogen can be removed, and the purity of the hydrogen can be ensured to meet specific requirements so as to ensure the normal operation of equipment and reaction. Water molecules and other impurities in hydrogen gas can cause corrosion and damage to metal equipment. The purified hydrogen can remove these corrosive and harmful components, protecting the integrity and life of the equipment.
Hydrogen produced by electrolysis of water to produce hydrogen is generally recognized as the highest purity hydrogen, but trace water molecules remain therein. The adsorption of molecular sieve and water in the hydrogen purification system mainly depends on the polar adsorption and shape selective adsorption of molecular sieve, the hydrophilicity of molecular sieve is critical to the removal of water molecules in hydrogen, the higher the hydrophilicity of molecular sieve, the stronger the adsorption of water molecules and the higher the hydrogen purity.
In the prior art, a type A or X zeolite molecular sieve is generally selected as an adsorbent for hydrogen purification, but the hydrophilia of the zeolite molecular sieve and the adsorbent is limited, so that in order to ensure the hydrogen purification effect, the volume of hydrogen purification equipment is generally increased, more molecular sieves are used as the adsorbent, and the adsorption effect is ensured, which can definitely lead to the large volume of the hydrogen purification equipment and the increase of the cost of the hydrogen purification equipment.
The present invention has been made to solve the above problems.
Disclosure of Invention
The invention aims to solve the problem that the A-type molecular sieve has poor hydrophilicity. The invention discloses a synthesis method of a super-hydrophilic molecular sieve for a hydrogen purification device, which comprises the following steps: preparing molecular sieve seed crystals; preparing a methyl modified silicon source species; adding seed crystal, silicon source and aluminum source into alkali liquor to hydrothermally synthesize an A-type molecular sieve; carrying out high-temperature treatment on the A-type molecular sieve to obtain an A-type zeolite molecular sieve rich in hydroxyl; ion exchange is carried out on the A-type zeolite molecular sieve to obtain the ion modified A-type molecular sieve. The invention has simple synthesis steps, shortens crystallization induction period by using the seed crystal, accelerates the crystallization process of the molecular sieve, and has high crystallinity and uniform particle size of the synthesized molecular sieve. In addition, silanol groups are introduced into the molecular sieve framework, so that the hydrophilicity of the molecular sieve is effectively improved, and the hydrophilicity of the molecular sieve is further improved by ion exchange. The super-hydrophilic molecular sieve prepared by the invention has a hydrophilic contact angle of 23-26 degrees, and more preferably has a hydrophilic contact angle of 23 degrees.
The invention provides a synthesis method of a super-hydrophilic molecular sieve for a hydrogen purification device, which comprises the steps of respectively preparing molecular sieve seed crystals and methyl modified silicon source species, adding the molecular sieve seed crystals, the methyl modified silicon source species and an aluminum source into alkali liquor, performing hydrothermal reaction to synthesize an A-type molecular sieve, and roasting the A-type molecular sieve to obtain a hydroxyl-containing A-type zeolite molecular sieve, namely the super-hydrophilic molecular sieve.
Preferably, the preparation method of the super hydrophilic molecular sieve comprises the following steps:
(1) Adding ethyl silicate and diethoxydimethylsilane into an aqueous solution containing ethanol and ammonia water, stirring at room temperature, vacuum distilling, and drying overnight to obtain amorphous silica modified by methyl;
(2) Respectively adding a silicon source and an aluminum source into a sodium hydroxide aqueous solution, and stirring for a period of time to obtain a molecular sieve seed crystal solution;
(3) Adding amorphous silicon dioxide, an aluminum source and a molecular sieve seed crystal solution into a sodium hydroxide aqueous solution, and aging for a period of time at room temperature to obtain molecular sieve gel;
(4) And pouring the molecular sieve liquid gel into a reaction kettle for crystallization, and carrying out solid-liquid separation after the crystallization is finished, wherein the solid contains the 4A molecular sieve.
