CN115869923B - Oxygen absorbing material, preparation method thereof and prepared adsorption material capable of simultaneously adsorbing oxygen and organic solvent - Google Patents
Oxygen absorbing material, preparation method thereof and prepared adsorption material capable of simultaneously adsorbing oxygen and organic solvent Download PDFInfo
- Publication number
- CN115869923B CN115869923B CN202211695380.6A CN202211695380A CN115869923B CN 115869923 B CN115869923 B CN 115869923B CN 202211695380 A CN202211695380 A CN 202211695380A CN 115869923 B CN115869923 B CN 115869923B
- Authority
- CN
- China
- Prior art keywords
- pyridine
- oxygen
- absorbing material
- solvent
- oxygen absorbing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 239000001301 oxygen Substances 0.000 title claims abstract description 158
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 158
- 239000011358 absorbing material Substances 0.000 title claims abstract description 74
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000003960 organic solvent Substances 0.000 title claims abstract description 22
- 239000003446 ligand Substances 0.000 claims abstract description 55
- 239000002904 solvent Substances 0.000 claims abstract description 55
- 238000010438 heat treatment Methods 0.000 claims abstract description 37
- -1 pyridine compound Chemical class 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 21
- 239000011261 inert gas Substances 0.000 claims abstract description 20
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 18
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 62
- 238000003756 stirring Methods 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 32
- 239000013067 intermediate product Substances 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000006227 byproduct Substances 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 25
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000853 adhesive Substances 0.000 claims description 18
- 230000001070 adhesive effect Effects 0.000 claims description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 12
- 150000003222 pyridines Chemical class 0.000 claims description 10
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- 238000005469 granulation Methods 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 claims description 8
- 229940011182 cobalt acetate Drugs 0.000 claims description 7
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 6
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 6
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 claims description 6
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 4
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 4
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- DHADXDMPEUWEAS-UHFFFAOYSA-N (6-methoxypyridin-3-yl)boronic acid Chemical compound COC1=CC=C(B(O)O)C=N1 DHADXDMPEUWEAS-UHFFFAOYSA-N 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- YNGDWRXWKFWCJY-UHFFFAOYSA-N 1,4-Dihydropyridine Chemical compound C1C=CNC=C1 YNGDWRXWKFWCJY-UHFFFAOYSA-N 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- JCIBFWRKAKESTL-UHFFFAOYSA-N 2-(16-bromohexadecyl)pyridine Chemical compound BrCCCCCCCCCCCCCCCCC1=CC=CC=N1 JCIBFWRKAKESTL-UHFFFAOYSA-N 0.000 claims description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 3
- NXMFJCRMSDRXLD-UHFFFAOYSA-N 2-aminopyridine-3-carbaldehyde Chemical compound NC1=NC=CC=C1C=O NXMFJCRMSDRXLD-UHFFFAOYSA-N 0.000 claims description 3
- PCFUWBOSXMKGIP-UHFFFAOYSA-N 2-benzylpyridine Chemical compound C=1C=CC=NC=1CC1=CC=CC=C1 PCFUWBOSXMKGIP-UHFFFAOYSA-N 0.000 claims description 3
- KMODISUYWZPVGV-UHFFFAOYSA-N 2-bromo-6-methoxypyridine Chemical compound COC1=CC=CC(Br)=N1 KMODISUYWZPVGV-UHFFFAOYSA-N 0.000 claims description 3
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 claims description 3
- FNRMMDCDHWCQTH-UHFFFAOYSA-N 2-chloropyridine;3-chloropyridine;4-chloropyridine Chemical compound ClC1=CC=NC=C1.ClC1=CC=CN=C1.ClC1=CC=CC=N1 FNRMMDCDHWCQTH-UHFFFAOYSA-N 0.000 claims description 3
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 claims description 3
- NRGGMCIBEHEAIL-UHFFFAOYSA-N 2-ethylpyridine Chemical compound CCC1=CC=CC=N1 NRGGMCIBEHEAIL-UHFFFAOYSA-N 0.000 claims description 3
- MTAODLNXWYIKSO-UHFFFAOYSA-N 2-fluoropyridine Chemical compound FC1=CC=CC=N1 MTAODLNXWYIKSO-UHFFFAOYSA-N 0.000 claims description 3
- CCZWSTFVHJPCEM-UHFFFAOYSA-N 2-iodopyridine Chemical compound IC1=CC=CC=N1 CCZWSTFVHJPCEM-UHFFFAOYSA-N 0.000 claims description 3
- HLTDBMHJSBSAOM-UHFFFAOYSA-N 2-nitropyridine Chemical compound [O-][N+](=O)C1=CC=CC=N1 HLTDBMHJSBSAOM-UHFFFAOYSA-N 0.000 claims description 3
- XVCCOEWNFXXUEV-UHFFFAOYSA-N 2-pyridin-3-ylacetic acid;hydrochloride Chemical compound Cl.OC(=O)CC1=CC=CN=C1 XVCCOEWNFXXUEV-UHFFFAOYSA-N 0.000 claims description 3
- FZWUIWQMJFAWJW-UHFFFAOYSA-N 3-bromo-5-methoxypyridine Chemical compound COC1=CN=CC(Br)=C1 FZWUIWQMJFAWJW-UHFFFAOYSA-N 0.000 claims description 3
- LMRJHNFECNKDKH-UHFFFAOYSA-N 4-(trifluoromethyl)nicotinic acid Chemical compound OC(=O)C1=CN=CC=C1C(F)(F)F LMRJHNFECNKDKH-UHFFFAOYSA-N 0.000 claims description 3
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 claims description 3
- MNNQIBXLAHVDDL-UHFFFAOYSA-N 5-bromopyridine-2-carboxylic acid Chemical compound OC(=O)C1=CC=C(Br)C=N1 MNNQIBXLAHVDDL-UHFFFAOYSA-N 0.000 claims description 3
- DVMILACIDBEACH-UHFFFAOYSA-N 6-fluoropyridine Chemical compound FC1=C=CC=C[N]1 DVMILACIDBEACH-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- CWQSNJSRIUPVNR-UHFFFAOYSA-M [OH-].[Fr+] Chemical compound [OH-].[Fr+] CWQSNJSRIUPVNR-UHFFFAOYSA-M 0.000 claims description 3
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 150000003927 aminopyridines Chemical class 0.000 claims description 3
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 3
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 3
- MPFLRYZEEAQMLQ-UHFFFAOYSA-N dinicotinic acid Chemical compound OC(=O)C1=CN=CC(C(O)=O)=C1 MPFLRYZEEAQMLQ-UHFFFAOYSA-N 0.000 claims description 3
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- SVWWNEYBEFASMP-UHFFFAOYSA-N methyl 2-aminopyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC(N)=C1 SVWWNEYBEFASMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 3
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 claims description 3
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 2
- 229960003943 hypromellose Drugs 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims description 2
- 229940070721 polyacrylate Drugs 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229940069328 povidone Drugs 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 2
- OPCJOXGBLDJWRM-UHFFFAOYSA-N 1,2-diamino-2-methylpropane Chemical compound CC(C)(N)CN OPCJOXGBLDJWRM-UHFFFAOYSA-N 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 229920006380 polyphenylene oxide Polymers 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 26
- 238000011069 regeneration method Methods 0.000 abstract description 23
- 230000008929 regeneration Effects 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003795 desorption Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 125000005594 diketone group Chemical group 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- FGGUAEKPLDMWSF-HMHFYOQSSA-N chembl2376821 Chemical compound O([C@@H]1[C@@H]2[C@@H]3O[C@]3(CO)[C@@H](O)[C@@]3(O)[C@H]([C@]2([C@H](C)C[C@@]1(O1)C(C)=C)O2)C[C@@H]([C@@H]3O)C)C21C1=CC=CC=C1 FGGUAEKPLDMWSF-HMHFYOQSSA-N 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Abstract
The invention provides an oxygen absorbing material and a preparation method thereof, wherein a metal compound, a ligand L, alkali metal hydroxide, a pyridine compound and a solvent are used as raw materials for synthesizing the oxygen absorbing material. The oxygen absorbing material prepared by the method has high synthesis yield, the prepared oxygen absorbing material has good oxygen absorbing effect and high oxygen absorbing rate, the oxygen absorbing material can be recycled, the good effect can be achieved by absorption and desorption at normal temperature, and the cost and energy are saved. The invention also provides an adsorption material which is prepared by taking the oxygen absorbing material as a main raw material and can simultaneously adsorb oxygen and an organic solvent, has excellent oxygen adsorption and solvent adsorption performance, is simple to regenerate, can be regenerated only by heating at a certain temperature, vacuumizing and replacing inert gas, and has no obvious reduction in material performance after multiple regenerations.
