CN113209833A - Corrosion-resistant mixed matrix molecular sieve membrane and preparation method thereof - Google Patents
Corrosion-resistant mixed matrix molecular sieve membrane and preparation method thereof Download PDFInfo
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- CN113209833A CN113209833A CN202110447445.4A CN202110447445A CN113209833A CN 113209833 A CN113209833 A CN 113209833A CN 202110447445 A CN202110447445 A CN 202110447445A CN 113209833 A CN113209833 A CN 113209833A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 71
- 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 71
- 239000011159 matrix material Substances 0.000 title claims abstract description 69
- 239000012528 membrane Substances 0.000 title claims abstract description 45
- 230000007797 corrosion Effects 0.000 title claims abstract description 35
- 238000005260 corrosion Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 69
- 239000002184 metal Substances 0.000 claims abstract description 68
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 54
- 230000003647 oxidation Effects 0.000 claims abstract description 38
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 38
- 239000011256 inorganic filler Substances 0.000 claims abstract description 31
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 27
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920000368 omega-hydroxypoly(furan-2,5-diylmethylene) polymer Polymers 0.000 claims abstract description 7
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 7
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 53
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000004140 cleaning Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 239000004698 Polyethylene Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 16
- 229920000573 polyethylene Polymers 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 13
- 229910021536 Zeolite Inorganic materials 0.000 claims description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 13
- 239000010457 zeolite Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
- 238000005868 electrolysis reaction Methods 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 229920000656 polylysine Polymers 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000005238 degreasing Methods 0.000 claims description 6
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000012459 cleaning agent Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 230000002431 foraging effect Effects 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 239000000945 filler Substances 0.000 abstract description 9
- 239000012766 organic filler Substances 0.000 abstract description 6
- 229920000620 organic polymer Polymers 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 17
- 239000001301 oxygen Substances 0.000 description 17
- 229910052760 oxygen Inorganic materials 0.000 description 17
- 239000010949 copper Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QBUKAFSEUHGMMX-MTJSOVHGSA-N (5z)-5-[[3-(1-hydroxyethyl)thiophen-2-yl]methylidene]-10-methoxy-2,2,4-trimethyl-1h-chromeno[3,4-f]quinolin-9-ol Chemical group C1=CC=2NC(C)(C)C=C(C)C=2C2=C1C=1C(OC)=C(O)C=CC=1O\C2=C/C=1SC=CC=1C(C)O QBUKAFSEUHGMMX-MTJSOVHGSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical group 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/148—Organic/inorganic mixed matrix membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention provides a corrosion-resistant mixed matrix molecular sieve membrane and a preparation method thereof, wherein the preparation raw materials of the molecular sieve membrane comprise the following components: valve metal-based porous inorganic filler, polyfurfuryl alcohol, diethyl ether, polyisocyanate, triblock copolymer, tetrahydrofuran and dichloromethane. 2-5 parts of dimethylformamide. The invention takes the poly furfuryl alcohol-ether-triblock copolymer as an organic polymer matrix, then valve metal based porous organic fillers with different pore size grades are doped as dispersed fillers to be dispersed into the organic polymer, the valve metal based porous organic fillers are anchored on organic functional groups of the poly furfuryl alcohol-ether-triblock copolymer as the organic polymer matrix, and then a final molecular sieve membrane is synthesized, and the molecular sieve membrane with excellent cycle performance, mechanical performance and corrosion resistance is provided by microporous hydrophilic poly furfuryl alcohol-ether-triblock copolymer, formed microporous crystallized anodic oxidation valve metal matrix and microporous molecular sieve with larger outer diameter.
Description
Technical Field
The invention belongs to the technical field of molecular sieve membranes for oxygenerators, and particularly relates to a corrosion-resistant mixed matrix molecular sieve membrane and a preparation method thereof.
Background
Oxygen is the first element for life maintenance, and is a powerful guarantee for the battle effectiveness of the regional troops in the plateau. Whether the wounded can absorb oxygen in time in the gold time or platinum time of treatment is an important factor for reducing the casualty rate and improving the treatment capacity of war wounds. The current common oxygen supply modes mainly comprise oxygen storage and supply, physical oxygen generation and chemical oxygen generation. Physical oxygen generation is most widely applied, oxygen enrichment is realized by selective adsorption of oxygen under pressure swing conditions through a molecular sieve, and although the oxygen enrichment can meet the use requirements under most conditions, the oxygen enrichment cannot meet the requirements of troops in practical use in plateau areas and special areas. Pressure Swing Adsorption (PSA) molecular sieve oxygen generation has been applied to the field of air separation and has been rapidly developed due to its outstanding advantages of high oxygen purity and cheap and easily available adsorption material. In the PSA gas separation technology, the adsorption capacity of the molecular sieve can directly affect the final separation effect, even the complexity of the process steps, and therefore, the development of efficient and stable adsorbents or adsorption films becomes the core of the PSA technology.
Most of molecular sieves adopted in the prior art are zeolite molecular sieves, but have the defects of poor recycling performance, poor air separation effect, high possibility of being corroded by trace impurities such as sulfide, moisture and the like.
Disclosure of Invention
Aiming at the defects, the invention provides the mixed matrix molecular sieve membrane with good cycle performance, excellent corrosion resistance, high permeability and selectivity and the preparation method thereof.
