CN108314214A - A kind of technique of heterogeneous ozone catalytic degradation dyeing waste water - Google Patents
A kind of technique of heterogeneous ozone catalytic degradation dyeing waste water Download PDFInfo
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- CN108314214A CN108314214A CN201810162908.0A CN201810162908A CN108314214A CN 108314214 A CN108314214 A CN 108314214A CN 201810162908 A CN201810162908 A CN 201810162908A CN 108314214 A CN108314214 A CN 108314214A
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- waste water
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- dyeing waste
- water
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- 239000002351 wastewater Substances 0.000 title claims abstract description 58
- 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 34
- 230000015556 catabolic process Effects 0.000 title claims abstract description 26
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 26
- 230000003197 catalytic effect Effects 0.000 title claims description 14
- 239000002071 nanotube Substances 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 32
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 20
- 239000010941 cobalt Substances 0.000 claims abstract description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 17
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 10
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 229920001661 Chitosan Polymers 0.000 claims description 35
- 239000002105 nanoparticle Substances 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 28
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 20
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229910052681 coesite Inorganic materials 0.000 claims description 13
- 229910052906 cristobalite Inorganic materials 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 229910052682 stishovite Inorganic materials 0.000 claims description 13
- 229910052905 tridymite Inorganic materials 0.000 claims description 13
- 239000012153 distilled water Substances 0.000 claims description 12
- 238000006385 ozonation reaction Methods 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 8
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000003643 water by type Substances 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 239000006249 magnetic particle Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- -1 30~60min is stirred Substances 0.000 claims description 3
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 230000004907 flux Effects 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 239000013618 particulate matter Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- 239000002245 particle Substances 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 11
- 230000000593 degrading effect Effects 0.000 abstract description 4
- 239000000306 component Substances 0.000 abstract 1
- 229910001868 water Inorganic materials 0.000 description 25
- 239000000975 dye Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000007639 printing Methods 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- IHRFTCGTRALYFG-UHFFFAOYSA-N 4-[[4-[(4,6-dichloro-1,3,5-triazin-2-yl)amino]-2-sulfophenyl]diazenyl]-5-oxo-1-(4-sulfophenyl)-4h-pyrazole-3-carboxylic acid Chemical compound OC(=O)C1=NN(C=2C=CC(=CC=2)S(O)(=O)=O)C(=O)C1N=NC(C(=C1)S(O)(=O)=O)=CC=C1NC1=NC(Cl)=NC(Cl)=N1 IHRFTCGTRALYFG-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920002101 Chitin Polymers 0.000 description 3
- 238000010521 absorption reaction Methods 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
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- 238000007210 heterogeneous catalysis Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000746 purification 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 125000003147 glycosyl group Chemical group 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- INOIOAWTVPHTCJ-UHFFFAOYSA-N 6-acetamido-4-hydroxy-3-[[4-(2-sulfooxyethylsulfonyl)phenyl]diazenyl]naphthalene-2-sulfonic acid Chemical compound CC(=O)NC1=CC=C2C=C(C(N=NC3=CC=C(C=C3)S(=O)(=O)CCOS(O)(=O)=O)=C(O)C2=C1)S(O)(=O)=O INOIOAWTVPHTCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910002451 CoOx Inorganic materials 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
- 241000238631 Hexapoda Species 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 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
- 238000004132 cross linking Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 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
- 235000013305 food Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000007788 liquid Substances 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
- 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
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000035755 proliferation Effects 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
- 239000002002 slurry Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000003911 water pollution 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
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B01J35/33—
-
- B01J35/40—
-
- 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
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention discloses a kind for the treatment of process of catalysis ozone degradation dyeing waste water, its catalyst used is nitrogen, cobalt codope Cerium Oxide Nanotubes magnetic catalyst, the doping of the special nano tubular structure of the catalyst activity component and nitrogen and cobalt element 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 nitrogen, cobalt codope Cerium Oxide Nanotubes catalyst degradation dyeing waste water, adopt
With nitrogen, cobalt codope Cerium Oxide Nanotubes chitosan magnetic catalyst, the special nano tube structure of the catalyst activity component with
And the doping of nonmetallic nitrogen and cobalt element makes it have efficient catalysis ozone degrading activity, which has
The advantages that easy to operate, of low cost, degradation efficiency is high.