Description
Technical Field
The invention belongs to the technical field of adsorption materials, and relates to an oxygen adsorption material and a preparation method thereof, and an adsorption material prepared by the oxygen adsorption material and capable of simultaneously adsorbing oxygen and an organic solvent.
Background
Some materials are very sensitive to oxygen and water vapor during preparation and processing, and can be realized under anhydrous and anaerobic conditions. Various industries such as lithium electricity, nuclear energy, medicine, and chemical industry are often involved in oxygen sensitive processes, some of which require high levels of oxygen, less oxygen, and better oxygen, and it is desirable that oxygen levels be minimized. The skilled person then uses various methods to want to adsorb and remove oxygen from the environment of use.
The existing oxygen adsorption modes include:
1. the hydrogen and oxygen in the mixed gas generate water by adding hydrogen into the gas and then introducing the device with the catalyst, so as to achieve the purpose of removing oxygen. This method requires a large consumption of hydrogen and catalyst, and consumes a large amount of energy.
2. Molecular sieve adsorption deoxygenation mainly relies on the internal gaps of molecular sieve to adsorb oxygen, and Pressure Swing Adsorption (PSA) is commonly used for molecular sieve adsorption of oxygen. Common oxygen adsorbing materials include silica gel, activated carbon, and the like.
The problems with such materials at present are: the oxygen capacity is insufficient, the oxygen can not be recycled, and the cost is high.
In addition, vacuum sealing systems need to provide a space filled with an inert atmosphere that is sealed from air. The atmosphere in the system contains oxygen, moisture, organic solvent and other impurities, the organic solvent can be removed by adsorption materials such as activated carbon, the molecular sieve, the activated alumina and other adsorbents can adsorb the moisture, and the active metal-containing materials such as copper catalysts are used for removing the oxygen. The adsorption column cannot be used during regeneration because hydrogen is required to be used in the process, and a higher temperature is required, so that the adsorption column has a certain danger. In addition, the adsorption efficiency of the traditional oxygen-absorbing regenerated material can be obviously reduced along with the increase of the regeneration times; the traditional purification column can not adsorb water and oxygen at the same time due to different regeneration conditions, and oxygen, adsorbed water and organic solvent are required to be adsorbed respectively, so that two sets of adsorption columns are required to be prepared at the same time in order to meet the uninterrupted experiment requirement in regeneration, and more needs to be paid in space planning and material cost.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a novel oxygen absorbing material and a preparation method thereof, and an absorbing material which is prepared by taking the oxygen absorbing material as a main raw material and can absorb oxygen and organic solvent simultaneously. The oxygen absorbing material has good oxygen absorbing effect, greatly reduced cost, and can be recycled, and the absorption and desorption at normal temperature can achieve good effect. The adsorption material capable of simultaneously adsorbing oxygen and the organic solvent can simultaneously adsorb oxygen and the organic solvent, is simple to regenerate, and can restore the original performance by heating, vacuumizing and inert gas replacement only at a certain temperature.
To achieve the purpose, the invention adopts the following technical scheme: an oxygen absorbing material, the oxygen absorbing material comprising: a metal compound, a ligand L, an alkali metal hydroxide, a pyridine compound, and a solvent; firstly, reacting a metal compound, a ligand L and a solvent, wherein the concentration of the metal compound and the ligand L in a reaction system is controlled to be 0.3-5mol.L -1 Obtaining COL product, and thenReacting alkali metal hydroxide, pyridine compound, solvent with COL product with reagent concentration of 0.3-5mol -1 The method comprises the steps of carrying out a first treatment on the surface of the Controlling the solid raw material ratio of alkali metal hydroxide: pyridine compounds: col=0.3-5: 0.3-5:1, reacting to obtain the oxygen absorbing material.
Wherein the ligand L is prepared according to the method in the patent 'preparation method and application of an oxygen absorbing material ligand'.
The invention also provides a preparation method of the oxygen absorbing material, which comprises the following steps:
1) Preparing a raw material, wherein the raw material comprises a metal compound, a ligand L, an alkali metal hydroxide, a pyridine compound and a solvent;
the metal compound is one or more of copper acetate, manganese acetate, zinc acetate, ferrous acetate, manganese sulfate, cobalt carbonate, cobalt oxalate and cobalt acetate;
the alkali metal hydroxide is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide and francium hydroxide;
the pyridine compound is one or more of alkyl pyridine, halogenated pyridine, aminopyridine, bromopyridine, methyl pyridine, iodopyridine, chloropyridine, nitropyridine, hydroxypyridine, benzyl pyridine, ethylpyridine, cyanopyridine, fluoropyridine, dihydropyridine, pyridine derivative bromohexadecylpyridine, 4-trifluoromethyl nicotinic acid, pyridine hydrochloride 2-hydroxypyridine, 4 '-dibromo-2, 2' -bipyridine, 3-bromo-5-methoxypyridine, 2-bromo-6-methoxypyridine, 2-amino isonicotinic acid methyl ester, pyridine-2, 6-dicarboxylic acid, isonicotinic acid 2-chloro-3-pyridine, methanol 4-acetylpyridine, 3, 5-dipicolinic acid, 5-bromo-2-pyridinecarboxylic acid, 2-methoxy-5-pyridineboronic acid, 2-amino-3-pyridinecarboxaldehyde, 6-fluoropyridine and pyridine-3-acetic acid hydrochloride;
the solvent is one or more of petroleum ether, n-hexane, n-octane, methanol, ethanol, isopropanol, butanol, hexanol, 2-ethylhexanol, cyclohexanone and methylcyclohexanol;
the ligand L is prepared according to the method in the patent 'preparation method and application of an oxygen absorbing material ligand';
2) Adding the metal compound, ligand L and solvent into a reaction kettle, and controlling the reagent concentration of the metal compound and ligand L to be 0.3-5mol.L in the reaction process -1 Obtaining a product COL; the COL yield of the product is more than 90%;
3) Taking COL, alkali metal hydroxide, pyridine compound and solvent which are products of the step 2) as raw materials, and putting the raw materials into a reaction kettle at one time; the reagent concentration of the alkali metal hydroxide is controlled between 0.3 and 5mol.L in the reaction process -1 The method comprises the steps of carrying out a first treatment on the surface of the The reagent concentration of the pyridine compound is controlled to be 0.3-5mol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the The concentration of COL reagent in the product of the step 2) is controlled to be 0.3-5mol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the Controlling the solid raw material ratio of alkali metal hydroxide: pyridine compounds: col=0.3-5: 0.3-5:1, reacting to obtain the oxygen absorbing material. The yield of the oxygen absorbing material is more than 95 percent.
