CN113402013A - Method for degrading perfluorooctanoic acid by coupling microbial electro-Fenton with sodium persulfate - Google Patents
Method for degrading perfluorooctanoic acid by coupling microbial electro-Fenton with sodium persulfate Download PDFInfo
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- CN113402013A CN113402013A CN202110765314.0A CN202110765314A CN113402013A CN 113402013 A CN113402013 A CN 113402013A CN 202110765314 A CN202110765314 A CN 202110765314A CN 113402013 A CN113402013 A CN 113402013A
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- China
- Prior art keywords
- perfluorooctanoic acid
- sodium persulfate
- fenton
- reactor
- electro
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- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 title claims abstract description 134
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 title claims abstract description 84
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 title claims abstract description 84
- 230000000813 microbial effect Effects 0.000 title claims abstract description 64
- 230000008878 coupling Effects 0.000 title claims abstract description 58
- 238000010168 coupling process Methods 0.000 title claims abstract description 58
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 58
- 230000000593 degrading effect Effects 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000006731 degradation reaction Methods 0.000 claims abstract description 56
- 230000015556 catabolic process Effects 0.000 claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 235000015097 nutrients Nutrition 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 244000005700 microbiome Species 0.000 claims abstract description 26
- 239000010802 sludge Substances 0.000 claims abstract description 22
- -1 potassium ferricyanide Chemical group 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 238000012258 culturing Methods 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 42
- 239000004917 carbon fiber Substances 0.000 claims description 42
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 42
- 229910002804 graphite Inorganic materials 0.000 claims description 32
- 239000010439 graphite Substances 0.000 claims description 32
- 238000002791 soaking Methods 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 229910001868 water Inorganic materials 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 17
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 16
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 16
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 16
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 16
- 238000004140 cleaning Methods 0.000 claims description 16
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 16
- LXNHXLLTXMVWPM-UHFFFAOYSA-N pyridoxine Chemical compound CC1=NC=C(CO)C(CO)=C1O LXNHXLLTXMVWPM-UHFFFAOYSA-N 0.000 claims description 16
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 9
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 claims description 8
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 claims description 8
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 claims description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229930003451 Vitamin B1 Natural products 0.000 claims description 8
- 229930003471 Vitamin B2 Natural products 0.000 claims description 8
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 8
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 8
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 8
- 229960000304 folic acid Drugs 0.000 claims description 8
- 235000019152 folic acid Nutrition 0.000 claims description 8
- 239000011724 folic acid Substances 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 8
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 8
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 8
- 229960003512 nicotinic acid Drugs 0.000 claims description 8
- 235000001968 nicotinic acid Nutrition 0.000 claims description 8
- 239000011664 nicotinic acid Substances 0.000 claims description 8
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 8
- 239000001103 potassium chloride Substances 0.000 claims description 8
- 235000011164 potassium chloride Nutrition 0.000 claims description 8
- RADKZDMFGJYCBB-UHFFFAOYSA-N pyridoxal hydrochloride Natural products CC1=NC=C(CO)C(C=O)=C1O RADKZDMFGJYCBB-UHFFFAOYSA-N 0.000 claims description 8
- 229960002477 riboflavin Drugs 0.000 claims description 8
- 239000001632 sodium acetate Substances 0.000 claims description 8
- 235000017281 sodium acetate Nutrition 0.000 claims description 8
- 229960003495 thiamine Drugs 0.000 claims description 8
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 claims description 8
- 235000010374 vitamin B1 Nutrition 0.000 claims description 8
- 239000011691 vitamin B1 Substances 0.000 claims description 8
- 235000019164 vitamin B2 Nutrition 0.000 claims description 8
- 239000011716 vitamin B2 Substances 0.000 claims description 8
- 235000019158 vitamin B6 Nutrition 0.000 claims description 8
- 239000011726 vitamin B6 Substances 0.000 claims description 8
- 229940011671 vitamin b6 Drugs 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000010865 sewage Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 238000011081 inoculation Methods 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 12
- 241000894006 Bacteria Species 0.000 abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- 239000013067 intermediate product Substances 0.000 description 26
- 238000004458 analytical method Methods 0.000 description 24
- 238000005273 aeration Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000009423 ventilation Methods 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- DCEPGADSNJKOJK-UHFFFAOYSA-N 2,2,2-trifluoroacetyl fluoride Chemical compound FC(=O)C(F)(F)F DCEPGADSNJKOJK-UHFFFAOYSA-N 0.000 description 2
- YLCLKCNTDGWDMD-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoyl fluoride Chemical compound FC(=O)C(F)(F)C(F)(F)F YLCLKCNTDGWDMD-UHFFFAOYSA-N 0.000 description 2
- 241000282412 Homo Species 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 2
- 229920001973 fluoroelastomer Polymers 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- LRMSQVBRUNSOJL-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)F LRMSQVBRUNSOJL-UHFFFAOYSA-N 0.000 description 1
- LQSJUQMCZHVKES-UHFFFAOYSA-N 6-iodopyrimidin-4-amine Chemical compound NC1=CC(I)=NC=N1 LQSJUQMCZHVKES-UHFFFAOYSA-N 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000194036 Lactococcus Species 0.000 description 1
- 241000425347 Phyla <beetle> Species 0.000 description 1
- 241000192142 Proteobacteria Species 0.000 description 1
- 241000589516 Pseudomonas Species 0.000 description 1
- 241000316848 Rhodococcus <scale insect> Species 0.000 description 1
- 241000863430 Shewanella Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 241000941622 Thelenota Species 0.000 description 1
- KQNSPSCVNXCGHK-UHFFFAOYSA-N [3-(4-tert-butylphenoxy)phenyl]methanamine Chemical compound C1=CC(C(C)(C)C)=CC=C1OC1=CC=CC(CN)=C1 KQNSPSCVNXCGHK-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000004996 female reproductive system Anatomy 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 230000008175 fetal development Effects 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 description 1
- ZWBAMYVPMDSJGQ-UHFFFAOYSA-N perfluoroheptanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZWBAMYVPMDSJGQ-UHFFFAOYSA-N 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 241001148471 unidentified anaerobic bacterium Species 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/005—Combined electrochemical biological processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention discloses a method for degrading perfluorooctanoic acid by coupling microbial electro-Fenton with sodium persulfate, which comprises the following steps: manufacturing an anode carbon brush required by the microbial electro-Fenton system, and pretreating; preparing nutrient solution required by the growth of microorganisms for culturing the electrogenesis microorganisms; anaerobic sludge and nutrient solution are added into the anode chamber of the reactor, nitrogen is introduced into the anode chamber, and the cathode chamber is potassium ferricyanide solution to culture and domesticate the electrogenic microorganisms; replacing the cathode solution of the reactor after the culture of the anode electrogenesis bacteria with a perfluorooctanoic acid solution, adding sodium persulfate, and applying voltage to obtain an electro-Fenton coupling sodium persulfate degradation perfluorooctanoic acid reactor; the reactor was maintained at a suitable temperature, air was introduced into the cathode chamber, and perfluorooctanoic acid was degraded under aerobic conditions. In the method, the electro-Fenton system which uses the electrogenic microorganisms as the anode can generate hydrogen peroxide under lower voltage; in the method, the hydroxyl free radical and the sodium persulfate are matched with each other, so that the degradation speed of the perfluorooctanoic acid can be accelerated.
