CN113023679A - Oxygen generation device of medical high-temperature molecular sieve membrane adsorption tower and use method thereof - Google Patents
Oxygen generation device of medical high-temperature molecular sieve membrane adsorption tower and use method thereof Download PDFInfo
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- CN113023679A CN113023679A CN202110456550.4A CN202110456550A CN113023679A CN 113023679 A CN113023679 A CN 113023679A CN 202110456550 A CN202110456550 A CN 202110456550A CN 113023679 A CN113023679 A CN 113023679A
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- 239000001301 oxygen Substances 0.000 title claims abstract description 182
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 182
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 131
- 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 131
- 239000012528 membrane Substances 0.000 title claims abstract description 127
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 113
- 238000000034 method Methods 0.000 title claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000000919 ceramic Substances 0.000 claims abstract description 76
- -1 oxygen ion Chemical class 0.000 claims abstract description 61
- 238000003860 storage Methods 0.000 claims abstract description 55
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 34
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 17
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 11
- 239000012510 hollow fiber Substances 0.000 claims description 65
- 239000002905 metal composite material Substances 0.000 claims description 40
- 239000011259 mixed solution Substances 0.000 claims description 40
- 239000000843 powder Substances 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000013078 crystal Substances 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 29
- 239000002608 ionic liquid Substances 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 21
- 239000000835 fiber Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000004642 Polyimide Substances 0.000 claims description 19
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 19
- 229920001721 polyimide Polymers 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 13
- 229920001046 Nanocellulose Polymers 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229920002678 cellulose Polymers 0.000 claims description 10
- 239000001913 cellulose Substances 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 8
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 8
- 229920001732 Lignosulfonate Polymers 0.000 claims description 8
- ZXLOSLWIGFGPIU-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCN1CN(C)C=C1 ZXLOSLWIGFGPIU-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- UCORDLUWXAPELE-UHFFFAOYSA-N C(CCCCC)N1CN(C=C1)C.C(C)(=O)O Chemical compound C(CCCCC)N1CN(C=C1)C.C(C)(=O)O UCORDLUWXAPELE-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 241000894006 Bacteria Species 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 6
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 241000700605 Viruses Species 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 230000001133 acceleration Effects 0.000 claims description 5
- 238000007872 degassing Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 239000004627 regenerated cellulose Substances 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 239000002918 waste heat Substances 0.000 claims description 5
- 238000004528 spin coating Methods 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- OLMFDKTUFUAGOW-UHFFFAOYSA-N methyl acetate;1h-pyrrole Chemical compound COC(C)=O.C=1C=CNC=1 OLMFDKTUFUAGOW-UHFFFAOYSA-N 0.000 claims description 3
- HCGMDEACZUKNDY-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCCCN1CN(C)C=C1 HCGMDEACZUKNDY-UHFFFAOYSA-N 0.000 claims description 2
- 238000003795 desorption Methods 0.000 claims description 2
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 2
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 210000004379 membrane Anatomy 0.000 description 54
- 230000008569 process Effects 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000010942 ceramic carbide Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000036512 infertility Effects 0.000 description 1
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- 239000013081 microcrystal Substances 0.000 description 1
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- 229920000368 omega-hydroxypoly(furan-2,5-diylmethylene) polymer Polymers 0.000 description 1
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- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000010457 zeolite 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
- 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
- C01B13/0251—Physical processing only by making use of membranes
- C01B13/0255—Physical processing only by making use of membranes characterised by the type of membrane
-
- 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
- C01B13/0274—Other molecular sieve materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/28—Polysaccharides or derivatives thereof
- C04B26/285—Cellulose or derivatives thereof
Abstract
The invention provides an oxygen generating device of a medical grade high temperature molecular sieve membrane adsorption tower and a using method thereof, comprising an air source access port, an air compressor, a C-grade filter, an air storage tank, a T-grade filter, an A-grade filter, an H-grade filter, 2-4 high temperature carbonized ceramic-based molecular sieve adsorption units, a vacuum pump, an oxygen storage tank and a nitrogen storage tank which are sequentially communicated; the vacuum pump is arranged in the high-temperature carbonized ceramic-based molecular sieve adsorption unit, the high-temperature carbonized ceramic-based molecular sieve adsorption unit is communicated with the oxygen gas storage tank through an oxygen flow distribution pipeline, and the high-temperature carbonized ceramic-based molecular sieve adsorption unit is communicated with the nitrogen gas storage tank through a nitrogen flow distribution pipeline. The oxygen generating device provided by the invention has the molecular sieve of the adsorption tower of the oxygen ion conductive carbonized ceramic-based molecular sieve membrane with good cyclic utilization rate, and the oxygen ions are adsorbed and desorbed under high-temperature vacuum so as to efficiently separate oxygen and nitrogen and improve the oxygen generating purity.
Description
Technical Field
The invention belongs to the technical field of oxygen generators, and particularly relates to an oxygen generation device of a medical high-temperature molecular sieve membrane adsorption tower and a using method thereof.
Background
With the economic development and the improvement of medical guarantee conditions, the demand of medical oxygen is increasing year by year. The medical molecular sieve oxygen generation system adopts a molecular sieve pressure swing adsorption technology at normal temperature and low pressure, and has the advantages of simple process flow, small investment and convenient maintenance, so that most of medium and small hospitals adopt the molecular sieve oxygen generation system as an oxygen source. At present, the medical molecular sieve oxygen generation systems available on the market have various models, but the technological process and the main structure are the same, and the core of the medical molecular sieve oxygen generation system is composed of an air compressor, an oxygen generator and an oxygen storage tank.
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, the adsorption of the molecular sieves is a physical adsorption principle, the recyclable performance is poor, before oxygen and nitrogen are prepared and separated, air needs to be subjected to cold treatment, and the separation of the oxygen and the nitrogen is performed at normal temperature to perform the adsorption and desorption of the nitrogen. This results in poor oxygen production efficiency, low purity, poor molecular sieve recycle, and other disadvantages.
Disclosure of Invention
Aiming at the defects, the invention provides the molecular sieve of the adsorption tower with the oxygen ion conductive carbonized ceramic-based molecular sieve membrane with good cyclic utilization rate, and the oxygen generation device of the medical high-temperature molecular sieve membrane adsorption tower, which can adsorb and desorb oxygen ions under high-temperature vacuum so as to efficiently separate oxygen and nitrogen and improve the oxygen generation purity, and the use method thereof.
The invention provides the following technical scheme: an oxygen generation device of a medical grade high temperature molecular sieve membrane adsorption tower comprises an air source access port, an air compressor, a C-grade filter, an air storage tank, a T-grade filter, an A-grade filter, an H-grade filter, 2-4 high temperature carbonized ceramic-based molecular sieve adsorption units, a vacuum pump, an oxygen storage tank and a nitrogen storage tank which are sequentially communicated, wherein a first stop valve is arranged at the tail end of the oxygen storage tank, and a second stop valve is arranged at the tail end of the nitrogen storage tank;
the vacuum pump is arranged in the high-temperature ceramic carbide-based molecular sieve adsorption unit, the high-temperature ceramic carbide-based molecular sieve adsorption unit is communicated with the oxygen gas storage tank through an oxygen flow distribution pipeline, and the high-temperature ceramic carbide-based molecular sieve adsorption unit is communicated with the nitrogen gas storage tank through a nitrogen flow distribution pipeline;
the high-temperature carbonized ceramic-based molecular sieve adsorption unit comprises a first valve, a vacuum pressure gauge, an adsorption tower of a molecular sieve with an oxygen ion conductive carbonized ceramic-based molecular sieve membrane connected in parallel and a second valve; and the bottom end of each high-temperature carbonized ceramic-based molecular sieve adsorption unit adsorption tower is provided with an oxygen outlet and a nitrogen outlet, all the oxygen outlets are communicated and converged with the oxygen distribution pipeline, and all the nitrogen outlets are communicated and converged with the nitrogen distribution pipeline.
