CN117125721A - Preparation method of Na-LSX type oxygen-making molecular sieve capable of releasing negative oxygen ions - Google Patents
Preparation method of Na-LSX type oxygen-making molecular sieve capable of releasing negative oxygen ions Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 110
- 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 110
- 239000001301 oxygen Substances 0.000 title claims abstract description 86
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 86
- -1 oxygen ions Chemical class 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 58
- 238000002156 mixing Methods 0.000 claims abstract description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 20
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 20
- 229960000892 attapulgite Drugs 0.000 claims abstract description 15
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 15
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 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 abstract description 8
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000013078 crystal Substances 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 18
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 16
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 14
- 239000004927 clay Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000010899 nucleation Methods 0.000 claims description 10
- 230000006911 nucleation Effects 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 8
- 230000003068 static effect Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000000087 stabilizing effect Effects 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 abstract description 8
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000005538 encapsulation Methods 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract 1
- 150000002910 rare earth metals Chemical class 0.000 abstract 1
- 238000007873 sieving Methods 0.000 abstract 1
- 238000011068 loading method Methods 0.000 description 18
- 150000002500 ions Chemical class 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000036772 blood pressure Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229940012957 plasmin Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000003860 sleep quality Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/22—Type X
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0229—Purification or separation processes
- C01B13/0248—Physical processing only
- C01B13/0259—Physical processing only by adsorption on solids
- C01B13/0262—Physical processing only by adsorption on solids characterised by the adsorbent
- C01B13/027—Zeolites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/026—After-treatment
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- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
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Abstract
The application provides a preparation method of a Na-LSX type oxygen-generating molecular sieve capable of releasing negative oxygen ions, and relates to the technical field of functional oxygen-generating molecular sieve materials. The molecular sieve capable of releasing negative oxygen ions to prepare oxygen is prepared from CeO 2 、La 2 O 3 、Nd 2 O 3 The rare earth oxide and reagent sodium metaaluminate, sodium silicate, sodium oxide, aluminum oxide and silicon oxide are used for obtaining LSX fraction loaded with rare earth oxideAnd (3) sub-sieving, and mixing with attapulgite, granulating and forming to obtain the product. The molecular sieve for preparing oxygen by releasing negative oxygen ions is characterized in that rare earth oxide is loaded in the holes of the molecular sieve in an in-situ encapsulation mode, the molecular sieve can realize the capability of releasing negative oxygen ions efficiently, the preparation method of the molecular sieve is simple, the rare earth oxide can be stably encapsulated in the holes of the molecular sieve, and the availability of the molecular sieve is improved.
Description
Technical Field
The application relates to the technical field of functional oxygen-making molecular sieve materials, in particular to a preparation method of a Na-LSX oxygen-making molecular sieve capable of releasing negative oxygen ions.
Background
Adsorbents are critical to the pressure swing adsorption separation gas technology. The commonly used oxygen-making molecular sieve has two types, namely A type and X type, and the nitrogen-oxygen separation coefficient of the A type molecular sieve is smaller than that of the X type. The X-type molecular sieve has a FAU structure and can be divided into an X-type (Si/Al=1.2-1.5) molecular sieve and a low-Si/Al-ratio X-type molecular sieve (LSX type, si/Al < 1.2) molecular sieve according to the Si/Al ratio. The LSX type and the A type molecular sieve have the same skeleton negative charge, maintain the pore volume and the pore diameter of the X type, and obviously improve the adsorption performance.
Air anions, also called negative oxygen ions, are oxygen ions that are negatively charged by the excess electrons obtained by oxygen molecules in the air. Negative oxygen ions have positive effects on human health and environmental protection. The negative oxygen ions can be combined with particles such as bacteria, smoke dust and the like in the air to enable the particles to settle, and simultaneously can absorb harmful volatile gases such as formaldehyde and the like to achieve the purpose of air crystallization. The negative oxygen ions are called as vitamin oxygen and longevity element in the medical field, and have the positive effects of relieving fatigue, improving sleep quality, reducing blood pressure and the like. In addition, the negative oxygen ions have a sterilization function, and the strong oxidation and biological activity of the negative oxygen ions lead the cell membrane of bacteria to be destroyed, so that the activity of the plasmin is reduced, and bacteria are killed.