The invention provides the following technical scheme: the corrosion-resistant mixed matrix molecular sieve membrane comprises the following raw materials in parts by weight:
further, the preparation method of the valve metal-based porous inorganic filler comprises the following steps:
s1: weighing tetrapropylammonium hydroxide, potassium hydroxide, tetraethoxysilane and deionized water in a mass-to-volume ratio of 0.2-0.5: 0.8-1.5: 2-5: 80-90, wherein the potassium hydroxide is in a mass ratio, and the balance is in a volume ratio;
s2: mixing the potassium hydroxide with the mass and the deionized water with the volume, stirring at 50-100 rpm for 5-10 min, and gradually dropwise adding the tetrapropylammonium hydroxide with the volume in the stirring process;
s3: continuously stirring for 3-5 min until the mixture is fully mixed, continuously dropwise adding the volume of tetraethoxysilane gradually under the stirring rotating speed state of 50-100 rpm, and continuously stirring for 1.5-1.8 h for aging to obtain the adhesive electrolyte for electrolysis;
s4: pouring the adhesive electrolyte for electrolysis obtained in the step S3 into a reaction kettle provided with an anodic oxidation valve metal matrix, carrying out hydrothermal crystallization at 200-240 ℃, continuously stirring at a rotating speed of 100-150 rpm for 45-60 min, and gradually adding 50-60 parts of porous inorganic filler and 10-20 parts of ammonium ceric nitrate during stirring;
s5: after the reaction is finished, the temperature is rapidly reduced in a cold water bath at 5-10 ℃, and the formed microporous crystallized anodic oxidation valve metal matrix is self-filled with the multi-mesoporous inorganic filler with different graft copolymerization particle sizes to form the valve metal multi-porous inorganic filler of the microporous crystallized anodic oxidation valve metal matrix with the inner diameter of 0.5-1.5 nm and the multi-mesoporous inorganic filler with the outer diameter of 30-50 nm.
Further, the metal in the metal matrix of the anodic oxidation valve in the step S1 is one of Fe, Al, Cu, or Zn.
Further, the preparation method of the metal matrix of the anodic oxidation valve comprises the following steps:
m1: immersing the valve metal plate in absolute ethyl alcohol, cleaning the valve metal plate in an ultrasonic cleaning agent at the frequency of 50 KHz-70 KHz for 30 min-40 min, and degreasing and cleaning the valve metal plate;
m2: placing the valve metal plate cleaned in the step M1 in NaOH solution with the concentration of 1.5-2M, soaking for 30-45 s at 90-100 ℃ to remove an oxide film on the surface of the valve metal plate, further degreasing and avoiding scratches during subsequent processing, then quickly taking out, cleaning for 2-4 times by using deionized water, and drying at 30-35 ℃;
m3: placing the valve metal plate cleaned in the M2 step in a 1.5-2M nitric acid solution, soaking for 30-45 s at 90-100 ℃ to further remove the hanging ash on the surface of the valve metal plate, avoiding the electrolyte pollution caused by the reaction with the electrolytic solution in the electrolytic process, then quickly taking out, cleaning for 2-4 times by using deionized water, and drying at 30-35 ℃;
m4: and (3) forming a closed circuit by taking a graphite plate as a cathode, a valve metal plate as an anode and phosphoric acid with the concentration of 4-5M as electrolyte under a constant-current voltage-stabilizing external power supply, and carrying out anodic oxidation for 45-60 min to obtain the anodic oxidation valve metal matrix.
Further, the valve metal plate has an area of 6 to 10cm × 10 to 15cm × 20 to 30 cm.
Further, the anodic oxidation working voltage in the M4 step is 4V-40V, and the working current is 10 mA-15 mA.
Further, the triblock copolymer is one or more of perfluoropolyoxypropylene-polyethylene glycol-perfluoropolyoxypropylene, methoxy-polyethylene glycol-polylactic acid-polylysine, polyethylene oxide-polypropylene oxide-polyethylene oxide and polyoxyethylene-polyoxypropylene-polyoxyethylene.
Further, the polyisocyanate is one or more of diphenylmethane-4, 4' -diiso-acid, 1, 6-diiso-hexylate, 4-diiso-hexylate and diiso-trimethylhexylate.
Further, the porous inorganic filler is one or more of NaY nano molecular sieve with the particle size of 30-50 nm, zeolite molecular sieve with the particle size of 40-50 nm and porous carbon with the particle size of 35-45 nm.
The invention also provides a preparation method of the corrosion-resistant mixed matrix molecular sieve membrane, which comprises the following steps:
1) uniformly mixing one third of the tetrahydrofuran in parts by weight with the dichloromethane in parts by weight, and then stirring the mixture with the triblock copolymer in parts by weight and the polyisocyanate in parts by weight at the temperature of between 50 and 60 ℃ for 1 to 1.5 hours to obtain an isocyanate-terminated triblock copolymer;
2) stirring and reacting the isocyanate-terminated triblock copolymer obtained in the step 1) with the polyfurfuryl alcohol, the ether and the dimethylformamide in parts by weight for 20-30 min at the temperature of 15-20 ℃ and the rotating speed of 80-150 rpm, and volatilizing organic matters under the conditions of nitrogen flow and the temperature of 25-27 ℃ to obtain the microporous polyfurfuryl alcohol-ether-triblock copolymer with the particle size of 0.2-0.4 nm;
3) uniformly mixing the polyfurfuryl alcohol-diethyl ether-triblock copolymer obtained in the step 2) with one third of tetrahydrofuran in parts by weight;
4) mixing the weight part of the valve metal-based porous inorganic filler with the remaining last third of the weight part of tetrahydrofuran uniformly;
5) mixing the mixed solution obtained in the step 3) and the mixed solution obtained in the step 4), stirring vigorously at the rotating speed of 300-500 rpm for 2-3 h, then carrying out ultrasonic treatment at the frequency of 30-40 KHz for 10-20 min to remove bubbles, then coating the mixed solution on a silicon substrate, volatilizing tetrahydrofuran at the temperature of 25-27 ℃, and drying to finally obtain the corrosion-resistant mixed matrix molecular sieve membrane.