Further, the preparation raw materials of the oxygen ion conductive carbonized ceramic-based molecular sieve membrane adopted by the molecular sieve in the adsorption tower comprise the following components in parts by weight:
said BaxCe1-xCoyFe1-yO3-zIn the formula, x is more than or equal to 0.1 and less than or equal to 0.6, y is more than or equal to 0.1 and less than or equal to 0.4, and z is more than or equal to 1 and less than or equal to 2.5.
Further, the acetate-form ionic liquid is one or more of 1-butyl-3-methylimidazole acetate, 1-methyl-3-ethylimidazole acetate, 1-hexyl-3-methylimidazole acetate, 1-2-methyl-2-pyrrole methyl acetate or 2-methylpyrrole-3-ethyl formate.
Further, the nano-cellulose is one or more of nano-hydroxymethyl cellulose, nano-hydroxyethyl cellulose, nano-sodium carboxymethyl cellulose or nano-lignosulfonate; the diameter of the nano-cellulose is 50 nm-80 nm.
Further, said BaxCe1-xCoyFe1-yO3-zThe preparation method of the hollow fiber membrane comprises the following steps:
s1: adding 15-20 parts by weight of EDTA into an ammonium hydroxide aqueous solution to form a water-soluble EDTA ammonium salt solution with the concentration of 3-3.5M;
s2: mixing BaCl according to the molar ratio of x:1-x: y:1-y2、CeCl3、CoCl2And FeCl3Powder, then mixing with 20 to 25 parts of sodium citrate, and dissolving in 500 to 1000ml of distilled water;
s3: stirring the water-soluble EDTA ammonium salt solution obtained in the step S1 and the mixed solution obtained in the step S2 at the temperature of 35-45 ℃ at the rotating speed of 300-350 rpm for 30-45 min;
s4: heating the mixed solution obtained in the step S3 at 90-120 ℃ for 2-2.5 h to remove excessive water to obtain viscous gel; heating and drying the viscous gel at the temperature of 200-250 ℃ for 1.5-2 h to obtain a metal composite powder precursor;
s5: performing heat treatment on the metal composite powder precursor obtained in the step S4 at 800-1000 ℃ for 45-60 min by using airflow of 0.3-0.6L/min to remove residual carbon, and forming metal composite crystal powder with a perovskite structure and a particle size of 30-35 mu m;
s6: adding half of the metal composite crystal powder with the perovskite structure obtained in the step S5 into 400-450 ml of ethanol, and carrying out ball milling in a planetary ball mill for 30-40 min to obtain metal composite crystal suspension liquid with the particle size of 2-2.5 microns;
s7: dissolving 30-40 parts by weight of polytetrafluoroethylene powder in 50-60 parts by weight of N-methyl-2-pyrrolidone, stirring at 180-200 rpm for 15min to form polytetrafluoroethylene polymer solution, mixing the remaining half of the metal composite crystalline powder with the perovskite structure obtained in the step S5 with the polytetrafluoroethylene polymer solution, and stirring at 150-200 rpm for 20-30 min to ensure uniform mixing;
s8: degassing the mixed solution obtained in the step S7, transferring the mixed solution into a stainless steel liquid storage tank, introducing nitrogen for pressurization, immersing fibers drawn out from a spinneret plate at the speed of 8-10 n/min into a water bath through an air gap of 3-5 cm by adopting a nozzle spinneret with the outer diameter of 2-2.5 mm and the inner diameter of 0.6-0.8 mm to form a gelled fiber film, thoroughly cleaning the gelled fiber film in water, and drying the gelled fiber film in an oven at the temperature of 140-160 ℃ to form a gel hollow fiber film;
s9: taking the metal composite crystal suspension with the particle size of 2-2.5 microns obtained in the step S6 as an external coating precursor solution, immersing the gel hollow fiber membrane obtained in the step S8 in the external coating precursor solution for 1-5S to obtain a coating hollow fiber membrane, and drying the obtained coating hollow fiber in the air for 15 min;
s10: repeating the step S9 for three to five times, gradually heating the obtained coating hollow fiber to 900 to 1000 ℃ in an air flow of 80 to 100ml/min, preserving heat for 1h to decompose and remove the polymer, sintering at 1100 to 1200 ℃ for 1h to 2h, and cooling to room temperature at a rate of 10 ℃/min to obtain the BaxCe1-xCoyFe1-yO3-zA hollow fiber membrane.
Further, the concentration of the ammonium hydroxide aqueous solution used in the step S1 is 25% to 30% by mass fraction concentration.
Further, nitrogen is introduced into the step S8 to pressurize to 250 KPa-300 KPa; the length of the gel hollow fiber membrane formed in the step S8 is 15 cm-20 cm.
Further, said prepared BaxCe1-xCoyFe1-yO3-zThe hollow fiber membrane has an outer diameter of 1.00mm to 1.20mm and an inner diameter of 0.65mm to 0.75 mm.
The invention also provides a preparation method of the oxygen ion conductive carbonized ceramic-based molecular sieve membrane, which comprises the following steps:
1) mixing the acetate ionic liquid, the nanocellulose with the polymerization degree of 480-520 and the dimethyl sulfoxide according to parts by weight, and stirring at the rotating speed of 100-150 rpm at 80-100 ℃ to form an acetate ionic liquid modified nanocellulose mixed solution;
2) filtering the mixed solution of the acetate ionic liquid modified nano-cellulose obtained in the step 1) through a polyvinylidene fluoride filter membrane with the thickness of 10-15 microns, and heating under vacuum at 40-50 ℃ to remove air in the liquid for 45 min;
3) mixing the mixed solution obtained in the step 2) with the polyimide, the polyacrylonitrile and the polyvinylpyrrolidone in parts by weight, and obtaining a polyacrylonitrile/polyimide grafted acetate ionic liquid modified nanocellulose solution at a rotation speed of 150 rpm-200 rpm at room temperature by means of the waste heat of the mixed solution obtained in the step 2);
4) mixing the said parts by weight of BaxCe1-xCoyFe1-yO3-zPlacing the hollow fiber membrane on a spin coater, rotating at the rotating speed of 1800 rpm-2200 rpm, and spin-coating the polyacrylonitrile/polyimide grafted acetate ionic liquid modified nanocellulose solution obtained in the step 3) on the Ba at the rotating speed acceleration of 1000rpm/sxCe1-xCoyFe1-yO3-z10-15 s on the hollow fiber membrane;
5) after coating, the membrane is immediately solidified in distilled water at room temperature to obtain a regenerated cellulose membrane, then the membrane is intensively cleaned for 10-20 min by distilled water to remove redundant ionic liquid, then the cleaned membrane is immersed in propylene glycol with the mass fraction of 5-7% for 30 s-1 min, and then the membrane is dried for 10min in an oven at the temperature of 90-100 ℃ to obtain the oxygen ion conductive carbonized ceramic-based molecular sieve membrane.
