CN108101267B - Process for degrading printing and dyeing wastewater by heterogeneous catalysis ozone - Google Patents
Process for degrading printing and dyeing wastewater by heterogeneous catalysis ozone Download PDFInfo
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- CN108101267B CN108101267B CN201810100272.7A CN201810100272A CN108101267B CN 108101267 B CN108101267 B CN 108101267B CN 201810100272 A CN201810100272 A CN 201810100272A CN 108101267 B CN108101267 B CN 108101267B
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- 239000002351 wastewater Substances 0.000 title claims abstract description 78
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000004043 dyeing Methods 0.000 title claims abstract description 44
- 238000007639 printing Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000008569 process Effects 0.000 title claims abstract description 23
- 230000000593 degrading effect Effects 0.000 title claims description 8
- 238000007210 heterogeneous catalysis Methods 0.000 title description 3
- 229920001661 Chitosan Polymers 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 239000011572 manganese Substances 0.000 claims abstract description 33
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 27
- 239000002135 nanosheet Substances 0.000 claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 230000015556 catabolic process Effects 0.000 claims abstract description 17
- 238000006731 degradation reaction Methods 0.000 claims abstract description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 239000002105 nanoparticle Substances 0.000 claims description 35
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 23
- 229910001868 water Inorganic materials 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052682 stishovite Inorganic materials 0.000 claims description 11
- 229910052905 tridymite Inorganic materials 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000006385 ozonation reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- JNMKPXXKHWQWFB-UHFFFAOYSA-L 2-aminoacetate;manganese(2+) Chemical compound [Mn+2].NCC([O-])=O.NCC([O-])=O JNMKPXXKHWQWFB-UHFFFAOYSA-L 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical group O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229910052755 nonmetal Inorganic materials 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 6
- QTTDXDAWQMDLOF-UHFFFAOYSA-J tetrasodium 3-[[4-[[4-[(6-amino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-6-sulfonatonaphthalen-1-yl]diazenyl]naphthalen-1-yl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].Nc1ccc2c(O)c(N=Nc3ccc(N=Nc4ccc(N=Nc5cc(c6cccc(c6c5)S([O-])(=O)=O)S([O-])(=O)=O)c5ccccc45)c4ccc(cc34)S([O-])(=O)=O)c(cc2c1)S([O-])(=O)=O QTTDXDAWQMDLOF-UHFFFAOYSA-J 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920002101 Chitin Polymers 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000009990 desizing Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000006249 magnetic particle Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 241000238557 Decapoda Species 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000009991 scouring Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 241000282836 Camelus dromedarius Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229910002451 CoOx Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005949 ozonolysis reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000009999 singeing Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000001291 vacuum drying Methods 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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
-
- B01J35/33—
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/78—Details relating to ozone treatment devices
- C02F2201/782—Ozone generators
-
- 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
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a treatment process for catalyzing ozone to degrade printing and dyeing wastewater, which adopts a manganese and nitrogen doped cerium-based magnetic chitosan catalyst, has high catalytic ozone degradation activity due to the special nanosheet structure of active components of the catalyst and the doping of metal manganese elements and non-metal nitrogen elements, and has the advantages of simple operation, low cost, high degradation efficiency and the like.
Description
Technical Field
The invention relates to a treatment process for degrading printing and dyeing wastewater by using a manganese and nitrogen doped cerium-based catalyst, which adopts a manganese and nitrogen doped cerium-based magnetic chitosan catalyst, has high catalytic ozone degradation activity due to the special nanosheet structure of the active component of the catalyst and the doping of metal manganese elements and non-metal nitrogen elements, and has the advantages of simple operation, low cost, high degradation efficiency and the like.