Background technology
Dyeing waste water is one of current pollution sources, and the content of organics and coloration reduced in waste water has become current Industry Waste
One hot spot of water harnessing, is the problem of environmentalist extremely pays close attention to.Due to the diversification of current various dyeing and printing products, manufacture
Method is also different, and organic matter dyestuff used is also more and more, and the ingredient in waste water is considerably complicated, biodegradable compared with
Difference.In general, dyeing waste water mainly has the characteristics that following：（1）High organic content, coloration are big.Dyeing waste water belongs to
Organic wastewater, natural and artificial synthesized dyestuff constitute main organic constituents in water.Generally can during dyeing and printing process
Using a large amount of dye materials, this substance can not possibly be transferred completely on fabric, trip residual the coloration of waste water can be caused to add in water
It is deep, also the difference of fibrous matter causes the dyestuff used in dyeing course also different, and with various New-type adjuvants in recent years and
The frequent use of slurry so that the constituent of waste water is more complicated, and COD can reach 2000~300mg/L sometimes, and BOD/
For COD less than 0.2, the biodegradable performance of organic matter is lower, so intractability bigger.（2）Change of water quality is big.Dyeing waste water
It is the general name for the various waste water that dyeing discharges in process of production.The production waste water of some enterprises discharge or auxiliary production are useless
Some sanitary sewage may be contained in water, the water quality for often leading to waste water often changes.Since discharge of wastewater and enterprise produce
Kind and fuel used type and quantity factor it is related, so change of water quality is big.（3）PH changes greatly.Various fabrics are contaminating
The technique used in material process is different, and dyeing will be carried out under different pH condition by, which needing, preferably to deposit dyestuff
On the fabric, the pH value of all kinds of printing and dyeing waste discharges be also not quite similar.（4）Water water temperature changes greatly.Due to dyeing and printing products and
The diversity of technique, leading to the water temperature water of waste water, also unstable this also virtually increases the difficulty of processing, generally requires more
Kind method, which is used in combination, to be handled.
For at present, the common processing method of dyeing waste water has absorption method, bioanalysis and chemical method etc..Common advanced oxygen
Change technology has Fenton classes oxidizing process, photocatalytic oxidation, Ozonation and catalytic ozonation method.
The principle of catalytic ozonation is as follows：Ozone is reacted with organic matter in water mainly passes through direct oxidation and free radical
React two ways.OH in water-Inducing action under, cause the chain reaction of ozone decomposed, including chain causes, chain proliferation and
Chain termination three phases.It can actually cause or terminate this chain reaction in water there are many substances, 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 to need urging
The chain reaction for causing ozone under the action of change, produces more hydroxyl radical free radicals, while can reduce and be likely to become free radical suppression
The intermediate product of preparation is to obtain the thorough removal to organic matter, because gunslinging free radical has more than ozone and other oxidants
High electrode potential, oxidability is stronger, and without selectivity, can be indistinguishably by almost all of organic substance in waste water
It is degraded into CO2And H2O, it is especially particularly suitable to the processing of organic wastewater difficult to degrade.
Homogeneous catalysis ozone technology causes new problem, i.e., adds in water while Organic substance in water is given up in removal
Excessive metal ion increase secondary pollution, other treatment process must also be increased after organic matter degradation come remove these gold
Belong to ion, to make process costs increase, and with the discharge of waste water, the concentration of waste water intermediate ion can also be gradually decreased, be led
Cause the decline of catalytic efficiency.In addition, catalyzed metal ion often has toxicity, this reduces treated, waste water returns
Receive the difficulty that utilizes, due to this various drawback, people gradually develop again be easier to separate and recover, heterogeneous urging of recycling
Change and is used for catalytic ozonation technical finesse waste water.
Heterogeneous catalysis ozonation technique is mainly combined with ozone technology to reach organic matter 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 wall in.Chitin hydrolyzes and sloughs that obtain shell after the acetyl group of part poly- under alkaline condition
Sugar.Free amino 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, also a small amount of second are dispersed in chitosan molecule chain
Acyl group, chitosan show many unique chemical property because of 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 can be used for decoloration, the heavy metal of waste water from dyestuff as adsorbent, ion-exchanger, flocculant and film preparation etc.
The recycling of ion, the purification of drinking water and water softening etc..Chitosan is a kind of novel material for water treatment of function admirable, property
It can increasingly be paid close attention to by 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 speed of raw free radical is slow, efficiency is low, the unstable problem for the treatment of effect, and conventional heterogeneous catalysis is not easily recycled,
Easily cause secondary pollution.
Invention content
In order to overcome the disadvantages of the above prior art, high, purification that the purpose of the present invention is to provide a kind of ozone utilization rates
Efficient printing-dyeing waste water treatment process.