More preferably, the preparation method of the super hydrophilic molecular sieve comprises the following steps:
(1) Adding ethanol into an aqueous solution containing ammonia water, fully stirring, then adding ethyl silicate and diethoxydimethylsilane, and stirring for a period of time to obtain an initial material;
(2) Vacuum distilling the initial material obtained in the step (1) to remove water and ethanol, and drying to obtain methyl modified amorphous silica solid powder SiO 2 -Me;
(3) Preparing two parts of sodium hydroxide solution with certain concentration, respectively adding sodium silicate and sodium metaaluminate, mixing the sodium silicate and the sodium metaaluminate after the sodium metaaluminate is completely dissolved, and stirring for a period of time to obtain a molecular sieve seed crystal solution;
(4) Preparing a sodium hydroxide solution with a certain concentration, adding sodium silicate, sodium metaaluminate, the amorphous silicon dioxide solid powder SiO 2 -Me modified by methyl obtained in the step (2) and the molecular sieve seed crystal solution obtained in the step (3), and stirring and aging for a period of time to obtain molecular sieve gel;
(5) Transferring the molecular sieve gel obtained in the step (4) into a reaction kettle for crystallization reaction;
(6) Filtering, washing and drying the reactant obtained in the step (5) to obtain a methyl modified 4A molecular sieve;
(7) And (3) transferring the 4A molecular sieve obtained in the step (6) into a muffle furnace for roasting treatment, removing the organic template, and converting methyl into hydroxyl to obtain the surface modified 4A molecular sieve, namely the super-hydrophilic molecular sieve.
Preferably, the super-hydrophilic molecular sieve has a hydrophilic contact angle of 23-26 °. More preferably, the super-hydrophilic molecular sieve has a hydrophilic contact angle of 23 °.
Preferably, in the step (1), the volume ratio of ethanol to water is 0.4-0.8:1, the volume ratio of ammonia water to water is 0.01-0.06:1, an alkaline environment is provided, the mass ratio of ethyl silicate to diethoxydimethylsilane is 10-15:1, and the mass ratio of ethyl silicate to diethoxydimethylsilane is 2-4% of the solution.
Preferably, in the step (1), the stirring time is 6-12h, and the stirring temperature is room temperature.
Preferably, in the step (2), the drying temperature is 80-120 ℃; the drying time is 12-16h.
Preferably, in step (3), sodium silicate in the molecular sieve seed solution: sodium aluminate: sodium hydroxide: the water is 15-17:2.4-3:4-5:40-50, the stirring time is 6-8h, and the stirring temperature is 40-60 ℃.
Preferably, in step (4), the silica solids in the molecular sieve gel: sodium silicate: sodium metaaluminate: molecular sieve seed crystal: sodium hydroxide: water is 1-1.8:3.8-8:1.22-1.8:2-4:1-1.2:30-50, stirring and aging for 30min-2h, and stirring at room temperature.
Preferably, in the step (5), the crystallization temperature is 80-130 ℃ and the crystallization time is 3-24h.
Preferably, in step (6), the filter cake is washed to a pH of 8 to 9, a drying temperature of 80 to 120 ℃ and a drying time of 4 to 24 hours.
Preferably, in the step (7), the roasting temperature of the muffle furnace is 500-600 ℃ and the roasting time is 2-6h.
Preferably, the preparation method of the super-hydrophilic molecular sieve further comprises a step (8), wherein the surface modified 4A molecular sieve obtained in the step (7) is subjected to ion exchange with a cationic solution, and then suction filtration is carried out, so that the obtained filter cake is dried.
Preferably, in the step (8), the cation solution comprises magnesium chloride solution and calcium chloride solution, the ion exchange time is 4-8h, the drying temperature is 80-120 ℃, and the drying time is 12-16h.
Preferably, the super-hydrophilic molecular sieve is used as an adsorbent for hydrogen purification devices.
Compared with the prior art, the invention has the following beneficial effects:
1. The invention develops a new method to synthesize the A-type zeolite molecular sieve by taking methyl modified amorphous silicon dioxide solid powder (SiO 2 -Me) synthesized by ethyl silicate and diethoxy dimethyl silane as a silicon source, and after the A-type zeolite molecular sieve is successfully synthesized, methyl groups are converted into hydroxyl groups by high-temperature roasting in a muffle furnace, so that the A-type zeolite molecular sieve rich in hydroxyl groups is successfully synthesized, and the hydrophilicity of the A-type zeolite molecular sieve is greatly improved.
2. Furthermore, the invention carries out ion exchange on the A-type molecular sieve baked at high temperature, and uses cations with more charges to replace sodium ions in a molecular sieve framework, thereby enhancing the polarity of the molecular sieve and further improving the hydrophilicity of the molecular sieve.
3. The synthesis method has simple synthesis steps, and the synthesized seed crystal solution is added into the molecular sieve gel, so that the crystallization induction period is shortened, the crystallization process of the molecular sieve is accelerated, and the synthesized molecular sieve has high crystallinity and uniform particle size.
