CN110627186B - Wastewater treatment method for generating singlet oxygen by catalyzing persulfate through modified cobalt oxide - Google Patents
Wastewater treatment method for generating singlet oxygen by catalyzing persulfate through modified cobalt oxide Download PDFInfo
- Publication number
- CN110627186B CN110627186B CN201910770204.6A CN201910770204A CN110627186B CN 110627186 B CN110627186 B CN 110627186B CN 201910770204 A CN201910770204 A CN 201910770204A CN 110627186 B CN110627186 B CN 110627186B
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- China
- Prior art keywords
- cobalt
- persulfate
- nitrate
- sulfate
- metal
- Prior art date
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 46
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 title claims abstract description 40
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000004065 wastewater treatment Methods 0.000 title claims description 16
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 55
- 239000010941 cobalt Substances 0.000 claims abstract description 55
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 claims abstract description 53
- 239000002184 metal Substances 0.000 claims abstract description 53
- 150000003839 salts Chemical class 0.000 claims abstract description 46
- 239000002351 wastewater Substances 0.000 claims abstract description 25
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000013110 organic ligand Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 21
- 229910044991 metal oxide Inorganic materials 0.000 claims description 18
- 150000004706 metal oxides Chemical class 0.000 claims description 18
- 239000012265 solid product Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 12
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 12
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical group [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 claims description 11
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 10
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 9
- 229910001510 metal chloride Inorganic materials 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 8
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 8
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 8
- 229940044175 cobalt sulfate Drugs 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 239000012425 OXONE® Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- YMGGAHMANIOXGP-UHFFFAOYSA-L disodium;oxido sulfate Chemical compound [Na+].[Na+].[O-]OS([O-])(=O)=O YMGGAHMANIOXGP-UHFFFAOYSA-L 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 4
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 4
- 150000003841 chloride salts Chemical class 0.000 claims description 4
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 4
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 4
- ZVLZZJUHYPMZAH-UHFFFAOYSA-L cobalt(2+) dinitrite Chemical compound [Co+2].[O-]N=O.[O-]N=O ZVLZZJUHYPMZAH-UHFFFAOYSA-L 0.000 claims description 4
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 claims description 4
- MJABMRHBVCGGOG-UHFFFAOYSA-L cobalt(2+);sulfite Chemical compound [Co+2].[O-]S([O-])=O MJABMRHBVCGGOG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- CGOSIVYNVKVZBK-UHFFFAOYSA-K sodium cobalt(2+) trinitrite Chemical compound [Na+].[Co++].[O-]N=O.[O-]N=O.[O-]N=O CGOSIVYNVKVZBK-UHFFFAOYSA-K 0.000 claims description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical class [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims 1
- 229940045032 cobaltous nitrate Drugs 0.000 claims 1
- 229910000358 iron sulfate Inorganic materials 0.000 claims 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 claims 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 229910000428 cobalt oxide Inorganic materials 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 5
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 4
- 229940079593 drug Drugs 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 description 5
- 229960000623 carbamazepine Drugs 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000013384 organic framework Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229960002885 histidine Drugs 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000008684 selective degradation Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
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Abstract
The invention provides a method for treating wastewater by catalyzing persulfate to generate singlet oxygen by regulating and controlling the performance of cobalt oxide. The method has the following characteristics: cobalt metal salt, extra added metal salt and organic ligand react in a reaction solvent, the obtained solid is calcined in the air at a certain heating rate to obtain modified cobalt oxide, and the modified cobalt oxide is mixed with persulfate and added into wastewater, so that singlet oxygen can be generated to remove organic pollutants in water. The method described by the invention is simple, does not need expensive equipment and medicines, and has low cost; the modification of the cobalt oxide changes the property of the cobalt oxide, so that the cobalt oxide can catalyze persulfate to generate singlet oxygen in a heterogeneous mode, and the problem of carbon dissolution of the traditional carbon-containing heterogeneous catalyst is solved.
Description
Technical Field
The invention relates to the field of advanced oxidation water treatment, in particular to a method for efficiently removing organic pollutants in water by enabling cobalt oxide to generate singlet oxygen when catalyzing persulfate through oxygen vacancy regulation.
Background
The advanced oxidation technology for degrading pollutants in water by utilizing strong oxidizing groups attracts extensive research and certain-scale application in the field of water treatment, and becomes an important component of the current water treatment technology and one of the main development directions in the future.