The molecular sieve for the oxygenerator in the market at present is mainly Li-LSX molecular sieve, does not have the function of generating negative oxygen ions, and has few researches and reports on Li-LSX oxygen-generating molecular sieves capable of releasing the negative oxygen ions. Publication No. CN115382504A discloses a Li-LSX type oxygen-generating molecular sieve capable of releasing negative oxygen ions and a preparation method thereof, wherein rare earth oxide nano particles are sprayed on the surface of the Li-LSX molecular sieve and then calcined to obtain the Li-LSX type oxygen-generating molecular sieve capable of releasing negative oxygen ions. Although they obtain molecular sieves capable of releasing negative oxygen ions, the rare earth oxide nanoparticles are loaded on the surfaces of the molecular sieves by adopting a spraying coverage method, and the problems that the rare earth oxide nanoparticles are not firmly loaded to be separated from the molecular sieves, so that the release efficiency of the negative oxygen ions is low, the service time of the molecular sieves is short and the like are solved. Accordingly, the present application is directed to an improvement in the preparation of Na-LSX oxygen producing molecular sieves that release negative oxygen ions, as described above.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the existing LSX oxygen-making molecular sieve capable of releasing negative oxygen ions in the preparation method, the application provides a preparation method of Na-LSX oxygen-making molecular sieve capable of releasing negative oxygen ions.
(II) technical scheme
In order to achieve the above purpose, the application is realized by the following technical scheme:
in one aspect, the application provides a method for preparing a Na-LSX type oxygen-generating molecular sieve capable of releasing negative oxygen ions, wherein the oxygen-generating molecular sieve is prepared by encapsulating rare earth oxide into the Na-LSX molecular sieve in situ.
Specifically, the oxygen-making molecular sieve is prepared according to the following steps:
(1) Uniformly mixing silicon oxide and a sodium silicate solution to obtain a mixture 1; mixing aluminum oxide with a sodium metaaluminate solution to obtain a mixture 2; uniformly mixing the mixture 1, the mixture 2 and sodium oxide to obtain a mixture 3, uniformly mixing the mixture 3 and rare earth oxide dispersion liquid, stirring for more than 1 hour at room temperature, and then aging and stabilizing nucleation at room temperature, wherein the aging and nucleation time is more than 3 hours; then placing the crystal in an oven at 60-80 ℃ for static crystal bloom for 12-24 hours to enable the crystal to continue growing; washing to pH value of less than 9, and drying at 120 deg.c to obtain Na-LSX molecular sieve loaded with RE oxide.
(2) Uniformly mixing Na-LSX molecular sieve and attapulgite clay mechanically according to the weight ratio of 3.0:0.3-0.8, adding water for granulating, drying the formed Na-LSX molecular sieve sample at 90-120 ℃ for 1h, heating to 400-480 ℃ at the heating rate of 5-8 ℃/min, and roasting at constant temperature for 6-8h to obtain the Na-LSX oxygen-producing molecular sieve product capable of releasing negative oxygen ions.
Preferably, the rare earth oxide in step (1) includes, but is not limited to, one or more of cerium oxide, lanthanum oxide, neodymium oxide; the rare earth oxide consists of cerium oxide with the molar ratio of 7-9.5:0.1-0.5:0.2-0.8: lanthanum oxide: neodymium oxide composition; the rare earth oxide dispersion liquid is prepared according to the following steps: weighing the raw materials according to the molar ratio, mixing the raw materials with deionized water, and performing ultrasonic dispersion for 20min, wherein the mass ratio of the deionized water to the rare earth oxide is 20:1; the dispersion is administered as it is.