Background
The waste water discharged from the printing and dyeing process is a mixture of various waste waters produced by reprocessing natural and man-made fiber materials in printing and dyeing mills, spinning mills, knitting mills, silk mills, and the like. The printing and dyeing process generally comprises four procedures of pretreatment (desizing, refining, bleaching, mercerizing), dyeing, printing, finishing and the like. In the pretreatment stage (comprising the working procedures of singeing, desizing, scouring, bleaching, mercerizing and the like), desizing wastewater, scouring wastewater, bleaching wastewater and mercerizing wastewater are removed, dyeing wastewater is discharged in the dyeing process, printing wastewater and soap lye wastewater are discharged in the printing process, and finishing wastewater is removed in the finishing process. The printing and dyeing wastewater is the mixture of the above various types of wastewater, but the most main source of the printing and dyeing wastewater is the dyeing wastewater. The dyeing process uses water as a medium and usually needs one or more times of water washing, so the water consumption is large. The quality of wastewater discharged from various processes varies greatly depending on the type of fiber, dye and slurry. For printing and dyeing enterprises, the quality of produced wastewater is different due to different processes. The waste water mainly contains impurities such as dye, slurry, assistant, oil agent, acid and alkali, fiber, inorganic salt and the like due to the complex types of the dye, and the chemical components of the waste water comprise benzene series, naphthalene series, anthraquinone series and the like. Therefore, the printing and dyeing wastewater has the characteristics of complex components, high content of refractory organic pollutants (up to 5 ten thousand mg/L), high chroma, high Chemical Oxygen Demand (COD), high Biochemical Oxygen Demand (BOD), high alkalinity, high toxicity, large water quantity, large water quality change and the like. If the water is drunk by animals or absorbed by plants, toxic and harmful pollutants in the water can be accumulated in the bodies of the animals and the plants and are difficult to discharge. The printing and dyeing wastewater contains various organic matters with biological toxicity or causing 'three causes' (carcinogenesis, teratogenesis and mutagenesis), is a difficult point in industrial sewage treatment and is a big problem to be continuously solved for controlling water pollution at home and abroad at present.
At present, the printing and dyeing wastewater is usually treated by adsorption, biological method, chemical method, and the like. Advanced Oxidation technologies (AOPs for short) are one of chemical methods,it refers to that two or more oxidants or catalysts are combined to generate synergistic effect by a physical or chemical method, and hydroxyl free radicals (. OH) with extremely strong chemical activity and no selectivity are generated to directly mineralize organic pollutants into CO2And H2O and other inorganic matters, and can also play a remarkable role in treating toxic and harmful substances which are difficult to biodegrade in the sewage. The technology has the advantages of high efficiency, thoroughness, no secondary pollution and the like, and becomes an object of hot spots and research and application which are widely concerned in recent years. Common advanced oxidation techniques are Fenton-type oxidation, photocatalytic oxidation, ozone oxidation, and catalytic ozonation.
The principle of catalytic ozonation is as follows: ozone reacts with organic substances in water mainly through two modes of direct oxidation and free radical reaction. OH in Water-Under the induction action of (2), the chain reaction of ozonolysis is initiated, and comprises three stages of chain initiation, chain proliferation and chain termination. In fact, the presence of many substances in water can initiate or terminate this chain reaction, which we have classified into radical initiators, accelerators and inhibitors, depending on the action.
The main objective of catalytic ozonation is to initiate the ozone chain reaction under the action of catalysis to produce more hydroxyl radicals, and simultaneously reduce the intermediate products which can become radical inhibitors to obtain complete removal of organic matters, because the gun-shot radicals have higher electrode potential, stronger oxidizing ability and no selectivity than ozone and other oxidants, and almost all organic matters in the wastewater can be indiscriminately degraded into CO2And H2O, is particularly suitable for the treatment of organic wastewater which is difficult to degrade.
The first catalytic ozonation technology is a homogeneous catalytic reaction, namely, the copper wastewater as a catalyst is a liquid phase system, and metal ions in water are used as the catalyst to initiate a chain reaction of ozone to degrade organic matters in the wastewater, wherein the metal ions with higher catalytic activity comprise: mn2+、Fe2+、Co2+、Ni2+、Cu2+、Zn2+、Cr3+Etc., wherein the pH of the solution and the kind of metal ion are not the sameOnly affects the ozone consumption and the catalytic reaction rate, and shows different degradation activities on different organic matters.
However, the homogeneous catalysis ozone technology causes new problems when removing organic matters in wastewater, namely, the secondary pollution is increased due to excessive metal ions added in water, and other treatment processes must be added to remove the metal ions after the organic matters are degraded, so that the process cost is increased, and the concentration of ions in the wastewater is gradually reduced along with the discharge of the wastewater, so that the catalytic efficiency is reduced. In addition, the metal ions used for catalysis are often toxic, which reduces the difficulty of recycling the treated wastewater, and due to the defects, heterogeneous catalysis which is easier to separate, recycle and recycle is gradually developed for treating wastewater by using a catalytic ozonation technology.