Description
Technical Field
The invention relates to a method for degrading perfluorooctanoic acid. More particularly relates to a method for degrading perfluorooctanoic acid by coupling microbial electro-Fenton with sodium persulfate.
Background
Perfluorooctanoic acid is a kind of perfluor compound, is an artificially synthesized organic matter, and its molecular formula is CF3(CF2)6COOH. Due to its chemical stability,The perfluorooctanoic acid is commonly used as a polymerization dispersant for producing fluorine-containing compounds such as polytetrafluoroethylene, fluoropolymer and fluororubber since the 50 th 20 th century, is also used as a dispersant for polymerization of tetrafluoroethylene and production of fluororubber as a surfactant, an emulsifier, perfluorooctanoic acid and a sodium salt or ammonium salt thereof, and is also used as a raw material and a beneficiation agent for preparing water and oil increasing agents. The compounds are widely applied to producing articles essential in daily life, such as non-stick coatings, waterproof films, breathable clothes, wire casings, fire-resistant and oil-resistant pipes and the like. Although some countries and factories are beginning to ban the production and use of perfluorooctanoic acid, these fluorine-containing products are still in use, and with the widespread use of fluorine-containing compounds, perfluorooctanoic acid is continuously diffused into the environment, and due to its high stability and difficult degradability, one is beginning to monitor perfluorooctanoic acid in various environmental media and even in human bodies. The perfluoro caprylic acid can enter a human body through the contact of a respiratory tract, a digestive tract and skin, has an elimination half-life period of 3.8 years in the human body, can stay in the human body for a long time, has different degrees of influence on aspects of hormone secretion, an immune system, a female reproductive system, fetal development and the like of the human body, and is also researched and found to be mainly enriched in the liver and blood of the human body, thereby causing great threat to the health of human bodies.
Perfluorooctanoic acid has high stability mainly because all carbon-hydrogen bonds are replaced by fluorocarbon bonds, which have strong bond energy and high energy required for breaking. As humans find perfluorooctanoic acid persistent, bioaccumulating in the environment, and hazardous to humans and other living beings, the control and degradation of perfluorooctanoic acid is becoming a focus of public attention. Currently available methods for removing perfluorooctanoic acid from the environment include physical and chemical methods. Physical methods such as traditional reverse osmosis, activated carbon adsorption and the like can effectively remove perfluorooctanoic acid from water, but the perfluorooctanoic acid is not completely degraded and can be completely removed from the environment only by subsequent treatment. Chemical methods such as thermal decomposition, oxidant oxidation, photocatalytic oxidation, etc. require harsh processing conditions and high costs.
In view of the above, it is desirable to provide a novel perfluorooctanoic acid degradation method, which can effectively degrade perfluorooctanoic acid and improve the degradation efficiency.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for degrading perfluorooctanoic acid by coupling microbial electro-Fenton with sodium persulfate. In the method, microorganism electro-Fenton and sodium persulfate are coupled to form a perfluorooctanoic acid degradation system, and the degradation system can accelerate the degradation speed of perfluorooctanoic acid; the fermentation system can reach 99% of perfluorooctanoic acid degradation rate, the treatment condition is mild, and the perfluorooctanoic acid is degraded thoroughly.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for degrading perfluorooctanoic acid by coupling microbial electro-Fenton with sodium persulfate comprises the following steps:
s1, manufacturing an anode carbon brush and a cathode electrode required by the microbial electro-Fenton system, and preprocessing;
s2, preparing nutrient solution required by the growth of the electrogenesis microorganisms for culturing the electrogenesis microorganisms;
s3, adding anaerobic sludge and nutrient solution into the anode chamber of the reactor, introducing nitrogen into the reactor, and culturing and domesticating the electrogenic microorganisms by using a potassium ferricyanide solution as a cathode chamber;
s4, replacing the cathode solution of the reactor with the perfluorooctanoic acid solution after the anodic electrogenesis microorganism culture, adding sodium persulfate, and applying voltage to obtain the reactor for degrading the perfluorooctanoic acid by electro-Fenton coupling with the sodium persulfate;
s5, maintaining the reactor at a proper temperature, introducing air into the cathode chamber, and degrading the perfluorooctanoic acid under an aerobic condition.
In the present invention, the term "microbial electro-fenton" is a novel decontamination technology formed by combining fenton technology with microbial fuel cell technology. At the anode of the reactor, the electricity-generating microorganisms degrade organic matters (such as domestic wastewater) to generate electrons and protons, then the electrons and the protons are transferred to the cathode chamber through an external circuit and a proton exchange membrane respectively, and a two-electron oxygen reduction reaction is carried out in the cathode to realize in-situ peroxidationHydrogen production followed by hydrogen peroxide with Fe2+The reaction generates hydroxyl free radical, and the hydroxyl free radical with strong oxidizing property can oxidize refractory organic matters.
In the present invention, the term "electrogenic microorganisms" is mainly focused on Proteobacteria and Thelenota phyla, such as Bacillus, Pseudomonas, Rhodococcus, Shewanella, lactococcus, Escherichia coli, etc. The microorganisms generate electrons in the process of metabolizing organic matters and assist electron transfer through an electron transfer chain, and the electricity-generating microorganisms on the anode can be considered as cell mixtures with different functions, and can be used for power generation and proliferation as a power source of the cells.
In the invention, the term "anaerobic sludge" refers to sludge containing anaerobic bacteria community after anaerobic culture in an anaerobic reactor, thereby achieving good organic matter settleability. The method is mainly used for sewage treatment, can degrade various organic pollutants in the original wastewater, and is more economic in cost.
In the present invention, the term "anolyte" refers to a liquid in which the nutrient solution prepared is mixed with sludge in the anode chamber and which is suitable for the growth of electrogenic microorganisms.