The earliest advanced oxidation technology utilized the catalytic reaction between hydrogen peroxide and ferrous iron to generate hydroxyl radicals, which degraded pollutants. However, the technology has the defects of narrow pH value application range, large amount of iron mud generated by reaction and the like, which are not overcome so far.
The heterogeneous persulfate system with recoverable catalyst and wide pH application range is a promising advanced oxidation technology at present as the development continuation of the traditional technology. The system can generate a plurality of oxidizing radicals such as sulfate radicals, hydroxyl radicals, singlet oxygen and the like, wherein the singlet oxygen is molecular oxygen in an excited state, has the characteristics of high reaction activity, long survival time, no generation of toxic and harmful byproducts after oxidation and the like, belongs to a green and environment-friendly oxidant, has the advantage of high selective degradation of specific pollutants, and has important significance in the field of organic pollutant control in water.
However, as far as we know, the heterogeneous catalyst capable of activating persulfate to generate singlet oxygen is mainly a carbon-containing catalyst, and the carbon element of the heterogeneous catalyst is oxidized into an organic matter, so that the risk of secondary pollution is introduced. In view of the application prospect of the heterogeneous persulfate system and the important significance of singlet oxygen in the water treatment process, the development of a novel carbon-free heterogeneous catalyst capable of catalyzing persulfate to generate singlet oxygen is significant.
Cobalt oxide is a commonly used heterogeneous persulfate catalyst that has proven to be excellent, but this process does not produce singlet oxygen. The cobalt oxide which has excellent performance, widely exists, is easy to commercialize and does not contain carbon is modified by a technical means, so that the cobalt oxide has the capacity of generating singlet oxygen in the process of catalyzing persulfate, a novel water treatment technology capable of avoiding secondary pollution is developed, and the method has important significance.
Disclosure of Invention
The invention aims to provide a wastewater treatment method for catalyzing persulfate to generate singlet oxygen by using modified cobalt oxide, which is characterized by comprising the following steps of:
dissolving cobalt metal salt, non-cobalt metal salt and organic ligand in a reaction solvent;
the mixture ratio of the raw materials is as follows:
1-50 parts by weight of non-cobalt metal salt
10-1000 parts by weight of organic ligand
The solid-liquid ratio of the solid raw material to the reaction solvent is 1: 10-1: 200
After the reaction is finished, separating to obtain a solid product;
heating the solid product in the step 2 to a fixed temperature, and then carrying out heat preservation and calcination;
putting the solid product treated in the step 3 and persulfate into wastewater to be treated, wherein the adding concentration of the persulfate is as follows: 0.05 g/L-5 g/L;
the mixture ratio is as follows:
1 to 200 parts by weight of persulfate
And 5, stirring to finish the treatment of the wastewater.
Similar to the above method, the present invention also provides a wastewater treatment method for catalyzing persulfate to generate singlet oxygen by using modified cobalt oxide in the case of using a catalyst carrier, which is characterized by comprising the following steps:
1, adding cobalt metal salt, non-cobalt metal salt, organic ligand and catalyst carrier into a reaction solvent together;
the mixture ratio of the raw materials is as follows:
the solid-liquid ratio of the solid raw material to the reaction solvent is 1: 1-1: 2000
Separating the loaded catalyst carrier after the reaction is finished;
heating the separated catalyst carrier in the step 2 to a fixed temperature, and then carrying out heat preservation and calcination;
placing the catalyst carrier subjected to heating treatment in wastewater to be treated, and adding persulfate into the wastewater, wherein the persulfate adding concentration is as follows: 0.05 g/L-5 g/L;
the mixture ratio is as follows:
catalyst carrier 1 part by weight
0.01 to 2 parts by weight of persulfate
And 5, allowing the wastewater to flow through a catalyst carrier to finish the treatment of the wastewater.
Further, in step 1), the cobalt metal salt is selected from: one or more of cobalt nitrate, cobalt sulfate and cobalt chloride; the non-cobalt metal salt is selected from: one or more of non-cobalt metal nitrate, non-cobalt metal sulfate and non-cobalt metal chloride are mixed; the organic ligand is selected from: one or more of methylimidazole, terephthalic acid, trimesic acid, 2-methylimidazole or 1, 4-terephthalic acid; the reaction solvent is selected from: one or more of methanol, dimethyl sulfoxide and high purity water.