Preferably, the molecular molar ratio of silica to alumina in step (1) is from 2.0:0.8 to 2.7:0.8; the molecular molar ratio of the sodium oxide to the silicon oxide is 1:0.9-2.2:0.9; the molecular molar ratio of water to sodium oxide is 40:1-60:1.
Preferably, the particle size of the attapulgite clay in the step (3) is 325 to 1250 meshes.
Preferably, the optimal firing temperature in step (6) is 435 ℃.
Preferably, the content of the rare earth oxide loaded in the Na-LSX type oxygen generation molecular sieve capable of releasing the negative oxygen ions accounts for 1-15% of the total weight of the molecular sieve.
(III) beneficial effects
The application provides a preparation method of a Na-LSX type oxygen-making molecular sieve capable of releasing negative oxygen ions. The molecular sieve capable of releasing negative oxygen ions to prepare oxygen is prepared from CeO 2 、La 2 O 3 、Nd 2 O 3 The rare earth oxide and reagent sodium metaaluminate, sodium silicate, sodium oxide, alumina and silicon oxide which are formed by mixing rare earth oxide with attapulgite, granulating and forming are carried out to obtain the LSX molecular sieve loaded with rare earth oxide. The molecular sieve for preparing oxygen by releasing negative oxygen ions is characterized in that rare earth oxide is loaded in the holes of the molecular sieve in an in-situ encapsulation mode, the molecular sieve can realize the capability of releasing negative oxygen ions efficiently, the preparation method of the molecular sieve is simple, the rare earth oxide can be stably encapsulated in the holes of the molecular sieve, and the availability of the molecular sieve is improved.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions in the embodiments of the present application will be clearly and completely described in the following in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
The Na-LSX type oxygen-making molecular sieve capable of releasing negative oxygen ions is prepared according to the following steps:
(1) Uniformly mixing silicon oxide and a sodium silicate solution to obtain a mixture 1; mixing aluminum oxide with a sodium metaaluminate solution to obtain a mixture 2; uniformly mixing the mixture 1, the mixture 2 and sodium oxide to obtain a mixture 3, uniformly mixing the mixture 3 and rare earth oxide dispersion liquid, stirring for more than 1 hour at room temperature, and then aging and stabilizing nucleation at room temperature, wherein the aging and nucleation time is more than 3 hours; then placing the crystal in an oven at 60-80 ℃ for static crystal bloom for 12-24 hours to enable the crystal to continue growing; washing to pH value of less than 9, and drying at 120 deg.c to obtain Na-LSX molecular sieve loaded with RE oxide.
(2) Uniformly mixing the Na-LSX molecular sieve and the attapulgite clay mechanically according to the weight ratio of 3.0:0.6, adding water for granulating, drying a formed Na-LSX molecular sieve sample at 90-120 ℃ for 1h, heating to 435 ℃ at the heating rate of 5-8 ℃/min, and roasting at constant temperature for 6-8h to obtain the Na-LSX oxygen-producing molecular sieve product capable of releasing negative oxygen ions. The final supported rare earth oxide content was 5% by weight of the total molecular sieve.
Wherein the molecular mole ratio of the silicon oxide to the aluminum oxide in the step (1) is 2.0:0.8; the molecular molar ratio of the sodium oxide to the silicon oxide is 1:0.9; the molecular molar ratio of water to sodium oxide was 40:1.
The rare earth oxide in the step (1) consists of cerium oxide with a molar ratio of 9.5:0.5:0.8: lanthanum oxide: neodymium oxide composition; the rare earth oxide dispersion liquid is prepared according to the following steps: weighing the raw materials according to the molar ratio, mixing the raw materials with deionized water, and performing ultrasonic dispersion for 20min, wherein the mass ratio of the deionized water to the rare earth oxide is 20:1; the dispersion is administered as it is.
The granularity of the attapulgite clay in the step (3) is 600 meshes.