The invention has the beneficial effects that:
1. the component of the valve metal-based porous inorganic filler adopted in the corrosion-resistant mixed matrix molecular sieve membrane and the preparation method thereof is self-prepared, in the preparation method process, the porous inorganic filler with a mesoporous level is grafted on the internal microporous crystallized anodic oxidation valve metal matrix with a certain content ratio of silicon and metal elements by utilizing ethyl orthosilicate and the anodic oxidation valve metal matrix prepared by a hydrothermal crystallization method, ammonium ceric nitrate is used as an initiator to form the valve metal-based porous inorganic filler with the smaller inner diameter of-0.5 nm-1.5 nm and the larger outer diameter of-30 nm-50 nm, and then a large amount of porous molecular sieve with the larger outer diameter enters the internal microporous crystallized anodic oxidation valve metal matrix formed by self-assembly in the process of adsorbing nitrogen, so that more attachment points are provided for the nitrogen due to the smaller inner pore diameter, the adsorption point and the accommodation surface area can further accommodate more adsorbed nitrogen, the nitrogen in the porous molecular sieve filler accommodated with larger outer diameter can be gradually released in the desorption process of the nitrogen, the nitrogen adsorbed inside can be further released, the blocking condition of the molecular sieve caused in the nitrogen desorption process can be avoided, the desorption is more thorough, the molecular sieve membrane with the valve metal-based porous inorganic filler has good cycle performance, the valve metal-based porous inorganic filler can be repeatedly used for 4-6 times, and the production cost and the replacement cost are saved.
2. The invention provides a method for preparing a molecular sieve membrane by using a polyfurfuryl alcohol-ether-triblock copolymer as an organic polymer matrix, then doping valve metal-based porous organic fillers with different aperture grades as dispersed fillers to be dispersed in the organic polymer, and carrying out condensation reaction on active groups of dimethylformamide and silicon hydroxyl groups of valve metal-based porous inorganic fillers with the outer diameter of mesoporous grade to generate corresponding covalent bonds, so that the valve metal-based porous organic fillers are anchored on organic functional groups of the polyfurfuryl alcohol-ether-triblock copolymer as the organic polymer matrix, and further synthesize a final molecular sieve membrane, wherein the filled valve metal-based porous organic fillers with different aperture grades can change the properties of adjacent polymer phases, are favorable for the integral transportation of the polymer to separated substances, and integrate the advantages of the microporous polymer formed by the valve metal-based porous organic fillers with different aperture grades and the polyfurfuryl alcohol-ether-triblock copolymer, thereby improving the separation efficiency of the oxygen and the nitrogen and improving the permeability and the selectivity of the oxygen and the nitrogen to the gas.
3. The valve metal-based porous inorganic filler adopted in the corrosion-resistant mixed matrix molecular sieve membrane and the preparation method thereof provided by the invention is a microporous crystallized anodic oxidation valve metal matrix formed by self-assembling an anodic oxidation valve metal matrix obtained by self-preparation through tetraethoxysilane.
4. The porous inorganic filler adopted by the invention has the characteristics of large specific surface area, small density, small heat conductivity, small relative density, large porosity and the like, and further can be well compatible with nitrogen, the probability of nitrogen being adsorbed and anchored on a molecular sieve membrane is improved, and the air content and oxygen generation efficiency of the molecular sieve are improved.
Drawings
The invention will be described in more detail hereinafter on the basis of embodiments and with reference to the accompanying drawings.
Wherein:
FIG. 1 is a scanning electron microscope image of a valve metal-based porous inorganic filler having a porous inorganic filler with an outer diameter of 50nm of a corrosion-resistant mixed matrix molecular sieve membrane provided by the present invention;
FIG. 2 is a scanning electron microscope image of a valve metal-based porous inorganic filler of a microporous crystallized anodized valve metal matrix with an inner diameter of 1.5nm of the corrosion-resistant mixed matrix molecular sieve membrane provided by the invention.
Detailed description of the preferred embodiments
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The raw materials for preparing the corrosion-resistant mixed matrix molecular sieve membrane provided by the embodiment comprise the following components in parts by weight:
the preparation method of the Fe-based NaY zeolite molecular sieve comprises the following steps:
s1: weighing 1.5g of potassium hydroxide, 0.5mL of tetrapropylammonium hydroxide, 5mL of ethyl orthosilicate and 80mL of deionized water in a mass-to-volume ratio of 0.5:1.5:5: 80;
s2: mixing 1.5g of potassium hydroxide with 80mL of deionized water, stirring at 100rpm for 10min, and gradually dropwise adding 0.5mL of tetrapropylammonium hydroxide in the stirring process;
s3: continuously stirring for 5min till the mixture is fully and uniformly mixed, continuously dropwise adding 5mL of tetraethoxysilane step by step under the stirring rotating speed state of 100rpm, and continuously stirring for 1.8h for aging to obtain the adhesive electrolyte for electrolysis;
s4: pouring the adhesive electrolyte for electrolysis obtained in the step S3 into a reaction kettle filled with an anodized Fe matrix, performing hydrothermal crystallization at 240 ℃, continuously stirring at 150rpm for 60min, and gradually adding 60 parts of cerium ammonium nitrate with the particle size of 20 parts in the stirring process;
s5: after the reaction is finished, the temperature is rapidly reduced in a cold water bath at 10 ℃, a microporous crystallized anodic oxidation Fe matrix with the inner diameter of 1.5nm is formed by self-assembly, and a microporous NaY molecular sieve with the outer diameter of 50nm is subjected to graft copolymerization to form a Fe-based porous inorganic filler with the inner diameter of 1.5nm and the outer diameter of 50nm, as shown in a figure 1, a scanning electron microscope image of the Fe-based NaY zeolite molecular sieve with the microporous crystallized anodic oxidation Fe matrix with the inner diameter of 1.5nm is shown, and as shown in a figure 2, a scanning electron microscope image of the Fe-based NaY zeolite molecular sieve filler with the mesoporous NaY molecular sieve filler with the outer diameter of 50nm is shown.