Drawings
FIG. 1 is an XRD pattern of the type A molecular sieve obtained in example 1, from which characteristic peaks of the type A molecular sieve can be observed;
FIG. 2 is an SEM image of the type A molecular sieve obtained in example 1, from which it can be seen that the synthesized type A molecular sieve has uniform morphology and uniform particle size;
FIG. 3 is a schematic diagram showing the equipment of the type A molecular sieve obtained in example 1 as an adsorbent applied to a hydrogen purification device;
Fig. 4 is a graph of the contact angle of water droplets on the surface of a commercial type a molecular sieve and the type a molecular sieve obtained in example 1, wherein the contact angle of the commercial type a molecular sieve is 37.5 ° and the contact angle of the type a molecular sieve obtained in example 1 is 23 °.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) 80ML of ethanol was added to 100mL of an aqueous solution containing 6mL of aqueous ammonia. 3.7g of ethyl silicate and 0.3g of diethoxydimethylsilane were added and stirred at room temperature for 8h.
(2) The initial material obtained in the step (1) is distilled in vacuum to remove water and ethanol, and is dried overnight at 100 ℃ to obtain methyl modified amorphous silica solid powder (SiO 2 -Me).
(3) To both 20mL of the aqueous solution, 2g of sodium hydroxide was added, and after complete dissolution, 10g of sodium silicate and 2g of sodium metaaluminate were added, respectively, and stirred at room temperature for 8 hours to obtain a molecular sieve seed solution.
(4) To two 20mL portions of the aqueous solution, 1.1g of sodium hydroxide, labeled A, B, was added, 1.66g of silica (the solid powder of amorphous silica modified with methyl in step (2)) was added to the A solution, 3.94g of sodium silicate was added after the completion of the dissolution, 1.3g of sodium metaaluminate was added to the B solution, after the completion of the dissolution, the B solution was added dropwise to the A solution, then 2mL of the molecular sieve seed solution was added, and stirring was performed at 25℃for 40 minutes, to obtain a molecular sieve gel.
(5) And (3) transferring the molecular sieve gel obtained in the step (4) into a reaction kettle for crystallization reaction, and crystallizing for 6 hours at 100 ℃.
(6) Filtering, washing and drying the reacted liquid obtained in the step (5) to obtain the methyl modified 4A molecular sieve.
(7) Transferring the 4A molecular sieve obtained in the step (6) into a muffle furnace, roasting for 5 hours at 550 ℃, removing an organic template, and converting methyl into hydroxyl to obtain the surface modified 4A molecular sieve;
(8) And (3) carrying out ion exchange on the surface modified hydrophilic molecular sieve obtained in the step (7) in a calcium chloride solution with the concentration of 1mol/L for 4 hours, carrying out suction filtration on the solution, and drying a filter cake overnight to obtain the Ca-A zeolite molecular sieve.
Example 2
(1) 80ML of ethanol was added to 100mL of an aqueous solution containing 6mL of aqueous ammonia. 3.7g of ethyl silicate and 0.3g of diethoxydimethylsilane were added and stirred at room temperature for 8h.
(2) The initial material obtained in the step (1) is distilled in vacuum to remove water and ethanol, and is dried overnight at 100 ℃ to obtain methyl modified amorphous silica solid powder (SiO 2 -Me).
(3) To both 20mL of the aqueous solution, 2g of sodium hydroxide was added, and after complete dissolution, 10g of sodium silicate and 2g of sodium metaaluminate were added, respectively, and stirred at room temperature for 8 hours to obtain a molecular sieve seed solution.
(4) To two 20mL portions of the aqueous solution, 1.1g of sodium hydroxide, labeled A, B, was added, 3.4g of silica (the amorphous silica solid powder modified by methyl in step (2)) was added to the A solution, 1.3g of sodium metaaluminate was added to the B solution, after the dissolution was completed, the B solution was added dropwise to the A solution, then 2mL of a molecular sieve seed solution was added, and stirring was performed at 25℃for 40 minutes to obtain a molecular sieve gel.
(5) And (3) transferring the molecular sieve gel obtained in the step (4) into a reaction kettle for crystallization reaction, and crystallizing for 6 hours at 100 ℃.
(6) Filtering, washing and drying the reacted liquid obtained in the step (5) to obtain the methyl modified 4A molecular sieve.
(7) Transferring the 4A molecular sieve obtained in the step (6) into a muffle furnace, roasting for 5 hours at 550 ℃, removing an organic template, and converting methyl into hydroxyl to obtain the surface modified 4A molecular sieve;
(8) And (3) carrying out ion exchange on the surface modified hydrophilic molecular sieve obtained in the step (7) in a magnesium chloride solution with the concentration of 1mol/L for 4 hours, carrying out suction filtration on the solution, and drying a filter cake overnight to obtain the Mg-A zeolite molecular sieve.