Example 2
The Na-LSX type oxygen-making molecular sieve capable of releasing negative oxygen ions is prepared according to the following steps:
(1) Uniformly mixing silicon oxide and a sodium silicate solution to obtain a mixture 1; mixing aluminum oxide with a sodium metaaluminate solution to obtain a mixture 2; uniformly mixing the mixture 1, the mixture 2 and sodium oxide to obtain a mixture 3, uniformly mixing the mixture 3 and rare earth oxide dispersion liquid, stirring for more than 1 hour at room temperature, and then aging and stabilizing nucleation at room temperature, wherein the aging and nucleation time is more than 3 hours; then placing the crystal in an oven at 60-80 ℃ for static crystal bloom for 12-24 hours to enable the crystal to continue growing; washing to pH value of less than 9, and drying at 120 deg.c to obtain Na-LSX molecular sieve loaded with RE oxide.
(2) Uniformly mixing the Na-LSX molecular sieve and the attapulgite clay mechanically according to the weight ratio of 3.0:0.6, adding water for granulating, drying a formed Na-LSX molecular sieve sample at 90-120 ℃ for 1h, heating to 450 ℃ at the heating rate of 5-8 ℃/min, and roasting at constant temperature for 6-8h to obtain the Na-LSX oxygen-producing molecular sieve product capable of releasing negative oxygen ions. The final supported rare earth oxide content was 5% by weight of the total molecular sieve.
Wherein the molecular mole ratio of the silicon oxide to the aluminum oxide in the step (1) is 2.7:0.8; the molecular molar ratio of sodium oxide to silicon oxide is 2.2:0.9; the molecular molar ratio of water to sodium oxide was 60:1.
The rare earth oxide in the step (1) consists of cerium oxide with a molar ratio of 7:0.1:0.2: lanthanum oxide: neodymium oxide composition; the rare earth oxide dispersion liquid is prepared according to the following steps: weighing the raw materials according to the molar ratio, mixing the raw materials with deionized water, and performing ultrasonic dispersion for 20min, wherein the mass ratio of the deionized water to the rare earth oxide is 20:1; the dispersion is administered as it is.
The granularity of the attapulgite clay in the step (3) is 800 meshes.
Example 3
The Na-LSX type oxygen-making molecular sieve capable of releasing negative oxygen ions is prepared according to the following steps:
(1) Uniformly mixing silicon oxide and a sodium silicate solution to obtain a mixture 1; mixing aluminum oxide with a sodium metaaluminate solution to obtain a mixture 2; uniformly mixing the mixture 1, the mixture 2 and sodium oxide to obtain a mixture 3, uniformly mixing the mixture 3 and rare earth oxide dispersion liquid, stirring for more than 1 hour at room temperature, and then aging and stabilizing nucleation at room temperature, wherein the aging and nucleation time is more than 3 hours; then placing the crystal in an oven at 60-80 ℃ for static crystal bloom for 12-24 hours to enable the crystal to continue growing; washing to pH value of less than 9, and drying at 120 deg.c to obtain Na-LSX molecular sieve loaded with RE oxide.
(2) Uniformly mixing the Na-LSX molecular sieve and the attapulgite clay mechanically according to the weight ratio of 3.0:0.6, adding water for granulating, drying a formed Na-LSX molecular sieve sample at 90-120 ℃ for 1h, heating to 435 ℃ at the heating rate of 5-8 ℃/min, and roasting at constant temperature for 6-8h to obtain the Na-LSX oxygen-producing molecular sieve product capable of releasing negative oxygen ions. The final supported rare earth oxide content was 5% by weight of the total molecular sieve.
Wherein the molecular mole ratio of the silicon oxide to the aluminum oxide in the step (1) is 2.5:0.8; the molecular molar ratio of sodium oxide to silicon oxide is 1.6:0.9; the molecular molar ratio of water to sodium oxide was 50:1.