As a further improvement of the technical solution, step S1 includes the following specific steps:
s1-1, processing the carbon fiber wire and the titanium wire with the diameter of 0.8-1.2mm into a carbon fiber brush, wherein the carbon fiber brush has a fixed size;
s1-2, 0.8-1.2 mol.L for the prepared carbon fiber brush-1Soaking the mixture in NaOH solution for 5.5 to 6.5 hours to remove impurity ions;
s1-3, and further 1 mol. L-1Soaking in HCl for 5.5-6.5h, and ultrasonically cleaning with deionized water to neutrality;
s1-4, boiling for 2.5-35 h by using deionized water, and replacing water every 30 min;
and S1-5, performing heating treatment by using a muffle furnace to obtain the anode carbon brush.
S1-6, cutting the graphite plate into squares of 4cm by 0.5 cm;
s1-7, firstly, soaking the mixture for 4.5 to 5.5 hours by using 1 mol. L-1 NaOH solution to remove impurity ions;
s1-8, soaking the graphite plate in 1 mol. L-1 HCl for 5.5-6.5h, and ultrasonically cleaning the graphite plate with deionized water to be neutral to obtain the graphite plate cathode electrode.
Preferably, in step S1-1, the fixed size refers to a carbon fiber brush length of 6cm and a diameter of 4 cm;
preferably, in the step S1-5, the muffle furnace treatment temperature is 480-520 ℃, and the treatment time is 8-12 minutes.
As a further improvement of the technical solution, in step S2, the nutrient solution has a formula containing the following substances per liter of solution: 3mg magnesium sulfate, 0.13mg zinc chloride, 0.005mg zinc sulfate heptahydrate, 1.5mg nitrilotriacetic acid, 0.5mg manganese sulfate monohydrate, 310mg ammonium chloride, 130mg potassium chloride, 0.01mg boric acid, 0.01mg cobalt chloride hexahydrate, 5mg nicotinic acid, 2mg folic acid, 0.01mg copper sulfate pentahydrate, 0.024mg nickel chloride hexahydrate, 0.024mg sodium tungstate dihydrate, 0.1mgB-12, 5mg vitamin B1, 6mg vitamin B2, 10mg vitamin B6, 6mg p-aminobenzoic acid, 2000mg glucose, 2000mg sodium acetate.
As a further improvement of the technical solution, step S3 includes the following specific steps:
s3-1, adopting anaerobic sludge at a concentration tank of a sewage treatment plant as inoculation sludge, settling the taken sludge, and pouring out supernatant;
s3-2, adding the sludge and the prepared nutrient solution into an anode chamber with a carbon fiber brush to form an anolyte;
s3-3, continuously introducing nitrogen into the anode chamber, removing oxygen in the anode chamber, and maintaining a strict anaerobic environment;
s3-4, using potassium ferricyanide solution (for example, 100mL) as catholyte;
s3-5, connecting the reactor and the external resistance in series to form a microbial fuel cell, and culturing and domesticating the electrogenic microbes at a proper temperature.
Preferably, in step S3-2, the pH of the anolyte is 7-7.5;
preferably, in step S3-2, the volume ratio of the sludge to the nutrient solution is 1:1 (e.g., 50mL each);
preferably, in the step S3-3, the nitrogen is introduced for 8-12 minutes;
preferably, in the step S3-4, the concentration of the potassium ferricyanide solution is 15-17 g/L;
preferably, in step S3-5, the suitable temperature is 30-37 ℃;
preferably, in step S3-5, the water inlet of the anode chamber is sealed by a rubber plug, and the anode chamber is maintained under anaerobic conditions for culturing;
preferably, in step S3-5, the external resistance in series with the reactor is 1000 Ω.
As a further improvement of the technical solution, step S4 includes the following specific steps:
s4-1, after the anode carbon brush culture is finished, discharging 1/2 of anolyte, and supplementing corresponding nutrient solution;
s4-2, preparing a perfluorooctanoic acid solution for degradation as a catholyte;
s4-3, injecting catholyte into the cathode chamber;
s4-4, connecting the reactor in series with a 10 omega external resistor;
and S4-5, applying a proper voltage to obtain the electro-Fenton coupling sodium persulfate degradation perfluorooctanoic acid reactor.
Preferably, in step S4-2, the catholyte includes the following per liter: 10-2000mg of perfluorooctanoic acid, 10-200g of sodium persulfate;
preferably, in step S4-5, the suitable voltage is 0-2.0V.
As a further improvement of the technical proposal, in the step S5, the air is introduced into the cathode chamber at the rate of 5-50 mL/min.
Preferably, in step S5, the suitable temperature is 10-50 deg.C and pH is 1-5.
In step S5 of the present invention, the following reaction may occur in the degradation process of the perfluorooctanoic acid:
2H++O2+2e-→H2O2
Fe2++H2O2+H+→Fe3++·OH+H2O
Fe3++e-→Fe2+
S2O8 2-→2SO4 -
C7F15COO-+SO4 -→C7F15·+SO4 2-+CO2
C7F15·+HO·→C7F15OH
C7F15OH→C6F13COF+HF
C6F13COF+H2O→C6F13COO-+HF+H+
C6F13COO-+SO4 -→C6F13·+SO4 2-+CO2
C6F13·+HO·→C6F13OH
C6F13OH→C5F11COF+HF
C5F11COF+H2O→C5F11COO-+HF+H+
C5F11COO-+SO4 -→C5F11·+SO4 2-+CO2
C5F11·+HO·→C5F11OH
C5F11OH→C4F9COF+HF
C4F9COF+H2O→C4F9COO-+HF+H+
C4F9COO-+SO4 -→C4F9·+SO4 2-+CO2
C4F9·+HO·→C4F9OH
C4F9OH→C3F7COF+HF
C3F7COF+H2O→C3F7COO-+HF+H+
C3F7COO-+SO4 -→C3F7·+SO4 2-+CO2
C3F7·+HO·→C3F7OH
C3F7OH→C2F5COF+HF
C2F5COF+H2O→C2F5COO-+HF+H+
C2F5COO-+SO4 -→C2F5·+SO4 2-+CO2
C2F5·+HO·→C2F5OH
C2F5OH→CF3COF+HF
CF3COF+H2O→CF3COO-+HF+H+。
any range recited herein is intended to include the endpoints and any number between the endpoints and any subrange subsumed therein or defined therein.
The starting materials of the present invention are commercially available, unless otherwise specified, and the equipment used in the present invention may be any equipment conventionally used in the art or may be any equipment known in the art.