Preferably, the metal compound in the raw material is any one of cobalt sulfate, cobalt carbonate, cobalt oxalate and cobalt acetate.
Preferably, the solvent in the feedstock controls the solvent moisture in the range of 0-500ppm.
Preferably, the principle of feeding the raw materials into the reaction kettle in the steps 2) and 3) is to firstly feed solid raw materials and then feed liquid raw materials.
Wherein, the preparation of the ligand L is carried out according to the method in the patent 'a preparation method of oxygen absorbing material ligand and application thereof', and the preparation of the ligand L comprises the following steps:
A. and (3) carrying out normal pressure reflux reaction: adding diketone compounds, anhydride and ester compounds into a reaction container filled with inert gas, wherein the adding proportion of the diketone compounds, the anhydride and the ester compounds is 1:1.5-4:1-3, mixing to fully react under the protection of inert gas, stirring and heating in the reaction process, controlling the temperature of the mixed solution to be 80-150 ℃, and after the mixed solution is reacted and reflowed for 1-3 hours at a temperature control point, closing heating, and cooling the mixed solution to room temperature under the protection of inert gas;
B. removal of reaction byproducts: connecting the reaction system to a reduced pressure distillation device, checking the air tightness of the system of the device, starting a condensation stirring device under the condition of ensuring good air tightness, stirring at 300-800rpm, slowly connecting vacuum into the system of the device at room temperature, adjusting the vacuum degree to 15-50KPa, controlling the boiling degree of the mixed liquid by adjusting the vacuum degree, improving the vacuum degree to 0-15KPa when liquid drops are not dripped, slowly raising the temperature of the solution to 50-80 ℃, gradually evaporating byproducts in the mixture, collecting the byproducts to a byproduct receiving container until no liquid drops drip, and recovering the system of the device to normal pressure;
C. collecting target intermediate products: changing the byproduct receiving container into a target intermediate product receiving container, adjusting the vacuum degree to be 0-15KPa, gradually heating the reaction mixed solution to be 80-100 ℃, starting boiling the solution, dripping liquid drops in the target intermediate product receiving container, controlling the temperature of the solution to be finally heated to be 100-120 ℃, collecting a target intermediate product, and calculating the yield of the target intermediate product;
D. synthesizing target product ligand: reacting the collected target intermediate product with a solvent and amine under the stirring condition, wherein the amine is used as a dropwise adding object for dropwise adding reaction, and the reaction proportion relationship among the target intermediate product, the amine and the solvent is 2:1-3:4-8, filtering and drying after the reaction to obtain a target product, namely the oxygen absorbing material ligand.
Wherein, the anhydride in the preparation step A of the ligand L is any one of acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride and phthalic anhydride.
Wherein, the ester compound in the preparation step A of the ligand L is any one of methyl orthoformate, ethyl acetoacetate, diethyl malonate orthoacetate and orthobenzoate.
Wherein the diketone compound in the preparation step A of the ligand L is any one of butanedione, diphenylethanedione, dithiopheneethanedione, dipyridylethyldione, 9, 10-phenanthrenedione and 2, 4-pentanedione.
Wherein, the reaction of diketone compounds, anhydride and ester compounds in the preparation step A of the ligand L is carried out at the stirring speed of 300-800rpm.
Wherein, the color of the mixed solution is gradually changed in the reaction process of the preparation step A of the ligand L, and the heating is turned off when the mixed solution is dark reddish brown.
Wherein, the solvent in the preparation step D of the ligand L can be any one of methanol, ethanol, isopropanol, glycerol, cyclohexanol and benzyl alcohol.
Wherein, the amine in the preparation step D of the ligand L can be any one of ethylenediamine, propylenediamine, o-phenylenediamine, m-phenylenediamine, 1, 2-diamine-2-methylpropane, triethylenetetramine, diethylenetriamine and diaminocyclohexane.
Wherein, the reaction vessel in the step A for preparing the ligand L is connected with a reflux condensing device, a constant pressure liquid dropping device, a temperature control device and a heating and stirring device.
Wherein the volume of the reaction vessel in the preparation A of the ligand L in the step is 1-10L.
The reaction by-product removal in the step B of preparing the ligand L is not limited to reduced pressure distillation, and rotary evaporation, freeze drying and column separation methods can be used.
The invention also provides application of the oxygen absorbing material, and the oxygen absorbing material is used as an oxygen adsorbent. The oxygen absorbing material has high oxygen absorbing rate, and the oxygen removing process can be continuously circulated, so that the oxygen absorbing material can be continuously recycled, is energy-saving and environment-friendly, and greatly reduces the use cost.
Further, the invention also provides an adsorption material which is prepared by taking an oxygen absorbing material as a main raw material and can simultaneously adsorb oxygen and an organic solvent, and the adsorption material which can simultaneously adsorb oxygen and the organic solvent is prepared by the following steps:
(1) adding the powdery adhesive into a solvent, heating and stirring to promote the dissolution of the adhesive until the adhesive is uniform and transparent to obtain an adhesive solution; (2) adding oxygen absorbing material powder and active carbon powder into a stirrer, and stirring and uniformly mixing; (3) adding the adhesive solution into a stirrer, and stirring and uniformly mixing the adhesive solution with the mixed powder in the step (2) until the mixture becomes sticky; the percentages of the adhesive, the solvent, the oxygen absorbing material and the activated carbon are 9-20%, 30-42%, 30-40% and 9-20%; (4) transferring the mixture to a granulator for extrusion granulation, and carrying out vacuum suction drying on the obtained adsorption material particles to obtain an adsorption material capable of simultaneously adsorbing oxygen and an organic solvent;
the oxygen absorbing material according to any one of claims 1 to 4.
Wherein the adhesive in the step (1) is one or more of polyurethane, epoxy resin, unsaturated resin, polyamide, polyphenyl ether, polyacrylate, povidone and hypromellose.
Wherein the solvent in the step (1) is one or more of diethyl ether, ethylene glycol dimethyl ether, n-hexane, cyclohexane, toluene, methyl acetate, acetone, ethyl acetate and carbon tetrachloride.
Wherein the active carbon powder is one or more of 100 meshes, 140 meshes, 200 meshes, 270 meshes, 325 meshes and 400 meshes.
Wherein the extraction and drying temperature in the step (4) is 50-100 ℃.
Wherein, after the step (4) is vacuum-dried, the components in the adsorption material account for 15-25 percent of the mass percentage of the adhesive, the oxygen absorbing material and the active carbon, 50-70 percent and 15-25 percent.