The invention also provides a use method of the oxygen generation device of the medical grade high temperature molecular sieve membrane adsorption tower, which comprises the following steps:
m1: when oxygen generation starts, air is introduced through the air source access port, compressed by the air compressor, filtered by the C-level filter and then enters the air storage tank, the air in the air storage tank is filtered by the T-level filter, the A-level filter and the H-level filter in sequence to remove bacteria and viruses, then enters the high-temperature carbonized ceramic-based molecular sieve adsorption unit, the first valve, the first stop valve and the second stop valve are closed, and the second valve is opened;
m2: heating the 1 st high-temperature carbonized ceramic-based molecular sieve adsorption unit to 150-180 ℃, keeping the temperature constant for 20-30 min, and vacuumizing for 10-15 min at the pressure of 100-150 MPa by using the vacuum pump during constant-temperature heat preservation;
m3: then closing the second valve, cooling to 40-45 ℃ in a vacuum state, preserving heat for 5-10 min, then opening the second valve and an oxygen outlet of the 1 st high-temperature carbonized ceramic-based molecular sieve adsorption unit, releasing oxygen and entering the oxygen storage tank through an oxygen diversion pipeline;
m4: judging whether the oxygen concentration entering the oxygen storage tank is impure through an oxygen concentration analyzer arranged on the oxygen diversion pipeline, closing an oxygen outlet, opening a nitrogen outlet, and cooling the 1 st high-temperature carbonized ceramic-based molecular sieve adsorption unit to room temperature;
m5: and (3) starting the 2 nd high-temperature carbonized ceramic-based molecular sieve adsorption unit, repeating the steps M2-M4 to separate and collect oxygen and nitrogen, and circularly heating the 2-4 high-temperature carbonized ceramic-based molecular sieve adsorption units to release and adsorb oxygen to complete the oxygen generation of the oxygen generation device.
The invention has the beneficial effects that:
1. according to the oxygen generation device of the medical-grade high-temperature molecular sieve membrane adsorption tower, the T-grade filter, the A-grade filter and the H-grade filter are arranged between the air storage tank and the high-temperature carbonized ceramic-based molecular sieve adsorption unit, and medical-grade bacteria and viruses of air before air separation and oxygen generation are filtered, so that the sterility rate of oxygen obtained by air separation is improved, and the requirement of the oxygen generation device for compounding medical-grade oxygen is met.
2. The invention provides an oxygen generator of a medical-grade high-temperature molecular sieve membrane adsorption tower, wherein a molecular sieve membrane adopted by the adsorption tower is selected in the aspect of preparing a raw material base membrane, and a polymer solution extrusion, gelation and sintering method is adopted to adopt BaCl2、CeCl3、CoCl2And FeCl3Self-prepared BaxCe1-xCoyFe1-yO3-zIn the preparation process of the hollow fiber membrane, Fe is replaced by Co to form metal composite crystal powder with a perovskite crystal structure, so that finally obtained BaxCe1-xCoyFe1- yO3-zThe hollow fiber membrane has higher hole conductivity and oxygen ion conductivity, can have higher affinity to oxygen in the air, and then fills the adsorption to the O (1) position of the perovskite crystal structure at normal temperature in the gradual temperature rise process, so that the process of chemically adsorbing the oxygen ions in the oxygen is realized, the perovskite crystal structure with an orthogonal phase structure is gradually converted into a tetragonal phase, the metallic conductive property of the orthogonal phase is converted into the semiconductor conductive property, the resistivity is further reduced along with the transition, and the reduction of the oxygen generation efficiency caused by the reduction of the oxygen ion conductive adsorption property due to the electromagnetic interference generated by an external electromagnetic valve is avoided.
3. The invention provides an oxygen generator of a medical grade high-temperature molecular sieve membrane adsorption tower, which prepares BaxCe1-xCoyFe1- yO3-zHollow fiber membraneIn the preparation process, the metal composite crystal powder with the perovskite structure is divided into two parts for subsequent preparation, one part is ball-milled to obtain 2-2.5 mu m metal composite crystal suspension, the other part and polytetrafluoroethylene polymer are used for obtaining a large-aperture membrane substrate to prepare a precursor mixed solution, then a hollow fiber membrane is obtained by spinning to obtain a hollow fiber membrane, the metal composite crystal suspension obtained by ball milling is coated with the metal composite crystal suspension with the diameter of 2-2.5 mu m to obtain a hollow fiber membrane with larger outer diameter and smaller inner diameter, so that a molecular sieve membrane substrate with different outer diameter and inner diameter porosity is formed, when oxygen ions in the air are subjected to affinity adsorption with a substrate film with larger outer diameter, the temperature is gradually increased to 150-180 ℃ in the using process and the temperature is kept for 20-30 min, so that the oxygen ions in the air can fill the O (1) position of the perovskite structure at normal temperature, further permeating into the base film with small internal porosity under the vacuum pressure of the vacuum pump, thereby further enabling Ba to be absorbedxCe1-xCoyFe1-yO3-zThe hollow fiber membrane is used as a basement membrane to increase the oxygen ion adsorption capacity, and Ba is further contained in the subsequent step of cooling M3 to 40-45 ℃ and keeping the temperature for 5-10 minxCe1-xCoyFe1-yO3-zThe material of the hollow fiber membrane is gradually changed into an orthogonal phase from a tetragonal phase, then oxygen ions contained in the hollow fiber membrane are gradually released, then oxygen is desorbed, and the oxygen is released and enters the oxygen storage tank through an oxygen diversion pipeline by opening the second valve and an oxygen outlet of the 1 st high-temperature carbonized ceramic-based molecular sieve adsorption unit.
4. The invention provides an oxygen generation device of a medical-grade high-temperature molecular sieve membrane adsorption tower.A molecular sieve membrane adopted by the adsorption tower adopts polyacrylonitrile, polyimide acetate ionic liquid and nanocellulose with the polymerization degree of 450-plus-500, in ionic liquid cations, the polyacrylonitrile is firstly grafted and copolymerized with the polyimide, then the position of a hydrogen bond acceptor in the ionic liquid in an anion structure and the lack of a hydrogen bond donor are beneficial to the dissolution of the cellulose, and acetic acid anions in the acetate ionic liquid form hydrogen bonds with hydroxyl protons of the cellulose, thereby being beneficial to the dissolution of the cellulose and the hydroxyl protons of the polyimideHydroxyl is subjected to charge attraction to finally form polyacrylonitrile/polyimide grafted acetate ionic liquid modified nanocellulose solution, and the solution is spin-coated on BaxCe1-xCoyFe1-yO3-zThe hollow fiber membrane is modified, so that the hole conductivity and the affinity charge attraction capability of oxygen ions are improved, the adsorption capability of the finally obtained oxygen ion conductive carbonized ceramic-based molecular sieve membrane on the oxygen ions is further improved, the adsorption capability on oxygen in the air can be further improved in the temperature rising process, and the hydrophilic performance of the polyfurfuryl alcohol can ensure that the blockage phenomenon of the base membrane after the polyacrylonitrile/polyimide grafted acetate ionic liquid modified nanocellulose is spin-coated and modified can not occur in the oxygen generation process;
5. the ionic liquid is a group of green solvent salts with poor ion coordination and low melting point, has wide melting temperature (-40-400 ℃), low vapor pressure, excellent dissolving capacity, high thermal stability (up to 400 ℃), nonflammability, chemical stability and easy recycling, can well dissolve the nano-cellulose, and has low crystallization tendency due to the large volume and asymmetric cation structure, so that the prepared carbonized ceramic molecular sieve membrane has high separation performance, mechanical resistance and stability.
6. The invention is in the preparation of BaxCe1-xCoyFe1-yO3-zIn the process of the hollow fiber membrane, the step S9 is repeated for three to five times in the step S10, then the obtained coated hollow fiber is gradually heated to 900 to 1000 ℃ in an air flow of 80 to 100ml/min and is kept for 1h, after the high-temperature carbonization step is completed, the coated hollow fiber membrane presents a highly aromatic structure formed by perfectly wrapping disordered sp hybridized carbon sheets, pores formed by stacking defects among microcrystal areas in the material are formed, and a microstructure with bimodal pore size distribution, namely micropores connected with ultramicropores is formed. The micropores provide adsorption sites for oxygen ions, while the ultramicropores can adsorb and desorb molecular sieve oxygen, so that finally prepared BaxCe1-xCoyFe1- yO3-zThe hollow fiber membrane has high permeability and high selectivityAnd (4) selectivity.