The heterogeneous catalytic ozonation technology mainly utilizes a solid catalyst to be combined with an ozone technology to achieve the purpose of more thoroughly removing organic matters. Common catalysts comprise noble metal simple substances Au, Ru and the like, and metal oxide MnO2、Al2O3、TiO2、CeO2、Co3O4、Ni2O3Active carbon, supported composite catalyst TiO2/Al2O3、CuO/ Al2O3、CoOx/ZrO2、Co/AC、TiO2and/AC, etc.
Chitosan ((1, 4) -2-amino-2-deoxy- β -D-glucose, chitosan, CTS) is a derivative of natural polysaccharide chitin, the storage amount of chitin in nature is second to cellulose, and the chitin is widely present in shells of crustaceans such as crabs, shrimps and insects and cell walls of phycomycetes3And the like. The chitosan backbone will slowly hydrolyze in dilute acid solutions. A large amount of hydroxyl and ammonia are distributed on the molecular chain of the chitosanThere are also small amounts of acetyl groups, and chitosan exhibits many unique chemical properties due to these groups. Chitosan has film forming and bacteriostatic properties, can be used as a thickener, an emulsifier and a stabilizer, and is widely applied in the food industry. Chitosan also has an extremely important application in water treatment, and can be used as an adsorbent, an ion exchanger, a flocculant, a membrane preparation and the like, and can be used for camel color of dye wastewater, recovery of heavy metal ions, purification of drinking water, softening of hard water and the like. Chitosan is a novel water treatment material with excellent performance, and the performance of chitosan is more and more concerned by researchers.
However, the problems of high wastewater treatment difficulty caused by high water quality fluctuation, low speed, low efficiency and unstable treatment effect of the catalyst for catalyzing ozone to generate free radicals generally exist in the prior art, and the conventional heterogeneous catalyst is not easy to recover and is easy to cause secondary pollution.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a printing and dyeing wastewater treatment process with high ozone utilization rate and high catalytic efficiency.
The invention provides a treatment process for degrading printing and dyeing wastewater by catalyzing ozone, which adopts a manganese and nitrogen-doped cerium-based magnetic chitosan catalyst as a heterogeneous catalyst to catalyze ozone to generate active free radicals, thereby realizing the efficient removal of various dyes in the printing and dyeing wastewater.
The treatment process for degrading printing and dyeing wastewater by catalytic ozone comprises the following steps:
filtering a certain amount of printing and dyeing wastewater to remove particles in the wastewater, adding the wastewater into a 1L flask, adjusting the pH of the wastewater to 6-8 by adding acid or alkali, and introducing N into the wastewater2Until no residual oxygen exists in the wastewater, adding a certain amount of manganese and nitrogen-doped cerium-based magnetic chitosan catalyst, introducing stable ozone airflow into the wastewater at room temperature, and controlling the ozone flow to be 12-24 mg.L by adjusting the current of an ozone generator-1H, catalyzing ozone to react for a period of time to complete the degradation of the printing and dyeing wastewater.
Wherein the mass volume ratio of the manganese-nitrogen-doped cerium-based magnetic chitosan catalyst to the printing and dyeing wastewater is 5-10 g: 1L, and the time for catalyzing the ozone reaction is 0.2-2 h.
The manganese and nitrogen doped cerium-based magnetic chitosan catalyst for catalyzing ozone degradation of printing and dyeing wastewater takes magnetic chitosan as a substrate, enhances the stability of the chitosan in an acid environment through crosslinking, and then loads Mn and N doped CeO2Nanosheets of Mn, N doped CeO2The nano-sheet is deposited on the pore and the surface of the substrate, and the preparation method comprises the following specific steps:
one, magnetic Fe3O4Preparing nano particles: preparation of Fe by chemical coprecipitation method3O4Nano-particles: in N2Under protection, FeCl is added2·4H2O and FeCl3·6H2Dissolving O in distilled water, and fully mixing under the action of magnetic stirring; heating the solution to 85-95 ℃, dropwise adding ammonia water, reacting at the rotating speed of 500-700 rpm for 1-2 h, separating by using a magnet after the reaction is finished, repeatedly washing by using distilled water until the solution is neutral, and then drying in vacuum to obtain magnetic Fe3O4And (3) nanoparticles.