The preparation method of the anodic oxidation Fe matrix comprises the following steps:
m1: immersing an iron plate with the length multiplied by the width multiplied by the height multiplied by 10cm multiplied by 15cm multiplied by 30cm into absolute ethyl alcohol, cleaning the iron plate in an ultrasonic cleaning agent for 40min at the frequency of 70KHz, and degreasing and cleaning the iron plate;
m2: placing the iron plate cleaned in the step M1 in a 2M NaOH solution, soaking for 45s at 100 ℃, then quickly taking out, cleaning for 4 times by using deionized water, and drying at 35 ℃;
m3: placing the valve metal plate cleaned in the M2 step in a 2M nitric acid solution, soaking for 45s at 100 ℃ to further remove the hanging ash on the surface of the iron plate, then quickly taking out, cleaning for 4 times by using deionized water, and drying at 35 ℃;
m4: and (2) forming a closed circuit under a constant-current voltage-stabilizing external power supply by taking a graphite plate as a cathode, an iron plate as an anode and phosphoric acid with the concentration of 5M as electrolyte, and carrying out anodic oxidation for 60min under the conditions of 40V working voltage and 15mA working current to obtain the anodic oxidation Fe matrix.
The embodiment also provides a preparation method of the corrosion-resistant mixed matrix molecular sieve membrane, which comprises the following steps:
1) uniformly mixing 10 parts of tetrahydrofuran and 10 parts of dichloromethane, and then stirring the mixture with 10 parts of methoxy-polyethylene glycol-polylactic acid-polylysine and 27 parts of 1, 6-diisohexanoic acid at the temperature of 60 ℃ for 1.5 hours to obtain isocyanate group-terminated methoxy-polyethylene glycol-polylactic acid-polylysine;
2) stirring and reacting the 1, 6-adipic acid-terminated methoxy-polyethylene glycol-polylactic acid-polylysine obtained in the step 1) with 40 parts of polyfurfuryl alcohol, 20 parts of ether and 5 parts of dimethylformamide at the rotating speed of 150rpm at 20 ℃ for 30min, and volatilizing organic matters at the temperature of 27 ℃ in nitrogen flow to obtain a 0.4nm microporous polyfurfuryl alcohol-ether-triblock copolymer;
3) uniformly mixing the polyfurfuryl alcohol-diethyl ether-methoxy-polyethylene glycol-polylactic acid-polylysine obtained in the step 2) with 10 parts of tetrahydrofuran;
4) uniformly mixing 50 parts of Fe-based NaY zeolite molecular sieve with the remaining 10 parts of tetrahydrofuran;
5) and (3) mixing the mixed solution obtained in the step (3) and the mixed solution obtained in the step (4), stirring vigorously at a rotating speed of 500rpm for 3h, carrying out ultrasonic treatment at a frequency of 40KHz for 0min to remove bubbles, coating the mixed solution on a silicon substrate, volatilizing tetrahydrofuran at a temperature of 27 ℃, and drying to finally obtain the corrosion-resistant mixed matrix molecular sieve membrane.
Example 2
The embodiment provides a corrosion-resistant mixed matrix molecular sieve membrane, which comprises the following raw materials in parts by weight:
the preparation method of the Cu-based porous zeolite molecular sieve comprises the following steps:
s1: weighing 1g of potassium hydroxide, 0.3mL of tetrapropylammonium hydroxide, 4mL of ethyl orthosilicate and 85mL of deionized water in a mass-to-volume ratio of 0.3:1:4: 85;
s2: mixing 1g of potassium hydroxide with the volume of deionized water, stirring at 85rpm for 7min, and gradually dropwise adding 0.3mL of tetrapropylammonium hydroxide in the stirring process;
s3: continuously stirring for 4min till the mixture is fully and uniformly mixed, continuously dropwise adding 4mL of tetraethoxysilane step by step under the stirring rotating speed state of 75rpm, and continuously stirring for 1.7h for aging to obtain the adhesive electrolyte for electrolysis;
s4: pouring the adhesive electrolyte for electrolysis obtained in the step S3 into a reaction kettle filled with an anodic oxidation Cu matrix, carrying out hydrothermal crystallization at 220 ℃, continuously stirring at the rotating speed of 120rpm for 50min, and gradually adding 55 parts of 45nm zeolite molecular sieve and 15 parts of ammonium ceric nitrate during stirring;
s5: after the reaction is finished, the temperature is rapidly reduced in a cold water bath at 7 ℃, and the microporous crystallized anodic oxidation Cu matrix with the inner diameter of 0.8nm is formed by self-assembly, and is subjected to graft copolymerization with a mesoporous zeolite molecular sieve with the outer diameter of 45nm to form a Cu-based porous zeolite molecular sieve with the inner diameter of 0.8nm and the outer diameter of 45 nm.
The preparation method of the anodic oxidation Cu matrix comprises the following steps:
m1: immersing a copper plate with the length multiplied by the width multiplied by the height multiplied by 8cm multiplied by 12cm multiplied by 25cm into absolute ethyl alcohol, cleaning for 35min in an ultrasonic cleaning agent at the frequency of 60KHz, and degreasing and cleaning the valve metal plate;
m2: placing the copper plate cleaned in the step M1 in a NaOH solution with the concentration of 1.8M, soaking for 40s at 95 ℃, then quickly taking out, cleaning for 3 times by using deionized water, and drying at 32 ℃;
m3: placing the valve metal plate cleaned in the M2 step in a 1.8M nitric acid solution, soaking at 95 ℃ for 40s to further remove the hanging ash on the surface of the copper plate, then quickly taking out, cleaning for 3 times by using deionized water, and drying at 32 ℃;
m4: and (3) forming a closed circuit by taking a graphite plate as a cathode, a valve metal plate as an anode and phosphoric acid with the concentration of 4.5M as electrolyte under a constant-current voltage-stabilizing external power supply, and carrying out anodic oxidation for 55min under the conditions of 20V working voltage and 12mA working current to obtain the anodic oxidation Cu matrix.
