CN114195170A - Nano CHA type molecular sieve membrane only containing potassium ion medium and preparation method thereof - Google Patents
Nano CHA type molecular sieve membrane only containing potassium ion medium and preparation method thereof Download PDFInfo
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- CN114195170A CN114195170A CN202111673596.8A CN202111673596A CN114195170A CN 114195170 A CN114195170 A CN 114195170A CN 202111673596 A CN202111673596 A CN 202111673596A CN 114195170 A CN114195170 A CN 114195170A
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- potassium ion
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 59
- 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 59
- 239000012528 membrane Substances 0.000 title claims abstract description 50
- 229910001414 potassium ion Inorganic materials 0.000 title claims abstract description 24
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 11
- -1 alkali metal cation Chemical class 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 150000001340 alkali metals Chemical class 0.000 abstract description 3
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 2
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 2
- 239000000084 colloidal system Substances 0.000 abstract description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000010457 zeolite Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910001593 boehmite Inorganic materials 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000004907 flux Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 108010023321 Factor VII Proteins 0.000 description 1
- 108010074864 Factor XI Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Images
Classifications
-
- 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
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention relates to a nanometer CHA type molecular sieve membrane only containing potassium ion medium and a preparation method thereof, belonging to the technical field of molecular sieve membranes, the preparation method of the nanometer CHA type molecular sieve membrane only containing potassium ion medium provided by the embodiment of the invention can influence the polymerization state, polycondensation state and colloid chemical property of silicate in a reaction system through a single alkali metal cation K +, and has a corresponding relation with a small cage basic structural unit finally forming zeolite, thereby realizing that only potassium ion alkali metal is contained, and the effect of replacing template agent can be achieved without using traditional alkali metals such as Cs2+, Sr2+, and the like.
Description
Technical Field
The invention belongs to the technical field of molecular sieve membranes, and particularly relates to a nano CHA type molecular sieve membrane only containing a potassium ion medium and a preparation method thereof.
Background
Compared with a polymer membrane, the molecular sieve membrane has the advantages of good separation performance, good thermal stability, good mechanical stability, good chemical resistance and the like, and can realize the separation of a mixture solution with a close boiling point and an isomer through the advantages of low energy consumption, low pollution, no limitation of component vapor-liquid balance in the separation process and the like by a pervaporation technology (PV), which cannot be realized by the traditional thermodynamic separation process (methods such as distillation, extraction, adsorption and the like).
The CHA-type molecular sieve has a silica to alumina ratio of 2-5, a three-dimensional pore structure, and very uniform pore size between the diameter of movement of water molecules and most organic molecules. The CHA-type molecular sieve membrane has high acid resistance and hydrothermal stability, high permeation flux and separation performance, and good development prospect in gas-phase and liquid-phase separation.
At present, most of molecular sieve membranes need to be added with an organic template in the synthesis process, and the organic template plays roles in influencing the liquid phase structure and promoting crystallization in the membrane synthesis process. However, the template agent can be removed only by calcining, the operation is complex, the cost is extremely high, the environment is polluted, and the defects are caused to the film layer. N, N, N-trimethyl-1-amino ammonium hydroxide (TMADAOH) is a more organic template agent adopted at present, and alkali metals such as strontium, cesium and the like are added into gel to replace the template agent, so that the pH value is adjusted.
Disclosure of Invention
In view of the above problems, the present invention has been made in order to provide a nanoscale CHA-type molecular sieve membrane containing only potassium ion medium and a method for preparing the same, which overcomes or at least partially solves the above problems.