Wherein FeCl2·4H2O and FeCl3·6H2The molar ratio of O is 1 (1.7-2); FeCl2·4H2O and NH in ammonia3The molar ratio of (1), (10-15), and magnetic Fe3O4The particle size of the nanoparticles is 20-50 nm.
II, SiO2Coated magnetic Fe3O4Preparing nano particles: to avoid magnetic Fe3O4The nanoparticles are dissolved in the process of loading on chitosan due to the existence of an acidic solvent, and a thin layer of SiO is coated on the surface of the nanoparticles2. Taking the Fe prepared in the step one3O4Placing the nano particles into a three-neck flask, sequentially adding 20-50% by volume of ethanol aqueous solution, ammonia water and tetraethyl orthosilicate, and reacting for 22-25 h at the temperature of 30-40 ℃ and the rotating speed of 200-300 rpm; after the reaction is finished, separating the product by using a magnet, repeatedly washing the product by using distilled water until the filtrate is neutral, and drying the filtrate in vacuum to obtain SiO2Coated magnetic Fe3O4A nanoparticle;
wherein Fe3O4The volume ratio of the ethanol water solution with the mass and volume fraction of 20-50% (0.1-1 g) is 100 mL; the volume ratio of the ammonia water to the tetraethyl orthosilicate to the ethanol water solution with the volume fraction of 20% -50% is 1: 3-5: 150 to 200 of SiO2The thickness of the thin layer is 5-10 nm.
Thirdly, preparing a substrate: dissolving chitosan in acetic acid solution, adding the above SiO2Encapsulated magnetic Fe3O4Uniformly stirring the nano particles, and then adding a cross-linking agent to obtain a gel substance, namely the chitosan substrate loaded with the magnetic particles;
wherein the concentration of the acetic acid solution is 0.5-1 wt%, and SiO2Encapsulated magnetic Fe3O4The mass ratio of the nano particles to the chitosan is 1: 5-8, the cross-linking agent is glutaraldehyde, and the addition amount of the cross-linking agent is 20-65 wt% of the mass of the chitosan;
doping CeO with Mn, N2Preparing a nano sheet: weighing 1.32-1.46 g Ce (NO)3)3·6H2Dissolving O and 0.38-0.54 g CTAB in 40mL of deionized water, and dropwise adding 8-10 mL of NH under rapid stirring3·H2O and 0.1-0.2 g manganese glycinate are stirred for 30-60 min after forming reddish brown floccules, then the floccules are transferred into a 100mL polytetrafluoroethylene lined hydrothermal reaction kettle, hydrothermal reaction is carried out for 24-36 h at 100-105 ℃, the floccules are cooled to room temperature and then filtered, absolute ethyl alcohol and deionized water are used for cleaning for 3 times respectively, and then drying is carried out for 12-24 h at 80-100 ℃, and the obtained yellow powder is Mn and N doped CeO2Nanosheets.
Ammonia water as CeO in hydrothermal process2The nucleation and formation of the nano-sheets provide a weak alkali environment, and manganese glycinate is used as a nitrogen source and a manganese source CeO2N, Mn in-situ co-doping in nanosheets, and enabling Mn to be in CeO after hydrothermal reaction2The content of the nano-sheets is 1.2-2.9 wt%, and N is in CeO2The content of the nano sheets is 1.3-3.4 wt%.
Fifthly, preparing a catalyst for catalyzing ozone to degrade printing and dyeing wastewater: CeO doped with Mn and N2Nano-sheetDispersing the chitosan into distilled water, performing ultrasonic dispersion to obtain a suspension, adding the suspension into 200mL of chitosan substrate solution containing the chitosan prepared in the step three, performing ultrasonic treatment for 20min at 40 ℃, then adjusting the water bath temperature to be 60 ℃, adjusting the pH value of the system to be 9-10, and stirring for reaction for 2-4 h to obtain the catalyst;
CeO in which Mn and N are doped2The mass ratio of the nanosheets to the chitosan substrate is 1:10 to 15.