Further, the cobalt metal salt is selected from: cobalt nitrate, cobalt nitrite, sodium cobalt nitrite, cobalt nitrate hexahydrate, cobalt sulfate, cobalt sulfite, cobalt sulfate heptahydrate, cobalt chloride. The non-cobalt metal salt is selected from: metal nitrates, sulfates or chlorides which can decompose metal oxides at high temperatures.
Further, the metal nitrate that can decompose the metal oxide at high temperature is selected from: zinc nitrate, copper nitrate, ferric nitrate, nickel nitrate, manganese nitrate, cadmium nitrate and chromium nitrate.
The metal sulfate that decomposes at high temperature to form metal oxides is selected from: one or more of zinc sulfate, copper sulfate, ferric sulfate, nickel sulfate, manganese sulfate, cadmium sulfate and chromium sulfate.
The metal chloride salt which decomposes at elevated temperature to form a metal oxide is selected from: zinc chloride, copper chloride, ferric chloride, nickel chloride, manganese chloride, cadmium chloride and/or chromium chloride.
Further, in the heating process of the step 3), the temperature of the solid sample is raised to 500 ℃ at the rate of 1-2 ℃ per minute in the air, and after the solid sample is subjected to heat preservation and calcination at 500 ℃ for 30 minutes to 4 hours at 300-.
Further, the persulfate is peroxymonosulfate.
Further, the salt of peroxymonosulfate is selected from the group consisting of: potassium peroxymonosulfate, sodium peroxymonosulfate, potassium peroxymonosulfate, and sodium peroxymonosulfate.
Further, the catalyst carrier is active carbon particles, aluminum oxide particles, a steel wire mesh or plastic filler.
It is worth to be noted that the basic concept of the present invention is to add one or more additional metal salts, mix them with cobalt salts in a reaction solvent and add an organic ligand to generate a cobalt-based polymetallic organic framework material, and calcine the cobalt-based polymetallic organic framework material in air at a certain temperature and a certain temperature rise rate to obtain a modified cobalt oxide; the modified cobalt oxide and the peroxymonosulfate are added into a water sample to be treated at the same time according to a certain proportion, and the organic matters in the water sample can be removed after stirring for a period of time. By controlling the heating rate and the additionally added metal salt, the oxygen vacancy content of the surface of the modified cobalt oxide is changed, and the generation of singlet oxygen during the catalysis of persulfate is realized.
The invention has the beneficial effects that: the invention provides a novel heterogeneous catalyst based on cobalt oxide, which realizes the generation of singlet oxygen in the persulfate catalyzing process, avoids the risk of secondary pollution caused by the traditional carbon-containing catalyst, and realizes the high-efficiency removal of organic pollutants cleanly. The method is simple, does not need expensive equipment and medicines, and has low cost.
Drawings
FIG. 1 TEM and energy spectrum of Zn doped modified cobalt oxide;
FIG. 2, the modified cobalt oxide catalyzes peroxymonosulfate to treat rhodamine B wastewater;
FIG. 3 shows capture agent experiments for degrading rhodamine B;
FIG. 4. Capture agent experiments for degradation of carbamazepine.
Detailed Description
The present invention is further illustrated by the following examples, but it should not be construed that the scope of the above-described subject matter is limited to the following examples. Various substitutions and alterations can be made without departing from the technical idea of the invention and the scope of the invention is covered by the present invention according to the common technical knowledge and the conventional means in the field.
Example 1:
a wastewater treatment method for catalyzing persulfate to generate singlet oxygen by using modified cobalt oxide is characterized by comprising the following steps:
dissolving cobalt metal salt, non-cobalt metal salt and organic ligand in a reaction solvent;
the mixture ratio of the raw materials is as follows:
1-50 parts by weight of non-cobalt metal salt
10-1000 parts by weight of organic ligand
The solid-liquid ratio of the solid raw material to the reaction solvent is 1: 10-1: 200
The cobalt metal salt is selected from: one or more of cobalt nitrate, cobalt sulfate and cobalt chloride; preferably, the cobalt metal salt is selected from: cobalt nitrate, cobalt nitrite, sodium cobalt nitrite, cobalt nitrate hexahydrate, cobalt sulfate, cobalt sulfite, cobalt sulfate heptahydrate, cobalt chloride.