In a first aspect, embodiments of the present invention provide a method for preparing a nanoscale CHA-type molecular sieve membrane containing only potassium ion media, the method comprising:
attaching the molecular sieve seed crystal suspension to the surface of a pretreatment carrier tube to obtain a molecular sieve carrier tube;
mixing and stirring a silicon source, an aluminum source, a potassium source and a solvent to obtain gel;
carrying out at least two hydrothermal synthesis reactions on the molecular sieve carrier tube and the gel under a preset pressure condition to obtain a molecular sieve membrane tube;
performing membrane tube separation on the molecular sieve membrane tube to obtain a nano CHA type molecular sieve membrane containing a potassium ion medium;
wherein the molar ratio of the silicon source, the aluminum source and the potassium source satisfies the following relationship:
silicon ion, aluminium ion, potassium ion 1, (0.3-0.6) and (0.6-1.4).
Optionally, the silicon source is at least one of silicon oxide, sodium metasilicate nonahydrate and ethyl orthosilicate, the aluminum source is at least one of aluminum oxide, aluminum hydroxide and aluminum nitrate, and the potassium source is at least one of potassium oxide, potassium hydroxide and potassium fluoride.
Optionally, the raw materials of the molecular sieve seed suspension comprise: the particle size of the nanoscale molecular sieve is 140-180nm, and the particle size of the micron-sized molecular sieve is 1.2-1.8 mu m.
In the embodiment of the present invention, the size of the seed crystal has a great influence on the finally formed molecular sieve membrane, such as the thickness of the membrane layer, the uniformity of the membrane surface, the pore size of the membrane and the porosity. The film layer is thicker due to the fact that the seed crystal is too large, and intercrystalline pores among particles are also larger; the small size of the seed particles facilitates the formation of thin films and the films are more dense and uniform.
Optionally, the mass concentration of the molecular sieve seed crystal suspension is 1-2 g/L.
Optionally, the pre-treatment of the pre-treatment carrier tube comprises:
and ultrasonically cleaning the carrier tube, sealing two ends of the carrier tube, and drying at the temperature of 170-190 ℃ after sealing to obtain the pretreated carrier tube.
Optionally, the solvent is water, and the molar ratio of the solvent satisfies the following relationship:
water, silicon ion (40-200) and 1.
Optionally, the preset pressure is 50-200 KPa.
In a second aspect, embodiments of the present invention provide a nanoscale CHA-type molecular sieve membrane containing only potassium ion medium, produced by the method of the first aspect.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
according to the preparation method of the nano CHA-type molecular sieve membrane only containing potassium ion media, provided by the embodiment of the invention, a molecular sieve seed crystal suspension is attached to the surface of a pretreatment carrier tube to obtain a molecular sieve carrier tube; mixing and stirring a silicon source, an aluminum source, a potassium source and a solvent to obtainObtaining gel; carrying out at least two hydrothermal synthesis reactions on the molecular sieve carrier tube and the gel under a preset pressure condition to obtain a molecular sieve membrane tube; performing membrane tube separation on the molecular sieve membrane tube to obtain a nano CHA type molecular sieve membrane containing a potassium ion medium; wherein the molar ratio of the silicon source, the aluminum source and the potassium source satisfies the following relationship: silicon ion, aluminium ion, potassium ion 1, (0.3-0.6) and (0.6-1.4). By a single alkali metal cation K+Can influence the polymerization state, polycondensation state and colloid chemical property of silicate in the reaction system, and has corresponding relation with the small cage basic structural unit finally constituting zeolite, so as to realize that only potassium ion alkali metal is contained without using traditional Cs2+，Sr2+And the alkali metal can replace the template agent.
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 shows a single K in an embodiment of the present invention+SEM plan view of CHA-type molecular sieve membrane synthesized in medium;
FIG. 2 shows a single K in an embodiment of the present invention+SEM cross-sectional view of CHA-type molecular sieve membrane synthesized in medium;
FIG. 3 shows a single K in an embodiment of the present invention+XRD diffraction pattern of CHA type molecular sieve membrane synthesized in medium.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods. The terms "first", "second", and the like used in the present invention do not denote order, and may be understood as nouns.
