CN114768854A - 负载于多孔碳基材料的化合物及其应用于水处理的方法 - Google Patents
负载于多孔碳基材料的化合物及其应用于水处理的方法 Download PDFInfo
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- CN114768854A CN114768854A CN202210503789.7A CN202210503789A CN114768854A CN 114768854 A CN114768854 A CN 114768854A CN 202210503789 A CN202210503789 A CN 202210503789A CN 114768854 A CN114768854 A CN 114768854A
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- Prior art keywords
- porous carbon
- compound
- water
- oxygen
- based material
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 150000001875 compounds Chemical class 0.000 title claims abstract description 33
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 26
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 61
- 150000003254 radicals Chemical class 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 8
- 238000005273 aeration Methods 0.000 claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 claims abstract description 5
- 239000000919 ceramic Substances 0.000 claims abstract description 4
- 230000014759 maintenance of location Effects 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract 6
- 230000003197 catalytic effect Effects 0.000 claims description 50
- 239000003054 catalyst Substances 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 239000012876 carrier material Substances 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000013110 organic ligand Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- -1 hydroxyl radicals Chemical class 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000003446 ligand Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000006731 degradation reaction Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 4
- 230000033558 biomineral tissue development Effects 0.000 claims description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 235000021317 phosphate Nutrition 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229960002885 histidine Drugs 0.000 claims description 3
- 150000003840 hydrochlorides Chemical class 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 229920001690 polydopamine Polymers 0.000 claims description 3
- LUARRPSPRYCMOT-UHFFFAOYSA-N propane-1,2-dithiol;sodium Chemical compound [Na].CC(S)CS LUARRPSPRYCMOT-UHFFFAOYSA-N 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 3
- WLOADVWGNGAZCW-UHFFFAOYSA-N 3-phenyl-23H-porphyrin-2,18,20,21-tetracarboxylic acid Chemical compound OC(=O)C=1C(N2C(O)=O)=C(C(O)=O)C(=N3)C(C(=O)O)=CC3=CC(N3)=CC=C3C=C(N=3)C=CC=3C=C2C=1C1=CC=CC=C1 WLOADVWGNGAZCW-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 2
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- 229910052804 chromium Inorganic materials 0.000 claims description 2
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- 239000000356 contaminant Substances 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims description 2
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims description 2
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- 230000001788 irregular Effects 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
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- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
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- 238000010525 oxidative degradation reaction Methods 0.000 claims description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 2
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- 229940068041 phytic acid Drugs 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
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- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