The present invention provides a kind for the treatment of process of ozone catalytic degradation dyeing waste water, use nitrogen, the oxidation of cobalt codope
Cerium nanotube magnetic catalyst is heterogeneous catalysis, and catalysis ozone generates OH living radicals, useless to printing and dyeing to realize
The efficient removal of all kinds of dyestuffs in water.
The treatment process of catalysis ozone degradation dyeing waste water, includes the following steps：
It takes a certain amount of dyeing waste water to remove particulate matter therein through filtering, is then added in 1L flasks, adjusted by acid adding or alkali
The pH to 4.5~8.5 of waste water, is then passed through N thereto2Exist to noresidue oxygen in waste water, is then added thereto certain
Nitrogen, the cobalt codope Cerium Oxide Nanotubes magnetic catalyst of amount, and it is passed through stable streams of ozone thereto at room temperature, pass through
The size of ozone generator electric current is adjusted, control ozone flow is 10~40mgL-1H, after catalysis ozone reacts a period of time
Complete the degradation to dyeing waste water.
Wherein the mass volume ratio of nitrogen, cobalt codope Cerium Oxide Nanotubes magnetic catalyst and dyeing waste water is 5~15g：
The time of 1L, catalysis ozone reaction are 0.1~2.5h.
Nitrogen, the cobalt codope Cerium Oxide Nanotubes magnetic catalyst of the catalysis ozone degradation dyeing waste water are poly- with magnetic crust
Sugar is substrate, by stability of the crosslinking enhancing chitosan in acidic environment, then loads the CeO of N, Co codope2Nanometer
Pipe, the wherein CeO of N, Co codope2For nanotube deposition in the duct of substrate and surface location, specific preparation process is as follows：
One, 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, is used in combination distilled water to wash repeatedly to solution and is in neutrality, and 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.
Two, SiO2Coated magnetic Fe3O4The preparation of nano particle：To avoid magnetic Fe3O4Nano particle is to be carried on shell poly-
It is dissolved due to the presence of acid flux material during on sugar, 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.
Three, the preparation of substrate：Chitosan is dissolved in acetum, above-mentioned SiO is added thereto2The magnetic Fe of package3O4
Nano particle stirs evenly, and crosslinking agent is then added, and it is the chitosan-based bottom after carried magnetic particle to obtain spawn；
The wherein a concentration of 0.5~1wt%, SiO of acetum2The magnetic Fe of package3O4The mass ratio of nano particle and chitosan
It is 1:5~8, crosslinking agent is glutaraldehyde, and addition is 20~65wt% of chitosan mass；
Four, N, Co codope CeO2The preparation of nanotube：Weigh 0.5~0.9g Ce (NO3)3·6H2O and 1.5~2.0g urea
It is dissolved in 80~100mL deionized waters, stirs 30~60min, solution is shifted in 200~250mL round-bottomed flasks, 80~90
DEG C oil bath in stir 24~48h, it is cooling after centrifugal drying obtain Ce (OH) CO3.Weigh 0.2~0.4g Ce (OH) CO3Solid
It is scattered in 40~80mL deionized waters, 0.05~0.1gCo (NH is added2)6Cl330~45min is stirred with 4.5~5g NaOH,
It is transferred in 100~150mL reaction kettles, 24~36h is reacted at 120~130 DEG C, is filtered after being cooled to room temperature and uses absolute ethyl alcohol
It is respectively washed 3 times with deionized water, the yellow powder that obtained solid obtains after 120 DEG C of dry 20h is N, Co codope CeO2
Nanotube.
NaOH is CeO in water-heat process2The nucleation of nanotube, tubular crimp offer strong alkali environment, and Co (NH2)6Cl3Then
Simultaneously as nitrogen source and cobalt source to CeO2Nanotube carries out doping in situ, N after hydro-thermal reaction, in CeO2Content in nanotube is
4.5~6.5wt%, Co are in CeO2Content in nanotube is 3.5~5.2wt%.
Five, the preparation of catalysis ozone degradation dyeing waste water catalyst：By the CeO of N, Co codope2Nanotube is scattered in steaming
Ultrasonic disperse is then added into the chitosan substrate solution that 200mL contains step 3 preparation, 40 at suspension in distilled water
Ultrasound 20min under the conditions of DEG C, 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 urging
Agent；
The wherein CeO of N, Co codope2Nanotube and the mass ratio at chitosan-based bottom are 1：10~15.
Reactive orange 14 is orange powder, soluble easily in water, 20 DEG C in water solubility be 60 g/L, be 130g/L at 50 DEG C,
It degrades containing multiple phenyl ring, heterocycle containing N, ketone group etc., difficulty or ease in its structure, if presence can cause water pollution in water, because
This selects reactive orange 14 as target contaminant to simulate the catalytic efficiency of assessment catalysis material.