The oxygen absorbing material adopted by the preparation of the absorbing material has oxygen absorbing performance, and the activated carbon powder has solvent absorbing performance, wherein the oxygen absorbing performance of the oxygen absorbing material is 5-8% (the oxygen absorbing mass accounts for the mass percent of the oxygen absorbing material), and the solvent absorbing performance of the activated carbon C powder is 5-10% (the solvent absorbing mass accounts for the mass percent of the activated carbon C powder). After the granulation is completed, the obtained adsorption material is subjected to an oxygen absorption performance test and a solvent adsorption test, and compared with the adsorption material before the granulation, the oxygen absorption performance and the solvent adsorption performance are not reduced.
The oxygen absorbing material is a metal organic complex, and the metal complex has unsaturated metal vacancies, so that oxygen and the metal vacancies can be reversibly absorbed. Because the electron cloud density around the metal is larger when oxygen is not absorbed, when oxygen is contacted with the metal, the electron cloud of the metal shifts, and the metal bond is promoted to be opened. The material forms metal unsaturated vacancy to make oxygen molecule form coordination bond with metal and be in stable state.
Compared with the deoxidizing mode in the prior art, the oxygen absorbing material has the advantages of low pressure, low energy consumption, high efficiency and the like, has high oxygen absorbing rate, can be continuously recycled, and saves cost and energy.
The ligand L is used as a main raw material to prepare the oxygen-absorbing material, so that the yield is high, the oxygen-absorbing material can be recycled at normal temperature, and a good oxygen-absorbing and deoxidizing effect is achieved; the oxygen absorbing material ligand can be well used for synthesizing the oxygen absorbing material, and the oxygen absorbing material ligand has the advantages of simple synthesis method, less equipment, higher yield, lower cost, strong operability and high safety coefficient; ligand synthesis conditions and ligand synthesis raw materials, low cost, wide sources and easy selection and purchase.
The adsorption material prepared by taking the oxygen absorbing material as a main raw material for granulation can simultaneously adsorb oxygen and organic solvent; the obtained adsorption material is subjected to an oxygen absorption performance test and a solvent absorption test, and the results show that the adsorption material has excellent oxygen absorption and solvent absorption performance.
The adsorption material of the invention is simple to regenerate, and can be regenerated only by heating at a certain temperature (50-90 ℃), vacuumizing and replacing inert gas, and the performance of the material is not obviously reduced after repeated regeneration; the adsorption material provided by the invention is subjected to TGA and solvent adsorption tests, and after oxygen adsorption and solvent adsorption are saturated, the regeneration method is simple. The method comprises the steps of heating the materials at a certain temperature, vacuumizing, replacing inert gas, performing TGA test and solvent adsorption test, and circulating the materials.
The adsorption material can exist in the forms of particles, spheres, honeycombs and the like, the granulation method of the adsorption material is simple, the adsorption material can be obtained by simply stirring and mixing and extruding granulation, and the raw materials and equipment are simple and easy to obtain.
Compared with the traditional adsorption material, the adsorption material has the advantages of excellent adsorption performance, high adsorption rate and good adsorption effect; the system such as glove box is not affected during regeneration, and the system can be used while regeneration. The method is characterized in that the water and oxygen index of the glove box is almost unchanged during regeneration, the water index of the glove box is less than 1ppm before regeneration, and the oxygen index is less than 1ppm; the water and oxygen index in the regeneration process and after regeneration still maintains the water index <1ppm, and the oxygen index <1ppm; the regeneration of the adsorption material of the invention does not affect the normal use of the glove box.
The adsorption material can efficiently replace the traditional adsorption material, can simultaneously adsorb oxygen and organic solvent, is simple to regenerate, and can recover the original performance by heating, vacuumizing and replacing inert gas at a certain temperature. In addition, the adsorption efficiency of the adsorption material is not obviously reduced along with the increase of the regeneration times, and the use requirements of customers on the glove box and the vacuum sealing system can be well met.
Detailed Description
The following examples are provided to further illustrate the technical aspects of the present invention for the purpose of fully understanding the objects, features and effects of the present invention, but the scope of the present invention is not limited to the following examples.
The implementation conditions employed in the examples may be further adjusted according to specific requirements, and the implementation conditions not specified are generally conventional conditions. In addition, when not specifically stated, the amounts of the components are the amounts (mol) and the percentages (%) of the substances, and the product indexes are obtained according to the industry standard test.
EXAMPLE 1 preparation of oxygen absorbing Material ligand L
Connecting a 3L reaction container with a reflux condensing device, a constant-pressure dropping device, a temperature control device and a heating stirring device, vacuumizing and replacing, then filling inert gas, adding 2mol of 2.4-pentanedione, 3mol of acetic anhydride and 2.4mol of ethyl acetoacetate into the reaction container, reacting under the protection of the inert gas at the stirring speed of 300rpm, controlling the temperature of the mixed solution at 90 ℃, and after the mixed reaction solution is reacted and reflowed for 2 hours at a temperature control point, closing heating, and cooling to room temperature under the protection of the inert gas;
connecting the reaction container with a reduced pressure distillation device, checking the air tightness of the system of the device, starting a condensation stirring device under the condition of ensuring good air tightness, slowly connecting vacuum into the system of the device at room temperature at the stirring speed of 300rpm, adjusting the vacuum degree to 30KPa, controlling the boiling degree of the mixed liquid through the adjustment of the vacuum degree, gradually extracting byproducts in the mixture after the liquid drops are not dripped, improving the vacuum degree to 15KPa, slowly raising the temperature of the solution to 60 ℃, collecting the byproducts in the byproduct receiving container until no liquid drops drip, and recovering the system of the device to normal pressure;
changing the byproduct receiving container into a target intermediate product receiving container, adjusting the vacuum degree to 10KPa, gradually heating the reaction mixed solution to 100 ℃, starting boiling the solution, dripping liquid drops in the target intermediate product receiving container, finally heating to 115 ℃ by controlling the temperature of the solution, collecting the target intermediate product, and weighing the target intermediate product with the yield of 85%;
the target intermediate product reacts with ethylenediamine and methanol under the stirring condition, and the ratio of reactants is 2:1: and 6, filtering and drying after the reaction to obtain a target product, namely the oxygen absorbing material ligand, with the yield of 90%.
EXAMPLE 2 preparation of oxygen absorbing Material ligand L
Connecting a 3L reaction container with a reflux condensing device, a constant-pressure dropping device, a temperature control device and a heating stirring device, vacuumizing and replacing, then filling inert gas, adding 2mol of 2.4-pentanedione, 3mol of acetic anhydride and 2.4mol of methyl orthoformate into the reaction container, reacting under the protection of the inert gas at the stirring speed of 300rpm, controlling the temperature of the mixed solution at 90 ℃, after the mixed reaction solution is reacted and reflowed for 2 hours at a temperature control point, closing heating, and cooling to room temperature under the protection of the inert gas;
connecting a reaction container with a reduced pressure distillation device, checking the air tightness of a device system, starting a condensation stirring device under the condition of ensuring good air tightness, slowly connecting vacuum into the device system at room temperature at the stirring speed of 300rpm, adjusting the vacuum degree to 30KPa, controlling the boiling degree of mixed liquid by adjusting the vacuum degree, gradually extracting byproducts in the mixture after the liquid drops are not dripped, improving the vacuum degree to 15KPa, gradually increasing the temperature of the solution to 60 ℃, collecting the byproducts in the mixture to a byproduct receiving container until no liquid drops are dripped, and recovering the device system to normal pressure;
changing the byproduct receiving container into a target intermediate product receiving container, adjusting the vacuum degree to 10KPa, gradually heating the reaction mixed solution to 100 ℃, starting boiling the solution, dripping liquid drops in the target intermediate product receiving container, finally heating to 115 ℃ by controlling the temperature of the solution, collecting the target intermediate product, and weighing the target intermediate product with the yield of 88%;
reacting the target intermediate product with o-phenylenediamine and methanol under the stirring condition, wherein the reactant ratio is 2:1: and 6, filtering and drying after the reaction to obtain a target product, namely the oxygen absorbing material ligand, with the yield of 95%.