Compared with the prior art, the invention has the following beneficial effects:
1) at present, the removal of perfluorooctanoic acid in a water body by a physical method has the defect of incomplete degradation, while chemical methods such as photocatalytic oxidation, thermal decomposition, electrocatalytic oxidation, oxidant oxidation and the like require harsh implementation conditions and high operation cost, and exercise products generated in the degradation process are incompletely mineralized to cause secondary pollution. The microbial electro-Fenton coupling sodium persulfate system has the advantages of mild reaction conditions, simple equipment structure and capability of efficiently degrading the perfluorooctanoic acid;
2) compared with the common Fenton method, the microbial electro-Fenton system is utilized, and hydrogen peroxide can be spontaneously generated by applying lower voltage without adding a large amount of hydrogen peroxide;
3) compared with the method for treating the perfluorooctanoic acid by using the sodium persulfate as the oxidizing agent, the activation of the sodium persulfate needs high temperature, so the activation cannot be carried out at room temperature, and the required amount of the sodium sulfate is large; the hydroxyl free radical generated by the microbial electro-Fenton system alone cannot degrade the perfluorooctanoic acid. Therefore, the system fuses the two components, sodium persulfate is used as a starter of the degradation reaction of the perfluorooctanoic acid, so that the sodium persulfate loses one electron, the hydroxyl radical can participate in the subsequent degradation reaction, and the synergistic effect of the two components achieves higher degradation efficiency of the perfluorooctanoic acid.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
A method for degrading perfluorooctanoic acid by coupling microbial electro-Fenton with sodium persulfate comprises the following steps:
1) processing the purchased carbon fiber wires and titanium wires with the diameter of 1mm into carbon fiber brushes, wherein the length of each carbon fiber brush is 6cm, and the diameter of each carbon fiber brush is 4 cm;
2) 1 mol. L is used for the prepared carbon fiber brush-1Soaking the mixture in NaOH solution for 6 hours to remove impurity ions;
3) 1 mol. L is used for the carbon brush treated in the step 2)-1Soaking in HCL for 6h, and ultrasonically cleaning with deionized water to neutrality;
4) boiling the carbon brush treated in the step 3) with deionized water for 3h, and replacing the water every 30 min;
5) heating the carbon brush treated in the step 4) by using a muffle furnace at 500 ℃ for 10 minutes to obtain an experimental carbon brush;
6) cutting the graphite plate into 4cm by 0.5cm squares, first using 1 mol. L-1Soaking the mixture in NaOH solution for 5 hours to remove impurity ions; with 1 mol. L-1Soaking the graphite plate in HCL for 6h, and ultrasonically cleaning the graphite plate to be neutral by using deionized water to obtain a graphite plate cathode required by an experiment;
7) anaerobic sludge and nutrient solution are added into the anode chamber of the reactor, nitrogen is introduced into the anode chamber, and the cathode chamber is potassium ferricyanide solution, so that the electrogenic microorganisms are cultured and domesticated. The formula of the nutrient solution is as follows: 3mg magnesium sulfate, 0.13mg zinc chloride, 0.005mg zinc sulfate heptahydrate, 1.5mg nitrilotriacetic acid, 0.5mg manganese sulfate monohydrate, 310mg ammonium chloride, 130mg potassium chloride, 0.01mg boric acid, 0.01mg cobalt chloride hexahydrate, 5mg nicotinic acid, 2mg folic acid, 0.01mg copper sulfate pentahydrate, 0.024mg nickel chloride hexahydrate, 0.024mg sodium tungstate dihydrate, 0.1mg B-12, 5mg vitamin B1, 6mg vitamin B2, 10mg vitamin B6, 6mg p-aminobenzoic acid, 2000mg glucose, 2000mg sodium acetate
8) Replacing the cathode solution of the reactor in which the domestication of the anode electrogenic bacteria is finished in the step 7) with a perfluorooctanoic acid solution, adding sodium persulfate, applying voltage, and introducing air into the cathode to obtain an electro-Fenton coupling sodium persulfate degradation perfluorooctanoic acid reactor;
in the step 8), the concentration of the perfluorooctanoic acid is 50 mg/L;
in the step 8), the voltage is 1.0V, the initial pH of the cathode is 3, and the temperature is 40 ℃; the aeration rate was 15 mL/min.
The analysis results of the intermediate product obtained by degrading perfluorooctanoic acid by coupling microbial electro-fenton with sodium persulfate and the perfluorooctanoic acid in the embodiment are shown in the following table 1:
table 1: analysis results of perfluorooctanoic acid and intermediate products in the reactor
In the embodiment, the degradation temperature of the microbial electro-Fenton coupling sodium persulfate reactor is 40 ℃, 84% of perfluorooctanoic acid is degraded in 24 hours, the degradation rate is high, and the total degradation rate is 99%. In the degradation process, short-chain intermediate products are generated, including perfluoroheptanoic acid, perfluorohexanoic acid, perfluoropentanoic acid, heptafluorobutyric acid, pentafluoropropionic acid and fluoroacetic acid, and the intermediate products are rapidly degraded. The system can be seen to degrade the perfluorooctanoic acid more thoroughly, and has the advantages of high reaction rate and mild operating conditions.
Example 2
A method for degrading perfluorooctanoic acid by coupling microbial electro-Fenton with sodium persulfate comprises the following steps:
1) processing the purchased carbon fiber wires and titanium wires with the diameter of 1mm into carbon fiber brushes, wherein the length of each carbon fiber brush is 6cm, and the diameter of each carbon fiber brush is 4 cm;
2) 1 mol. L is used for the prepared carbon fiber brush-1Soaking the mixture in NaOH solution for 6 hours to remove impurity ions;
3) 1 mol. L is used for the carbon brush treated in the step 2)-1Soaking in HCL for 6h, and ultrasonically cleaning with deionized water to neutrality;
4) boiling the carbon brush treated in the step 3) with deionized water for 3h, and replacing the water every 30 min;
5) heating the carbon brush treated in the step 4) by using a muffle furnace at 500 ℃ for 10 minutes to obtain an experimental carbon brush;
6) cutting the graphite plate into 4cm by 0.5cm squares, first using 1 mol. L-1Soaking the mixture in NaOH solution for 5 hours to remove impurity ions; with 1 mol. L-1Soaking the graphite plate in HCL for 6h, and ultrasonically cleaning the graphite plate to be neutral by using deionized water to obtain a graphite plate cathode required by an experiment;
7) anaerobic sludge and nutrient solution are added into the anode chamber of the reactor, nitrogen is introduced into the anode chamber, and the cathode chamber is potassium ferricyanide solution, so that the electrogenic microorganisms are cultured and domesticated. The formula of the nutrient solution is as follows: 3mg magnesium sulfate, 0.13mg zinc chloride, 0.005mg zinc sulfate heptahydrate, 1.5mg nitrilotriacetic acid, 0.5mg manganese sulfate monohydrate, 310mg ammonium chloride, 130mg potassium chloride, 0.01mg boric acid, 0.01mg cobalt chloride hexahydrate, 5mg nicotinic acid, 2mg folic acid, 0.01mg copper sulfate pentahydrate, 0.024mg nickel chloride hexahydrate, 0.024mg sodium tungstate dihydrate, 0.1mgB-12, 5mg vitamin B1, 6mg vitamin B2, 10mg vitamin B6, 6mg p-aminobenzoic acid, 2000mg glucose, 2000mg sodium acetate
8) Replacing the cathode solution of the reactor in which the domestication of the anode electrogenic bacteria is finished in the step 7) with a perfluorooctanoic acid solution, adding sodium persulfate, applying voltage, and introducing air into the cathode to obtain an electro-Fenton coupling sodium persulfate degradation perfluorooctanoic acid reactor;
in the step 8), the concentration of the perfluorooctanoic acid is 50 mg/L;
in the step 8), the voltage is 1.0V, the initial pH of the cathode is 3, and the temperature is 10 ℃. The aeration rate was 15 mL/min.