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- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
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- 239000012528 membrane Substances 0.000 description 6
- 238000004065 wastewater treatment Methods 0.000 description 5
- NTZRDKVFLPLTPU-UHFFFAOYSA-N CC[Na] Chemical compound CC[Na] NTZRDKVFLPLTPU-UHFFFAOYSA-N 0.000 description 4
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- 229910000361 cobalt sulfate Inorganic materials 0.000 description 4
- 229940044175 cobalt sulfate Drugs 0.000 description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
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- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000003642 reactive oxygen metabolite Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
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- 238000001556 precipitation Methods 0.000 description 3
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical class OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及水处理技术领域,公开了负载于多孔碳基材料的化合物及其应用于水处理的方法,以固定床的形式装填于底部设置微米陶瓷曝气盘的反应器,气泡尺寸为50‑400μm,气源为空气,变压吸附制氧机制备的90%±3%浓度的富氧气和纯氧气,进水为下进上出的溢流方式,通过调节进水端水泵流速调节反应的水力停留时间,有机污染物降解通过自由基和非自由基两种路径。本发明兼具原材料廉价易得、制造工艺简单、运行成本低廉等优点,并且具备能够在常温常压的操作条件下,即通过自由基路径,又通过活性氧物种的非自由基路径降解难降解有机物的能力。
Description
技术领域
本发明涉及水处理技术领域,具体涉及负载于多孔碳基材料的化合物及其应用于水处理的方法。
背景技术
水中的难降解有机污染物(POPs)是一类具有长期残留性、生物累积性、半挥发性和高毒性,并通过各种环境介质(大气、水、生物等)能够长距离迁移对人类健康和环境具有严重危害的天然的或人工合成的有机污染物。联合国环境规划署(UNEP)主持下,迄今为止已有超过20大类有机物被列为狭义上的POPs物质,他们主要是有机氯农药(OCPs)、氯苯和多氯联苯类(PCBs),二噁英类(PCDD),全氟辛磺酸类(PFOS),多环芳烃和硫丹等。这诸多种类的POPs有机物,或因其化学惰性、或极强的生物毒性,难以被传统生物法降解,也难于被低氧化能级(Eoxidation)的氧化物种破坏其相对稳定的化学结构,如氧气、过氧化氢、纯臭氧等。因此,高级氧化技术(AOPs),一种通过催化过氧化氢、臭氧和过硫酸根产生更高氧化能级的羟基自由基或硫酸根自由基,或在高温高压下激发分子氧产生活性氧物种(ROS)的化学氧化技术,常被用于此类水体的修复,并取得了一定效果。但此类方法的应用仍具一定缺陷,如过氧化氢属于易爆化学品,获得臭氧的方法能耗较高,过硫酸根的引入容易造成水体的二次污染,高温高压的反应条件对反应器和安全的要求较为苛刻。除了上述产生氧化性自由基的物质以外,氧气,尤其是空气中或水溶性的分子氧,作为另一种获取自由基和活性氧物质的原材料,因其廉价易得,无二次污染,无论是学界还是工业界都将其视为一种适用于水体净化技术的理想物质,与之对应的分子氧活化从而产生自由基或活性氧物种的技术成为业界公认的前沿水体净化技术。