EXAMPLE 3 preparation of oxygen absorbing Material ligand L
Connecting a 3L reaction container with a reflux condensing device, a constant-pressure dropping device, a temperature control device and a heating stirring device, vacuumizing and replacing, then filling inert gas, adding 2mol of 2.4-pentanedione, 3mol of acetic anhydride and 2.4mol of triethyl orthoformate into the reaction container, reacting under the protection of the inert gas at the stirring speed of 300rpm, controlling the temperature of the mixed solution at 90 ℃, after the mixed reaction solution is reacted and reflowed for 2 hours at a temperature control point, closing heating, and cooling to room temperature under the protection of the inert gas;
the reaction container is connected with a reduced pressure distillation device instead, the air tightness of the system of the device is checked, under the condition of ensuring good air tightness, a condensation stirring device is started, the stirring speed is 300rpm, a vacuum is slowly connected into the system of the device at room temperature, the vacuum degree is regulated to 30KPa, the boiling degree of a mixed solution is controlled through the regulation of the vacuum degree, when liquid drops are not dripped any more, the vacuum degree is increased to 15KPa, then the temperature of the solution is slowly increased to 60 ℃, byproducts in the mixture are gradually extracted, and the byproducts are collected into a byproduct receiving container until no liquid drops drip, and the system of the device is restored to normal pressure;
changing the byproduct receiving container into a target intermediate product receiving container, adjusting the vacuum degree to 10KPa, gradually heating the reaction mixed solution to 100 ℃, starting boiling the solution, dripping liquid drops in the target intermediate product receiving container, finally heating to 115 ℃ by controlling the temperature of the solution, collecting the target intermediate product, and weighing the target intermediate product with the yield of 86%;
reacting the target intermediate product with diaminocyclohexane and methanol under stirring, wherein the reaction ratio is 2:1:6, carrying out reaction, filtering and drying to obtain the target product, namely the oxygen absorbing material ligand, with the yield of 89%.
EXAMPLE 4 preparation of oxygen absorbing Material
Preparation of raw materials: cobalt acetate, ligand prepared in example 1 is ligand L, isopropanol, potassium hydroxide, picoline;
step1: into a 250mL beaker, 0.1mol of cobalt acetate and 0.1mol of ligand L were added, isopropyl alcohol was added, and the reagent concentration was controlled to be cobalt acetate and ligand L4mol.L -1 Under heating (controlled temperature at 50-60 ℃), stirring was started and the stirring rate was set at 400rpm, to obtain a mixed solution 1. In addition, 0.1mol of potassium hydroxide and isopropanol reagent are added into a 250mL conical flask, and the concentration is controlled to be 4mol -1 Heating and stirring at 60 ℃ until the solid is completely dissolved to obtain a mixed solution 2. Under the condition of heating and stirring the mixed solution 1, the mixed solution 2 is added into the mixed solution 1, and the addition is completed within 30 minutes. After holding the temperature for 4 hours, the reaction was stopped. The reaction solution was suction-filtered to obtain a reddish brown solid product COL in 95% yield.
Step2: into a 250mlL beaker, 0.15mol of COL product, 0.12mol of potassium hydroxide, 0.14mol of picoline and solvent isopropanol were added, and the reagent concentration was controlled to be 4mol of potassium hydroxide -1 The experiment was started under heating and stirring conditions, the stirring rate was set at 300rpm, and the temperature was slowly raised to 75-85 ℃. After holding the temperature for 6 hours, the reaction was stopped.
And (3) treating a reaction solution: the reaction solution was filtered by a vacuum pump, and the obtained product was dried in 97% yield. The product was used as an oxygen absorbing material and tested for TGA, showing an oxygen absorption of 6.02%. The oxygen absorption rate refers to the percentage of oxygen absorption mass to oxygen absorption material mass.
The target product is subjected to a cyclic oxygen absorption test, and the continuous oxygen absorption analysis cycle is carried out for 6 times by adopting continuous circulation modes such as oxygen blowing, nitrogen blowing, oxygen blowing again, nitrogen blowing again and the like, so that the oxygen absorption rate is unchanged. After the nitrogen is used for purging, the oxygen absorbing material can be desorbed to the original state, and the oxygen is circularly absorbed. The oxygen absorbing material can continuously absorb oxygen in a circulating way by means of the gas purging mode, and after the oxygen absorbing material is circulated for a plurality of times, the oxygen absorbing rate is 6%, and the oxygen absorbing rate is kept unchanged. Proved by the invention, the oxygen absorbing material has high oxygen absorbing rate, can be continuously recycled, and has convenient and quick operation, energy conservation and environmental protection.
Example 5 preparation of adsorbent Material capable of simultaneously adsorbing oxygen and organic solvent
400g of ethylene glycol dimethyl ether is weighed as a solvent, added into a 2L glass flask, heated and stirred, the temperature is set to 50 ℃, 160g of polyacrylate is slowly added into the solvent until the solvent is uniform and transparent, and a uniform solution is obtained; weighing 320g of the prepared oxygen absorbing material (6.5% of the oxygen absorption rate in a TGA test) and 160g of activated carbon C powder (8% of the solvent absorption rate in a solvent absorption performance test) which is pumped and dried by 200 meshes, adding the materials into a stirrer, and uniformly stirring; with stirring, the transparent homogeneous solution was added to the stirrer and stirred until the mixture became viscous. Transferring the mixture into a granulator for extrusion granulation, and carrying out suction drying on the obtained adsorption material at 80 ℃ by using aperture extrusion of 2mm for 20 hours, wherein the weight of the obtained adsorption material is 795g; yield 99.4%; respectively testing oxygen absorption performance and solvent absorption performance; wherein the oxygen absorption rate is 3.9%; the solvent adsorption rate is 1.6%, and the obtained adsorption material almost completely maintains the original adsorption efficiency according to mass percent; can effectively adsorb oxygen and solvent at the same time; placing the adsorption material into a glove box for testing; and performing simple pumping, drying and regenerating operation; the adsorption performance of the regenerated adsorption material is almost not attenuated. The system such as glove box is not affected during regeneration, and the system can be used while regeneration. The method is characterized in that the water and oxygen index of the glove box is almost unchanged during regeneration, the water index of the glove box is less than 1ppm before regeneration, and the oxygen index is less than 1ppm; the water and oxygen index in the regeneration process and after regeneration still maintains the water index <1ppm, and the oxygen index <1ppm; the regeneration of the novel oxygen absorbing material is not influenced by the normal use of the glove box.