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 schematic structural diagram of an oxygen generation device of a medical grade high-temperature molecular sieve membrane adsorption tower provided by the invention;
fig. 2 is a schematic structural diagram of a high-temperature carbonized ceramic-based molecular sieve adsorption unit 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
As shown in fig. 1, the oxygen generation apparatus for a medical-grade high-temperature molecular sieve membrane adsorption tower provided by this embodiment includes an air source access port 1, an air compressor 2, a C-stage filter 3, an air storage tank 4, a T-stage filter, an a-stage filter, an H-stage filter, 4 high-temperature carbonized ceramic-based molecular sieve adsorption units 5, a vacuum pump 6, an oxygen storage tank 7, and a nitrogen storage tank 8, which are sequentially communicated, wherein a first stop valve 7-3 is disposed at a tail end of the oxygen storage tank 7, and a second stop valve 8-3 is disposed at a tail end of the nitrogen storage tank 8;
the vacuum pump 6 is arranged in the high-temperature carbonized ceramic-based molecular sieve adsorption unit 5, the high-temperature carbonized ceramic-based molecular sieve adsorption unit 5 is communicated with the oxygen gas storage tank 7 through an oxygen diversion pipeline 7-2, and the high-temperature carbonized ceramic-based molecular sieve adsorption unit 5 is communicated with the nitrogen gas storage tank 8 through a nitrogen diversion pipeline 8-2;
the high-temperature carbonized ceramic-based molecular sieve adsorption unit 5 comprises a first valve 5-1, a vacuum pressure gauge 5-2, an adsorption tower 5-3 of a molecular sieve with an oxygen ion conductive carbonized ceramic-based molecular sieve membrane connected in parallel and a second valve 5-4; the bottom end of each high-temperature carbonized ceramic-based molecular sieve adsorption unit 5 is provided with an oxygen gas outlet 7-1 and a nitrogen gas outlet 8-1, all the oxygen gas outlets 7-1 are communicated and converged with an oxygen flow distribution pipeline 7-2, and all the nitrogen gas outlets 8-1 are communicated and converged with a nitrogen flow distribution pipeline 8-2.
The preparation raw materials of the oxygen ion conductive carbonized ceramic-based molecular sieve membrane adopted by the molecular sieve in the adsorption tower comprise the following components in parts by weight:
the diameter of the nano hydroxyethyl cellulose with the polymerization degree of 500 adopted in the embodiment is 50 nm.
Ba in this example0.6Ce0.4Co0.4Fe0.1O2The preparation method of the hollow fiber membrane comprises the following steps:
s1: adding 20 parts by weight of EDTA into 30% ammonium hydroxide aqueous solution by mass fraction to form 3.5M concentration water-soluble EDTA ammonium salt solution;
s2: mixing BaCl according to a molar ratio of 6:4:4:12、CeCl3、CoCl2And FeCl3Powder, then mixed with 25 parts of sodium citrate and dissolved in 1000ml of distilled water;
s3: stirring the water-soluble EDTA ammonium salt solution obtained in the step S1 and the mixed solution obtained in the step S2 at the rotating speed of 350rpm for 45min at the temperature of 45 ℃;
s4: heating the mixed solution obtained in the step S3 at 120 ℃ for 2.5 hours to remove excessive water to obtain viscous gel; heating and drying the viscous gel at 250 ℃ for 2h to obtain a metal composite powder precursor;
s5: carrying out heat treatment on the metal composite powder precursor obtained in the step S4 at 1000 ℃ for 60min by using airflow of 0.6L/min to remove residual carbon, and forming metal composite crystal powder with a particle size of 35 mu m and a perovskite structure;
s6: adding one half of the metal composite crystal powder with the perovskite structure obtained in the step S5 into 450ml of ethanol, and performing ball milling in a planetary ball mill for 40min to obtain metal composite crystal suspension with the particle size of 2.5 mu m;
s7: dissolving 40 parts by weight of polytetrafluoroethylene powder in 60 parts by weight of N-methyl-2-pyrrolidone, stirring at 200rpm for 15min to form polytetrafluoroethylene polymer solution, mixing the remaining half of metal composite crystal powder with the perovskite structure obtained in step S5 with the polytetrafluoroethylene polymer solution, and stirring at 200rpm for 30min to ensure uniform mixing;
s8: degassing the mixed solution obtained in the step S7, transferring the mixed solution into a stainless steel liquid storage tank, introducing nitrogen to pressurize to 300KPa, immersing fibers drawn out from a spinneret plate at the speed of 10n/min into a water bath through an air gap of 5cm by adopting a nozzle spinneret with the outer diameter of 2.5mm and the inner diameter of 0.8mm to form a gelled fiber film with the length of 20cm by adopting a nozzle spinneret with the outer diameter of 2.5mm and the inner diameter of 0.8mm, and then completely cleaning the gelled fiber film in water and drying the gelled fiber film in an oven at 160 ℃ to form a gelled hollow fiber film;
s9: taking the metal composite crystal suspension with the particle size of 2.5 microns obtained in the step S6 as an external coating precursor solution, immersing the gel hollow fiber membrane obtained in the step S8 in the external coating precursor solution for 5S to obtain a coating hollow fiber membrane, and drying the obtained coating hollow fiber in the air for 15 min;
s10: repeating the step S9 for five times, gradually heating the obtained coated hollow fiber to 1000 deg.C in 100ml/min air flow, maintaining for 1h to decompose and remove polymer, sintering at 1200 deg.C for 2h, and cooling to room temperature at 10 deg.C/min to obtain Ba with outer diameter of 1.20mm and inner diameter of 0.75mm0.6Ce0.4Co0.4Fe0.1O2A hollow fiber membrane.
The invention also provides a preparation method of the oxygen ion conductive carbonized ceramic-based molecular sieve membrane, which comprises the following steps:
1) mixing 30 parts of 1-hexyl-3-methylimidazole acetate, 20 parts of nano hydroxyethyl cellulose with the polymerization degree of 520 and 70 parts of dimethyl sulfoxide, and stirring at 100 ℃ at the rotating speed of 150rpm to form a 1-hexyl-3-methylimidazole acetate modified nano hydroxyethyl cellulose mixed solution;
2) filtering the 1-hexyl-3-methylimidazole acetate modified nano hydroxyethyl cellulose mixed solution obtained in the step 1) by using a polyvinylidene fluoride filter membrane with the thickness of 10 microns, and heating at 50 ℃ under vacuum to remove air in the liquid for 45 min;
3) mixing the mixed solution obtained in the step 2) with 20 parts of polyimide, 20 parts of polyacrylonitrile and 5 parts of polyvinylpyrrolidone, and obtaining a polyacrylonitrile/polyimide grafted 1-hexyl-3-methylimidazole acetate modified nano hydroxyethyl cellulose solution at room temperature at a rotation speed of 200rpm by means of the waste heat of the mixed solution obtained in the step 2);
4) 50 parts of Ba0.6Ce0.4Co0.4Fe0.1O2Placing the hollow fiber membrane on a spin coater, rotating at the speed of 2200rpm, and spin-coating the polyacrylonitrile/polyimide grafted 1-hexyl-3-methylimidazole acetate modified nano hydroxyethyl cellulose solution obtained in the step 3) on Ba at the acceleration of 1000rpm/s0.6Ce0.4Co0.4Fe0.1O215s on the hollow fiber membrane;
5) immediately after coating, the membrane was coagulated in distilled water at room temperature to obtain a regenerated cellulose membrane, then the membrane was intensively washed with distilled water for 20min to remove excess ionic liquid, then the washed membrane was immersed in propylene glycol containing 7% by mass for 1min, and then dried in an oven at 100 ℃ for 10min to obtain the oxygen ion conductive carbonized ceramic-based molecular sieve membrane.