The embodiment also provides a preparation method of the corrosion-resistant mixed matrix molecular sieve membrane, which comprises the following steps:
1) uniformly mixing 9 parts of tetrahydrofuran and 9 parts of dichloromethane, and then stirring the mixture with 8 parts of polyoxyethylene-polyoxypropylene-polyoxyethylene and the polyisocyanate by weight at 55 ℃ for 1.2 hours to obtain an isocyanate-terminated triblock copolymer;
2) stirring and reacting the isocyanate-terminated polyoxyethylene-polyoxypropylene-polyoxyethylene obtained in the step 1) with 37.5 parts of polyfurfuryl alcohol, 17.5 parts of diethyl ether and 3.5 parts of dimethylformamide at the rotating speed of 120rpm at 18 ℃ for 25min, and volatilizing organic matters at the temperature of 26 ℃ in nitrogen flow to obtain microporous polyfurfuryl alcohol-diethyl ether-polyoxyethylene-polyoxypropylene-polyoxyethylene of 0.3 nm;
3) uniformly mixing the polyfurfuryl alcohol-diethyl ether-polyoxyethylene-polyoxypropylene-polyoxyethylene obtained in the step 2) with 9 parts of tetrahydrofuran;
4) uniformly mixing 45 parts of Cu-based porous zeolite molecular sieve and the remaining 9 parts of tetrahydrofuran;
5) and (3) mixing the mixed solution obtained in the step (3) and the mixed solution obtained in the step (4), stirring vigorously at a rotating speed of 40rpm for 2.5h, carrying out ultrasonic treatment at a frequency of 35KHz for 15min to remove bubbles, coating the mixed solution on a silicon substrate, volatilizing tetrahydrofuran at a temperature of 26 ℃, and drying to finally obtain the corrosion-resistant mixed matrix molecular sieve membrane.
Example 3
The embodiment provides a corrosion-resistant mixed matrix molecular sieve membrane, which is characterized in that the molecular sieve membrane comprises the following raw materials in parts by weight:
the preparation method of the Al-based porous carbon filler comprises the following steps:
s1: weighing 0.8g of potassium hydroxide, 0.2mL of tetrapropylammonium hydroxide, 2mL of ethyl orthosilicate and 80mL of deionized water in a mass-to-volume ratio of 0.2:0.8:2: 80;
s2: mixing 0.8g of potassium hydroxide with 80mL of deionized water, stirring at 50rpm for 5min, and gradually dropwise adding 0.2mL of tetrapropylammonium hydroxide in the stirring process;
s3: continuously stirring for 3min till the mixture is fully and uniformly mixed, continuously dropwise adding 2mL of tetraethoxysilane step by step under the stirring rotating speed state of 50rpm, and continuously stirring for 1.5h for aging to obtain the adhesive electrolyte for electrolysis;
s4: pouring the adhesive electrolyte for electrolysis obtained in the step S3 into a reaction kettle filled with an anodic oxidation Cu matrix, carrying out hydrothermal crystallization at 200 ℃, continuously stirring at the rotating speed of 100rpm for 45min, and gradually adding 50 parts of 35nm porous carbon and 10 parts of ammonium ceric nitrate in the stirring process;
s5: after the reaction is finished, the temperature is rapidly reduced in a cold water bath at 5 ℃, the formed microporous crystallized anodic oxidation Cu matrix with the inner diameter of 0.5nm is automatically assembled to graft copolymerize porous carbon with the diameter of 35nm, and the Al-based porous carbon filler of the microporous crystallized anodic oxidation Cu matrix with the inner diameter of 0.5nm and the mesoporous inorganic filler with the outer diameter of 30nm is formed.
The preparation method of the anodic oxidation Al matrix comprises the following steps:
m1: immersing an aluminum plate with the length multiplied by the width multiplied by the height multiplied by 6cm multiplied by 10cm multiplied by 20cm into absolute ethyl alcohol, cleaning for 30min in an ultrasonic cleaning agent at the frequency of 50KHz, and degreasing and cleaning the valve metal plate;
m2: placing the aluminum plate cleaned in the step M1 in a NaOH solution with the concentration of 1.5M, soaking at 90 ℃ for 30s, then quickly taking out, cleaning for 2 times by using deionized water, and drying at 30 ℃;
m3: placing the aluminum plate cleaned in the M2 step in a 1.5M nitric acid solution, soaking at 90 ℃ for 30s to further remove the ash on the surface of the valve metal plate, then quickly taking out, cleaning for 2 times by using deionized water, and drying at 30 ℃;
m4: and (2) forming a closed circuit by taking a graphite plate as a cathode, an aluminum plate as an anode and phosphoric acid with the concentration of 4M as electrolyte under a constant-current voltage-stabilizing external power supply, and carrying out anodic oxidation for 45min under the conditions of 4V working voltage and 10mA working current to obtain the anodic oxidation Al matrix.