The oxygen absorbing material of the invention has good oxygen absorbing effect and greatly reduced cost, and can be recycled, and can achieve good absorption and desorption effects at normal temperature.
The adsorption material prepared by granulation can adsorb oxygen and organic solvent simultaneously; the obtained adsorption material is subjected to an oxygen absorption performance test and a solvent absorption test, and the results show that the adsorption material has excellent oxygen absorption and solvent absorption performance. The adsorption material is easy to regenerate, and can be regenerated only by heating at a certain temperature, vacuumizing and replacing inert gas, and the performance of the material is not obviously reduced after multiple regenerations.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (9)
1. An oxygen absorbing material, characterized in that the oxygen absorbing material comprises the following raw materials: a metal compound, a ligand L, an alkali metal hydroxide, a pyridine compound, and a solvent;
wherein the metal compound is one or more of copper acetate, manganese acetate, zinc acetate, ferrous acetate, manganese sulfate, cobalt carbonate, cobalt oxalate and cobalt acetate;
the preparation method of the oxygen absorbing material comprises the following steps:
1) The metal compound, ligand L and solvent in the raw materials are thrownThe mixture is put into a reaction kettle, and the concentration of the reagent of the metal compound and the ligand L is controlled between 0.3 and 5mol.L in the reaction process -1 Heating and stirring to obtain a mixed solution 1; mixing alkali metal hydroxide with a solvent, heating and stirring to obtain a mixed solution 2; adding the mixed solution 2 into the mixed solution 1, and reacting to obtain a product COL;
2) Taking COL, alkali metal hydroxide, pyridine compound and solvent which are products of the step 1) as raw materials, and putting the raw materials into a reaction kettle; the reagent concentration of the alkali metal hydroxide is controlled between 0.3 and 5mol.L in the reaction process -1 The method comprises the steps of carrying out a first treatment on the surface of the The reagent concentration of the pyridine compound is controlled to be 0.3-5mol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the The concentration of COL reagent in the product of the step 1) is controlled to be 0.3-5mol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the Controlling the solid raw material ratio to be alkali metal hydroxide: pyridine compounds: col=0.3-5: 0.3-5:1, filtering the reaction liquid after the reaction, and drying the product to obtain the oxygen absorbing material;
the preparation method of the ligand L comprises the following steps:
a) 2, 4-pentanedione, acetic anhydride, methyl orthoformate or triethyl orthoformate is reacted under the protection of inert gas, the reaction temperature is 90 ℃, and the reflux is carried out for 2 hours;
b) Connecting a reaction container with a reduced pressure distillation device, checking the air tightness of a device system, starting a condensation stirring device under the condition of ensuring good air tightness, slowly connecting vacuum into the device system at room temperature at the stirring speed of 300rpm, adjusting the vacuum degree to 30kPa, controlling the boiling degree of mixed liquid through the adjustment of the vacuum degree, gradually extracting byproducts in the mixture after the liquid drops are not dripped, improving the vacuum degree to 15kPa, slowly raising the solution temperature to 60 ℃, collecting the byproducts in the byproduct receiving container until no liquid drops are dripped, and recovering the device system to normal pressure;
c) Changing the byproduct receiving container into a target intermediate product receiving container, adjusting the vacuum degree to 10kPa, gradually heating the reaction mixed solution to 100 ℃, starting boiling the solution, dripping liquid drops in the target intermediate product receiving container, and finally heating to 115 ℃ by controlling the temperature of the solution to collect the target intermediate product;
d) And (3) reacting the target intermediate product with amine and a solvent under the stirring condition, filtering after the reaction, and drying to obtain a target product, namely the ligand L.
2. The oxygen absorbing material of claim 1, wherein the alkali metal hydroxide is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, francium hydroxide;
the pyridine compound is one or more of alkyl pyridine, halogenated pyridine, aminopyridine, bromopyridine, methyl pyridine, iodopyridine, chloropyridine, nitropyridine, hydroxypyridine, benzyl pyridine, ethylpyridine, cyanopyridine, fluoropyridine, dihydropyridine, pyridine derivative bromohexadecylpyridine, 4-trifluoromethyl nicotinic acid, pyridine hydrochloride 2-hydroxypyridine, 4 '-dibromo-2, 2' -bipyridine, 3-bromo-5-methoxypyridine, 2-bromo-6-methoxypyridine, 2-amino isonicotinic acid methyl ester, pyridine-2, 6-dicarboxylic acid, isonicotinic acid 2-chloro-3-pyridine, methanol 4-acetylpyridine, 3, 5-dipicolinic acid, 5-bromo-2-pyridinecarboxylic acid, 2-methoxy-5-pyridineboronic acid, 2-amino-3-pyridinecarboxaldehyde, 6-fluoropyridine and pyridine-3-acetic acid hydrochloride;
the solvent used in the preparation step 1) and the step 2) of the oxygen absorbing material is one or more of petroleum ether, normal hexane, normal octane, methanol, ethanol, isopropanol, butanol, hexanol, 2-ethylhexanol, cyclohexanone and methylcyclohexanol.
3. The oxygen absorbing material according to claim 1, wherein the amine in the ligand L preparation step D is any one of ethylenediamine, propylenediamine, o-phenylenediamine, m-phenylenediamine, 1, 2-diamino-2-methylpropane, triethylenetetramine, diethylenetriamine, and diaminocyclohexane;
the solvent in the ligand L preparation step D is any one of methanol, ethanol, isopropanol, glycerol, cyclohexanol and benzyl alcohol.
4. The preparation method of the oxygen absorbing material is characterized by comprising the following steps of:
1) Preparing a raw material, wherein the raw material comprises a metal compound, a ligand L, an alkali metal hydroxide, a pyridine compound and a solvent;
the metal compound is one or more of copper acetate, manganese acetate, zinc acetate, ferrous acetate, manganese sulfate, cobalt carbonate, cobalt oxalate and cobalt acetate;
2) Adding the metal compound, ligand L and solvent into a reaction kettle, and controlling the reagent concentration of the metal compound and ligand L to be 0.3-5mol.L in the reaction process -1 Heating and stirring to obtain a mixed solution 1; mixing alkali metal hydroxide with a solvent, heating and stirring to obtain a mixed solution 2; adding the mixed solution 2 into the mixed solution 1, and reacting to obtain a product COL;
3) Taking COL, alkali metal hydroxide, pyridine compound and solvent which are products of the step 2) as raw materials, and putting the raw materials into a reaction kettle; the reagent concentration of the alkali metal hydroxide is controlled between 0.3 and 5mol.L in the reaction process -1 The method comprises the steps of carrying out a first treatment on the surface of the The reagent concentration of the pyridine compound is controlled to be 0.3-5mol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the The concentration of COL reagent in the product of the step 2) is controlled to be 0.3-5mol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the Controlling the solid raw material ratio of alkali metal hydroxide: pyridine compounds: col=0.3-5: 0.3-5:1, filtering the reaction liquid after the reaction, and drying the product to obtain the oxygen absorbing material;
the preparation method of the ligand L comprises the following steps:
a) 2, 4-pentanedione, acetic anhydride, methyl orthoformate or triethyl orthoformate is reacted under the protection of inert gas, the reaction temperature is 90 ℃, and the reflux is carried out for 2 hours;
b) Connecting a reaction container with a reduced pressure distillation device, checking the air tightness of a device system, starting a condensation stirring device under the condition of ensuring good air tightness, slowly connecting vacuum into the device system at room temperature at the stirring speed of 300rpm, adjusting the vacuum degree to 30kPa, controlling the boiling degree of mixed liquid through the adjustment of the vacuum degree, gradually extracting byproducts in the mixture after the liquid drops are not dripped, improving the vacuum degree to 15kPa, slowly raising the solution temperature to 60 ℃, collecting the byproducts in the byproduct receiving container until no liquid drops are dripped, and recovering the device system to normal pressure;
c) Changing the byproduct receiving container into a target intermediate product receiving container, adjusting the vacuum degree to 10kPa, gradually heating the reaction mixed solution to 100 ℃, starting boiling the solution, dripping liquid drops in the target intermediate product receiving container, and finally heating to 115 ℃ by controlling the temperature of the solution to collect the target intermediate product;
d) And (3) reacting the target intermediate product with amine and a solvent under the stirring condition, filtering after the reaction, and drying to obtain a target product, namely the ligand L.