The non-cobalt metal salt is selected from: one or more of non-cobalt metal nitrate, non-cobalt metal sulfate and non-cobalt metal chloride are mixed; preferably, the metal salt other than cobalt is selected from: metal nitrates, sulfates or chlorides which can decompose metal oxides at high temperatures. More preferably, the metal nitrate that can decompose to a metal oxide at high temperature is selected from: zinc nitrate, copper nitrate, ferric nitrate, nickel nitrate, manganese nitrate, cadmium nitrate and chromium nitrate. The metal sulfate that decomposes at high temperature to form metal oxides is selected from: one or more of zinc sulfate, copper sulfate, ferric sulfate, nickel sulfate, manganese sulfate, cadmium sulfate and chromium sulfate. The metal chloride salt which decomposes at elevated temperature to form a metal oxide is selected from: zinc chloride, copper chloride, ferric chloride, nickel chloride, manganese chloride, cadmium chloride and/or chromium chloride.
The organic ligand is selected from: one or more of methylimidazole, terephthalic acid, trimesic acid, 2-methylimidazole or 1, 4-terephthalic acid;
the reaction solvent is selected from: one or more of methanol, dimethyl sulfoxide and high purity water.
After the reaction is finished, separating to obtain a solid product;
heating the solid product in the step 2);
in the heating process, after the solid sample is heated to 300-500 ℃ in the air at the heating rate of 1-2 ℃ per minute and is kept for 30 minutes to 4 hours, the newly obtained product is recovered, cleaned and dried.
Putting the solid product treated in the step 3 and persulfate into wastewater to be treated;
the mixture ratio is as follows:
1 to 200 parts by weight of persulfate
Preferably, the persulfate is a peroxymonosulfate. More preferably, the salt of peroxymonosulfate is selected from the group consisting of: the peroxymonosulfate is selected from the group consisting of: potassium peroxymonosulfate, sodium peroxymonosulfate, potassium peroxymonosulfate, and sodium peroxymonosulfate.
And 5, stirring to finish the treatment of the wastewater.
Example 2:
a wastewater treatment method for catalyzing persulfate to generate singlet oxygen by using modified cobalt oxide is characterized by comprising the following steps:
1, adding cobalt metal salt, non-cobalt metal salt, organic ligand and catalyst carrier into a reaction solvent together;
the mixture ratio of the raw materials is as follows:
the solid-liquid ratio of the solid raw material to the reaction solvent is 1: 1-1: 2000
The cobalt metal salt is selected from: one or more of cobalt nitrate, cobalt sulfate and cobalt chloride; preferably, the cobalt metal salt is selected from: cobalt nitrate, cobalt nitrite, sodium cobalt nitrite, cobalt nitrate hexahydrate, cobalt sulfate, cobalt sulfite, cobalt sulfate heptahydrate, cobalt chloride.
The non-cobalt metal salt is selected from: one or more of non-cobalt metal nitrate, non-cobalt metal sulfate and non-cobalt metal chloride are mixed; preferably, the metal salt other than cobalt is selected from: metal nitrates, sulfates or chlorides which can decompose metal oxides at high temperatures. More preferably, the metal nitrate that can decompose to a metal oxide at high temperature is selected from: zinc nitrate, copper nitrate, ferric nitrate, nickel nitrate, manganese nitrate, cadmium nitrate and chromium nitrate. The metal sulfate that decomposes at high temperature to form metal oxides is selected from: one or more of zinc sulfate, copper sulfate, ferric sulfate, nickel sulfate, manganese sulfate, cadmium sulfate and chromium sulfate. The metal chloride salt which decomposes at elevated temperature to form a metal oxide is selected from: zinc chloride, copper chloride, ferric chloride, nickel chloride, manganese chloride, cadmium chloride and/or chromium chloride.
The organic ligand is selected from: one or more of methylimidazole, terephthalic acid, trimesic acid, 2-methylimidazole or 1, 4-terephthalic acid;
the reaction solvent is selected from: one or more of methanol, dimethyl sulfoxide and high purity water.
The catalyst carrier is active carbon particles, aluminum oxide particles, a steel wire mesh and plastic fillers.
Separating the loaded catalyst carrier after the reaction is finished;
heating the separated catalyst carrier in the step 2); in the thermal process, after the solid sample is heated to 300-500 ℃ in the air at the heating rate of 1-2 ℃ per minute and is kept for 30 minutes to 4 hours, the newly obtained product is recovered, cleaned and dried.