Compared with prior art, the present invention has the following advantages：
1, 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 easy control
It makes, is of low cost, there is potential industrial applications foreground；
2, 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
It answers, reduces the resistance that active group OH spreads between dye molecule, reacts, improve the degradation efficiency of dyeing waste water；
3, 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；
4, in the catalyst of catalysis ozone degradation dyeing waste water of the present invention, NaOH CeO2The nucleation of nanotube provides suitable strong
Alkaline environment, and Co (NH2)6Cl3Then simultaneously as nitrogen source and cobalt source to CeO2Nanotube carries out doping in situ, N, Co element
Codope can be obviously improved the rate that catalyst ozone generates OH active groups, and it is useless to improve catalysis ozone degradation printing and dyeing
The efficiency of water.
Specific implementation mode
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
One, magnetic Fe3O4The preparation of nano particle：Fe is prepared using chemical coprecipitation3O4Nano particle：In N2Under protection, press
1:1.9 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 detached by magnet, is used in combination distilled water to wash repeatedly to solution and is in neutrality,
Then vacuum drying obtains the magnetic Fe that average grain diameter is 30nm3O4Nano particle.
Two, SiO2Coated magnetic Fe3O4The preparation of nano particle：To avoid magnetic Fe3O4Nano particle is to be carried on shell poly-
It is dissolved due to the presence of acid flux material during on sugar, 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 ethanol water, 1mL ammonium hydroxide that 200mL volume fractions are 20%
With 3mL tetraethyl orthosilicates, 22h is reacted under conditions of 30 DEG C, rotating speed 20rpm；After the completion of reaction, is detached and produced using magnet
Object is washed to filtrate with distilled water and is in neutrality repeatedly, and vacuum drying obtains SiO2Coated magnetic Fe3O4Nano particle；Wherein SiO2
The thickness of thin layer is 5nm.
Three, the preparation of chitosan magnetic substrate：8g chitosans are dissolved in 0.5wt% acetums, are added thereto above-mentioned
1g SiO2The magnetic Fe of package3O4Nano particle stirs evenly, and the glutaraldehyde of 10wt% is then added, obtains spawn i.e.
For the chitosan-based bottom after carried magnetic particle；
2 nitrogen of embodiment, cobalt codope CeO2The preparation of nanotube
Weigh 0.7g Ce (NO3)3·6H2O and 1.8g urea is dissolved in 80mL deionized waters, stirs 40min, solution is shifted
It in 200mL round-bottomed flasks, is stirred in 80 DEG C of oil bath for 24 hours, centrifugal drying obtains Ce (OH) CO after cooling3.Weigh 0.3g Ce
(OH)CO3Solid is scattered in 50mL deionized waters, and 0.08g Co (NH are added2)6Cl330min is stirred with 5g NaOH, is transferred to
In 100mL reaction kettles, at 120 DEG C, reaction for 24 hours, filters after being cooled to room temperature and is respectively washed 3 with absolute ethyl alcohol and deionized water
Time, the yellow powder that obtained solid obtains after 120 DEG C of dry 20h is N, Co codope CeO2Nanotube.
The preparation of 3 catalysis ozone of embodiment degradation dyeing waste water catalyst
By the CeO of N, Co codope made from embodiment 22Nanotube is scattered in distilled water that ultrasonic disperse is at suspension, then
It adds it in the chitosan substrate solution that 200mL contains the preparation of embodiment 1, ultrasound 20min under the conditions of 40 DEG C, then adjusts
Bath temperature is 60 DEG C, and system pH is 9, is stirred to react 4h to get to catalyst；The wherein CeO of N, Co codope2Nanotube with
The mass ratio at chitosan-based bottom is 1：11.
1 routine CeO of comparative example2The preparation of nano particle supported catalyst
Choose the CeO that commercially available average grain diameter is 30nm2Nano particle is carried on magnetic crust and is gathered according to the method for embodiment 3
On glycosyl bottom, wherein CeO2Nano particle and the mass ratio at chitosan-based bottom are 1:11.
The preparation of 2 nitrogen-free of comparative example, cobalt codope catalysis ozone degradation dyeing waste water catalyst
According to the CeO of method preparation nitrogen-free, cobalt codope in embodiment 22Nanotube, difference lies in be not added in preparation process
Enter Co (NH2)6Cl3, then according to the method for embodiment 3 by the nitrogen-free, the CeO of cobalt codope2It is nano tube supported poly- in magnetic crust
On glycosyl bottom, wherein nitrogen-free, cobalt codope CeO2Nanotube and the mass ratio at chitosan-based bottom are 1:11.