The embodiment also provides a preparation method of the corrosion-resistant mixed matrix molecular sieve membrane, which comprises the following steps:
1) uniformly mixing 8 parts of tetrahydrofuran and 7 parts of dichloromethane, and then stirring the mixture with 6 parts of perfluoropolyoxypropylene-polyethylene glycol-perfluoropolyoxypropylene and 18 parts of 4, 4-dihexylmethanediisopropanoic acid at 50 ℃ for 1 hour to obtain isocyanate-terminated perfluoropolyoxypropylene-polyethylene glycol-perfluoropolyoxypropylene;
2) stirring and reacting the isocyanate-terminated perfluoro polyoxypropylene-polyethylene glycol-perfluoro polyoxypropylene obtained in the step 1) with 35 parts of polyfurfuryl alcohol, 15 parts of ether and 2 parts of dimethylformamide at the rotating speed of 80rpm at 15 ℃ for 20min, and volatilizing organic matters at the temperature of 25 ℃ in nitrogen flow to obtain a microporous polyfurfuryl alcohol-ether-triblock copolymer with the particle size of 0.2 nm;
3) uniformly mixing the polyfurfuryl alcohol-diethyl ether-triblock copolymer obtained in the step 2) with 8 parts of tetrahydrofuran;
4) uniformly mixing 40 parts of the Al-based porous carbon filler with the remaining last 8 parts of tetrahydrofuran;
5) and (3) mixing the mixed solution obtained in the step (3) and the mixed solution obtained in the step (4), stirring vigorously at a rotating speed of 300rpm for 2 hours, carrying out ultrasonic treatment at a frequency of 30KHz for 10 minutes to remove bubbles, coating the mixed solution on a silicon substrate, volatilizing tetrahydrofuran at 25 ℃ and drying to finally obtain the corrosion-resistant mixed matrix molecular sieve membrane.
Comparative example 1
This comparative example differs from example 1 only in that, instead of using a valve metal-based porous inorganic filler, it was prepared directly using an inorganic porous filler,
comparative example 2
The difference between the comparative example and the example 1 is that in the preparation process of the valve metal-based porous inorganic filler, tetrapropylammonium hydroxide, potassium hydroxide, ethyl orthosilicate and deionized water in a mass-volume ratio of 0.2-0.5: 0.8-1.5: 2-5: 80-90 are not used as electrolyte solution, the prepared anodic oxidation valve metal matrix and the porous inorganic filler are heated and mixed in a reaction kettle, dimethylformamide is not added, and then the mixture is cooled again, mixed with tetrahydrofuran in the subsequent step 4) in the preparation process of the molecular sieve membrane, and then coated on a silicon substrate together with a tetrahydrofuran mixture of the polyfurfuryl alcohol-ethyl ether-triblock copolymer to prepare the molecular sieve membrane.
Comparative example 3
This comparative example differs from example 1 only in that microporous polyfurfuryl alcohol-ether-methoxy-polyethylene glycol-polylactic acid-polylysine was prepared without using polyisocyanate and polyfurfuryl alcohol as a substrate for preparing a molecular sieve membrane by the following method:
1) uniformly mixing 10 parts of tetrahydrofuran and 10 parts of dichloromethane, and then stirring the mixture with 10 parts of methoxy-polyethylene glycol-polylactic acid-polylysine at the temperature of 60 ℃ for 1.5 hours;
2) stirring the mixture obtained in the step 1) with 20 parts of diethyl ether and 5 parts of dimethylformamide at the rotating speed of 150rpm at 20 ℃ for 30min, and volatilizing organic matters at 27 ℃ in nitrogen flow to obtain a diethyl ether-triblock copolymer;
3) uniformly mixing the diethyl ether-methoxy-polyethylene glycol-polylactic acid-polylysine obtained in the step 2) with 10 parts of tetrahydrofuran;
4) uniformly mixing 50 parts of Fe-based NaY zeolite molecular sieve with the remaining 10 parts of tetrahydrofuran;
5) mixing the mixed solution obtained in the step 3) and the mixed solution obtained in the step 4), stirring vigorously at a rotating speed of 500rpm for 3h, then carrying out ultrasonic treatment at a frequency of 40KHz for 0min to remove bubbles, then coating the mixed solution on a silicon substrate, volatilizing tetrahydrofuran at a temperature of 27 ℃ and drying,
test example
The number of cycles, hydrophilic angle, mechanical strength, corrosion resistance (salt spray corrosion test), oxygen production purity, total porosity of the molecular sieve membranes of examples 1 to 3 and comparative examples 1 to 3 were measured, respectively. The results are shown in Table 1.
TABLE 1
While the invention has been described with reference to a preferred embodiment, various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In particular, the technical features mentioned in the embodiments can be combined in any manner as long as there is no technical solution conflict. It is intended that the invention not be limited to the particular embodiments disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (10)
1. The corrosion-resistant mixed matrix molecular sieve membrane is characterized by comprising the following raw materials in parts by weight:
2. the corrosion-resistant mixed matrix molecular sieve membrane of claim 1, wherein the valve metal-based porous inorganic filler is prepared by a method comprising the steps of:
s1: weighing tetrapropylammonium hydroxide, potassium hydroxide, tetraethoxysilane and deionized water in a mass-to-volume ratio of 0.2-0.5: 0.8-1.5: 2-5: 80-90, wherein the potassium hydroxide is in a mass ratio, and the balance is in a volume ratio;
s2: mixing the potassium hydroxide with the mass and the deionized water with the volume, stirring at 50-100 rpm for 5-10 min, and gradually dropwise adding the tetrapropylammonium hydroxide with the volume in the stirring process;
s3: continuously stirring for 3-5 min until the mixture is fully mixed, continuously dropwise adding the volume of tetraethoxysilane gradually under the stirring rotating speed state of 50-100 rpm, and continuously stirring for 1.5-1.8 h for aging to obtain the adhesive electrolyte for electrolysis;
s4: pouring the adhesive electrolyte for electrolysis obtained in the step S3 into a reaction kettle provided with an anodic oxidation valve metal matrix, carrying out hydrothermal crystallization at 200-240 ℃, continuously stirring at a rotating speed of 100-150 rpm for 45-60 min, and gradually adding 50-60 parts of porous inorganic filler and 10-20 parts of ammonium ceric nitrate during stirring;
s5: after the reaction is finished, the temperature is rapidly reduced in a cold water bath at 5-10 ℃, and the formed microporous crystallized anodic oxidation valve metal matrix is self-filled with the multi-mesoporous inorganic filler with different graft copolymerization particle sizes to form the valve metal multi-porous inorganic filler of the microporous crystallized anodic oxidation valve metal matrix with the inner diameter of 0.5-1.5 nm and the multi-mesoporous inorganic filler with the outer diameter of 30-50 nm.