The analysis results of the intermediate product obtained by degrading perfluorooctanoic acid by coupling microbial electro-fenton with sodium persulfate and the perfluorooctanoic acid in the embodiment are shown in the following table 2:
table 2: analysis results of perfluorooctanoic acid and intermediate products in the reactor
In the embodiment, the degradation temperature of the microbial electro-Fenton coupling sodium persulfate reactor is 10 ℃, 52% of perfluorooctanoic acid is degraded within 24 hours, the degradation rate is much slower than that of the microbial electro-Fenton coupling sodium persulfate reactor at 40 ℃, and the total degradation rate is only 70%. The reduction in temperature slowed the activity of the electrogenic microorganisms at the anode compared to example 1, and the low temperature was also less favorable for the activation of sodium persulfate, thus resulting in a slower degradation rate.
Example 3
A method for degrading perfluorooctanoic acid by coupling microbial electro-Fenton with sodium persulfate comprises the following steps:
1) processing the purchased carbon fiber wires and titanium wires with the diameter of 1mm into carbon fiber brushes, wherein the length of each carbon fiber brush is 6cm, and the diameter of each carbon fiber brush is 4 cm;
2) 1 mol. L is used for the prepared carbon fiber brush-1Soaking the mixture in NaOH solution for 6 hours to remove impurity ions;
3) 1 mol. L is used for the carbon brush treated in the step 2)-1Soaking in HCL for 6h, and ultrasonically cleaning with deionized water to neutrality;
4) boiling the carbon brush treated in the step 3) with deionized water for 3h, and replacing the water every 30 min;
5) heating the carbon brush treated in the step 4) by using a muffle furnace at 500 ℃ for 10 minutes to obtain an experimental carbon brush;
6) cutting the graphite plate into 4cm by 0.5cm squares, first using 1 mol. L-1Soaking the mixture in NaOH solution for 5 hours to remove impurity ions; with 1 mol. L-1Soaking the graphite plate in HCL for 6h, and ultrasonically cleaning the graphite plate to be neutral by using deionized water to obtain a graphite plate cathode required by an experiment;
7) anaerobic sludge and nutrient solution are added into the anode chamber of the reactor, nitrogen is introduced into the anode chamber, and the cathode chamber is potassium ferricyanide solution, so that the electrogenic microorganisms are cultured and domesticated. The formula of the nutrient solution is as follows: 3mg magnesium sulfate, 0.13mg zinc chloride, 0.005mg zinc sulfate heptahydrate, 1.5mg nitrilotriacetic acid, 0.5mg manganese sulfate monohydrate, 310mg ammonium chloride, 130mg potassium chloride, 0.01mg boric acid, 0.01mg cobalt chloride hexahydrate, 5mg nicotinic acid, 2mg folic acid, 0.01mg copper sulfate pentahydrate, 0.024mg nickel chloride hexahydrate, 0.024mg sodium tungstate dihydrate, 0.1mgB-12, 5mg vitamin B1, 6mg vitamin B2, 10mg vitamin B6, 6mg p-aminobenzoic acid, 2000mg glucose, 2000mg sodium acetate
8) Replacing the cathode solution of the reactor in which the domestication of the anode electrogenic bacteria is finished in the step 7) with a perfluorooctanoic acid solution, adding sodium persulfate, applying voltage, and introducing air into the cathode to obtain an electro-Fenton coupling sodium persulfate degradation perfluorooctanoic acid reactor;
in the step 8), the concentration of the perfluorooctanoic acid is 50 mg/L;
in the step 8), the voltage is 1.0V, the initial pH of the cathode is 3, and the temperature is 20 ℃. The aeration rate was 15 mL/min.
The analysis results of the intermediate product obtained by degrading perfluorooctanoic acid by coupling microbial electro-fenton with sodium persulfate and the perfluorooctanoic acid in the present example are shown in table 3 below:
table 3: analysis results of perfluorooctanoic acid and intermediate products in the reactor
In the embodiment, the degradation temperature of the microbial electro-Fenton coupling sodium persulfate reactor is 20 ℃, 61% of perfluorooctanoic acid is degraded within 24 hours, the degradation rate is slower than that at the temperature of 40 ℃, and the total degradation rate is only 78%. The reduction in temperature slowed the activity of the electrogenic microorganisms at the anode, and the lower temperature was also less favorable for the activation of sodium persulfate, compared to example 1, thus resulting in a slower degradation rate.