The direct blue 71 is used as an azo dye and is mainly used for dyeing cellulose fibers such as cotton, viscose and the like, and if the dye exists in water, water pollution is caused, so that the direct blue 71 is selected as a target pollutant to simulate and evaluate the catalytic efficiency of the catalytic material.
Compared with the prior art, the invention has the following advantages:
1. compared with the prior art, the method for treating printing and dyeing wastewater by catalytic ozone has the advantages of simple operation, easily controlled reaction conditions, low cost and potential industrial application prospect;
2. the chitosan has stronger adsorption performance, can be used as a substrate of a catalyst for catalyzing ozone degradation of printing and dyeing wastewater, can realize the enrichment of dye by utilizing the adsorption of the chitosan on the dye in the wastewater, is beneficial to the reaction between the generated OH and dye molecules, reduces the resistance of the diffusion and reaction between active groups OH and the dye molecules, and improves the degradation efficiency of the printing and dyeing wastewater;
3. the introduction of the magnetic particles can improve the recyclability of the catalyst, reduce the loss of the catalyst and reduce the cost of the degradation of the printing and dyeing wastewater;
4. in the catalyst for catalyzing ozone to degrade printing and dyeing wastewater, ammonia water is CeO2The nucleation of the nano-sheets provides a proper alkalescent environment, and manganese glycinate is used as a nitrogen source and a manganese source CeO2The in-situ co-doping of N, Mn is carried out in the nanosheets, and the co-doping of Mn and N elements can obviously improve the speed of the catalyst for catalyzing ozone to generate OH active groups, so that the efficiency of catalyzing ozone to degrade printing and dyeing wastewater is improved.
Detailed Description
The invention will now be further illustrated by reference to specific examples.
Example 1 preparation of magnetic Chitosan substrate
One, magnetic Fe3O4Preparing nano particles: preparation of Fe by chemical coprecipitation method3O4Nano-particles: in N2Under protection, FeCl is added according to a molar ratio of 1:22·4H2O and FeCl3·6H2Dissolving O in distilled water, and fully mixing under the action of magnetic stirring; heating the solution to 90 deg.C according to FeCl2·4H2O and NH3Adding ammonia water dropwise at a molar ratio of 1:10, reacting at 600rpm for 1h, separating with magnet after reaction, washing with distilled water repeatedly until the solution is neutral, and vacuum drying to obtain magnetic Fe with average particle diameter of 35nm3O4And (3) nanoparticles.
II, SiO2Coated magnetic Fe3O4Preparing nano particles: to avoid magnetic Fe3O4The nanoparticles are dissolved in the process of loading on chitosan due to the existence of an acidic solvent, and a thin layer of SiO is coated on the surface of the nanoparticles2. 0.2g of Fe obtained in step one3O4Placing the nano particles into a three-neck flask, sequentially adding 200mL of ethanol aqueous solution with the volume fraction of 20%, 1mL of ammonia water and 3mL of tetraethyl orthosilicate, and reacting for 22h at the temperature of 30 ℃ and the rotating speed of 20 rpm; after the reaction is finished, separating the product by using a magnet, repeatedly washing the product by using distilled water until the filtrate is neutral, and drying the filtrate in vacuum to obtain SiO2Coated magnetic Fe3O4A nanoparticle; wherein SiO is2The thickness of the thin layer was 5 nm.
Thirdly, preparing the magnetic chitosan substrate: 8g of chitosan was dissolved in 0.5wt% acetic acid solution, to which the above 1g of SiO was added2Encapsulated magnetic Fe3O4Uniformly stirring the nano particles, and then adding 10wt% of glutaraldehyde to obtain a gel substance, namely the chitosan substrate loaded with the magnetic particles;
example 2 doping of CeO with manganese and Nitrogen2Preparation of nanosheets
Weighing 1.32g Ce (NO)3)3·6H2O and 0.38g CTAB were dissolved in 40mL of deionized water, and 8mL of NH was added dropwise with rapid stirring3·H2O and 0.1g manganese glycinate to form reddish brown floccule, continuously stirring for 30min, then transferring into a 100mL polytetrafluoroethylene-lined hydrothermal reaction kettle, keeping the hydrothermal reaction at 100 ℃ for 24h, cooling to room temperature, filtering, respectively washing for 3 times by using absolute ethyl alcohol and deionized water, and drying at 100 ℃ for 12h to obtain yellow powder, namely manganese and nitrogen-doped CeO2Nanosheets.