The embodiment also provides a use method of the oxygen generation device of the medical grade high temperature molecular sieve membrane adsorption tower, which comprises the following steps:
m1: when oxygen generation starts, air is introduced through an air source inlet 1, compressed by an air compressor 2, filtered by a C-level filter 3 and then enters an air storage tank 4, the air in the air storage tank 4 is filtered by a T-level filter, an A-level filter and an H-level filter in sequence to remove bacteria and viruses and then enters a high-temperature carbonized ceramic-based molecular sieve adsorption unit 5, a first valve 5-1, a first stop valve 7-3 and a second stop valve 8-3 are closed, and a second valve 5-2 is opened;
m2: heating the 1 st high-temperature carbonized ceramic-based molecular sieve adsorption unit for 5-180 ℃, keeping the temperature constant for 30min, and vacuumizing for 15min under the pressure of 150MPa by using a vacuum pump during constant-temperature heat preservation;
m3: then closing the second valve 5-2, cooling to 45 ℃ in a vacuum state, preserving heat for 10min, then opening the second valve 5-2 and an oxygen outlet 7-1 of the 1 st high-temperature carbonized ceramic-based molecular sieve adsorption unit 5, releasing oxygen and entering an oxygen storage tank 7 through an oxygen diversion pipeline 7-2;
m4: judging that the oxygen concentration entering the oxygen gas storage tank 7 is impure by an oxygen concentration analyzer arranged on the oxygen flow dividing pipeline 7-2, closing an oxygen gas outlet 7-1, opening a nitrogen gas outlet 8-1, and cooling a 1 st high-temperature carbonized ceramic-based molecular sieve adsorption unit 5 to room temperature and desorbing;
m5: and (3) starting the 2 nd high-temperature carbonized ceramic-based molecular sieve adsorption unit 5, repeating the steps M2-M4 to separate and collect oxygen and nitrogen, and circularly heating the 4 nd high-temperature carbonized ceramic-based molecular sieve adsorption units 5 to release and adsorb oxygen to complete the oxygen generation of the oxygen generation device.
Example 2
The only difference in structure between this example and example 1 is that the apparatus provided in this example contains 3 high temperature carbonized ceramic-based molecular sieve adsorption units 5.
The raw material for preparing the oxygen ion conductive carbonized ceramic-based molecular sieve membrane adopted by the molecular sieve in the adsorption tower of the device provided by the embodiment comprises the following components in parts by weight:
the diameter of the nanometer sodium carboxymethyl cellulose with the polymerization degree of 475 adopted in the embodiment is 65 nm.
Wherein, said Ba0.3Ce0.7Co0.2Fe0.8The preparation method of the O hollow fiber membrane comprises the following steps:
s1: adding 17.5 parts by weight of EDTA into 26% ammonium hydroxide aqueous solution by mass fraction to form 3.3M concentration water-soluble EDTA ammonium salt solution;
s2: mixing BaCl according to a molar ratio of 3:7:2:82、CeCl3、CoCl2And FeCl3The powder is then mixed with 22.5 parts of sodium citrate and dissolved in 750ml of distilled water;
s3: stirring the water-soluble EDTA ammonium salt solution obtained in the step S1 and the mixed solution obtained in the step S2 at the temperature of 40 ℃ at the rotating speed of 325rpm for 37.5 min;
s4: heating the mixed solution obtained in the step S3 at 105 ℃ for 2.2 hours to remove excessive water to obtain viscous gel; heating and drying the viscous gel at 225 ℃ for 1.75h to obtain a metal composite powder precursor;
s5: carrying out heat treatment on the metal composite powder precursor obtained in the step S4 at 900 ℃ for 50min by using airflow of 0.45L/min to remove residual carbon, and forming metal composite crystal powder with a perovskite structure and a particle size of 32 mu m;
s6: adding half of the metal composite crystal powder with the perovskite structure obtained in the step S5 into 430ml of ethanol, and performing ball milling in a planetary ball mill for 35min to obtain metal composite crystal suspension with the particle size of 2.25 mu m;
s7: dissolving 35 parts of polytetrafluoroethylene powder in 55 parts of N-methyl-2-pyrrolidone, stirring at 190rpm for 15min to form polytetrafluoroethylene polymer solution, mixing the remaining half of the metal composite crystalline powder with the perovskite structure obtained in the step S5 with the polytetrafluoroethylene polymer solution, and stirring at 175rpm for 25min to ensure uniform mixing;
s8: degassing the mixed solution obtained in the step S7, transferring the mixed solution into a stainless steel liquid storage tank, introducing nitrogen to pressurize to 270KPa, immersing fibers drawn out from a spinneret plate at the speed of 9n/min into a water bath through a 4cm air gap by adopting a nozzle spinneret with the outer diameter of 2.25mm and the inner diameter of 0.7mm to form a gelled fiber film, then thoroughly cleaning the gelled fiber film in water, and drying the gelled fiber film in an oven at the temperature of 150 ℃ to form a gelled hollow fiber film with the length of 18 cm;
s9: taking the metal composite crystal suspension with the particle size of 2.25 mu m obtained in the step S6 as an external coating precursor solution, immersing the gel hollow fiber membrane obtained in the step S8 in the external coating precursor solution for 3S to obtain a coated hollow fiber membrane, and drying the obtained coated hollow fiber in the air for 15 min;
s10: repeating the step S9 for four times, gradually heating the obtained coated hollow fiber to 950 ℃ in 90ml/min of airflow, preserving heat for 1h to decompose and remove the polymer, then sintering at 1165 ℃ for 1.5h, and then cooling to room temperature at the speed of 10 ℃/min to obtain Ba with the outer diameter of 1.15mm and the inner diameter of 0.70mm0.3Ce0.7Co0.2Fe0.8O hollow fiber membrane.
The embodiment also provides a preparation method of the oxygen ion conductive carbonized ceramic-based molecular sieve membrane, which comprises the following steps:
1) mixing 27.5 parts of 1-2 methyl-2 pyrrole methyl acetate, 16 parts of nano sodium carboxymethyl cellulose with the polymerization degree of 500 and 65 parts of dimethyl sulfoxide, and stirring at 90 ℃ at the rotating speed of 125rpm to form a 1-2 methyl-2 pyrrole methyl acetate modified nano sodium carboxymethyl cellulose mixed solution;
2) filtering the acetate ionic liquid modified nano-cellulose obtained in the step 1) through a polyvinylidene fluoride filter membrane with the thickness of 12 microns, and heating at the temperature of 45 ℃ under vacuum for 45min to remove air in the liquid;
3) mixing the mixed solution obtained in the step 2) with 17.5 parts of polyimide, 17.5 parts of polyacrylonitrile and 4 parts of polyvinylpyrrolidone, and obtaining a polyacrylonitrile/polyimide grafted 1-2 methyl pyrrolidone modified nano sodium carboxymethyl cellulose solution at room temperature at a rotating speed of 180rpm by means of the waste heat of the mixed solution obtained in the step 2);
4) 45 parts of Ba0.3Ce0.7Co0.2Fe0.8Placing the O hollow fiber membrane on a spin coater, rotating at 2000rpm, and grafting 1 the polyacrylonitrile/polyimide obtained in the step 3)The-2 methyl-2 pyrrole methyl acetate modified sodium carboxymethylcellulose solution is spin-coated on the Ba at the rotating speed acceleration of 1000rpm/s0.3Ce0.7Co0.2Fe0.8O on the hollow fiber membrane for 12 s;
5) and after coating, immediately solidifying the membrane in distilled water at room temperature to obtain a regenerated cellulose membrane, then intensively cleaning the membrane for 15min by using the distilled water to remove redundant ionic liquid, then soaking the cleaned membrane in propylene glycol with the mass fraction of 6% for 30 s-1 min, and then drying in an oven at 95 ℃ for 10min to obtain the oxygen ion conductive carbonized ceramic-based molecular sieve membrane.