Example 4
A method for degrading perfluorooctanoic acid by coupling microbial electro-Fenton with sodium persulfate comprises the following steps:
1) processing the purchased carbon fiber wires and titanium wires with the diameter of 1mm into carbon fiber brushes, wherein the length of each carbon fiber brush is 6cm, and the diameter of each carbon fiber brush is 4 cm;
2) 1 mol. L is used for the prepared carbon fiber brush-1Soaking the mixture in NaOH solution for 6 hours to remove impurity ions;
3) 1 mol. L is used for the carbon brush treated in the step 2)-1Soaking in HCL for 6h, and ultrasonically cleaning with deionized water to neutrality;
4) boiling the carbon brush treated in the step 3) with deionized water for 3h, and replacing the water every 30 min;
5) heating the carbon brush treated in the step 4) by using a muffle furnace at 500 ℃ for 10 minutes to obtain an experimental carbon brush;
6) cutting the graphite plate into 4cm by 0.5cm squares, first using 1 mol. L-1Soaking the mixture in NaOH solution for 5 hours to remove impurity ions; with 1 mol. L-1Soaking the graphite plate in HCL for 6h, and ultrasonically cleaning the graphite plate to be neutral by using deionized water to obtain a graphite plate cathode required by an experiment;
7) anaerobic sludge and nutrient solution are added into the anode chamber of the reactor, nitrogen is introduced into the anode chamber, and the cathode chamber is potassium ferricyanide solution, so that the electrogenic microorganisms are cultured and domesticated. The formula of the nutrient solution is as follows: 3mg magnesium sulfate, 0.13mg zinc chloride, 0.005mg zinc sulfate heptahydrate, 1.5mg nitrilotriacetic acid, 0.5mg manganese sulfate monohydrate, 310mg ammonium chloride, 130mg potassium chloride, 0.01mg boric acid, 0.01mg cobalt chloride hexahydrate, 5mg nicotinic acid, 2mg folic acid, 0.01mg copper sulfate pentahydrate, 0.024mg nickel chloride hexahydrate, 0.024mg sodium tungstate dihydrate, 0.1mgB-12, 5mg vitamin B1, 6mg vitamin B2, 10mg vitamin B6, 6mg p-aminobenzoic acid, 2000mg glucose, 2000mg sodium acetate
8) Replacing the cathode solution of the reactor in which the domestication of the anode electrogenic bacteria is finished in the step 7) with a perfluorooctanoic acid solution, adding sodium persulfate, applying voltage, and introducing air into the cathode to obtain an electro-Fenton coupling sodium persulfate degradation perfluorooctanoic acid reactor;
in the step 8), the concentration of the perfluorooctanoic acid is 50 mg/L;
in the step 8), the voltage is 1.0V, the initial pH of the cathode is 3, and the temperature is 30 ℃. The aeration rate was 15 mL/min.
The analysis results of the intermediate product obtained by degrading perfluorooctanoic acid by coupling microbial electro-fenton with sodium persulfate and the perfluorooctanoic acid in the present example are shown in table 4 below:
table 4: analysis results of perfluorooctanoic acid and intermediate products in the reactor
In the embodiment, the degradation temperature of the microbial electro-Fenton coupling sodium persulfate reactor is 30 ℃, 66% of perfluorooctanoic acid is degraded within 24 hours, the degradation rate is slower than that of the microbial electro-Fenton coupling sodium persulfate reactor at 40 ℃ and is improved compared with that of the microbial electro-Fenton coupling sodium persulfate reactor at 20 ℃, and the total degradation rate reaches 95%.
Example 5
A method for degrading perfluorooctanoic acid by coupling microbial electro-Fenton with sodium persulfate comprises the following steps:
1) processing the purchased carbon fiber wires and titanium wires with the diameter of 1mm into carbon fiber brushes, wherein the length of each carbon fiber brush is 6cm, and the diameter of each carbon fiber brush is 4 cm;
2) 1 mol. L is used for the prepared carbon fiber brush-1Soaking the mixture in NaOH solution for 6 hours to remove impurity ions;
3) 1 mol. L is used for the carbon brush treated in the step 2)-1Soaking in HCL for 6h, and ultrasonically cleaning with deionized water to neutrality;
4) boiling the carbon brush treated in the step 3) with deionized water for 3h, and replacing the water every 30 min;
5) heating the carbon brush treated in the step 4) by using a muffle furnace at 500 ℃ for 10 minutes to obtain an experimental carbon brush;
6) cutting the graphite plate into 4cm by 0.5cm squares, first using 1 mol. L-1Soaking the mixture in NaOH solution for 5 hours to remove impurity ions; with 1 mol. L-1Soaking the graphite plate in HCL for 6h, and ultrasonically cleaning the graphite plate to be neutral by using deionized water to obtain a graphite plate cathode required by an experiment;
7) anaerobic sludge and nutrient solution are added into the anode chamber of the reactor, nitrogen is introduced into the anode chamber, and the cathode chamber is potassium ferricyanide solution, so that the electrogenic microorganisms are cultured and domesticated. The formula of the nutrient solution is as follows: 3mg magnesium sulfate, 0.13mg zinc chloride, 0.005mg zinc sulfate heptahydrate, 1.5mg nitrilotriacetic acid, 0.5mg manganese sulfate monohydrate, 310mg ammonium chloride, 130mg potassium chloride, 0.01mg boric acid, 0.01mg cobalt chloride hexahydrate, 5mg nicotinic acid, 2mg folic acid, 0.01mg copper sulfate pentahydrate, 0.024mg nickel chloride hexahydrate, 0.024mg sodium tungstate dihydrate, 0.1mgB-12, 5mg vitamin B1, 6mg vitamin B2, 10mg vitamin B6, 6mg p-aminobenzoic acid, 2000mg glucose, 2000mg sodium acetate
8) Replacing the cathode solution of the reactor in which the domestication of the anode electrogenic bacteria is finished in the step 7) with a perfluorooctanoic acid solution, adding sodium persulfate, applying voltage, and introducing air into the cathode to obtain an electro-Fenton coupling sodium persulfate degradation perfluorooctanoic acid reactor;
in the step 8), the concentration of the perfluorooctanoic acid is 50 mg/L;
in the step 8), the voltage is 1.0V, the initial pH of the cathode is 3, and the temperature is 50 ℃. The aeration rate was 15 mL/min.
The analysis results of the intermediate product obtained by degrading perfluorooctanoic acid by coupling microbial electro-fenton with sodium persulfate and the perfluorooctanoic acid in the present example are shown in table 5 below:
table 5: analysis results of perfluorooctanoic acid and intermediate products in the reactor
In the embodiment, the degradation temperature of the microbial electro-Fenton coupling sodium persulfate reactor is 50 ℃, 68% of perfluorooctanoic acid is degraded within 24 hours, the degradation rate is slower than that of 40 ℃, and the reason may be that the power generation bacteria die due to overhigh temperature and the hydrogen peroxide production capacity of the system is reduced.