EXAMPLE 3 preparation of catalyst for catalyzing ozone degradation of printing and dyeing wastewater
The Mn and N-doped CeO prepared in example 22Dispersing the nanosheets in distilled water, performing ultrasonic dispersion to obtain a suspension, adding the suspension into 200mL of chitosan substrate solution containing the chitosan prepared in the embodiment 1, performing ultrasonic treatment at 40 ℃ for 20min, adjusting the water bath temperature to 60 ℃ and the system pH to 9, and stirring for reacting for 4h to obtain a catalyst; CeO in which Mn and N are doped2The mass ratio of the nanosheets to the chitosan substrate is 1: 14.
comparative example 1 conventional CeO2Preparation of nanoparticle-supported catalyst
Selecting commercially available CeO with average particle size of 25nm2Nanoparticles, loaded on a magnetic chitosan substrate according to the method of example 3, with CeO2The mass ratio of the nanoparticles to the chitosan substrate was 1: 14.
Comparative example 2 preparation of catalyst for degrading printing and dyeing wastewater by using manganese-free and nitrogen-doped catalytic ozone
Manganese-and nitrogen-free CeO was prepared as in example 22Nanosheets, except that manganese glycinate was not added during preparation, and the manganese-free, nitrogen-free CeO was subsequently applied as in example 32The nano-sheet is loaded on a magnetic chitosan substrate, wherein, CeO doped with manganese and nitrogen is not contained2The mass ratio of the nano-sheets to the chitosan substrate is 1: 14.
Example 4 method for degrading direct blue 71 wastewater
The direct blue 71 is taken as a model dye molecule to investigate the catalytic activity of the catalyst on ozone degradation: 3 parts of direct blue 71 solution with the concentration of 1mol/L are prepared, each 600mL, then adding into a 1L flask, respectively, adjusting the pH of the wastewater to 6 by adding acid or alkali, and then introducing N into the flask2Until no residual oxygen exists in the wastewater, 5g of the catalysts prepared in example 3, comparative example 1 and comparative example 2 are added into the wastewater respectively, a stable ozone gas flow is introduced into the wastewater at room temperature, and the flow rate of the ozone is controlled to be 15 mg.L by adjusting the current of an ozone generator-1H, catalyzing ozone reaction, sampling 5mL every 10min to analyze the purification degree of wastewater by different catalysts, and the specific data are shown in the following table 1:
TABLE 1 degradation Activity of different samples on direct blue 71
As can be seen from the data analysis in Table 1, compared with ordinary CeO2Catalyst is loaded on nano particles, CeO is added2The morphology of (A) is adjusted into nanosheets, and further CeO is added2After Mn and N co-doping, the catalyst has remarkable improvement on the activity of inducing ozone to generate active groups OH, because the specific surface area of the nano sheet is larger than that of the nano particle, the exposed active surface is relatively more, and the Mn and N co-doping can further improve the activity of the catalyst, so that the printing and dyeing wastewater can be efficiently and completely degraded.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (4)
1. A treatment process for degrading printing and dyeing wastewater by catalytic ozonation is characterized by comprising the following steps:
filtering a certain amount of printing and dyeing wastewater to remove particles in the wastewater, adding the wastewater into a 1L flask, adjusting the pH of the wastewater to 6-8 by adding acid or alkali, and introducing N into the wastewater2Until no residual oxygen exists in the wastewater, adding a certain amount of manganese and nitrogen-doped cerium-based magnetic chitosan catalyst, introducing stable ozone airflow into the wastewater at room temperature, and controlling the ozone flow to be 12-24 mg.L by adjusting the current of an ozone generator-1H, catalyzing ozone to react for a period of time and then finishing degradation of the printing and dyeing wastewater;
the preparation method of the manganese and nitrogen doped cerium-based magnetic chitosan catalyst comprises the following steps:
one, magnetic Fe3O4Preparing nano particles: preparation of Fe by chemical coprecipitation method3O4Nano-particles: in N2Under protection, FeCl is added2·4H2O and FeCl3·6H2Dissolving O in distilled water, and fully mixing under the action of magnetic stirring; heating the mixed solution to 85-95 ℃, dropwise adding ammonia water, reacting at the rotating speed of 500-700 rpm for 1-2 h, separating by using a magnet after the reaction is finished, repeatedly washing by using distilled water until the solution is neutral, and then drying in vacuum to obtain magnetic Fe3O4A nanoparticle;
II, SiO2Coated magnetic Fe3O4Preparing nano particles: to avoid magnetic Fe3O4The nanoparticles are dissolved in the process of loading on chitosan due to the existence of an acidic solvent, and a thin layer of SiO is coated on the surface of the nanoparticles2Taking the Fe prepared in the step one3O4Placing the nano particles into a three-neck flask, sequentially adding 20-50% by volume of ethanol aqueous solution, ammonia water and tetraethyl orthosilicate, and reacting for 22-25 h at the temperature of 30-40 ℃ and the rotating speed of 200-300 rpm; after the reaction is finished, separating the product by using a magnet, repeatedly washing the product by using distilled water until the filtrate is neutral, and drying the filtrate in vacuum to obtain SiO2Coated magnetic Fe3O4A nanoparticle;
thirdly, preparing a substrate: dissolving chitosan in acetic acid solution, adding the above SiO2Encapsulated magnetic Fe3O4Stirring the nano particles uniformly, adding a cross-linking agent to obtain a gel substance, namely a shell loaded with the magnetic particlesA glycan substrate;
doping CeO with Mn, N2Preparing a nano sheet: weighing 1.32-1.46 g Ce (NO)3)3·6H2Dissolving O and 0.38-0.54 g CTAB in 40mL of deionized water, and dropwise adding 8-10 mL of NH under rapid stirring3·H2O and 0.1-0.2 g manganese glycinate are stirred for 30-60 min after forming reddish brown floccules, then the floccules are transferred into a 100mL polytetrafluoroethylene lined hydrothermal reaction kettle, hydrothermal reaction is carried out for 24-36 h at 100-105 ℃, the floccules are cooled to room temperature and then filtered, absolute ethyl alcohol and deionized water are used for cleaning for 3 times respectively, and then drying is carried out for 12-24 h at 80-100 ℃, and the obtained yellow powder is Mn and N doped CeO2Nanosheets;
fifthly, preparing a catalyst for catalyzing ozone to degrade printing and dyeing wastewater: CeO doped with Mn and N2Dispersing the nanosheets in distilled water, performing ultrasonic dispersion to obtain a suspension, adding the suspension into 200mL of chitosan substrate solution containing the chitosan prepared in the step III, performing ultrasonic treatment at 40 ℃ for 20min, then adjusting the water bath temperature to 60 ℃, adjusting the pH of the system to 9-10, and performing stirring reaction for 2-4 h to obtain the catalyst; CeO in which Mn and N are doped2The mass ratio of the nanosheets to the chitosan substrate is 1:10 to 15.
2. The process for treating printing and dyeing wastewater by catalytic ozone oxidation degradation according to claim 1, wherein FeCl is added in the first step2·4H2O and FeCl3·6H2The molar ratio of O is 1 (1.7-2); FeCl2·4H2O and NH in ammonia3The molar ratio of (1), (10-15), and magnetic Fe3O4The particle size of the nanoparticles is 20-50 nm.
3. The process for treating printing and dyeing wastewater by catalytic ozonation degradation according to claim 1, wherein in the second step, Fe3O4The volume ratio of the ethanol water solution with the mass and volume fraction of 20-50% (0.1-1 g) is 100 mL; the volume ratio of the ammonia water to the tetraethyl orthosilicate to the ethanol water solution with the volume fraction of 20% -50% is 1: 3-5: 150 to 200 of SiO2The thickness of the thin layer is 5-10 nm.
4. The process for treating printing and dyeing wastewater by catalytic ozonation degradation according to claim 1, wherein the concentration of the acetic acid solution is 0.5 to 1wt%, and SiO is2Encapsulated magnetic Fe3O4The mass ratio of the nano particles to the chitosan is 1: 5-8, the cross-linking agent is glutaraldehyde, and the addition amount of the cross-linking agent is 20-65 wt% of the mass of the chitosan.
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