目前的分子氧活化方法需借助包括高温高压的湿式氧化技术,电化学、光照辐射和常温常压下的催化剂活化等技术,其中分子氧催化活化技术,因温和的反应条件,最具大规模应用前景,但该技术所应用的催化剂技术尚存不足,诸如(a)采用贵金属活性成份的成本高昂,(b)需借助甲醛等助剂帮助活化催化反应,(c)反应速率低或反应温度较高,以及(d)制作工艺复杂等因素均限制了该技术的发展。因此亟待一种成本低廉,合成工艺简单,兼具自由基和非自由基路径降解有机物能力的高效分子氧活化催化剂。目前涉及常温常压下活化分子氧降解有机污染物的水处理技术的报道较少,CN102173500B中公布了一种活化分子氧的催化氧化水处理技术,对多种实际废水取得了较好的处理效果,文中并未详细阐述其氧化作用是通过自由基、还是非自由基路径,而且采用的均相催化剂和非均相催化剂粉末,存在引入二次污染物质和产水中催化剂的分离问题。在空气净化领域,有较多关于活化分子氧降解有机物的报道,但大多涉及使用较高成本的贵金属活性成分。CN106807239A中使用含有贵金属的双金属中心催化剂,如钯-铜催化体系,需要以甲醛作为助剂,或在一百摄氏度以上的高温条件下,才能活化空气中的氧气降解挥发性有机物苯;专利CN109772297中,以铝粉、高锰酸钾和金属钨的多聚氧酸盐通过共沉淀法制备的颗粒状及多孔海泡石负载成型的催化剂,对无取代基的苯,甲苯和萘有一定去除能力;文献报道的钯-金催化剂(JPhys Chem C,2015,119,11754-11762)活化的氧气,在室温下仅能氧化降解一氧化碳、烯烃和醇;使用纳米贵金属微粒活化空气中的氧气,如铂、金、银等催化剂(ACSCatalysis,2013,3,478-486),室温下无法降解无取代芳香族有机物,且催化成分易聚合变形导致快速失活;过量零价铁牺牲法用于活化氧气的技术(Environ.Eng.Res.,2015,20(3),205-211)并非真正的催化反应,且存在零价铁迅速消耗的寿命问题。
综上所述,水处理行业内亟待一款高效活化分子氧降解有机物的固定床催化剂,兼具原材料廉价易得、制造工艺简单、运行成本低廉等优点,并且具备能够在常温常压的操作条件下,即通过自由基路径,又通过活性氧物种的非自由基路径降解难降解有机物的能力。
发明内容
本发明专利公开了一种通过自由基和非自由基路径降解有机污染物的活化分子氧的水处理催化剂的制备方法,以及使用该催化剂在富氧源和纯氧源曝气的情况下处理难降解有机污染物的水处理技术。
为实现上述目的,本发明所涉及的催化剂材料的制备采用以下技术方案实现,首先通过原位元素掺杂的方式制备多孔碳载体材料,之后将催化剂活性组分与掺杂元素相对应的配体反应制备为配位化合物,并负载于多孔碳载体材料上,经热解反应后与碳表面相键合,所形成的结构有助于分子氧的吸附及活化,如获得的负载多孔碳催化材料为粉体,可添加粘结剂造粒成型为适合的形貌,最终可用于在水体中活化分子氧进行有机污染物的降解,如用于负载的多孔碳材料为颗粒,可直接用于水体中有机污染物的降解。
所述以原位元素掺杂方式制备的多孔碳载体材料的制造工艺包括如下步骤:
步骤一:将一定量的含氮、含硫和含磷的小分子物质均匀混合配置成一定浓度的溶液。
步骤二:将上述溶液转移至高压密封反应釜中,添加一定量的多孔碳材料进行掺杂改性,在90-210℃的条件下进行水热反应5-12小时,经过滤、冷却、洗涤和110℃条件下干燥4-8小时,转移至马弗炉内在300-400°及氮气保护的条件下煅烧2-4小时,隔氧冷却至室温,得到相应元素掺杂的多孔碳材料前驱体。
步骤三:将上述前驱体浸泡于3-7M的浓碱液中,进行12-18小时的表面强化处理,将处理后的多孔碳材料过滤分离,用清水清洗至清洗液呈中性,干燥后做载体备用,剩余的浸泡浓碱液可循环套用。
所述含氮小分子物质为硝酸铵、硝酸钠、亚硝酸钠、苯胺、聚多巴胺、尿素、N,N-二甲基乙二胺、N,N-二乙基乙二胺、双氰胺、三聚氰胺,占载体材料的质量分数为50-80%,优选的为聚多巴胺和三聚氰胺。