Example 6
A method for degrading perfluorooctanoic acid by coupling microbial electro-Fenton with sodium persulfate comprises the following steps:
1) processing the purchased carbon fiber wires and titanium wires with the diameter of 1mm into carbon fiber brushes, wherein the length of each carbon fiber brush is 6cm, and the diameter of each carbon fiber brush is 4 cm;
2) 1 mol. L is used for the prepared carbon fiber brush-1Soaking the mixture in NaOH solution for 6 hours to remove impurity ions;
3) 1 mol. L is used for the carbon brush treated in the step 2)-1Soaking in HCL for 6h, and ultrasonically cleaning with deionized water to neutrality;
4) boiling the carbon brush treated in the step 3) with deionized water for 3h, and replacing the water every 30 min;
5) heating the carbon brush treated in the step 4) by using a muffle furnace at 500 ℃ for 10 minutes to obtain an experimental carbon brush;
6) cutting the graphite plate into 4cm by 0.5cm squares, first using 1 mol. L-1Soaking the mixture in NaOH solution for 5 hours to remove impurity ions; with 1 mol. L-1Soaking the graphite plate in HCL for 6h, and ultrasonically cleaning the graphite plate to be neutral by using deionized water to obtain a graphite plate cathode required by an experiment;
7) anaerobic sludge and nutrient solution are added into the anode chamber of the reactor, nitrogen is introduced into the anode chamber, and the cathode chamber is potassium ferricyanide solution, so that the electrogenic microorganisms are cultured and domesticated. The formula of the nutrient solution is as follows: 3mg magnesium sulfate, 0.13mg zinc chloride, 0.005mg zinc sulfate heptahydrate, 1.5mg nitrilotriacetic acid, 0.5mg manganese sulfate monohydrate, 310mg ammonium chloride, 130mg potassium chloride, 0.01mg boric acid, 0.01mg cobalt chloride hexahydrate, 5mg nicotinic acid, 2mg folic acid, 0.01mg copper sulfate pentahydrate, 0.024mg nickel chloride hexahydrate, 0.024mg sodium tungstate dihydrate, 0.1mgB-12, 5mg vitamin B1, 6mg vitamin B2, 10mg vitamin B6, 6mg p-aminobenzoic acid, 2000mg glucose, 2000mg sodium acetate
8) Replacing the cathode solution of the reactor in which the domestication of the anode electrogenic bacteria is finished in the step 7) with a perfluorooctanoic acid solution, adding sodium persulfate, applying voltage, and introducing air into the cathode to obtain an electro-Fenton coupling sodium persulfate degradation perfluorooctanoic acid reactor;
in the step 8), the concentration of the perfluorooctanoic acid is 50 mg/L;
in the step 8), the voltage is 2.0V, the initial pH of the cathode is 3, and the temperature is 40 ℃. The aeration rate was 15 mL/min.
The analysis results of the intermediate product obtained by degrading perfluorooctanoic acid by coupling microbial electro-fenton with sodium persulfate and the perfluorooctanoic acid in the present example are shown in table 6 below:
table 6: analysis results of perfluorooctanoic acid and intermediate products in the reactor
In the embodiment, the applied voltage of the microbial electro-Fenton coupling sodium persulfate reactor is 2.0V, 60% of perfluorooctanoic acid is degraded within 24 hours, the degradation rate is reduced compared with that when the applied voltage is 1.0V, and the total degradation rate is 77%.
Example 7
Example 1 was repeated with the difference that in step 8) the microbial electro-fenton coupling to the sodium persulfate reactor cathode had an initial pH of 1.
The analysis results of the intermediate product obtained by degrading perfluorooctanoic acid by coupling microbial electro-fenton with sodium persulfate and the perfluorooctanoic acid in the present example are shown in table 7 below:
table 7: analysis results of perfluorooctanoic acid and intermediate products in the reactor
In this example, the initial cathode pH of the microbial electro-fenton coupled sodium persulfate reactor was 1, 64% of the perfluorooctanoic acid was degraded within 24 hours, the degradation rate was slower than that when the initial cathode pH was 3, and the total degradation rate was 89%.
Example 8
Example 1 was repeated with the difference that in step 8) the microbial electro-fenton coupling was carried out at an initial pH of 5 with the cathode of the sodium persulfate reactor.
The analysis results of the intermediate product obtained by degrading perfluorooctanoic acid by coupling microbial electro-fenton with sodium persulfate and the perfluorooctanoic acid in the present example are shown in table 8 below:
table 8: analysis results of perfluorooctanoic acid and intermediate products in the reactor
In this example, the initial cathode pH of the microbial electro-fenton coupled sodium persulfate reactor was 5, 66% of the perfluorooctanoic acid was degraded within 24 hours, the degradation rate was slower than that of the case where the initial cathode pH was 3 in example 1, and the total degradation rate was 92%.
Example 9
Example 1 was repeated, with the difference that in step 8) the cathode aeration rate of the microbial electro-fenton coupled sodium persulfate reactor was 5 ml/min.
The analysis results of the intermediate product obtained by degrading perfluorooctanoic acid by coupling microbial electro-fenton with sodium persulfate and the perfluorooctanoic acid in this example are shown in table 9 below:
table 9: analysis results of perfluorooctanoic acid and intermediate products in the reactor
In the embodiment, the cathode ventilation rate of the microbial electro-Fenton coupling sodium persulfate reactor is 5ml/min, 60% of perfluorooctanoic acid is degraded within 24 hours, the degradation rate is lower than that of the cathode ventilation rate of 15ml/min in the embodiment 1, and the total degradation rate is 81%.
Example 10
Example 1 was repeated with the difference that in step 8) the cathode aeration rate of the microbial electro-fenton coupled sodium persulfate reactor was 25 ml/min. The analysis results of the intermediate product obtained by degrading perfluorooctanoic acid by coupling microbial electro-fenton with sodium persulfate and the perfluorooctanoic acid in this example are shown in table 10 below:
table 10: analysis results of perfluorooctanoic acid and intermediate products in the reactor
In the embodiment, the cathode ventilation rate of the microbial electro-Fenton coupling sodium persulfate reactor is 25ml/min, 65% of perfluorooctanoic acid is degraded within 24 hours, the degradation rate is lower than that of the cathode ventilation rate of 15ml/min in the embodiment 1, and the total degradation rate is 83%.
Comparative example 1
Example 1 was repeated, with the difference that in step 8), no sodium persulfate was added to the catholyte in the microbial electro-fenton reactor.
The intermediate product of the microbial electro-fenton reactor for degrading perfluorooctanoic acid and the analysis results of perfluorooctanoic acid are shown in the following table 11:
table 11: analysis results of perfluorooctanoic acid and intermediate products in the reactor
In this comparative example, the catholyte of the microbial electro-fenton reactor was not added with sodium persulfate, 9% of the perfluorooctanoic acid was degraded within 24 hours, and was hardly degraded after 6 hours, and the degradation rate of the perfluorooctanoic acid was greatly reduced compared to example 1 because the hydroxyl radical was inert to the degradation of the perfluorooctanoic acid.
Comparative example 2
Example 1 was repeated with the difference that in step 8) the applied voltage was 0V, i.e. no applied voltage.
The analysis results of the intermediate product of the microbial electro-fenton coupled sodium persulfate reactor for degrading the perfluorooctanoic acid and the perfluorooctanoic acid in the comparative example are shown in the following table 12:
table 12: analysis results of perfluorooctanoic acid and intermediate products in the reactor
In the comparative example, the microbial electro-Fenton coupling sodium persulfate reactor has no external voltage, 64 percent of perfluorooctanoic acid is degraded within 24 hours, the degradation rate is slower than that of example 1 when the external voltage is 1.0V, and the total degradation rate is 84 percent.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. All obvious changes and modifications which are obvious to the technical scheme of the invention are covered by the protection scope of the invention.