Example 1:
s101, preparation of seed crystal suspension: weighing 1g of molecular sieve membrane powder with the sizes of 140nm, 160nm, 180nm, 1.2 mu m, 1.5 mu m and 1.8 mu m respectively, dissolving the powder in 500mL of deionized water to prepare a seed crystal suspension with the concentration of 2g/L, and performing ultrasonic treatment for 1h to uniformly disperse the seed crystal suspension;
s102, pretreatment of a carrier tube: selecting 5 alpha-Al with smooth surface and no obvious defect2O3The carrier tube is put into ultrasonic to be cleaned, then two ends of the carrier tube are sealed and are arranged in a drying box in order, and the carrier tube is heated for 3 hours at 180 ℃ so as to fully remove the moisture in the carrier and enable the surface of the carrier tube to be better coated with the crystal seed particles;
s103, pre-coating seed crystals: the seed crystal is coated by a hot dipping method. Quickly putting the heated carrier into the seed crystal suspension while the carrier is hot, taking out the carrier after 30s, and airing the carrier for later use;
s104, preparation of gel: dissolving 17.99g of boehmite and 32.95g of potassium hydroxide in 366mL of deionized water, stirring at room temperature to fully dissolve the boehmite, then dropwise adding 128.18g of silica sol into the solution, and stirring at room temperature for 8 hours to fully and uniformly mix the solution;
s105, synthesis of a molecular sieve membrane: putting the high-pressure reaction kettle filled with the carrier coated with the seed crystal and the gel into an oven, and crystallizing for 20 hours at 150 ℃;
and S106, repeating the operation of S105, and crystallizing again for 20 hours at 150 ℃.
TABLE 1
Example 2:
s201, preparation of seed crystal suspension: weighing 1g of molecular sieve membrane powder with the size of 160nm (the silicon-aluminum ratio is 5, 10, 15 and 20), respectively dissolving the molecular sieve membrane powder in 500mL of deionized water to prepare seed crystal suspension with the concentration of 2g/L, and performing ultrasonic treatment for 1h to uniformly disperse the seed crystal suspension;
the remaining steps (S202-S206) are the same as those in the first embodiment, and are not described again.
TABLE 2
| Membrane tube numbering | Silicon to aluminum ratio of seed crystal | Permeate side Water content (%) | Flux (kg. m)-2·h-1) | Separation factor |
| 7 | 5 | 92.796 | 10.3353 | 50.9123 |
| 8 | 10 | 99.700 | 9.2337 | 1314.1854 |
| 9 | 15 | 85.875 | 9.6122 | 22.5358 |
| 10 | 20 | 80.812 | 11.5222 | 16.6461 |
Example 3:
the first three steps (S301-S303) are the same as the first embodiment and are not described again;
s304, preparation of gel: three different aluminium sources were used to prepare the gel. Aluminum nitrate: 100.79g of aluminum nitrate and 47.68g of potassium hydroxide are dissolved in 480.54mL of deionized water, and are stirred at room temperature to be fully dissolved, then 185.44g of silica sol is dropwise added into the solution, and the solution is stirred at room temperature for 8 hours to be fully and uniformly mixed; aluminum hydroxide: dissolving 24.26g of aluminum hydroxide and 27.39g of potassium hydroxide in 300.31mL of deionized water, stirring at room temperature to fully dissolve the aluminum hydroxide and the potassium hydroxide, then dropwise adding 106.53g of silica sol into the solution, and stirring at room temperature for 8 hours to fully and uniformly mix the solution; the preparation method of the gel taking boehmite as an aluminum source is the same as the first step;
the fifth step to the sixth step are the same as those in the first embodiment, and are not described again.