The rare earth oxide in the step (1) consists of cerium oxide with a molar ratio of 8.2:0.3:0.4: lanthanum oxide: neodymium oxide composition; the rare earth oxide dispersion liquid is prepared according to the following steps: weighing the raw materials according to the molar ratio, mixing the raw materials with deionized water, and performing ultrasonic dispersion for 20min, wherein the mass ratio of the deionized water to the rare earth oxide is 20:1; the dispersion is administered as it is.
The granularity of the attapulgite clay in the step (3) is 1000 meshes.
Example 4
This embodiment differs from embodiment 3 in that
CeO in step (1) 2 、La 2 O 3 、Nd 2 O 3 The molar ratio of (2) is 9.5:0.5:0.8.
Example 5
This embodiment differs from embodiment 3 in that
CeO in step (1) 2 、La 2 O 3 、Nd 2 O 3 The molar ratio of (2) is 7:0.1:0.2.
Example 6
This embodiment differs from embodiment 3 in that
CeO in step (1) 2 、La 2 O 3 、Nd 2 O 3 The molar ratio of (2) is 7.8:0.2:0.5.
Example 7
The present embodiment differs from embodiment 1 in that
The rare earth oxide dispersion liquid in the step (1) only contains CeO 2 。
Example 8
The present embodiment differs from embodiment 1 in that
The final loading of rare earth oxide in step (3) was 1%.
Example 9
The present embodiment differs from embodiment 1 in that
The final loading of rare earth oxide in step (3) was 8%.
Example 10
The present embodiment differs from embodiment 1 in that
The final loading of rare earth oxide in step (3) was 10%.
Example 11
The present embodiment differs from embodiment 1 in that
The final loading of rare earth oxide in step (3) was 15%.
Comparative example 1
The Na-LSX type oxygen-making molecular sieve capable of releasing negative oxygen ions is prepared according to the following steps:
(1) Uniformly mixing silicon oxide and a sodium silicate solution to obtain a mixture 1; mixing aluminum oxide with a sodium metaaluminate solution to obtain a mixture 2; uniformly mixing the mixture 1, the mixture 2 and sodium oxide to obtain a mixture 3, stirring the mixture 3 at room temperature for more than 1 hour, and then aging and stably nucleating at room temperature for more than 3 hours; then placing the crystal in an oven at 60-80 ℃ for static crystal bloom for 12-24 hours to enable the crystal to continue growing; washing to pH <9, and drying at 120 ℃ to obtain the Na-LSX molecular sieve.
(2) Mechanically and uniformly mixing the Na-LSX molecular sieve and the attapulgite clay according to the weight ratio of 3.0:0.6; ceO is added with 2 、La 2 O 3 、Nd 2 O 3 Uniformly mixing according to a molar ratio of 8.2:0.3:0.4 to obtain rare earth oxide mixed powder, mixing the powder with deionized water according to a mass ratio of 1:20, and performing ultrasonic dispersion for more than 20 minutes to obtain rare earth oxide dispersion; the upper dispersion liquid is mechanically mixed with the Li-LSX molecular sieve and the attapulgite clay mixture, and the mixture is granulated, the formed Na-LSX molecular sieve sample is dried for 1h at 90-120 ℃, then is heated to 435 ℃ at the heating rate of 5-8 ℃/min, and is baked for 6-8h at constant temperature, thus obtaining the Na-LSX oxygen-producing molecular sieve product capable of releasing negative oxygen ions. The final supported rare earth oxide content was 5% by weight of the total molecular sieve.
Wherein the molecular mole ratio of the silicon oxide to the aluminum oxide in the step (1) is 2.5:0.8; the molecular mole ratio of silicon oxide to sodium oxide to silicon oxide is 1.6:0.9; the molecular molar ratio of water to sodium oxide was 50:1.
The granularity of the attapulgite clay in the step (3) is 1000 meshes.
Comparative example 2
Li-LSX oxygen-generating molecular sieves were prepared according to the method disclosed in publication No. CN 115382504A.