所述含硫小分子物质为硫代硫酸钠、硫化钠、二硫化碳、2-巯基乙醇、2,3-二巯基丙磺酸钠、二苯二硫醚、硫脲,占载体材料的质量分数为50-80%,优选的为2,3-二巯基丙磺酸钠和硫脲。
所述含磷小分子物质为磷酸、磷酸二氢钠、三氯化磷,五氧化二磷、肌醇六磷酸和膦基聚羧酸,占载体材料的质量分数为50-80%,优选的为膦基聚羧酸。
配置步骤一中所述溶液,根据所需溶解物质的溶解度,可选择去离子水、乙醇、乙二醇、丙二醇、乙酸乙酯、石油醚、甲苯、四氢呋喃中的一种或两种,优选的为水合乙醇,元素掺杂后的溶液可循环套用;
步骤二中所述多孔碳材料为活性炭、石墨、石墨烯或碳纳米管的325目以上的粉体、3-5mm不规格颗粒、3mm球体或3-4mm柱状颗粒中的一种;
步骤三中所述浓碱液为氢氧化钠或氢氧化钾的水溶液。
所述活性成分配位化合物的制备,及其负载于多孔碳基材料的工艺,包括如下步骤:
将金属混合盐与有机配体分别溶于对应溶解度的溶剂中,超声溶解并分散均匀,在搅拌条件下将上述两种溶液充分混合,然后转移至冷凝回流反应釜中,在80-180℃下进行2-4小时水热反应,得到负载了混合金属盐的混合配体化合物,将特定量的经元素掺杂的多孔碳载体材料投入到上述的反应液中,继续反应4-8小时,反应后经冷却、抽滤,并用对应溶剂反复洗涤后烘干,将含水率低于8%的转移至惰性气体保护的煅烧炉中,在800-950℃的条件下保温1-4h,即得到最终的化合物。
其中,金属混合盐为按照一定摩尔比例配置的1-2种主催化成份,1-2种助催化成份,以及1-2种有机配体化合物。
其中,所述主催化成份为过渡金属铁、铜、钴、锰、钒、铬和镍的硫酸盐、盐酸盐、磷酸盐和硝酸盐中的一种或两种,优选的为铁、锰和钴的对应掺杂元素的离子盐。
其中,所述助催化成份为钼、钨、铌、碲、锌、镁、锶、铯、铋、铈、镧和钕的硫酸盐、盐酸盐、磷酸盐和硝酸盐中的一种或两种,优选的为钼、钨和铈的对应掺杂元素的离子盐。
其中,所述有机配体化合物为含氮配体,包括乙二胺四乙酸、四羧基苯基卟啉和乙二胺甘氨酸;含磷配体,包括三环己基膦;含硫配体,包括乙二胺基乙磺酸钠。
其中,所述有机溶剂为去离子水、乙醇、乙二醇、异丙醇、正己烷、丙酮、四氢呋喃、石油醚或乙酸乙酯中的一种或两种。
其中,所述主催化成份占载体材料的质量分数为4-20%,当主催化成份为两种金属的混合盐时,其摩尔比为8:1至1:1。
其中,所述助催化成份占载体材料的质量分数为2-10%,当助催化成份为两种金属的混合盐时,其摩尔比为4:1至1:1。
其中,所述主催化成份和助催化成份的摩尔比为10:1至4:1。
其中,所述配体材料与催化成份的摩尔比为1.2:1至1:1。
其中,所述元素掺杂的多孔碳材料占总质量的70-94%。
其中,所述惰性气体保护所使用的保护气为氮气,氦气或二氧化碳。
其中,所述催化剂粉体的成型工艺为螺杆挤出或液压挤出造粒。
其中,所述粘结剂为铝溶胶、硅溶胶、凹凸棒土或钠基膨润土中的一种,所需用量为总质量的15-30%。
其中,所述颗粒形貌和尺寸为3mm柱状、3mm三叶草或3mm蝶形。
本发明涉及的活化分子氧催化氧化降解水中有机物的水处理方法,具体实施方法如下:
将催化剂颗粒以固定床的形式装填于底部设置微米陶瓷曝气盘的反应器,气泡尺寸为50-400μm,气源为空气,变压吸附制氧机制备的90%±3%浓度的富氧气和纯氧气,进水为下进上出的溢流方式,通过调节进水端水泵流速调节反应的水力停留时间。有机污染物降解通过自由基和非自由基两种路径,其中自由基路径常见的氧化物质为羟基自由基和硫酸根自由基,非自由基路径常见的氧化物质为超氧自由基O2·和单线态氧1O2,定性何种降解路径通过使用特定湮灭剂对氧化降解反应效率的削弱程度,间接定量。
所述湮灭剂具体为,湮灭羟基自由基使用仲丁醇,硫酸根自由基使用甲醇,超氧自由基使用对苯醌,单线态氧使用L-组氨酸。
有机污染物的矿化程度由TOC去除率表征。
与现有技术相比,本发明负载于多孔碳基材料的化合物及其应用于水处理的方法,具有以下优点:
1、本发明涉及的催化活化分子氧催化剂,相比借助甲醛等助剂的分子氧活化催化剂,无需额外添加助剂;
2、相比在高温下使用的分子氧活化催化剂,可在室温下催化活化分子氧;