TABLE 3
| Membrane tube numbering | Aluminum source | Permeate side Water content (%) | Flux (kg. m)-2·h-1) | Separation factor |
| 11 | Aluminium nitrate | 94.859 | 7.1579 | 63.5988 |
| 12 | Aluminum hydroxide | 96.062 | 1.4469 | 92.7650 |
| 13 | Boehmite (BO) | 99.478 | 3.2450 | 753.5972 |
The detailed description of the drawings: as can be seen from FIG. 1, the molecular sieves are uniformly distributed on the surface of the carrier tube, and the film layer is relatively dense; as can be seen from fig. 2, the thickness of the film layer is about 3 microns, and the thickness is uniform; as can be seen from fig. 3, the CHA membrane characteristic peak coincides with the standard characteristic peak position, indicating successful synthesis of the CHA molecular sieve membrane.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
1. k in the examples of the present invention+Relative to other metal cations (Cs)2+，Sr2+Etc.), a lot of costs are saved.
2. The nano-scale seed crystal is introduced into the embodiment of the invention, the seed crystal with the size can ensure that the synthesized film layer is more compact and uniform, the thickness of the film is thinner, and the small-size seed crystal can also reduce the formation of the surface defects of the film.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (8)
1. A method for preparing a nanoscale CHA-type molecular sieve membrane containing only potassium ion mediator, comprising:
attaching the molecular sieve seed crystal suspension to the surface of a pretreatment carrier tube to obtain a molecular sieve carrier tube;
mixing and stirring a silicon source, an aluminum source, a potassium source and a solvent to obtain gel;
carrying out at least two hydrothermal synthesis reactions on the molecular sieve carrier tube and the gel under a preset pressure condition to obtain a molecular sieve membrane tube;
performing membrane tube separation on the molecular sieve membrane tube to obtain a nano CHA type molecular sieve membrane containing a potassium ion medium;
wherein the molar ratio of the silicon source, the aluminum source and the potassium source satisfies the following relationship:
silicon ion, aluminium ion, potassium ion 1, (0.3-0.6) and (0.6-1.4).
2. The nanoscale CHA-type molecular sieve membrane containing only potassium ionic media of claim 1, wherein the silicon source is at least one of silica, sodium metasilicate nonahydrate, and ethyl orthosilicate, the aluminum source is at least one of alumina, aluminum hydroxide, and aluminum nitrate, and the potassium source is at least one of potassium oxide, potassium hydroxide, and potassium fluoride.
3. The nanoscale CHA-type molecular sieve membrane containing only potassium ion media of claim 1, wherein the starting materials of the molecular sieve seed suspension comprise: the particle size of the nanoscale molecular sieve is 140-180nm, and the particle size of the micron-sized molecular sieve is 1.2-1.8 mu m.
4. The nanoscale CHA-type molecular sieve membrane containing only potassium ion media of claim 1, wherein the mass concentration of the molecular sieve seed suspension is 1-2 g/L.
5. The nanoscale CHA-type molecular sieve membrane containing only potassium ion media of claim 1, wherein pretreatment of the pretreated support tube comprises:
and ultrasonically cleaning the carrier tube, sealing two ends of the carrier tube, and drying at the temperature of 170-190 ℃ after sealing to obtain the pretreated carrier tube.
6. The nanoscale CHA-type molecular sieve membrane containing only potassium ion media of claim 1, wherein said solvent is water and the molar ratio of said solvent satisfies the following relationship:
water, silicon ion (40-200) and 1.
7. The nanoscale CHA-type molecular sieve membrane containing only potassium ion media of claim 1, wherein the predetermined pressure is 50-200 KPa.
8. A nanoscale CHA-type molecular sieve membrane containing only potassium ion mediator, produced by the method of any of claims 1-7.
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| CN202111673596.8A CN114195170A (en) | 2021-12-31 | 2021-12-31 | Nano CHA type molecular sieve membrane only containing potassium ion medium and preparation method thereof |
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Non-Patent Citations (2)
| Title |
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| JI JIANG等: "Fabrication of pure-phase CHA zeolite membranes with ball-milled seeds at low Kt concentration", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
| XIANSEN LI等: "Influence of the hydrothermal synthetic parameters on the pervaporative separation performances of CHA-type zeolite membranes", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
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