3. The corrosion-resistant mixed matrix molecular sieve membrane of claim 2, wherein the metal in the metal matrix of the anodic oxidation valve in step S1 is one of Fe, Al, Cu, or Zn.
4. The corrosion-resistant mixed matrix molecular sieve membrane of claim 2, wherein the preparation method of the anodized valve metal substrate comprises the following steps:
m1: immersing the valve metal plate in absolute ethyl alcohol, cleaning the valve metal plate in an ultrasonic cleaning agent at the frequency of 50 KHz-70 KHz for 30 min-40 min, and degreasing and cleaning the valve metal plate;
m2: placing the valve metal plate cleaned in the step M1 in NaOH solution with the concentration of 1.5-2M, soaking for 30-45 s at 90-100 ℃, then quickly taking out, cleaning for 2-4 times by using deionized water, and drying at 30-35 ℃;
m3: placing the valve metal plate cleaned in the M2 step in a 1.5-2M nitric acid solution, soaking for 30-45 s at 90-100 ℃ to further remove the hanging ash on the surface of the valve metal plate, then quickly taking out, cleaning for 2-4 times by using deionized water, and drying at 30-35 ℃;
m4: and (3) forming a closed circuit by taking a graphite plate as a cathode, a valve metal plate as an anode and phosphoric acid with the concentration of 4-5M as electrolyte under a constant-current voltage-stabilizing external power supply, and carrying out anodic oxidation for 45-60 min to obtain the anodic oxidation valve metal matrix.
5. The corrosion-resistant mixed matrix molecular sieve membrane of claim 4, wherein the valve metal plate has an area of 6 to 10cm x 10 to 15cm x 20 to 30 cm.
6. The corrosion-resistant mixed matrix molecular sieve membrane of claim 4, wherein the anodic oxidation operating voltage in the M4 step is 4V-40V, and the operating current is 10 mA-15 mA.
7. The corrosion-resistant mixed matrix molecular sieve membrane of claim 1, wherein the triblock copolymer is one or more of perfluoropolyoxypropylene-polyethylene glycol-perfluoropolyoxypropylene, methoxy-polyethylene glycol-polylactic acid-polylysine, polyethylene oxide-polypropylene oxide-polyethylene oxide, and polyoxyethylene-polyoxypropylene-polyoxyethylene.
8. The corrosion-resistant mixed matrix molecular sieve membrane of claim 1, wherein the polyisocyanate is one or more of diphenylmethanediisocynate, 1, 6-hexanediisocynate, 4-dihexylmethanediisocynate, and trimethylhexanediisocynate.
9. The corrosion-resistant mixed matrix molecular sieve membrane of claim 2, wherein the porous inorganic filler is one or more of NaY nano molecular sieve with a particle size of 30nm to 50nm, zeolite molecular sieve with a particle size of 40nm to 50nm, and porous carbon with a particle size of 35nm to 45 nm.
10. The method for preparing a corrosion-resistant mixed matrix molecular sieve membrane according to any one of claims 1 to 9, comprising the steps of:
1) uniformly mixing one third of the tetrahydrofuran in parts by weight with the dichloromethane in parts by weight, and then stirring the mixture with the triblock copolymer in parts by weight and the polyisocyanate in parts by weight at the temperature of between 50 and 60 ℃ for 1 to 1.5 hours to obtain an isocyanate-terminated triblock copolymer;
2) stirring and reacting the isocyanate-terminated triblock copolymer obtained in the step 1) with the polyfurfuryl alcohol, the ether and the dimethylformamide in parts by weight for 20-30 min at the temperature of 15-20 ℃ and the rotating speed of 80-150 rpm, and volatilizing organic matters under the conditions of nitrogen flow and the temperature of 25-27 ℃ to obtain the microporous polyfurfuryl alcohol-ether-triblock copolymer with the particle size of 0.2-0.4 nm;
3) uniformly mixing the polyfurfuryl alcohol-diethyl ether-triblock copolymer obtained in the step 2) with one third of tetrahydrofuran in parts by weight;
4) mixing the weight part of the valve metal-based porous inorganic filler with the remaining last third of the weight part of tetrahydrofuran uniformly;
5) mixing the mixed solution obtained in the step 3) and the mixed solution obtained in the step 4), stirring vigorously at the rotating speed of 300-500 rpm for 2-3 h, then carrying out ultrasonic treatment at the frequency of 30-40 KHz for 10-20 min to remove bubbles, then coating the mixed solution on a silicon substrate, volatilizing tetrahydrofuran at the temperature of 25-27 ℃, and drying to finally obtain the corrosion-resistant mixed matrix molecular sieve membrane.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220165619A1 (en) * | 2019-08-16 | 2022-05-26 | Fujifilm Corporation | Method for manufacturing structure |
| CN116272421A (en) * | 2023-03-24 | 2023-06-23 | 泰州九润环保科技有限公司 | Molecular sieve/polyamide mixed matrix membrane |