3、相比使用贵金属的催化剂,成本低廉;
4、相比仅能活化分子氧产生活性氧物种ROS的催化剂,可产生羟基自由基,并以自由基和非自由基两种路径降解有机物;
5、本发明涉及的催化活化分子氧水处理工艺,相比(a)使用双氧水和产生铁泥的芬顿工艺、(b)使用高温高压的湿式氧化工艺、(c)使用光催化和电催化的高能耗激发产生氧化物种的反应法师、以及(d)使用臭氧作为氧化剂的臭氧催化氧化工艺,其使用空气、富氧气源或纯氧曝气作为分子氧来源,原料清洁、且廉价易得,运行成本优势明显。
附图说明
附图用来提供对本发明的进一步理解,并且构成说明书的一部分,与本发明的实施例一起用于解释本发明,并不构成对本发明的限制,在附图中:
图1为使用实施例1-4中的催化剂进行分子氧活化降解有机污染物工艺对不同废水的COD去除率及不同氧化物质淬灭剂存在条件下对COD去除率的抑制。
图2为自由基路径(羟基自由基和硫酸根自由基)和非自由基路径(超氧自由基和单线态氧)对实施例1-4中COD去除的贡献率以及有机物完全矿化率(TOC去除率)。
图3为通过液相色谱-质谱联用分析实施例1中煤制甲醇废水膜系统废水原水、活化分子氧处理后产水和臭氧催化氧化处理产水的总离子流图对比。其中x-轴出峰(时间)代表该析出时间析出的有机物,峰面积对应该析出时间有机物的总量。
图4为对比实施例1中原水、经分子氧活化氧化产水和臭氧催化氧化产水的中的有机物HPLC出峰的峰总数,峰面积占比前10特征峰的析出时间和峰高占比。
图5为实施例1中原水、分子氧活化氧化产水和臭氧催化氧化产水中有机物在HPLC特定时间析出特征峰的一级质谱荷质比分布(m/z)。
图6为实施例1-4中元素掺杂多孔碳载体和催化剂成品表面扫描电子显微镜(SEM)照片。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1:
将占载体材料的质量分数为50%的硝酸铵和质量分数50%的硫脲配置成去离子水溶液,用于对3mm柱状颗粒活性炭的N,S元素掺杂,在110℃条件下,水热反应6小时,在氮气保护条件下经350℃煅烧处理3h,最终获得的干燥粉末经5M浓碱液处理得到N,S掺杂的多孔碳载体材料。
浸渍液的主催化成份为硫酸高铁和硫酸锰,其摩尔比为1:1,助催化成分为硫酸铈,主催化和助催化成分的摩尔比为4:1,有机配体为的乙二胺四乙酸和乙二胺基乙磺酸钠,其摩尔比为1:1,催化成分和有机配体的摩尔比为1:1.2,所使用的浸渍溶剂为去离子水,上述溶液在90℃下,经冷凝回流反应8h。向上述溶液中投加上述N,S掺杂多孔碳材料,催化成份占掺杂载体的质量分数为25%,在保证溶液一定程度搅拌的条件下浸渍12h,经抽滤,洗涤,干燥得到催化剂的半成品颗粒,在惰性气体保护下,经850℃煅烧2h得到分子氧活化催化剂成品。
将上述的催化剂颗粒以填料床的形式装填到底部设置由陶瓷曝气盘的圆柱形反应器中,总装填量为容器有效容积的60%,曝气气源为变压吸附制氧机产生的浓度为90±3%富氧气流,反应废水为山西某企业的煤制甲醇生产废水水处理系统的RO膜系统浓水,反应时间为1h,用于判定氧化路径为自由基或非自由基的淬灭试验,在浓度为90mM的叔丁醇(羟基自由基),90mM的甲醇(硫酸根自由基),1mM的对苯醌(超氧自由基)或12mM的L-组氨酸(单线态氧)存在的条件下进行,对比淬灭剂存在条件下对COD去除率的抑制程度,即为特定氧化物质对COD去除率的贡献程度,有机污染物的完全矿化程度,由TOC去除率表征。
本实施例中所采用的煤制甲醇废水处理膜系统废水原水和分子活化氧化处理(自由基/非自由基降解路径)的产水中的不同种类有机物还通过液相色谱-质谱联用技术定量表征,并与使用本实施例中的催化剂进行臭氧催化氧化处理后(COD去除率88.2%,自由基降解路径得到增强)的产水中的剩余有机物进行对比,用以分析经不同氧化物质对特征有机污染物氧化降解能力之间的差异。结果显示,相较于原水,无论是分子氧活化还是臭氧催化氧化降解,总出峰数量均有所减少,且有较高占比的新特征峰出现,证明原水中部分有机物被完全转化为其他物质或被完全降解。相比于催化臭氧氧化的产水,活化分子氧产水中新产生的1.79min附近析出的占比总量分别超过40%的新特征峰,在一级质谱下,两者荷质比分布非常接近,可推测为结构类似的氧化产物。但在1.39min的析出峰(占比15%),其一级质谱下的荷质比分布与臭氧催化氧化在附近时间的析出峰差异明显,可推测为不同氧化路径的不同产物。