5. The method for preparing oxygen absorbing material according to claim 4, wherein the alkali metal hydroxide is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, francium hydroxide;
the solvent in the steps 1), 2) and 3) is one or more of petroleum ether, normal hexane, normal octane, methanol, ethanol, isopropanol, butanol, hexanol, 2-ethylhexanol, cyclohexanone and methylcyclohexanol;
the pyridine compound is one or more of alkyl pyridine, halogenated pyridine, aminopyridine, bromopyridine, methyl pyridine, iodopyridine, chloropyridine, nitropyridine, hydroxypyridine, benzyl pyridine, ethylpyridine, cyanopyridine, fluoropyridine, dihydropyridine, pyridine derivative bromohexadecylpyridine, 4-trifluoromethyl nicotinic acid, pyridine hydrochloride 2-hydroxypyridine, 4 '-dibromo-2, 2' -bipyridine, 3-bromo-5-methoxypyridine, 2-bromo-6-methoxypyridine, 2-amino isonicotinic acid methyl ester, pyridine-2, 6-dicarboxylic acid, isonicotinic acid 2-chloro-3-pyridine, methanol 4-acetylpyridine, 3, 5-dipicolinic acid, 5-bromo-2-pyridinecarboxylic acid, 2-methoxy-5-pyridineboronic acid, 2-amino-3-pyridinecarboxaldehyde, 6-fluoropyridine and pyridine-3-acetic acid hydrochloride;
the amine in the ligand L preparation step D is any one of ethylenediamine, propylenediamine, o-phenylenediamine, m-phenylenediamine, 1, 2-diamine-2-methylpropane, triethylenetetramine, diethylenetriamine and o-diamine cyclohexane;
the solvent in the ligand L preparation step D is any one of methanol, ethanol, isopropanol, glycerol, cyclohexanol and benzyl alcohol.
6. An adsorbent material capable of simultaneously adsorbing oxygen and an organic solvent, characterized in that the preparation method of the adsorbent material comprises the following steps:
(1) adding the powdery adhesive into a solvent, heating and stirring to promote the dissolution of the adhesive until the adhesive is uniform and transparent to obtain an adhesive solution; (2) adding oxygen absorbing material powder and active carbon powder into a stirrer, and stirring and uniformly mixing; (3) adding the adhesive solution into a stirrer, and stirring and uniformly mixing the adhesive solution with the mixed powder in the step (2) until the mixture becomes sticky; the percentages of the adhesive, the solvent, the oxygen absorbing material and the active carbon are 5-15%, 35-44%, 30-42% and 9-20%; (4) transferring the mixture to a granulator for extrusion granulation, and carrying out vacuum suction drying on the obtained adsorption material particles to obtain an adsorption material capable of simultaneously adsorbing oxygen and an organic solvent;
the oxygen absorbing material is the oxygen absorbing material of any one of claims 1 to 3 or the oxygen absorbing material prepared by the method of any one of claims 4 to 5.
7. The method for preparing an adsorption material capable of simultaneously adsorbing oxygen and an organic solvent according to claim 6, wherein the adhesive is one or more of polyurethane, epoxy resin, unsaturated resin, polyamide, polyphenylene oxide, polyacrylate, povidone and hypromellose; the solvent is one or more of diethyl ether, ethylene glycol dimethyl ether, n-hexane, cyclohexane, toluene, ethyl acetate, acetone, ethyl acetate and carbon tetrachloride.
8. The method for preparing an adsorbent material capable of simultaneously adsorbing oxygen and an organic solvent according to claim 6, wherein the suction drying temperature in the step (4) is 50-100 ℃.
9. The method for preparing an adsorption material capable of simultaneously adsorbing oxygen and an organic solvent according to claim 6, wherein after the step (4) is performed with vacuum suction and baking, the mass percentages of each component in the adsorption material are 15-25%, 50-70% and 15-25% of the mass percentages of the adhesive, the oxygen absorbing material and the active carbon.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211695380.6A CN115869923B (en) | 2022-12-28 | 2022-12-28 | Oxygen absorbing material, preparation method thereof and prepared adsorption material capable of simultaneously adsorbing oxygen and organic solvent |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211695380.6A CN115869923B (en) | 2022-12-28 | 2022-12-28 | Oxygen absorbing material, preparation method thereof and prepared adsorption material capable of simultaneously adsorbing oxygen and organic solvent |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115869923A CN115869923A (en) | 2023-03-31 |
CN115869923B true CN115869923B (en) | 2024-03-22 |
Family
ID=85754910
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211695380.6A Active CN115869923B (en) | 2022-12-28 | 2022-12-28 | Oxygen absorbing material, preparation method thereof and prepared adsorption material capable of simultaneously adsorbing oxygen and organic solvent |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115869923B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115869923B (en) * | 2022-12-28 | 2024-03-22 | 威格科技(苏州)股份有限公司 | Oxygen absorbing material, preparation method thereof and prepared adsorption material capable of simultaneously adsorbing oxygen and organic solvent |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02191545A (en) * | 1989-01-19 | 1990-07-27 | Nippon Sanso Kk | Oxygen absorbing and desorbing agent and its production |
EP0475053A1 (en) * | 1990-08-15 | 1992-03-18 | Praxair Technology, Inc. | Oxygen-separating porous membranes |
JPH09151192A (en) * | 1995-11-29 | 1997-06-10 | Nippon Sanso Kk | Cobalt schiff base complex, complex solution for separating oxygen and separation of oxygen |
CN1327877A (en) * | 1999-12-10 | 2001-12-26 | 普莱克斯技术有限公司 | Transition element complex for selectively adsorbing oxygen to combine in molecule with molecule |
WO2007040168A1 (en) * | 2005-10-05 | 2007-04-12 | Kuraray Co., Ltd. | Oxygen absorbent, oxygen-absorbing composition, method of producing the same and laminate and packaging material using the oxygen-absorbing composition |
CN101688020A (en) * | 2007-05-10 | 2010-03-31 | 康斯达国际公司 | Oxygen is removed molecule, is comprised goods and using method thereof that described oxygen is removed molecule |
CN102015860A (en) * | 2008-05-06 | 2011-04-13 | 巴斯夫欧洲公司 | Oxygen-scavenging mixtures |
CN102093429A (en) * | 2009-12-14 | 2011-06-15 | 新疆大学 | Method for preparing g pyridyl alanine oxygen-absorbing complex |