Example 3
(1) 80ML of ethanol was added to 100mL of an aqueous solution containing 6mL of aqueous ammonia. 5g of ethyl silicate and 1g of diethoxydimethylsilane were added and stirred at room temperature for 16h.
(2) The initial material obtained in the step (1) is distilled in vacuum to remove water and ethanol, and is dried overnight at 100 ℃ to obtain methyl modified amorphous silica solid powder (SiO 2 -Me).
(3) To both 20mL of the aqueous solution, 2g of sodium hydroxide was added, and after complete dissolution, 10g of sodium silicate and 2g of sodium metaaluminate were added, respectively, and stirred at room temperature for 8 hours to obtain a molecular sieve seed solution.
(4) To two 20mL portions of the aqueous solution, 1.1g of sodium hydroxide, labeled A, B, was added, 3g of silica (the amorphous silica solid powder modified by methyl in step (2)) was added to the A solution, 1.3g of sodium metaaluminate was added to the B solution, after the dissolution was completed, the B solution was added dropwise to the A solution, then 4mL of a molecular sieve seed solution was added, and stirring was carried out at 25℃for 2 hours, to obtain a molecular sieve gel.
(5) And (3) transferring the molecular sieve gel obtained in the step (4) into a reaction kettle for crystallization reaction, and crystallizing for 10 hours at 120 ℃.
(6) Filtering, washing and drying the reacted liquid obtained in the step (5) to obtain the methyl modified 4A molecular sieve.
(7) Transferring the 4A molecular sieve obtained in the step (6) into a muffle furnace, roasting for 5 hours at 550 ℃, removing an organic template, and converting methyl into hydroxyl to obtain the surface modified 4A molecular sieve;
(8) And (3) carrying out ion exchange on the surface modified hydrophilic molecular sieve obtained in the step (7) in a calcium chloride solution with the concentration of 1mol/L for 4 hours, carrying out suction filtration on the solution, and drying a filter cake overnight to obtain the Ca-A zeolite molecular sieve.
Example 4
(1) 80ML of ethanol was added to 100mL of an aqueous solution containing 6mL of aqueous ammonia. 3.7g of ethyl silicate and 0.3g of diethoxydimethylsilane were added and stirred at room temperature for 12h.
(2) The initial material obtained in the step (1) is distilled in vacuum to remove water and ethanol, and is dried overnight at 100 ℃ to obtain methyl modified amorphous silica solid powder (SiO 2 -Me).
(3) To both 20mL of the aqueous solution, 2g of sodium hydroxide was added, and after complete dissolution, 14g of sodium silicate and 3g of sodium metaaluminate were added, respectively, and stirred at room temperature for 24 hours to obtain a molecular sieve seed solution.
(4) To two 20mL portions of the aqueous solution, 1.1g of sodium hydroxide, labeled A, B, was added, 4g of silica (the amorphous silica solid powder modified by methyl in step (2)) was added to the A solution, 1.3g of sodium metaaluminate was added to the B solution, after the dissolution was completed, the B solution was added dropwise to the A solution, then 3mL of a molecular sieve seed solution was added, and stirring was performed at 40℃for 60 minutes to obtain a molecular sieve gel.
(5) And (3) transferring the molecular sieve gel obtained in the step (4) into a reaction kettle for crystallization reaction, and crystallizing for 9 hours at 110 ℃.
(6) Filtering, washing and drying the reacted liquid obtained in the step (5) to obtain the methyl modified 4A molecular sieve.
(7) Transferring the 4A molecular sieve obtained in the step (6) into a muffle furnace, roasting for 5 hours at 550 ℃, removing an organic template, and converting methyl into hydroxyl to obtain the surface modified 4A molecular sieve;
(8) And (3) carrying out ion exchange on the surface modified hydrophilic molecular sieve obtained in the step (7) in a calcium chloride solution with the concentration of 1mol/L for 6 hours, carrying out suction filtration on the solution, and drying a filter cake overnight to obtain the Ca-A zeolite molecular sieve.
Contact angle data for surface water drops of different examples synthetic molecular sieves are shown in table 1 below.
TABLE 1 contact angle data for surface Water drops of synthetic molecular sieves of different examples
| Example 1 | Example 2 | Example 3 | Example 4 | Commercial molecular sieves | |
| Contact angle | 23° | 25° | 24° | 26° | 37.5° |
From the data in table 1, and in combination with fig. 4, it can be found that the preparation method of the present invention can greatly improve the hydrophilicity of the a-type molecular sieve, and the hydrophilic contact angle of the super-hydrophilic molecular sieve prepared by the present invention is 23-26 °, wherein the contact angle of the commercial a-type molecular sieve is 37.5 °, and the contact angle of the a-type molecular sieve obtained in example 1 is 23 °.