实施例2:
将占载体材料的质量分数为70%的N,N-二乙基乙二胺和质量分数50%的膦基聚羧酸配置成无水乙醇和去离子水的混合溶液,用于对粉末活性炭材料的N,P元素掺杂,在120℃条件下,水热反应6小时,在氮气保护条件下经350℃煅烧处理3h,最终获得的干燥粉末经5M浓碱液处理得到N,S掺杂的多孔碳载体材料。
浸渍液的主催化成份为硫酸铜和硫酸镍,其摩尔比为4:1,助催化成分为钼酸钠和氯化锌,其摩尔比为1:1主催化和助催化成分的摩尔比为8:1,有机配体为的乙二胺四乙酸和膦基聚羧酸,其摩尔比为1:1,催化成分和有机配体的摩尔比为1:1,所使用的浸渍溶剂为去离子水,上述溶液在90℃下,经冷凝回流反应8h。向上述溶液中投加上述N,S掺杂多孔碳材料,催化成份占掺杂载体的质量分数为20%,在保证溶液一定程度搅拌的条件下浸渍12h,经抽滤,洗涤,干燥得到催化剂的粉体。
将上述催化剂分体通过螺杆挤出造粒成3mm的柱状颗粒,所用粘结剂为铝溶胶,在惰性气体保护下,经850℃煅烧2h得到分子氧活化催化剂成品。
评价催化剂的活化分子氧降解有机污染物的能力,按照实施例1中的实验方法进行,气源为液氧,所用废水为山东某企业的精对苯二甲酸生产废水水处理系统的RO膜系统浓水。
实施例3:
将占载体材料的质量分数为70%的尿素和质量分数50%的硫代硫酸钠配置成去离子水溶液,用于氧化石墨烯粉末材料的N,S元素掺杂,在110℃条件下,水热反应6小时,在氮气保护条件下经350℃煅烧处理3h,最终获得的干燥粉末经5M浓碱液处理得到N,S掺杂的多孔碳载体材料。
浸渍液的主催化成份为硫酸锰和硫酸钴,其摩尔比为2:1,助催化成分为硫酸钨和硫酸镁,其摩尔比为1:1主催化和助催化成分的摩尔比为4:1,有机配体为的乙二胺四乙酸和乙二胺基乙磺酸钠,其摩尔比为1:1,催化成分和有机配体的摩尔比为1:1.2,所使用的浸渍溶剂为去离子水,上述溶液在90℃下,经冷凝回流反应8h。向上述溶液中投加上述N,S掺杂多孔碳材料,催化成份占掺杂载体的质量分数为25%,在保证溶液一定程度搅拌的条件下浸渍12h,经抽滤,洗涤,干燥得到催化剂的粉体。
将上述催化剂分体通过螺杆挤出造粒成3mm的柱状颗粒,所用粘结剂为硅溶胶,在惰性气体保护下,经950℃煅烧2h得到分子氧活化催化剂成品。
评价催化剂的活化分子氧降解有机污染物的能力,按照实施例1中的实验方法进行,气源为液氧所用废水为陕西某焦化生产废水水处理系统的RO膜系统浓水。
实施例4:
将占载体材料的质量分数为40%的三聚氰胺和质量分数50%的膦基聚羧酸配置成乙醇溶液,用于对3mm颗粒活性炭材料的N,P元素掺杂,在120℃条件下,水热反应6小时,在氮气保护条件下经350℃煅烧处理3h,最终获得的干燥粉末经5M浓碱液处理得到N,S掺杂的多孔碳载体材料。
浸渍液的主催化成份为硫酸铜和硫酸钴,其摩尔比为4:1,助催化成分为氯化锶和硫酸铈,其摩尔比为1:1主催化和助催化成分的摩尔比为4:1,有机配体为乙二胺甘氨酸和三环己基膦,其摩尔比为1:1,催化成分和有机配体的摩尔比为1:1,所使用的溶解为去离子水,上述溶液在90℃下,经冷凝回流反应8h。向上述溶液中投加上述N,P掺杂多孔碳材料,催化成份占掺杂载体的质量分数为25%,在保证溶液一定程度搅拌的条件下浸渍12h,经抽滤,洗涤,干燥得到催化剂的半成品颗粒,在惰性气体保护下,经800℃煅烧2h得到分子氧活化催化剂成品。
评价催化剂的活化分子氧降解有机污染物的能力,按照实施例1中的实验方法进行,所用废水为山西某煤制甲醇生产废水水处理系统的RO膜系统浓水。
尽管已经示出和描述了本发明的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由所附权利要求及其等同物限定。
Claims (10)
1.一种负载于多孔碳基材料的化合物,其特征在于,按照以下步骤制备:将金属混合盐与有机配体分别溶于对应溶解度的溶剂中,超声溶解并分散均匀,在搅拌条件下将上述两种溶液充分混合,然后转移至冷凝回流反应釜中,在80-180℃下进行2-4小时水热反应,得到负载了混合金属盐的混合配体化合物,将特定量的经元素掺杂的多孔碳载体材料投入到上述的反应液中,继续反应4-8小时,反应后经冷却、抽滤,并用对应溶剂反复洗涤后烘干,将含水率低于8%的转移至惰性气体保护的煅烧炉中,在800-950℃的条件下保温1-4h,即得到最终化合物。