Claims (10)
1. A method for degrading perfluorooctanoic acid by coupling microbial electro-Fenton with sodium persulfate comprises the following steps:
s1, manufacturing an anode carbon brush and a cathode electrode required by the microbial electro-Fenton system, and preprocessing;
s2, preparing nutrient solution required by the growth of the electrogenesis microorganisms for culturing the electrogenesis microorganisms;
s3, adding anaerobic sludge and nutrient solution into the anode chamber of the reactor, introducing nitrogen into the reactor, and culturing and domesticating the electrogenic microorganisms by using a potassium ferricyanide solution as a cathode chamber;
s4, replacing the cathode solution of the reactor with the perfluorooctanoic acid solution after the anodic electrogenesis microorganism culture, adding sodium persulfate, and applying voltage to obtain the reactor for degrading the perfluorooctanoic acid by electro-Fenton coupling with the sodium persulfate;
s5, maintaining the reactor at a proper temperature, introducing air into the cathode chamber, and degrading the perfluorooctanoic acid under an aerobic condition.
2. The method for degrading perfluorooctanoic acid by coupling microbial electro-fenton reaction with sodium persulfate according to claim 1, wherein the step S1 comprises the following specific steps:
s1-1, processing the carbon fiber wire and the titanium wire with the diameter of 0.8-1.2mm into a carbon fiber brush, wherein the carbon fiber brush has a fixed size;
s1-2, 0.8-1.2 mol.L for the prepared carbon fiber brush-1Soaking the mixture in NaOH solution for 5.5 to 6.5 hours to remove impurity ions;
s1-3, and further 1 mol. L-1Soaking in HCl for 5.5-6.5h, and ultrasonically cleaning with deionized water to neutrality;
s1-4, boiling for 2.5-35 h by using deionized water, and replacing water every 30 min;
s1-5, performing heating treatment by using a muffle furnace to obtain an anode carbon brush;
s1-6, cutting the graphite plate into squares of 4cm by 0.5 cm;
s1-7, firstly, soaking the mixture for 4.5 to 5.5 hours by using 1 mol. L-1 NaOH solution to remove impurity ions;
s1-8, soaking the graphite plate in 1 mol. L-1 HCl for 5.5-6.5h, and ultrasonically cleaning the graphite plate with deionized water to be neutral to obtain the graphite plate cathode electrode.
3. The method for degrading perfluorooctanoic acid by coupling microbial electro-fenton with sodium persulfate according to claim 2, wherein: in the step S1-1, the fixed size refers to that the carbon fiber brush is 6cm long and 4cm in diameter;
preferably, in the step S1-5, the muffle furnace treatment temperature is 480-520 ℃, and the treatment time is 8-12 minutes.
4. The method for degrading perfluorooctanoic acid by coupling microbial electro-fenton with sodium persulfate according to claim 1, wherein: in step S2, the nutrient solution has a formula containing the following substances per liter of solution: 3mg magnesium sulfate, 0.13mg zinc chloride, 0.005mg zinc sulfate heptahydrate, 1.5mg nitrilotriacetic acid, 0.5mg manganese sulfate monohydrate, 310mg ammonium chloride, 130mg potassium chloride, 0.01mg boric acid, 0.01mg cobalt chloride hexahydrate, 5mg nicotinic acid, 2mg folic acid, 0.01mg copper sulfate pentahydrate, 0.024mg nickel chloride hexahydrate, 0.024mg sodium tungstate dihydrate, 0.1mgB-12, 5mg vitamin B1, 6mg vitamin B2, 10mg vitamin B6, 6mg p-aminobenzoic acid, 2000mg glucose, 2000mg sodium acetate.
5. The method for degrading perfluorooctanoic acid by coupling microbial electro-fenton reaction with sodium persulfate according to claim 1, wherein the step S3 comprises the following specific steps:
s3-1, adopting anaerobic sludge at a concentration tank of a sewage treatment plant as inoculation sludge, settling the taken sludge, and pouring out supernatant;
s3-2, adding the sludge and the prepared nutrient solution into an anode chamber with a carbon fiber brush to form an anolyte;
s3-3, continuously introducing nitrogen into the anode chamber, removing oxygen in the anode chamber, and maintaining a strict anaerobic environment;
s3-4, using potassium ferricyanide solution as catholyte;
s3-5, connecting the reactor and the external resistance in series to form a microbial fuel cell, and culturing and domesticating the electrogenic microbes at a proper temperature.
6. The method for degrading perfluorooctanoic acid by coupling microbial electro-fenton reaction with sodium persulfate according to claim 5, wherein: in step S3-2, the pH of the anolyte is 7-7.5.
Preferably, in the step S3-2, the volume ratio of the sludge to the nutrient solution is 1: 1;
preferably, in the step S3-3, the nitrogen is introduced for 8-12 minutes;
preferably, in the step S3-4, the concentration of the potassium ferricyanide solution is 15-17 g/L;
preferably, in step S3-5, the suitable temperature is 30-37 ℃;
preferably, in step S3-5, the water inlet of the anode chamber is sealed by a rubber plug, and the anode chamber is maintained under anaerobic conditions for culturing;
preferably, in step S3-5, the external resistance in series with the reactor is 1000 Ω.
7. The method for degrading perfluorooctanoic acid by coupling microbial electro-fenton with sodium persulfate according to claim 1, wherein: step S4 includes the following specific steps:
s4-1, after the anode carbon brush culture is finished, discharging 1/2 of anolyte, and supplementing corresponding nutrient solution;
s4-2, preparing a perfluorooctanoic acid solution for degradation as a catholyte;
s4-3, injecting catholyte into the cathode chamber;
s4-4, connecting the reactor in series with a 10 omega external resistor;
and S4-5, applying a proper voltage to obtain the electro-Fenton coupling sodium persulfate degradation perfluorooctanoic acid reactor.
8. The method for degrading perfluorooctanoic acid by coupling microbial electro-fenton with sodium persulfate according to claim 7, wherein: in step S4-2, the catholyte includes the following substances per liter: 10-2000mg of perfluorooctanoic acid, 10-200g of sodium persulfate;
preferably, in step S4-5, the suitable voltage is 0-2.0V.
9. The method for degrading perfluorooctanoic acid by coupling microbial electro-fenton with sodium persulfate according to claim 1, wherein: in step S5, air is introduced into the cathode chamber at a rate of 5 to 50 mL/min.
10. The method for degrading perfluorooctanoic acid by coupling microbial electro-fenton with sodium persulfate according to claim 1, wherein: in step S5, the suitable temperature is 10-50 deg.C and pH is 1-5.
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