Claims (10)
1. A method for synthesizing a super-hydrophilic molecular sieve for a hydrogen purification device is characterized by respectively preparing a molecular sieve seed crystal and a methyl modified silicon source species, adding the molecular sieve seed crystal, the methyl modified silicon source species and an aluminum source into alkali liquor, then performing hydrothermal reaction to synthesize an A-type molecular sieve, and roasting the A-type molecular sieve to obtain the hydroxyl-containing A-type zeolite molecular sieve, namely the super-hydrophilic molecular sieve.
2. The method according to claim 1, wherein the preparation method of the super hydrophilic molecular sieve comprises the following steps:
(1) Adding ethanol into an aqueous solution containing ammonia water, stirring, then adding ethyl silicate and diethoxydimethylsilane, and stirring for a period of time to obtain an initial material;
(2) Vacuum distilling the initial material obtained in the step (1) to remove water and ethanol, and drying to obtain methyl modified amorphous silica solid powder SiO 2 -Me;
(3) Preparing two parts of sodium hydroxide solution with certain concentration, respectively adding sodium silicate and sodium metaaluminate, mixing the two after dissolution, and stirring for a period of time to obtain molecular sieve seed crystal solution;
(4) Preparing a sodium hydroxide solution with a certain concentration, adding sodium silicate, sodium metaaluminate, the amorphous silicon dioxide solid powder SiO 2 -Me modified by methyl obtained in the step (2) and the molecular sieve seed crystal solution obtained in the step (3), and stirring and aging for a period of time to obtain molecular sieve gel;
(5) Transferring the molecular sieve gel obtained in the step (4) into a reaction kettle for crystallization reaction;
(6) Filtering, washing and drying the reactant obtained in the step (5) to obtain a methyl modified 4A molecular sieve;
(7) And (3) transferring the 4A molecular sieve obtained in the step (6) into a muffle furnace for roasting treatment, removing the organic template, and converting methyl into hydroxyl to obtain the surface modified 4A molecular sieve, namely the super-hydrophilic molecular sieve.
3. The method of claim 1, wherein the super-hydrophilic molecular sieve has a hydrophilic contact angle of 23 ° to 26 °.
4. The method of claim 1, wherein in step (1) the volume ratio of ethanol to water is 0.4-0.8:1, the volume ratio of ammonia to water is 0.01-0.06:1, an alkaline environment is provided, the mass ratio of ethyl silicate to diethoxydimethylsilane is 10-15:1, and the mass ratio of ethyl silicate to diethoxydimethylsilane is 2-4% of the solution;
In the step (1), the stirring time is 6-12h, and the stirring temperature is room temperature;
in the step (2), the drying temperature is 80-120 ℃; the drying time is 12-16h.
5. The method of claim 1, wherein in step (3), sodium silicate in the molecular sieve seed solution: sodium aluminate: sodium hydroxide: the water is 15-17:2.4-3:4-5:40-50, the stirring time is 6-8h, and the stirring temperature is 40-60 ℃.
6. The method of claim 1, wherein in step (4), the silica solids in the molecular sieve gel: sodium silicate: sodium metaaluminate: molecular sieve seed crystal: sodium hydroxide: water is 1-1.8:3.8-8:1.22-1.8:2-4:1-1.2:30-50, stirring and aging for 30min-2h, and stirring at room temperature.
7. The method according to claim 1, wherein in the step (5), the crystallization temperature is 80-130 ℃ and the crystallization time is 3-24 hours;
In the step (6), the filter cake is washed to pH 8-9, the drying temperature is 80-120 ℃, and the drying time is 4-24h.
8. The method according to claim 1, wherein in the step (7), the muffle furnace is baked at 500-600 ℃ for 2-6 hours.
9. The method according to claim 1, further comprising a step (8) of subjecting the surface-modified 4A molecular sieve obtained in the step (7) to ion exchange with a cationic solution, followed by suction filtration, and drying the obtained cake;
In the step (8), the cation solution comprises magnesium chloride solution and calcium chloride solution, the ion exchange time is 4-8h, the drying temperature is 80-120 ℃, and the drying time is 12-16h.
10. The method of claim 1, wherein the synthesized super hydrophilic molecular sieve is applied as an adsorbent to a hydrogen purification device.
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