2.根据权利要求1所述一种负载于多孔碳基材料的化合物,其特征在于:所述多孔碳载体材料按照以下步骤制备:
步骤一:将一定量的含氮、含硫和含磷的小分子物质均匀混合配置成一定浓度的溶液,
步骤二:将上述溶液转移至高压密封反应釜中,添加一定量的多孔碳材料进行掺杂改性,在90-210℃的条件下进行水热反应5-12小时,经过滤、冷却、洗涤和110℃条件下干燥4-8小时,转移至马弗炉内在300-400°及氮气保护的条件下煅烧2-4小时,隔氧冷却至室温,得到相应元素掺杂的多孔碳材料前驱体,
步骤三:将上述前驱体浸泡于3-7M的浓碱液中,进行12-18小时的表面强化处理,将处理后的多孔碳材料过滤分离,用清水清洗至清洗液呈中性,干燥后做载体备用,剩余的浸泡浓碱液可循环套用。
3.根据权利要求2所述一种负载于多孔碳基材料的化合物,其特征在于:所述含氮小分子物质包括硝酸铵、硝酸钠、亚硝酸钠、苯胺、聚多巴胺、尿素、N,N-二甲基乙二胺、N,N-二乙基乙二胺、双氰胺、三聚氰胺,占载体材料的质量分数为50-80%;所述含硫小分子物质包括硫代硫酸钠、硫化钠、二硫化碳、2-巯基乙醇、2,3-二巯基丙磺酸钠、二苯二硫醚、硫脲,占载体材料的质量分数为50-80%;所述含磷小分子物质包括磷酸、磷酸二氢钠、三氯化磷,五氧化二磷、肌醇六磷酸和膦基聚羧酸,占载体材料的质量分数为50-80%。
4.根据权利要求2所述一种负载于多孔碳基材料的化合物,其特征在于:步骤一中所述溶液,根据所需溶解物质的溶解度,选择去离子水、乙醇、乙二醇、丙二醇、乙酸乙酯、石油醚、甲苯、四氢呋喃中的一种至两种,且元素掺杂后的溶液可循环套用;步骤二中所述多孔碳材料为活性炭、石墨、石墨烯或碳纳米管的325目以上的粉体、3-5mm不规格颗粒、3mm球体或3-4mm柱状颗粒中的一种;步骤三中所述浓碱液为氢氧化钠或氢氧化钾的水溶液。
5.根据权利要求1所述一种负载于多孔碳基材料的化合物,其特征在于:所述金属混合盐为按照一定摩尔比例配置的1-2种主催化成份,1-2种助催化成份,以及1-2种有机配体化合物。
6.根据权利要求1所述一种负载于多孔碳基材料的化合物,其特征在于:所述主催化成份为过渡金属铁、铜、钴、锰、钒、铬和镍的硫酸盐、盐酸盐、磷酸盐和硝酸盐中的一种至两种,所述助催化成份为钼、钨、铌、碲、锌、镁、锶、铯、铋、铈、镧和钕的硫酸盐、盐酸盐、磷酸盐和硝酸盐中的一种至两种,所述有机配体化合物为含氮配体,包括乙二胺四乙酸、四羧基苯基卟啉和乙二胺甘氨酸;含磷配体,包括三环己基膦;含硫配体,包括乙二胺基乙磺酸钠。
7.根据权利要求1所述一种负载于多孔碳基材料的化合物,其特征在于:所述有机溶剂为去离子水、乙醇、乙二醇、异丙醇、正己烷、丙酮、四氢呋喃、石油醚或乙酸乙酯中的一种至两种。
8.根据权利要求1所述一种负载于多孔碳基材料的化合物,其特征在于:所述主催化成份占载体材料的质量分数为4-20%;所述助催化成份占载体材料的质量分数为2-10%;所述元素掺杂的多孔碳材料占总质量的70-94%。
9.一种负载于多孔碳基材料的化合物应用于水处理的方法,其特征在于:将如权利要求1-9任意一项所述配位化合物催化剂颗粒以固定床的形式装填于底部设置微米陶瓷曝气盘的反应器,气泡尺寸为50-400μm,气源为空气,变压吸附制氧机制备的90%±3%浓度的富氧气和纯氧气,进水为下进上出的溢流方式,通过调节进水端水泵流速调节反应的水力停留时间,有机污染物降解通过自由基和非自由基两种路径,其中自由基路径常见的氧化物质为羟基自由基和硫酸根自由基,非自由基路径常见的氧化物质为超氧自由基O2·和单线态氧1O2,定性何种降解路径通过使用特定湮灭剂对氧化降解反应效率的削弱程度,间接定量。
10.根据权利要求9所述一种负载于多孔碳基材料的化合物应用于水处理的方法,其特征在于:所述湮灭剂具体为,湮灭羟基自由基使用仲丁醇,硫酸根自由基使用甲醇,超氧自由基使用对苯醌,单线态氧使用L-组氨酸。有机污染物的矿化程度由TOC去除率表征。
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