Test examples
Negative oxygen ion release capability test
The testing method comprises the following steps: the space for the negative ion release test of the material is v=1m 3 The mass of the negative oxygen ion molecular sieve is 500g, and the molecular sieve is tiled to ensure that the contact area S=0.5m 2 The test time is 12h, the test condition is normal temperature and pressure, the humidity is 60%, the model of the ion counter is AN-500 type air-borne negative ion detector, the air-borne negative ion detector is purchased from Chongqing An Naien environmental technology Co., ltd, and the resolution is 1/cm 3 The measurement accuracy of negative oxygen ions is +/-15 percent. The negative ion concentration test method is according to JC/T2110-2012, method for testing indoor air ion concentration.
Table 1 shows molecular sieves prepared in examples 1-11 and comparative examples 1-2And (5) testing the concentration of negative oxygen ions. The molecular sieves obtained in examples 1-11 were prepared by the method provided by the present application, and from the test results, it is known that the concentration of negative oxygen ions releasable by the Na-LSX type oxygen-generating molecular sieve prepared by the preparation method provided by the present application can be maintained at 2550-3450 (S.cm 3 ) Is a higher level of (c). As can be seen from comparison of examples 1 and examples 8-11, the final loading of the rare earth oxide nanoparticles has a certain effect on releasing negative oxygen ions from the molecular sieve, and excessive loading (8%, 10%, 15%) or insufficient loading (1%) of the rare earth oxide nanoparticles can reduce the concentration of negative oxygen ions released from the molecular sieve, which may be due to the fact that excessive loading can cause stacking of rare earth oxides in the cavities of the molecular sieve, resulting in smaller pores, insufficient contact with air and further influence on releasing negative air ions by electrolysis; the too small load quantity weakens the effect of releasing negative ions by the product; wherein when the rare earth oxide loading is 5%, the concentration of the negative oxygen ions released by the novel Na-LSX type oxygen-generating molecular sieve capable of releasing the negative oxygen ions obtained by the preparation method provided by the application is highest, and can be kept at 3450 (S cm 3 ) Is a high water content. Compared with comparative examples 1-2, the in-situ loading provided by the application can enable the surface layer and the interior of the formed Li-LSX molecular sieve pellet to gather a large amount of energy for dissociating air so as to generate high-concentration air anions, and compared with the common mode of mechanically mixing and doping and then forming or the coating/spraying process, the molecular sieve prepared by the in-situ loading rare earth oxide provided by the application has higher concentration of anions (see Table 1). This is probably due to the fact that the simple mechanical mixing doping can cause the rare earth oxide to be combined with the molecular sieve in a weak way and to fall off, even though the loading is the same, the availability of the rare earth oxide is not high, and the amount of negative ions released by electrolysis is less, as shown by the test results, when the loading of the rare earth oxide nano particles is 1-15%, the loading is CeO 2 With La 2 O 3 、Nd 2 O 3 One or two of them are adopted as the raw materialsIn the in-situ loading integrated forming process, the prepared Na-LSX oxygen generation molecular sieve capable of releasing negative oxygen ions can realize higher capability of releasing negative oxygen ions, wherein the loading amount of rare earth oxide nano particles is 5%, and the loading amount is CeO 2 、La 2 O 3 、Nd 2 O 3 The Na-LSX type oxygen-generating molecular sieve capable of releasing negative oxygen ions, which is prepared by adopting and adopting the in-situ loading integrated forming process, has the best capability of releasing the negative oxygen ions according to the molar ratio of 8.2:0.3:0.4.
Table 1 negative oxygen ion concentrations of the molecular sieves prepared in examples 1-11 and comparative examples 1-2.
| Sample of | Negative oxygen ion concentration is small (S.cm) 3 ) |
| Example 1 | 3000 |
| Example 2 | 3150 |
| Example 3 | 3450 |
| Example 4 | 3150 |
| Example 5 | 3050 |
| Example 6 | 3250 |
| Example 7 | 2650 |
| Example 8 | 2900 |
| Example 9 | 3100 |
| Example 10 | 2950 |
| Example 11 | 2550 |
| Comparative example 1 | 840 |
| Comparative example 2 | 2250 |
The above embodiments are only for illustrating the technical solution of the present application, and are not limiting; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present application.