| US12002713B2 (en) * | 2019-08-16 | 2024-06-04 | Fujifilm Corporation | Method for manufacturing structure |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6060415A (en) * | 1997-02-10 | 2000-05-09 | National Science Council | Aligned molecular sieve crystals grown on anodic alumina membrane |
| US20050029114A1 (en) * | 2003-08-05 | 2005-02-10 | Tripp Terrance B. | Method of passing electric current through highly resistive anodic oxide films |
| CN101084052A (en) * | 2004-11-19 | 2007-12-05 | 切夫里昂美国公司 | Mixed matrix membrane with mesoporous particles and methods for making the same |
| CN101934231A (en) * | 2010-07-20 | 2011-01-05 | 浙江大学 | Synthetic method of molecular sieve ZSM-5 on porous anodic oxide film of stainless steel screen |
| CN102274710A (en) * | 2011-05-19 | 2011-12-14 | 浙江大学 | Method for preparing zeolite socony mobile-5 (ZSM-5) molecular sieve membrane reactor loaded with Cu/stainless steel screen mesh catalyst |
| CN103112854A (en) * | 2013-01-31 | 2013-05-22 | 黑龙江大学 | Method for synthesizing carbide/porous graphitized carbon nano compound through one-step method |
| CN103182251A (en) * | 2013-03-20 | 2013-07-03 | 北京工业大学 | Method for preparing organic/inorganic alcohol-permselective pervaporation composite membrane |
| CN106000132A (en) * | 2016-06-17 | 2016-10-12 | 哈尔滨工业大学宜兴环保研究院 | Preparation method of metal organic frame ZIF-8/polydopamine hybrid molecular sieve gas separation membrane |
| EP3110879A1 (en) * | 2014-02-27 | 2017-01-04 | Kyoto University | Crosslinked polymer, method for producing the same, molecular sieve composition and material separation membranes |
| CN106378013A (en) * | 2016-11-10 | 2017-02-08 | 南京工业大学 | Preparation method and application of hierarchical porous molecular sieve membrane |
| CN111423577A (en) * | 2020-03-03 | 2020-07-17 | 蜂巢能源科技有限公司 | Composite polymer and preparation method and application thereof |
| TW202041722A (en) * | 2019-02-15 | 2020-11-16 | 日商富士軟片股份有限公司 | Anodizing method and method for fabrication of anisotropic conductive member |
-
2021
- 2021-04-25 CN CN202110447445.4A patent/CN113209833B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6060415A (en) * | 1997-02-10 | 2000-05-09 | National Science Council | Aligned molecular sieve crystals grown on anodic alumina membrane |
| US20050029114A1 (en) * | 2003-08-05 | 2005-02-10 | Tripp Terrance B. | Method of passing electric current through highly resistive anodic oxide films |
| CN101084052A (en) * | 2004-11-19 | 2007-12-05 | 切夫里昂美国公司 | Mixed matrix membrane with mesoporous particles and methods for making the same |
| CN101934231A (en) * | 2010-07-20 | 2011-01-05 | 浙江大学 | Synthetic method of molecular sieve ZSM-5 on porous anodic oxide film of stainless steel screen |
| CN102274710A (en) * | 2011-05-19 | 2011-12-14 | 浙江大学 | Method for preparing zeolite socony mobile-5 (ZSM-5) molecular sieve membrane reactor loaded with Cu/stainless steel screen mesh catalyst |
| CN103112854A (en) * | 2013-01-31 | 2013-05-22 | 黑龙江大学 | Method for synthesizing carbide/porous graphitized carbon nano compound through one-step method |
| CN103182251A (en) * | 2013-03-20 | 2013-07-03 | 北京工业大学 | Method for preparing organic/inorganic alcohol-permselective pervaporation composite membrane |
| EP3110879A1 (en) * | 2014-02-27 | 2017-01-04 | Kyoto University | Crosslinked polymer, method for producing the same, molecular sieve composition and material separation membranes |
| CN106000132A (en) * | 2016-06-17 | 2016-10-12 | 哈尔滨工业大学宜兴环保研究院 | Preparation method of metal organic frame ZIF-8/polydopamine hybrid molecular sieve gas separation membrane |
| CN106378013A (en) * | 2016-11-10 | 2017-02-08 | 南京工业大学 | Preparation method and application of hierarchical porous molecular sieve membrane |
| TW202041722A (en) * | 2019-02-15 | 2020-11-16 | 日商富士軟片股份有限公司 | Anodizing method and method for fabrication of anisotropic conductive member |
| CN111423577A (en) * | 2020-03-03 | 2020-07-17 | 蜂巢能源科技有限公司 | Composite polymer and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| QADIR, D; NASIR, R; ET AL.: "Synthesis, characterization, and performance analysis of carbon molecular sieve-embedded polyethersulfone mixed-matrix membranes for the removal of dissolved ions", 《WATER ENVIRONMENT RESEARCH》 * |
| 张小勇: "酚醛树脂基混合基质炭分子筛膜的制备及应用", 《中国博士学位论文全文数据库 工程科技Ⅱ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220165619A1 (en) * | 2019-08-16 | 2022-05-26 | Fujifilm Corporation | Method for manufacturing structure |
| US12002713B2 (en) * | 2019-08-16 | 2024-06-04 | Fujifilm Corporation | Method for manufacturing structure |
| CN116272421A (en) * | 2023-03-24 | 2023-06-23 | 泰州九润环保科技有限公司 | Molecular sieve/polyamide mixed matrix membrane |
| CN116272421B (en) * | 2023-03-24 | 2024-03-29 | 泰州九润环保科技有限公司 | Molecular sieve/polyamide mixed matrix membrane |
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