The embodiment also provides a use method of the oxygen generation device of the medical grade high temperature molecular sieve membrane adsorption tower, which comprises the following steps:
m1: when oxygen generation starts, air is introduced through an air source inlet 1, compressed by an air compressor 2, filtered by a C-level filter 3 and then enters an air storage tank 4, the air in the air storage tank 4 is filtered by a T-level filter, an A-level filter and an H-level filter in sequence to remove bacteria and viruses and then enters a high-temperature carbonized ceramic-based molecular sieve adsorption unit 5, a first valve 5-1, a first stop valve 7-3 and a second stop valve 8-3 are closed, and a second valve 5-2 is opened;
m2: heating the 1 st high-temperature carbonized ceramic-based molecular sieve adsorption unit for 5-165 ℃, keeping the temperature constant for 25min, and vacuumizing for 12min under the pressure of 125MPa by using a vacuum pump during constant-temperature heat preservation;
m3: then closing the second valve 5-2, cooling to 42 ℃ in a vacuum state, preserving heat for 7min, then opening the second valve 5-2 and an oxygen outlet 7-1 of the 1 st high-temperature carbonized ceramic-based molecular sieve adsorption unit 5, releasing oxygen, and entering an oxygen storage tank 7 through an oxygen diversion pipeline 7-2;
m4: judging that the oxygen concentration entering the oxygen gas storage tank 7 is impure by an oxygen concentration analyzer arranged on the oxygen flow dividing pipeline 7-2, closing an oxygen gas outlet 7-1, opening a nitrogen gas outlet 8-1, and cooling a 1 st high-temperature carbonized ceramic-based molecular sieve adsorption unit 5 to room temperature and desorbing;
m5: and (3) starting the 2 nd high-temperature carbonized ceramic-based molecular sieve adsorption unit 5, repeating the steps M2-M4 to separate and collect oxygen and nitrogen, and circularly heating the 3 nd high-temperature carbonized ceramic-based molecular sieve adsorption unit 5 to release and adsorb oxygen to complete the oxygen generation of the oxygen generation device.
Example 3
The only difference in structure between this example and example 1 is that the apparatus provided in this example contains 2 high temperature carbonized ceramic-based molecular sieve adsorption units 5.
The raw material for preparing the oxygen ion conductive carbonized ceramic-based molecular sieve membrane adopted by the molecular sieve in the adsorption tower of the device provided by the embodiment comprises the following components in parts by weight:
the diameter of the nano lignosulfonate with the polymerization degree of 450 adopted in the embodiment is 80 nm.
Ba0.1Ce0.9Co0.1Fe0.9O0.5The preparation method of the hollow fiber membrane comprises the following steps:
s1: adding 15 parts of EDTA into 25% ammonium hydroxide aqueous solution by mass to form 3M-concentration water-soluble EDTA ammonium salt solution;
s2: mixing BaCl according to a molar ratio of 1:9:1:92、CeCl3、CoCl2And FeCl3Powder, then mixed with 20 parts of sodium citrate and dissolved in 500ml of distilled water;
s3: stirring the water-soluble EDTA ammonium salt solution obtained in the step S1 and the mixed solution obtained in the step S2 at 35 ℃ at the rotating speed of 300rpm for 30 min;
s4: heating the mixed solution obtained in the step S3 at 90 ℃ for 2h to remove excessive water to obtain viscous gel; heating and drying the viscous gel at 200 ℃ for 1.5h to obtain a metal composite powder precursor;
s5: carrying out heat treatment on the metal composite powder precursor obtained in the step S4 at 800 ℃ for 45min by using airflow of 0.3L/min to remove residual carbon, and forming metal composite crystal powder with a perovskite structure and a particle size of 30 mu m;
s6: adding half of the metal composite crystal powder with the perovskite structure obtained in the step S5 into 400ml of ethanol, and performing ball milling in a planetary ball mill for 30min to obtain metal composite crystal suspension with the particle size of 2 microns;
s7: dissolving 30 parts of polytetrafluoroethylene powder in 50 parts of N-methyl-2-pyrrolidone, stirring at 180rpm for 15min to form polytetrafluoroethylene polymer solution, mixing the remaining half of the metal composite crystalline powder with the perovskite structure obtained in the step S5 with the polytetrafluoroethylene polymer solution, and stirring at 150rpm for 20min to ensure uniform mixing;
s8: degassing the mixed solution obtained in the step S7, transferring the mixed solution into a stainless steel liquid storage tank, introducing nitrogen to pressurize to 250KPa, immersing fibers drawn out from a spinneret plate at a speed of 8n/min into a water bath through an air gap of 3cm by adopting a nozzle spinneret with an outer diameter of 2mm and an inner diameter of 0.6mm to form a gelled fiber film, then thoroughly cleaning the gelled fiber film in water, and drying the gelled fiber film in an oven at 140 ℃ to form a gelled hollow fiber film with the length of 15 cm;
s9: taking the metal composite crystal suspension with the particle size of 2 microns obtained in the step S6 as an external coating precursor solution, immersing the gel hollow fiber membrane obtained in the step S8 in the external coating precursor solution for 1S to obtain a coated hollow fiber membrane, and drying the obtained coated hollow fiber in the air for 15 min;
s10: repeating the step S9 for three times, gradually heating the obtained coated hollow fiber to 900 ℃ in an air flow of 80ml/min, preserving heat for 1h to decompose and remove the polymer, then sintering at 1100 ℃ for 1h, and then cooling to room temperature at a rate of 10 ℃/min to obtain Ba with an outer diameter of 1.00mm and an inner diameter of 0.65mm0.1Ce0.9Co0.1Fe0.9O0.5A hollow fiber membrane.
The embodiment also provides a preparation method of the oxygen ion conductive carbonized ceramic-based molecular sieve membrane, which comprises the following steps:
1) mixing 25 parts of 1-methyl-3-ethylimidazole acetate, 15 parts of nano lignosulfonate with the polymerization degree of 480 and 60 parts of dimethyl sulfoxide, and stirring at 80 ℃ at a rotating speed of 100rpm to form a 1-methyl-3-ethylimidazole acetate modified nano lignosulfonate mixed solution;
2) filtering the 1-methyl-3-ethylimidazole acetate modified nano lignosulfonate mixed solution obtained in the step 1) through a polyvinylidene fluoride filter membrane of 15 microns, and heating at 40 ℃ under vacuum to remove air in the liquid for 45 min;
3) mixing the mixed solution obtained in the step 2) with 15 parts of polyimide, 15 parts of polyacrylonitrile and 3 parts of polyvinylpyrrolidone, and obtaining polyacrylonitrile/polyimide grafted 1-methyl-3-ethylimidazole acetate modified nano lignosulfonate solution at room temperature at a rotating speed of 150rpm by means of the waste heat of the mixed solution obtained in the step 2);
4) 40 parts of Ba0.1Ce0.9Co0.1Fe0.9O0.5Placing the hollow fiber membrane on a spin coater, rotating at the rotating speed of 1800rpm, and spin-coating the polyacrylonitrile/polyimide grafted 1-methyl-3-ethylimidazole acetate modified nano lignosulfonate solution obtained in the step 3) on the Ba at the rotating speed acceleration of 1000rpm/s0.1Ce0.9Co0.1Fe0.9O0.510s on the hollow fiber membrane;
5) immediately after coating, the membrane was coagulated in distilled water at room temperature to obtain a regenerated cellulose membrane, then the membrane was intensively washed with distilled water for 10min to remove excess ionic liquid, then the washed membrane was immersed in propylene glycol containing 5% by mass for 30s, and then dried in an oven at 90 ℃ for 10min to obtain an oxygen ion conductive carbonized ceramic-based molecular sieve membrane.