CN102639625A (en) * | 2009-12-02 | 2012-08-15 | 巴斯夫欧洲公司 | Use of metal complexes as oxygen absorber/scavenger elements for packaging applications |
CN115869923A (en) * | 2022-12-28 | 2023-03-31 | 威格科技(苏州)股份有限公司 | Oxygen absorbing material, preparation method thereof and prepared adsorbing material capable of adsorbing oxygen and organic solvent simultaneously |
CN116023294A (en) * | 2022-12-28 | 2023-04-28 | 威格科技(苏州)股份有限公司 | Preparation method and application of oxygen absorbing material ligand |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7754798B2 (en) * | 2003-08-28 | 2010-07-13 | Cryovac, Inc. | Oxygen scavenger block copolymers and compositions |
-
2022
- 2022-12-28 CN CN202211695380.6A patent/CN115869923B/en active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02191545A (en) * | 1989-01-19 | 1990-07-27 | Nippon Sanso Kk | Oxygen absorbing and desorbing agent and its production |
EP0475053A1 (en) * | 1990-08-15 | 1992-03-18 | Praxair Technology, Inc. | Oxygen-separating porous membranes |
JPH09151192A (en) * | 1995-11-29 | 1997-06-10 | Nippon Sanso Kk | Cobalt schiff base complex, complex solution for separating oxygen and separation of oxygen |
CN1327877A (en) * | 1999-12-10 | 2001-12-26 | 普莱克斯技术有限公司 | Transition element complex for selectively adsorbing oxygen to combine in molecule with molecule |
WO2007040168A1 (en) * | 2005-10-05 | 2007-04-12 | Kuraray Co., Ltd. | Oxygen absorbent, oxygen-absorbing composition, method of producing the same and laminate and packaging material using the oxygen-absorbing composition |
CN101688020A (en) * | 2007-05-10 | 2010-03-31 | 康斯达国际公司 | Oxygen is removed molecule, is comprised goods and using method thereof that described oxygen is removed molecule |
CN102015860A (en) * | 2008-05-06 | 2011-04-13 | 巴斯夫欧洲公司 | Oxygen-scavenging mixtures |
CN102639625A (en) * | 2009-12-02 | 2012-08-15 | 巴斯夫欧洲公司 | Use of metal complexes as oxygen absorber/scavenger elements for packaging applications |
CN102093429A (en) * | 2009-12-14 | 2011-06-15 | 新疆大学 | Method for preparing g pyridyl alanine oxygen-absorbing complex |
CN115869923A (en) * | 2022-12-28 | 2023-03-31 | 威格科技(苏州)股份有限公司 | Oxygen absorbing material, preparation method thereof and prepared adsorbing material capable of adsorbing oxygen and organic solvent simultaneously |
CN116023294A (en) * | 2022-12-28 | 2023-04-28 | 威格科技(苏州)股份有限公司 | Preparation method and application of oxygen absorbing material ligand |
Non-Patent Citations (7)
Title |
---|
Correlation between oxygen adsorption energy and electronic structure of transition metal macrocyclic complexes;Liu K等;The Journal of chemical physics;20131231;第139卷(第20期);全文 * |
Effect of ligand structures on oxygen absorbability and viscosity o metal-containing ionic liquids;Matsuoka A等;JOURNAL OF MOLECULAR LIQUIDS;20201115;第318卷;全文 * |
Investigation of the oxygen affinity of manganese(II), cobalt(II) and nickel(II) complexes with some tetradentate Schiff bases;Emara AAA等;JOURNAL OF SAUDI CHEMICAL SOCIETY;20141231;第18卷(第6期);762-773 * |
Surface-Adsorbed Carboxylate Ligands on Layered Double Hydroxides/Metal-Organic Frameworks Promote the Electrocatalytic Oxygen Evolution Reaction;Li CF等;ANGEWANDTE CHEMIE-INTERNATIONAL EDITION;20210731;第60卷(第33期);18129-18137 * |
Syntheses, solubilities and oxygen absorption properties of new cobalt(II) Schiff-base complexes;Park S等;POLYHEDRON;19981231;第17卷(第2-3期);325-330 * |
丙氨酸钴配合物的氧合性能研究及其在氧化降解木质素中的应用;周柯;中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑);20200915(第9期);B014-35 * |
尾式金属卟啉配合物的研究――Ⅱ.新型尾式金属卟啉配合物的催化和载氧功能;计亮年, 覃夏, 黄锦汪;中山大学学报(自然科学版);19930725(04);全文 * |
Also Published As
Publication number | Publication date |
---|---|
CN115869923A (en) | 2023-03-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN115869923B (en) | Oxygen absorbing material, preparation method thereof and prepared adsorption material capable of simultaneously adsorbing oxygen and organic solvent | |
CN101927152B (en) | High-strength gas purifying and separating adsorbent as well as preparation and application thereof | |
CN103483200B (en) | A kind of method of transesterify Catalysts of Preparing Methyl Ethyl Carbonate | |
CN111995635B (en) | Method for preparing organosilicon compound by catalyzing chitosan loaded copper film material | |
CN112892501A (en) | Double-imidazole polyionic liquid and metal organic framework composite material as well as preparation method and application thereof | |
CN111303169B (en) | Preparation method of fubitavir | |
CN101220418B (en) | Method for separating molybdenum, rhenium from molybdenum mineral | |
CN111116296A (en) | Method for separating benzene and cyclohexane | |
CN113617334B (en) | Preparation method of metal organic framework material | |
CN113578275A (en) | For NOxManganese-cobalt binary metal-based MOF adsorbent for gas removal and preparation method thereof | |
CN116023294A (en) | Preparation method and application of oxygen absorbing material ligand | |
CN105195184B (en) | A method of low-mercury catalyst is prepared using high mesoporosity activated carbon | |
KR101009310B1 (en) | Sintered adsorbents, preparation method thereof and use of same for the drying of organic compounds | |
CN109012629A (en) | A kind of method and its application preparing magnetic carboxymethyl-β-cyclodextrin polymer | |
CN111205297A (en) | Preparation method of forbitasvir RRRR type enantiomer | |
CN101007766A (en) | Method for catalytic synthesis of diamyl carbonate and methyl amyl carbonate | |
CN114349973B (en) | Lanthanum-manganese bimetal quasi-organic framework material and preparation method and application thereof | |
CN115043812A (en) | Method for preparing vinylene carbonate | |
CN111303084B (en) | Method for separating 2-methylfuran and 2, 5-dimethylfuran | |
CN111205298A (en) | Preparation method of forbitasvir RRRS type isomer | |
CN114561025B (en) | Pyridinium-modified UiO-66 compound, preparation method and application | |
CN109369544B (en) | Method for preparing 5-methylpyrazine-2-carboxylic acid by catalytic oxidation | |
CN115804999A (en) | Gas purification device, glove box and regeneration method | |
CN1104924C (en) | Thermally-managed separation and dewatering processes for recovering acid products | |
CN112958041B (en) | Core-shell structure nano composite resin, preparation method and application in electroplating wastewater treatment |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |