CN108101267A - A kind of technique of heterogeneous catalysis ozone degradation dyeing waste water - Google Patents
A kind of technique of heterogeneous catalysis ozone degradation dyeing waste water Download PDFInfo
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- CN108101267A CN108101267A CN201810100272.7A CN201810100272A CN108101267A CN 108101267 A CN108101267 A CN 108101267A CN 201810100272 A CN201810100272 A CN 201810100272A CN 108101267 A CN108101267 A CN 108101267A
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- chitosan
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- 239000002351 wastewater Substances 0.000 title claims abstract description 66
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000004043 dyeing Methods 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000015556 catabolic process Effects 0.000 title claims abstract description 31
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 31
- 238000007210 heterogeneous catalysis Methods 0.000 title description 6
- 229920001661 Chitosan Polymers 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 19
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000011282 treatment Methods 0.000 claims abstract description 14
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 12
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000002105 nanoparticle Substances 0.000 claims description 33
- 238000002360 preparation method Methods 0.000 claims description 28
- 229910001868 water Inorganic materials 0.000 claims description 26
- 239000011572 manganese Substances 0.000 claims description 22
- 229910052748 manganese Inorganic materials 0.000 claims description 21
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229910052681 coesite Inorganic materials 0.000 claims description 15
- 229910052906 cristobalite Inorganic materials 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 229910052682 stishovite Inorganic materials 0.000 claims description 15
- 229910052905 tridymite Inorganic materials 0.000 claims description 15
- 238000006385 ozonation reaction Methods 0.000 claims description 14
- 230000003197 catalytic effect Effects 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 239000000908 ammonium hydroxide Substances 0.000 claims description 12
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 8
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 230000009471 action Effects 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
- 239000006249 magnetic particle Substances 0.000 claims description 4
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical group O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 230000004907 flux Effects 0.000 claims description 3
- 125000003147 glycosyl group Chemical group 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 239000003643 water by type Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000013618 particulate matter Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000593 degrading effect Effects 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 5
- 241001062009 Indigofera Species 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 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
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- -1 Hydroxyl radical free radical Chemical class 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009990 desizing Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 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
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- HBSIZTHMGIORHW-UHFFFAOYSA-N 2-aminoacetic acid;manganese Chemical compound [Mn].NCC(O)=O HBSIZTHMGIORHW-UHFFFAOYSA-N 0.000 description 1
- 241000282836 Camelus dromedarius Species 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
- 241000238557 Decapoda Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003277 amino group Chemical group 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
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 210000000170 cell membrane 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
- 238000004140 cleaning Methods 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
- 239000000356 contaminant Substances 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
- 238000004821 distillation 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
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000009992 mercerising Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 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
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000005406 washing 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
Abstract
The invention discloses a kind for the treatment of process of catalysis ozone degradation dyeing waste water, its catalyst used is manganese, N doping cerium base chitosan magnetic catalyst, the doping of the special nanometer chip architecture of the catalyst activity component and metal manganese element and nonmetallic nitrogen makes it have efficient catalysis ozone degrading activity, which has many advantages, such as that easy to operate, of low cost, degradation efficiency is high.
Description
Technical field
The present invention relates to the treatment process of a kind of manganese, N doping cerium base catalyst degradation dyeing waste water, using manganese, N doping
Cerium base chitosan magnetic catalyst, the special nanometer chip architecture of the catalyst activity component and metal manganese element and nonmetallic nitrogen
The doping of element makes it have efficient catalysis ozone degrading activity, which has easy to operate, of low cost, degradation
The advantages that efficient.
Background technology
The waste water that dyeing and printing process is discharged is printing and dyeing mill, woollen mill, knitting mill, silk mill etc. to natural and staple fibre material
Expect the mixing for the various waste water reprocessed and generated.Dyeing and printing process generally comprises pretreatment（Desizing, refining, bleaching, silk
Light）, dyeing, stamp, four procedures such as arrangement.Pretreatment stage（Including singing, desizing, boiling-off, bleaching, the processes such as mercerising）It will
Exclude desized wastewater, boiled-off waste water, bleaching effluent and mercerizing waste water, dyeing discharge dyeing waste-water, printing technology discharge print
Flower waste water and soap lye waste water, finishing technique exclude to arrange waste water.Dyeing waste water be exactly more than all kinds of waste water mixing, but it is useless to print and dye
The most important source of water or dyeing waste-water.Since dyeing engineering is using water as medium, and generally require one or many
Washing, therefore water consumption is bigger.The waste water quality that various processes are discharged is had by the difference of kinds of fibers, dyestuff and slurry
Very big difference.For printing and dyeing enterprise, since its technique is different, the water quality for generating waste water is different.Since dyes is answered
It is miscellaneous, the impurity such as dyestuff, slurry, auxiliary agent, finish, soda acid, fiber and inorganic salts are mainly contained in waste water, chemical composition composition has
Benzene series, naphthalene system, anthraquinone system etc..Just because of this, dyeing waste water has complicated component, persistent organic pollutants content height（Up to 5
Ten thousand mg/L）, colourity is high, COD（COD）High, biochemical oxygen demand (BOD)（BOD）High, alkalescence is greatly, toxicity is big, water is big, water quality
Change the features such as big.If it is drunk or plant absorption by animal, wherein poisonous and hazardous pollutant can also be in animal and plant body inner product
It is tired, it is not easy to discharge.Dyeing waste water is containing there are many have bio-toxicity or cause " three cause "（Carcinogenic, teratogenesis, mutagenesis）It is organic
Object is always the difficult point in Industrial Waste Water Treatments and the current a great problem for continuing to solve both at home and abroad to water pollution control.
For at present, the common processing method of dyeing waste water has absorption method, bioanalysis and chemical method etc..High-level oxidation technology
（Advanced Oxidation Process abbreviations AOPs）, it is one kind in chemical method, refers to through side physically or chemically
Using two or more oxidants or catalyst combination synergistic effect occurs for method, generates that chemism is extremely strong and non-selectivity
Hydroxyl radical free radical（·OH）It is CO by the direct mineralising of organic pollution2And H2O and other inorganic matters, moreover it is possible to being difficult in sewage
Biodegradable poisonous and harmful substance plays significant processing effect.This technology is excellent with efficient, thorough, non-secondary pollution etc.
Point has become in recent years by the hot spot of extensive concern and the object of research application.Common high-level oxidation technology has Fenton class oxygen
Change method, photocatalytic oxidation, Ozonation and catalytic ozonation method.
The principle of catalytic ozonation is as follows：Ozone is in water with organic matter reaction mainly by direct oxidation and free radical
React two ways.OH in water-Inducing action under, trigger the chain reaction of ozone decomposed, including chain trigger, chain multiplication and
Chain termination three phases.It can actually trigger there are many substances in water or terminate this chain reaction, we are according to effect
Difference be classified as the initiator, accelerating agent and inhibitor of free radical.
The purpose of catalytic ozonation is exactly mainly the chain reaction for needing to trigger under the action of catalysis ozone, and production is more
Hydroxyl radical free radical, while can reduce be likely to become the intermediate product of free radical inhibitors with obtain to organic matter thoroughly go
It removes, because gunslinging free radical has higher electrode potential than ozone and other oxidants, oxidability is stronger, and does not select
Property, can almost all of organic substance in waste water be indistinguishably degraded into CO2And H2O, the especially organic wastewater to difficult degradation
Processing it is particularly suitable.
The catalytic ozonation technology most started is homogeneous catalytic reaction, i.e., catalyst copper waste water is all liquid-phase system, is utilized
Metal ion in water is as the catalyst to trigger the chain reaction of ozone to degrade the organic matter in waste water, wherein being catalyzed
The higher metal ion of activity has：Mn2+、Fe2+、Co2+、Ni2+、Cu2+、Zn2+、Cr3+Deng, the wherein pH of solution and metal ion
Species not only affects the consumption of ozone and the rate of catalytic reaction, and different degradations is more shown to different organic matters and is lived
Property.
But homogeneous catalysis ozone technology causes the problem of new, i.e., throws in water while removal useless Organic substance in water
The excessive metal ion added adds secondary pollution, must also increase other treatment process after organic matter degradation to remove these
Metal ion, so that process costs increase, and with the discharge of waste water, the concentration of waste water intermediate ion can also gradually decrease,
Cause the decline of catalytic efficiency.In addition, catalyzed metal ion often has toxicity, this reduces treated waste water
The difficulty of recycling, due to this variety of drawback, people gradually develop again be easier to separate and recover, recycle it is heterogeneous
Catalysis is for catalytic ozonation technical finesse waste water.
Heterogeneous catalysis ozonation technique mainly is combined to reach organic matter with ozone technology using solid catalyst
The purpose more thoroughly removed.Common catalyst has precious metal simple substance Au, Ru etc., metal oxide MnO2、Al2O3、TiO2、
CeO2、Co3O4、Ni2O3Deng, activated carbon, support type composite catalyst TiO2/Al2O3、CuO/ Al2O3、CoOx/ZrO2、Co/AC、
TiO2/ AC etc..
Chitosan（(Isosorbide-5-Nitrae) -2- amino -2- deoxidations-β-D-Glucose, chitosan, CTS）It is natural polysaccharide chitin
Derivative.Chitin reserves in nature are only second to cellulose, universally present in crustaceans such as crab, shrimp and insects
Shell and algal fungi cell membrane in.Chitin is hydrolyzed and sloughed and obtains shell after the acetyl group of part and gather in alkaline conditions
Sugar.Free amino group in chitosan molecule chain makes it show alkalescent, is unique existing alkaline polysaccharide in nature.Shell
Glycan is not soluble in water and alkaline solution, dissolves in most of organic acids and part inorganic acid for example dilute HCl, HNO3Deng.It is molten in diluted acid
Chitosan main chain can be hydrolyzed slowly in liquid.Great amount of hydroxy group and amino are dispersed in chitosan molecule chain, also has a small amount of second
Acyl group, chitosan show the chemical property of many uniquenesses due to these groups.Chitosan has film forming and biocidal property, can use
Make thickener, emulsifier and stabilizer, in the food industry extensive use.Chitosan also has extremely important in terms of water process
Using chitosan is as adsorbent, ion-exchanger, flocculant and film preparation etc., the colour of camel's hair, heavy metal available for waste water from dyestuff
The recycling of ion, the purification of drinking water and water softening etc..Chitosan is a kind of new material for water treatment of function admirable, property
It can increasingly be paid close attention to be subject to researcher.
But generally existing causes greatly wastewater treatment difficulty big due to variation water quality in the prior art, the production of catalyst ozone
The problem of speed of raw free radical is slow, efficiency is low, and treatment effect is unstable, and conventional heterogeneous catalysis is not easily recycled,
Easily cause secondary pollution.
The content of the invention
The shortcomings that in order to overcome the above-mentioned prior art, it is an object of the invention to provide a kind of ozone utilization rate height, catalysis
Efficient printing-dyeing waste water treatment process.
The present invention provides a kind for the treatment of process of catalysis ozone degradation dyeing waste water, use manganese, N doping cerium base magnetic
Property chitosan catalyst be heterogeneous catalysis, catalysis ozone generate living radical, so as to fulfill to all kinds of in dyeing waste water
The efficient removal of dyestuff.
The treatment process of catalysis ozone degradation dyeing waste water, includes the following steps：
The filtered removal particulate matter therein of a certain amount of dyeing waste water is taken, then adds in 1L flasks, is adjusted by acid adding or alkali
The pH of waste water to 6~8, is then passed through N thereto2Into waste water, noresidue oxygen exists, and then adds in thereto a certain amount of
Manganese, N doping cerium base chitosan magnetic catalyst, and it is passed through stable streams of ozone thereto at room temperature, by adjusting ozone
The size of generator electric current, it is 12~24mgL to control ozone flow-1H, catalysis ozone are completed after reaction a period of time to print
Contaminate the degradation of waste water.
Wherein the mass volume ratio of manganese, N doping cerium base chitosan magnetic catalyst and dyeing waste water is 5~10g：1L is urged
The time for changing ozone reaction is 0.2~2h.
The manganese of catalysis ozone degradation dyeing waste water, N doping cerium base chitosan magnetic catalyst using chitosan magnetic as
Substrate by stability of the crosslinking enhancing chitosan in sour environment, then loads the CeO that Mn, N are adulterated2Nanometer sheet, wherein
The CeO of Mn, N doping2Nanometer sheet is deposited on duct and the surface location of substrate, and specific preparation process is as follows：
First, magnetic Fe3O4The preparation of nano particle：Fe is prepared using chemical coprecipitation3O4Nano particle：In N2It, will under protection
FeCl2·4H2O and FeCl3·6H2O is dissolved in distilled water, is sufficiently mixed under the action of magnetic agitation；Above-mentioned solution is added
Ammonium hydroxide is added dropwise to 85~95 DEG C in heat, and 1~2h is reacted under the rotating speed of 500~700rpm, after the completion of reaction, passes through magnet
Separation, and washed to solution and be in neutrality repeatedly with distilled water, then vacuum drying obtains magnetic Fe3O4Nano particle.
Wherein FeCl2·4H2O and FeCl3·6H2The molar ratio of O is 1:(1.7~2)；FeCl2·4H2O and NH in ammonium hydroxide3
Molar ratio be 1:(10~15), magnetic Fe3O4The grain size of nano particle is 20~50nm.
2nd, SiO2Coated magnetic Fe3O4The preparation of nano particle：To avoid magnetic Fe3O4Nano particle gathers being carried on shell
It is dissolved during on sugar due to the presence of acid flux material, in its surface package a thin layer SiO2.It takes made from step 1
Fe3O4Nano particle is placed in three-necked flask, sequentially adds ethanol water, ammonium hydroxide and positive silicon that volume fraction is 20%~50%
Sour tetra-ethyl ester reacts 22~25h under conditions of 30~40 DEG C, 200~300rpm of rotating speed；After the completion of reaction, magnet point is utilized
It from product, is washed to filtrate and is in neutrality repeatedly with distilled water, vacuum drying obtains SiO2Coated magnetic Fe3O4Nano particle；
Wherein Fe3O4Quality and volume fraction be 20%~50% the volume ratio of ethanol water be (0.1g~1g):
100mL；The volume ratio for the ethanol water that ammonium hydroxide and tetraethyl orthosilicate are 20%~50% with volume fraction is 1:3~5：150
~200, SiO2The thickness of thin layer is 5~10nm.
3rd, the preparation of substrate：Chitosan is dissolved in acetum, adds in above-mentioned SiO thereto2The magnetic Fe of package3O4
Nano particle stirs evenly, and then adds in crosslinking agent, and it is the chitosan-based bottom after carried magnetic particle to obtain spawn；
Wherein the concentration of acetum is 0.5~1wt%, SiO2The magnetic Fe of package3O4The mass ratio of nano particle and chitosan
For 1:5~8, crosslinking agent is glutaraldehyde, and addition is 20~65wt% of chitosan mass；
4th, Mn, N adulterate CeO2The preparation of nanometer sheet：Weigh 1.32~1.46g Ce (NO3)3·6H2O and 0.38~0.54g
CTAB is dissolved in 40mL deionized waters, and 8~10mL NH are added dropwise under fast stirring3·H2O and 0.1~0.2g glycine
Manganese continues 30~60min of stirring after forming rufous floccule, is then transferred to the hydro-thermal reaction of 100mL polytetrafluoroethyllining linings
In kettle, 100~105 DEG C of 24~36h of hydro-thermal reaction are kept, are filtered after being cooled to room temperature, distinguished with absolute ethyl alcohol and deionized water
After cleaning 3 times dry 12 at 80 DEG C~100 DEG C~for 24 hours, obtained yellow powder is the CeO of Mn, N doping2Nanometer sheet.
Ammonium hydroxide is CeO in water-heat process2The nucleation of nanometer sheet forms offer mild alkaline conditions, and Mn-Gly is then used as nitrogen source
Manganese source CeO is used as again2The codope in situ of N, Mn are carried out in nanometer sheet, Mn is in CeO after hydro-thermal reaction2Content in nanometer sheet is
1.2~2.9wt%, N are in CeO2Content in nanometer sheet is 1.3~3.4wt%.
5th, the preparation of catalysis ozone degradation dyeing waste water catalyst：The CeO that Mn, N are adulterated2Nanometer sheet is scattered in distillation
Ultrasonic disperse is then added into the chitosan substrate solution that 200mL contains step 3 preparation, 40 DEG C into suspension in water
Under the conditions of ultrasound 20min, it is 60 DEG C then to adjust bath temperature, and system pH is 9~10, is stirred to react 2~4h to get to catalysis
Agent；
The wherein CeO of Mn, N doping2The mass ratio at nanometer sheet and chitosan-based bottom is 1：10~15.
Directly indigo plant 71 is used as a kind of azo dyes, is mainly used for the dyeing of the cellulose fibres such as cotton, viscose glue, if in water
Middle presence can cause water pollution, therefore directly indigo plant 71 is selected to be imitated as target contaminant to simulate the catalysis of assessment catalysis material
Rate.
Compared with prior art, the present invention has the following advantages：
1st, compared with prior art, the method for catalysis ozone processing dyeing waste water of the present invention is easy to operate, and reaction condition is easily controlled
It makes, is of low cost, there is potential industrial applications prospect；
2nd, chitosan has stronger absorption property, is used as the substrate of catalysis ozone degradation dyeing waste water catalyst, can be with
The enrichment to dyestuff is realized to the absorption of Wastewater Dyes using chitosan, is conducive to anti-between the OH and dye molecule that generate
Should, the resistance for spreading, reacting between active group OH and dye molecule is reduced, improves the degradation efficiency of dyeing waste water；
3rd, the introducing of magnetic-particle can promote the recuperability of catalyst, reduce the loss of catalyst, and it is useless to reduce printing and dyeing
The cost of water degradation；
4th, in the catalyst of catalysis ozone degradation dyeing waste water of the present invention, ammonium hydroxide CeO2The nucleation of nanometer sheet provides suitable weak
Alkaline environment, Mn-Gly are then used as manganese source CeO again as nitrogen source2The codope in situ of N, Mn, Mn, N member are carried out in nanometer sheet
The codope of element can be obviously improved the rate of catalyst ozone generation OH active groups, improve catalysis ozone degradation print
Contaminate the efficiency of waste water.
Specific embodiment
With reference to specific embodiment the present invention is further elaborated the solution of the present invention.
The preparation of 1 chitosan magnetic substrate of embodiment
First, magnetic Fe3O4The preparation of nano particle：Fe is prepared using chemical coprecipitation3O4Nano particle：In N2Under protection, press
1:2 molar ratio is by FeCl2·4H2O and FeCl3·6H2O is dissolved in distilled water, fully mixed under the action of magnetic agitation
It closes；Above-mentioned solution is heated to 90 DEG C, by FeCl2·4H2O and NH3Molar ratio be 1:10 are added dropwise ammonium hydroxide thereto,
1h is reacted under the rotating speed of 600rpm, after the completion of reaction, is separated by magnet, and is washed to solution and is in neutrality repeatedly with distilled water,
Then vacuum drying obtains the magnetic Fe that average grain diameter is 35nm3O4Nano particle.
2nd, SiO2Coated magnetic Fe3O4The preparation of nano particle：To avoid magnetic Fe3O4Nano particle gathers being carried on shell
It is dissolved during on sugar due to the presence of acid flux material, in its surface package a thin layer SiO2.Take 0.2g step 1 systems
The Fe obtained3O4Nano particle is placed in three-necked flask, sequentially adds the ethanol water that 200mL volume fractions are 20%, 1mL ammonium hydroxide
With 3mL tetraethyl orthosilicates, 22h is reacted under conditions of 30 DEG C, rotating speed 20rpm；After the completion of reaction, separated and produced using magnet
Object with distilled water is washed to filtrate and is in neutrality repeatedly, and vacuum drying obtains SiO2Coated magnetic Fe3O4Nano particle；Wherein SiO2
The thickness of thin layer is 5nm.
3rd, the preparation of chitosan magnetic substrate：8g chitosans are dissolved in 0.5wt% acetums, are added in thereto above-mentioned
1g SiO2The magnetic Fe of package3O4Nano particle stirs evenly, and then adds in the glutaraldehyde of 10wt%, obtains spawn i.e.
For the chitosan-based bottom after carried magnetic particle；
2 manganese of embodiment, N doping CeO2The preparation of nanometer sheet
Weigh 1.32g Ce (NO3)3·6H2O and 0.38g CTAB are dissolved in 40mL deionized waters, are added dropwise under fast stirring
Enter 8mL NH3·H2O and 0.1g Mn-Glies continue to stir 30min, are then transferred to 100mL poly- four after forming rufous floccule
It in the hydrothermal reaction kettle of vinyl fluoride liner, keeps 100 DEG C of hydro-thermal reactions for 24 hours, is filtered after being cooled to room temperature, with absolute ethyl alcohol and go
Ionized water dries 12h after being respectively washed 3 times at 100 DEG C, and obtained yellow powder is the CeO of manganese, N doping2Nanometer sheet.
The preparation of 3 catalysis ozone of embodiment degradation dyeing waste water catalyst
The CeO that Mn, N made from embodiment 2 are adulterated2Nanometer sheet is scattered in ultrasonic disperse in distilled water and, into suspension, then will
It is added in the chitosan substrate solution that 200mL contains the preparation of embodiment 1, and ultrasound 20min, then adjusts water under the conditions of 40 DEG C
Bath temperature is 60 DEG C, and system pH is 9, is stirred to react 4h to get to catalyst；The wherein CeO of Mn, N doping2Nanometer sheet is gathered with shell
The mass ratio at glycosyl bottom is 1：14.
1 routine CeO of comparative example2The preparation of nano particle supported catalyst
Choose the CeO that commercially available average grain diameter is 25nm2Nano particle according to the method for embodiment 3, is carried on magnetic crust and is gathered
On glycosyl bottom, wherein CeO2Nano particle and the mass ratio at chitosan-based bottom are 1:14.
Preparation of the comparative example 2 without manganese, N doping catalysis ozone degradation dyeing waste water catalyst
It is prepared according to the method in embodiment 2 without manganese, nitrogen CeO2Nanometer sheet, difference lies in be added without glycine in preparation process
Manganese, then according to the method for embodiment 3 by this without manganese, nitrogen CeO2Nanometer sheet is carried in chitosan magnetic substrate, wherein without manganese,
The CeO of N doping2The mass ratio at nanometer sheet and chitosan-based bottom is 1:14.
Embodiment 4 is degraded the methods of directly blue 71 waste water
The activity of catalyst ozone degradation is investigated for model dye molecule with directly indigo plant 71：It is 1mol/L to prepare 3 parts of concentration
Direct blue each 600mL of 71 solution, be then respectively adding in 1L flasks, pass through the pH to 6, Ran Houfen that acid adding or alkali adjust waste water
N is not passed through thereto2Into waste water, noresidue oxygen exists, and then adds in 5g embodiments 3, comparative example 1, comparison thereto respectively
Catalyst prepared by example 2, and it is passed through stable streams of ozone thereto at room temperature, by adjusting the big of ozone generator electric current
Small, it is 15mgL to control ozone flow-1H, catalysis ozone reaction sample 5mL to analyze different catalysts pair every 10min
The degree of purification of waste water, specific data are referring to the following table 1：
The different samples of table 1. are to the degrading activity of directly indigo plant 71
From the data analysis of table 1, compared to common CeO2Nano particle supported catalyst, by CeO2Pattern be adjusted to nanometer
Piece and further to CeO2After carrying out Mn, N codope, catalyst generates the activity of active group OH for inducing ozone
All have and be obviously improved, this is because nanometer sheet is compared with its specific surface area bigger of nano particle, the active surface exposed
Also it is relatively more, and Mn, N codope then can further promote the activity of catalyst, it is high so as to be realized to dyeing waste water
It imitates and completely degrades.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (7)
1. a kind for the treatment of process of catalytic ozonation degradation dyeing waste water, which is characterized in that include the following steps：
The filtered removal particulate matter therein of a certain amount of dyeing waste water is taken, then adds in 1L flasks, is adjusted by acid adding or alkali
The pH of waste water to 6~8, is then passed through N thereto2Into waste water, noresidue oxygen exists, and then adds in thereto a certain amount of
Manganese, N doping cerium base chitosan magnetic catalyst, and it is passed through stable streams of ozone thereto at room temperature, by adjusting ozone
The size of generator electric current, it is 12~24mgL to control ozone flow-1H, catalysis ozone are completed after reaction a period of time to print
Contaminate the degradation of waste water；
The manganese, the preparation method of N doping cerium base chitosan magnetic catalyst include the following steps：
First, magnetic Fe3O4The preparation of nano particle：Fe is prepared using chemical coprecipitation3O4Nano particle：In N2It, will under protection
FeCl2·4H2O and FeCl3·6H2O is dissolved in distilled water, is sufficiently mixed under the action of magnetic agitation；Above-mentioned solution is added
Ammonium hydroxide is added dropwise to 85~95 DEG C in heat, and 1~2h is reacted under the rotating speed of 500~700rpm, after the completion of reaction, passes through magnet
Separation, and washed to solution and be in neutrality repeatedly with distilled water, then vacuum drying obtains magnetic Fe3O4Nano particle；
2nd, SiO2Coated magnetic Fe3O4The preparation of nano particle：To avoid magnetic Fe3O4Nano particle is on chitosan is carried on
During be dissolved due to the presence of acid flux material, in its surface package a thin layer SiO2, take Fe made from step 13O4
Nano particle is placed in three-necked flask, sequentially adds ethanol water, ammonium hydroxide and positive silicic acid four that volume fraction is 20%~50%
Ethyl ester reacts 22~25h under conditions of 30~40 DEG C, 200~300rpm of rotating speed；After the completion of reaction, separated and produced using magnet
Object with distilled water is washed to filtrate and is in neutrality repeatedly, and vacuum drying obtains SiO2Coated magnetic Fe3O4Nano particle.
2. the treatment process of catalytic ozonation degradation dyeing waste water as described in claim 1, which is characterized in that in step 1
FeCl2·4H2O and FeCl3·6H2The molar ratio of O is 1:(1.7~2)；FeCl2·4H2O and NH in ammonium hydroxide3Molar ratio be 1:
(10~15), magnetic Fe3O4The grain size of nano particle is 20~50nm.
3. the treatment process of catalytic ozonation degradation dyeing waste water as described in claim 1, which is characterized in that in step 2
Fe3O4Quality and volume fraction be 20%~50% the volume ratio of ethanol water be (0.1g~1g):100mL；Ammonium hydroxide and just
The volume ratio for the ethanol water that tetraethyl orthosilicate is 20%~50% with volume fraction is 1:3~5：150~200, SiO2Thin layer
Thickness be 5~10nm.
4. such as the treatment process of claims 1 to 3 any one of them catalytic ozonation degradation dyeing waste water, feature exists
In manganese, the preparation method of N doping cerium base chitosan magnetic catalyst further include following steps：3rd, the preparation of substrate：Shell is gathered
Sugar is dissolved in acetum, adds in above-mentioned SiO thereto2The magnetic Fe of package3O4Nano particle stirs evenly, and then adds in and hands over
Join agent, it is the chitosan-based bottom after carried magnetic particle to obtain spawn.
5. the treatment process of catalytic ozonation degradation dyeing waste water as claimed in claim 4, which is characterized in that wherein acetic acid
The concentration of solution is 0.5~1wt%, SiO2The magnetic Fe of package3O4The mass ratio of nano particle and chitosan is 1:5~8, crosslinking
Agent is glutaraldehyde, and addition is 20~65wt% of chitosan mass.
6. the treatment process of catalytic ozonation degradation dyeing waste water as claimed in claim 4, which is characterized in that manganese, nitrogen are mixed
The preparation method of miscellaneous cerium base chitosan magnetic catalyst further includes following steps：4th, Mn, N adulterate CeO2The preparation of nanometer sheet：Claim
Take 1.32~1.46g Ce (NO3)3·6H2O and 0.38~0.54g CTAB are dissolved in 40mL deionized waters, under fast stirring
8~10mL NH are added dropwise3·H2O and 0.1~0.2g Mn-Glies, formed rufous floccule after continue stirring 30~
Then 60min is transferred in the hydrothermal reaction kettle of 100mL polytetrafluoroethyllining linings, and 100~105 DEG C of hydro-thermal reactions 24 of holding~
36h is filtered after being cooled to room temperature, after being respectively washed 3 times with absolute ethyl alcohol and deionized water dry 12 at 80 DEG C~100 DEG C~
For 24 hours, the yellow powder obtained is the CeO of Mn, N doping2Nanometer sheet.
7. the treatment process of catalytic ozonation degradation dyeing waste water as claimed in claim 6, which is characterized in that manganese, nitrogen are mixed
The preparation method of miscellaneous cerium base chitosan magnetic catalyst further includes following steps：5th, catalysis ozone degradation dyeing waste water catalyst
Preparation：The CeO that Mn, N are adulterated2Nanometer sheet is scattered in ultrasonic disperse in distilled water and, into suspension, is then added into
200mL contains in the chitosan substrate solution of step 3 preparation, ultrasound 20min under the conditions of 40 DEG C, then adjusts bath temperature and is
60 DEG C, system pH is 9~10, is stirred to react 2~4h to get to catalyst；The wherein CeO of Mn, N doping2Nanometer sheet is gathered with shell
The mass ratio at glycosyl bottom is 1：10~15.
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