The embodiment also provides a use method of the oxygen generation device of the medical grade high temperature molecular sieve membrane adsorption tower, which comprises the following steps:
m1: when oxygen generation starts, air is introduced through an air source inlet 1, compressed by an air compressor 2, filtered by a C-level filter 3 and then enters an air storage tank 4, the air in the air storage tank 4 is filtered by a T-level filter, an A-level filter and an H-level filter in sequence to remove bacteria and viruses and then enters a high-temperature carbonized ceramic-based molecular sieve adsorption unit 5, a first valve 5-1, a first stop valve 7-3 and a second stop valve 8-3 are closed, and a second valve 5-2 is opened;
m2: heating the 1 st high-temperature carbonized ceramic-based molecular sieve adsorption unit for 5-150 ℃, keeping the temperature constant for 20min, and vacuumizing for 10min under the pressure of 100MPa by using a vacuum pump during constant-temperature heat preservation;
s3: then closing the second valve 5-2, cooling to 40 ℃ in a vacuum state, preserving heat for 5min, then opening the second valve 5-2 and an oxygen outlet 7-1 of the 1 st high-temperature carbonized ceramic-based molecular sieve adsorption unit 5, releasing oxygen and entering an oxygen storage tank 7 through an oxygen diversion pipeline 7-2;
s4: judging that the oxygen concentration entering the oxygen gas storage tank 7 is impure by an oxygen concentration analyzer arranged on the oxygen flow dividing pipeline 7-2, closing an oxygen gas outlet 7-1, opening a nitrogen gas outlet 8-1, and cooling a 1 st high-temperature carbonized ceramic-based molecular sieve adsorption unit 5 to room temperature and desorbing;
s5: and (3) starting the 2 nd high-temperature carbonized ceramic-based molecular sieve adsorption unit 5, repeating the steps S2-S4 to separate and collect oxygen and nitrogen, and circularly heating the 3 nd high-temperature carbonized ceramic-based molecular sieve adsorption unit 5 to release and adsorb oxygen to complete the oxygen generation of the oxygen generation device.
While the invention has been described with reference to a preferred embodiment, various modifications 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 way as long as there is no structural 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. An oxygen generation device of a medical grade high temperature molecular sieve membrane adsorption tower is characterized by comprising an air source access port (1), an air compressor (2), a C-grade filter (3), an air storage tank (4), a T-grade filter, an A-grade filter, an H-grade filter, 2-4 high temperature carbonized ceramic-based molecular sieve adsorption units (5), a vacuum pump (6), an oxygen storage tank (7) and a nitrogen storage tank (8) which are sequentially communicated, wherein a first stop valve (7-3) is arranged at the tail end of the oxygen storage tank (7), and a second stop valve (8-3) is arranged at the tail end of the nitrogen storage tank (8);
the vacuum pump (6) is arranged in the high-temperature carbonized ceramic-based molecular sieve adsorption unit (5), the high-temperature carbonized ceramic-based molecular sieve adsorption unit (5) is communicated with the oxygen gas storage tank (7) through an oxygen diversion pipeline (7-2), and the high-temperature carbonized ceramic-based molecular sieve adsorption unit (5) is communicated with the nitrogen gas storage tank (8) through a nitrogen diversion pipeline (8-2);
the high-temperature carbonized ceramic-based molecular sieve adsorption unit (5) comprises a first valve (5-1), a vacuum pressure gauge (5-2), an adsorption tower (5-3) of a molecular sieve with an oxygen ion conductive carbonized ceramic-based molecular sieve membrane connected in parallel and a second valve (5-4); the bottom end of each high-temperature carbonized ceramic-based molecular sieve adsorption unit (5) adsorption tower is provided with an oxygen gas outlet (7-1) and a nitrogen gas outlet (8-1), all the oxygen gas outlets (7-1) are communicated with the oxygen flow distribution pipeline (7-2) and converged, and all the nitrogen gas outlets (8-1) are communicated with the nitrogen flow distribution pipeline (8-2) and converged.
2. The oxygen generation device of the medical-grade high-temperature molecular sieve membrane adsorption tower according to claim 1, wherein the raw materials for preparing the oxygen ion conductive carbonized ceramic-based molecular sieve membrane adopted by the molecular sieve in the adsorption tower comprise the following components in parts by weight:
said BaxCe1-xCoyFe1-yO3-zIn the range of 0.1 to lessx is less than or equal to 0.6, y is less than or equal to 0.1 and less than or equal to 0.4, and z is less than or equal to 1 and less than or equal to 2.5.
3. The oxygen generation device of the medical grade high temperature molecular sieve membrane adsorption tower according to claim 2, wherein the acetate form ionic liquid is one or more of 1-butyl-3 methylimidazole acetate, 1-methyl-3-ethylimidazole acetate, 1-hexyl-3-methylimidazole acetate, 1-2 methyl-2 pyrrole methyl acetate or 2-methyl pyrrole-3-ethyl formate.
4. The oxygen generation device of the medical-grade high-temperature molecular sieve membrane adsorption tower according to claim 2, wherein the nanocellulose is one or more of nano-hydroxymethyl cellulose, nano-hydroxyethyl cellulose, nano-carboxymethyl cellulose sodium salt or nano-lignosulfonate; the diameter of the nano-cellulose is 50 nm-80 nm.