Claims (9)
1. The Na-LSX type oxygen-generating molecular sieve capable of releasing negative oxygen ions is characterized in that rare earth oxide is encapsulated in situ into the Na-LSX molecular sieve.
2. The Na-LSX type oxygen producing molecular sieve capable of releasing negative oxygen ions according to claim 1, wherein the oxygen producing molecular sieve is prepared according to the following steps:
(1) Uniformly mixing silicon oxide and a sodium silicate solution to obtain a mixture 1; mixing aluminum oxide with a sodium metaaluminate solution to obtain a mixture 2; uniformly mixing the mixture 1, the mixture 2 and sodium oxide to obtain a mixture 3, uniformly mixing the mixture 3 and rare earth oxide dispersion liquid, stirring for more than 1 hour at room temperature, and then aging and stabilizing nucleation at room temperature, wherein the aging and nucleation time is more than 3 hours; then placing the crystal in an oven at 60-80 ℃ for static crystal bloom for 12-24 hours to enable the crystal to continue growing; washing until the pH value is less than 9, and drying at 120 ℃ to obtain the Na-LSX molecular sieve loaded with rare earth oxide;
(2) Uniformly mixing Na-LSX molecular sieve and attapulgite clay mechanically according to the weight ratio of 3.0:0.3-0.8, adding water for granulating, drying the formed Na-LSX molecular sieve sample at 90-120 ℃ for 1h, heating to 400-480 ℃ at the heating rate of 5-8 ℃/min, and roasting at constant temperature for 6-8h to obtain the Na-LSX oxygen-producing molecular sieve product capable of releasing negative oxygen ions.
3. A negative oxygen ion releasable Na-LSX oxygen generating molecular sieve as claimed in claim 1, wherein the rare earth oxide comprises, but is not limited to, one or more of cerium oxide, lanthanum oxide, neodymium oxide.
4. The Na-LSX type oxygen generating molecular sieve capable of releasing negative oxygen ions according to claim 1, wherein the rare earth oxide comprises cerium oxide with a molar ratio of 7-9.5:0.1-0.5:0.2-0.8: lanthanum oxide: neodymium oxide.
5. The negative oxygen ion releasable Na-LSX type oxygen producing molecular sieve of claim 1, wherein the content of rare earth oxide loaded in the negative oxygen ion releasable Li-LSX type oxygen producing molecular sieve is 1-15% of the total weight of the molecular sieve.
6. The method for preparing the Na-LSX type oxygen-generating molecular sieve capable of releasing negative oxygen ions according to claim 2, wherein the rare earth oxide dispersion liquid is prepared according to the following steps: cerium oxide in the molar ratio of 7-9.5:0.1-0.5:0.2-0.8: lanthanum oxide: weighing the raw materials, mixing the raw materials with deionized water, and performing ultrasonic dispersion for more than 20 minutes, wherein the mass ratio of the deionized water to the rare earth oxide is 20:1; the dispersion is administered as it is.
7. The method for preparing a Na-LSX type oxygen-generating molecular sieve capable of releasing negative oxygen ions according to claim 2, wherein the molecular molar ratio of silicon oxide to aluminum oxide in the step (1) is 2.0:0.8-2.7:0.8; the molecular molar ratio of the sodium oxide to the silicon oxide is 1:0.9-2.2:0.9; the molecular molar ratio of water to sodium oxide is 40:1-60:1.
8. The method for preparing a Na-LSX type oxygen-generating molecular sieve capable of releasing negative oxygen ions according to claim 2, wherein the granularity of the attapulgite clay in the step (2) is 325-1250 meshes.
9. The method for preparing a negative oxygen ion releasable Na-LSX type oxygen producing molecular sieve according to claim 2, wherein the optimal calcination temperature in the step (2) is 435 ℃.
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