Placing the catalyst carrier subjected to heating treatment in wastewater to be treated, and adding peroxymonosulfate into the wastewater, wherein the adding concentration of the peroxymonosulfate is as follows: 0.05 g/L-5 g/L;
and 5, allowing the wastewater to flow through a catalyst carrier to finish the treatment of the wastewater.
Example 3:
the main steps of this example are the same as example 1, specifically:
a wastewater treatment method for catalyzing persulfate to generate singlet oxygen by using modified cobalt oxide is characterized by comprising the following steps:
dissolving cobalt metal salt, non-cobalt metal salt and organic ligand in a reaction solvent;
the mixture ratio of the raw materials is as follows:
cobalt nitrate 1 part by weight
1 part by weight of zinc nitrate
2-methylimidazole 4 parts by weight
The solid-liquid ratio of the solid raw material to the reaction solvent is 1:20
The reaction solvent is methanol
And 2, standing the mixed system in the step 1 at room temperature for 24 hours, and then performing suction filtration and separation to obtain a solid.
And 3, placing the solid in the step 2) into an open tubular furnace, raising the temperature of a solid sample to 400 ℃ in air at a heating rate of 2 ℃ per minute, keeping the temperature for 2 hours, recovering, cleaning and drying a new product.
The modified cobalt oxide was characterized by transmission electron microscopy and X-ray energy scattering spectroscopy by X-ray diffraction, the results are shown in fig. 1. The spectrum shows that zinc is uniformly doped into cobalt oxide.
Putting the solid product treated in the step 3 and potassium hydrogen peroxymonosulfate into wastewater to be treated;
the mixture ratio is as follows:
solid product 1 part by weight
1 part by weight of potassium hydrogen peroxymonosulfate
The pollutant in the wastewater (water sample) to be treated is dye rhodamine B, and the concentration is 50 mg/L. The adding concentration of the solid product is 200 mg/L, and the adding concentration of potassium peroxymonosulfate is 200 mg/L.
And 5, after stirring and reacting for 10 min, the rhodamine B decolorization rate can reach 100 percent.
The pollutant removal effect was measured by uv-vis spectroscopy, and the control group was measured, and the results are shown in fig. 2. The degradation rate of the modified cobalt oxide is greatly improved. The active group types mainly acting in the reaction are confirmed by utilizing a trapping agent experiment, and the result is shown in figure 3, ethanol cannot obviously inhibit the degradation effect, and L-histidine completely inhibits the reaction effect, so that singlet oxygen is a main active group in the reaction, and the modified cobalt oxide is proved to generate singlet oxygen in the process of catalyzing persulfate.
Example 4:
the main steps of this example are the same as example 1, specifically:
a wastewater treatment method for catalyzing persulfate to generate singlet oxygen by using modified cobalt oxide is characterized by comprising the following steps:
dissolving cobalt metal salt, non-cobalt metal salt and organic ligand in a reaction solvent;
the mixture ratio of the raw materials is as follows:
cobalt nitrate 1 part by weight
1 part by weight of zinc nitrate
2 parts by weight of 2-methylimidazole
The solid-to-liquid ratio of the solid starting material to the reaction solvent (high purity water) was 1: 25.
And 2, standing the mixed system in the step 1 at room temperature for 12 hours, and then performing suction filtration and separation to obtain a solid.
And 3, placing the solid in the step 2) into an open tubular furnace, heating the solid sample from room temperature to 400 ℃ in the air at the heating rate of 2 ℃ per minute, preserving the temperature for 2 hours, and then naturally cooling to obtain the modified cobalt oxide.
Putting the solid product treated in the step 3 and potassium hydrogen peroxymonosulfate into wastewater to be treated;
the mixture ratio is as follows:
modified cobalt oxide 1 part by weight
1.5 parts by weight of potassium hydrogen peroxymonosulfate
The pollutant in the wastewater (water sample) to be treated is a drug carbamazepine with the concentration of 5mg/L, the adding concentration of the modified cobalt oxide is 50 mg/L, and the adding concentration of potassium hydrogen peroxymonosulfate is 75 mg/L.
And 5, after stirring and reacting for 5 min, the removal rate of the carbamazepine can reach 100 percent.
The concentration of carbamazepine before and after the reaction was measured by high performance liquid chromatography, and a trapping agent experiment was performed, and the results are shown in fig. 4. The modified cobalt oxide can catalyze the peroxymonosulfate system to generate singlet oxygen and efficiently degrade carbamazepine.
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