5. The oxygen generation device of the medical grade high temperature molecular sieve membrane adsorption tower as claimed in claim 2, wherein said Ba is added in a liquid phasexCe1-xCoyFe1-yO3-zThe preparation method of the hollow fiber membrane comprises the following steps:
s1: adding 15-20 parts by weight of EDTA into an ammonium hydroxide aqueous solution to form a water-soluble EDTA ammonium salt solution with the concentration of 3-3.5M;
s2: mixing BaCl according to the molar ratio of x:1-x: y:1-y2、CeCl3、CoCl2And FeCl3Powder, then mixing with 20 to 25 parts of sodium citrate, and dissolving in 500 to 1000ml of distilled water;
s3: stirring the water-soluble EDTA ammonium salt solution obtained in the step S1 and the mixed solution obtained in the step S2 at the temperature of 35-45 ℃ at the rotating speed of 300-350 rpm for 30-45 min;
s4: heating the mixed solution obtained in the step S3 at 90-120 ℃ for 2-2.5 h to remove excessive water to obtain viscous gel; heating and drying the viscous gel at the temperature of 200-250 ℃ for 1.5-2 h to obtain a metal composite powder precursor;
s5: performing heat treatment on the metal composite powder precursor obtained in the step S4 at 800-1000 ℃ for 45-60 min by using airflow of 0.3-0.6L/min to remove residual carbon, and forming metal composite crystal powder with a perovskite structure and a particle size of 30-35 mu m;
s6: adding half of the metal composite crystal powder with the perovskite structure obtained in the step S5 into 400-450 ml of ethanol, and carrying out ball milling in a planetary ball mill for 30-40 min to obtain metal composite crystal suspension liquid with the particle size of 2-2.5 microns;
s7: dissolving 30-40 parts by weight of polytetrafluoroethylene powder in 50-60 parts by weight of N-methyl-2-pyrrolidone, stirring at 180-200 rpm for 15min to form polytetrafluoroethylene polymer solution, mixing the remaining half of the metal composite crystalline powder with the perovskite structure obtained in the step S5 with the polytetrafluoroethylene polymer solution, and stirring at 150-200 rpm for 20-30 min to ensure uniform mixing;
s8: degassing the mixed solution obtained in the step S7, transferring the mixed solution into a stainless steel liquid storage tank, introducing nitrogen for pressurization, immersing fibers drawn out from a spinneret plate at the speed of 8-10 n/min into a water bath through an air gap of 3-5 cm by adopting a nozzle spinneret with the outer diameter of 2-2.5 mm and the inner diameter of 0.6-0.8 mm to form a gelled fiber film, thoroughly cleaning the gelled fiber film in water, and drying the gelled fiber film in an oven at the temperature of 140-160 ℃ to form a gel hollow fiber film;
s9: taking the metal composite crystal suspension with the particle size of 2-2.5 microns obtained in the step S6 as an external coating precursor solution, immersing the gel hollow fiber membrane obtained in the step S8 in the external coating precursor solution for 1-5S to obtain a coating hollow fiber membrane, and drying the obtained coating hollow fiber in the air for 15 min;
s10: repeating the step S9 for three to five times, gradually heating the obtained coating hollow fiber to 900 to 1000 ℃ in an air flow of 80 to 100ml/min, preserving the heat for 1h to decompose and remove the polymer, sintering the hollow fiber at 1100 to 1200 ℃ for 1h to 2h, and cooling the hollow fiber to room temperature at the speed of 10 ℃/minObtaining said BaxCe1-xCoyFe1-yO3-zA hollow fiber membrane.
6. The oxygen generation apparatus of the medical grade high temperature molecular sieve membrane adsorption tower according to claim 5, wherein the concentration of the ammonium hydroxide aqueous solution used in the step S1 is 25 to 30 mass percent.
7. The oxygen generation device of the medical grade high temperature molecular sieve membrane adsorption tower according to claim 5, wherein nitrogen is introduced in the step S8 to pressurize to 250KPa to 300 KPa; the length of the gel hollow fiber membrane formed in the step S8 is 15 cm-20 cm.
8. The oxygen generation device of the medical grade high temperature molecular sieve membrane adsorption tower as claimed in claim 5, wherein the prepared Ba isxCe1-xCoyFe1-yO3-zThe hollow fiber membrane has an outer diameter of 1.00mm to 1.20mm and an inner diameter of 0.65mm to 0.75 mm.
9. The oxygen generation device of the medical grade high temperature molecular sieve membrane adsorption tower according to claim 2, wherein the preparation method of the oxygen ion conductive carbonized ceramic based molecular sieve membrane comprises the following steps:
1) mixing the acetate ionic liquid, the nanocellulose with the polymerization degree of 480-520 and the dimethyl sulfoxide according to parts by weight, and stirring at the rotating speed of 100-150 rpm at 80-100 ℃ to form an acetate ionic liquid modified nanocellulose mixed solution;
2) filtering the mixed solution of the acetate ionic liquid modified nano-cellulose obtained in the step 1) through a polyvinylidene fluoride filter membrane with the thickness of 10-15 microns, and heating under vacuum at 40-50 ℃ to remove air in the liquid for 45 min;
3) mixing the mixed solution obtained in the step 2) with the polyimide, the polyacrylonitrile and the polyvinylpyrrolidone in parts by weight, and obtaining a polyacrylonitrile/polyimide grafted acetate ionic liquid modified nanocellulose solution at a rotation speed of 150 rpm-200 rpm at room temperature by means of the waste heat of the mixed solution obtained in the step 2);
4) mixing the said parts by weight of BaxCe1-xCoyFe1-yO3-zPlacing the hollow fiber membrane on a spin coater, rotating at the rotating speed of 1800 rpm-2200 rpm, and spin-coating the polyacrylonitrile/polyimide grafted acetate ionic liquid modified nanocellulose solution obtained in the step 3) on the Ba at the rotating speed acceleration of 1000rpm/sxCe1-xCoyFe1-yO3-z10-15 s on the hollow fiber membrane;
5) after coating, the membrane is immediately solidified in distilled water at room temperature to obtain a regenerated cellulose membrane, then the membrane is intensively cleaned for 10-20 min by distilled water to remove redundant ionic liquid, then the cleaned membrane is immersed in propylene glycol with the mass fraction of 5-7% for 30 s-1 min, and then the membrane is dried for 10min in an oven at the temperature of 90-100 ℃ to obtain the oxygen ion conductive carbonized ceramic-based molecular sieve membrane.
10. The use method of the oxygen generation device of the medical grade high temperature molecular sieve membrane adsorption tower according to any one of claims 1 to 9, characterized by comprising the following steps:
m1: when oxygen generation starts, air is introduced through the air source inlet (1), compressed by the air compressor (2), filtered by the C-level filter (3) and then enters the air storage tank (4), air in the air storage tank (4) is filtered by the T-level filter, the A-level filter and the H-level filter in sequence to remove bacteria and viruses and then enters the high-temperature carbonized ceramic-based molecular sieve adsorption unit (5), the first valve (5-1), the first stop valve (7-3) and the second stop valve (8-3) are closed, and the second valve (5-2) is opened;
m2: heating the 1 st high-temperature carbonized ceramic-based molecular sieve adsorption unit (5) to 150-180 ℃, keeping the temperature constant for 20-30 min, and vacuumizing for 10-15 min at the pressure of 100-150 MPa by using the vacuum pump during constant-temperature heat preservation;
m3: then closing the second valve (5-2), cooling to 40-45 ℃ in a vacuum state, preserving heat for 5-10 min, then opening the second valve (5-2) and an oxygen gas outlet (7-1) of the 1 st high-temperature carbonized ceramic-based molecular sieve adsorption unit (5), releasing oxygen, and introducing the oxygen into the oxygen gas storage tank (7) through an oxygen shunt pipeline (7-2);
m4: judging that the oxygen concentration entering the oxygen storage tank (7) is impure by an oxygen concentration analyzer arranged on the oxygen diversion pipeline (7-2), closing an oxygen gas outlet (7-1), opening a nitrogen gas outlet (8-1), and cooling the 1 st high-temperature carbonized ceramic-based molecular sieve adsorption unit (5) to room temperature for desorption;
m5: and (3) starting the 2 nd high-temperature carbonized ceramic-based molecular sieve adsorption unit (5), repeating the steps M2-M4 to separate and collect oxygen and nitrogen, and circularly heating the 2-4 high-temperature carbonized ceramic-based molecular sieve adsorption units (5) to release and adsorb oxygen to complete the oxygen production of the oxygen production device.
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| CN113251700A (en) * | 2021-05-12 | 2021-08-13 | 成都绿建工程技术有限公司 | Frostless type heat pump oxygen-making air conditioning unit |
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| WO2020075075A1 (en) * | 2018-10-08 | 2020-04-16 | Universidade Do Porto | Process for preparation of cellulose based carbon molecular sieve membranes and membranes thereof |
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Denomination of invention: A kind of oxygen generator of medical grade high temperature molecular sieve membrane adsorption tower and using method thereof Effective date of registration: 20220901 Granted publication date: 20220701 Pledgee: China Construction Bank Corporation Shaoyang Jianshe Road Sub-branch Pledgor: HUNAN VENT MEDICAL TECHNOLOGY Co.,Ltd. Registration number: Y2022980014316 |
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