The method of orange 14 waste water of 4 degrading activity of embodiment
It is the activity that model dye molecule investigates catalyst ozone degradation with reactive orange 14：Prepare 3 parts of a concentration of 1mol/L
Reactive orange each 600mL of 14 solution, be then respectively adding in 1L flasks, the pH to 7.5 of waste water adjusted by acid adding or alkali, then
It is passed through N thereto respectively2Exist to noresidue oxygen in waste water, 4g embodiments 3, comparative example 1, right are then added thereto respectively
Catalyst prepared by ratio 2, and it is passed through stable streams of ozone thereto at room temperature, by adjusting ozone generator electric current
Size, control ozone flow are 15mgL-1H, catalysis ozone reaction sample 5mL to analyze different catalysts every 10min
To the degree of purification of waste water, specific data are referring to the following table 1：
Degrading activity of the different samples of table 1. to reactive orange 14
By the data analysis of table 1 it is found that comparing common CeO2Nano particle supported catalyst, by CeO2Pattern be adjusted to nanometer
Pipe, and further to CeO2After carrying out N, Co doping, catalyst generates the activity of active group OH all for inducing ozone
With being obviously improved, this is because nanotube is to be crimped, shunk in strong basicity environment by nanometer sheet, under same quality
Relative to its specific surface area bigger of nano particle, the active surface exposed is also relatively more, and the doping of N, Co then can be into
One step promotes the activity that catalyst ozone generates active group, is completely dropped so as to be realized efficiently to dyeing waste water
Solution.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (5)
1. a kind for the treatment of process of catalytic ozonation degradation dyeing waste water, which is characterized in that include the following steps：
It takes a certain amount of dyeing waste water to remove particulate matter therein through filtering, is then added in 1L flasks, adjusted by acid adding or alkali
The pH to 4.5~8.5 of waste water, is then passed through N thereto2Exist to noresidue oxygen in waste water, is then added thereto certain
Nitrogen, the cobalt codope Cerium Oxide Nanotubes magnetic catalyst of amount, and it is passed through stable streams of ozone thereto at room temperature, pass through
The size of ozone generator electric current is adjusted, control ozone flow is 10~40mgL-1H, after catalysis ozone reacts a period of time
Complete the degradation to dyeing waste water；
Wherein the mass volume ratio of nitrogen, cobalt codope Cerium Oxide Nanotubes magnetic catalyst and dyeing waste water is 5~15g：1L is urged
The time for changing ozone reaction is 0.1~2.5h；
The preparation method of the nitrogen, cobalt codope Cerium Oxide Nanotubes magnetic catalyst includes the following steps：
One, 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, is used in combination distilled water to wash repeatedly to solution and is in neutrality, and then vacuum drying obtains magnetic Fe3O4Nano particle；
Two, SiO2Coated magnetic Fe3O4The preparation of nano particle：To avoid magnetic Fe3O4Nano particle is on being carried on chitosan
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, is detached and produced using magnet
Object is washed to filtrate with distilled water and is in neutrality repeatedly, and vacuum drying obtains SiO2Coated magnetic Fe3O4Nano particle；
Three, the preparation of substrate：Chitosan is dissolved in acetum, above-mentioned SiO is added thereto2The magnetic Fe of package3O4Nanometer
Particle stirs evenly, and crosslinking agent is then added, and it is the chitosan-based bottom after carried magnetic particle to obtain spawn；
Four, N, Co codope CeO2The preparation of nanotube：Weigh 0.5~0.9g Ce (NO3)3·6H2O and 1.5~2.0g urea are molten
In 80~100mL deionized waters, 30~60min is stirred, solution is shifted in 200~250mL round-bottomed flasks, at 80~90 DEG C
Oil bath in stir 24~48h, it is cooling after centrifugal drying obtain Ce (OH) CO3, weigh 0.2~0.4g Ce (OH) CO3Solid point
It dissipates in 40~80mL deionized waters, 0.05~0.1gCo (NH is added2)6Cl330~45min is stirred with 4.5~5g NaOH, is turned
Move on in 100~150mL reaction kettles, at 120~130 DEG C react 24~36h, after being cooled to room temperature filter and with absolute ethyl alcohol with
Deionized water is respectively washed 3 times, and the yellow powder that obtained solid obtains after 120 DEG C of dry 20h is N, Co codope CeO2It receives
Mitron, N after hydro-thermal reaction, in CeO2Content in nanotube is 4.5~6.5wt%, and Co is in CeO2Content in nanotube is 3.5
~5.2wt%.
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 the wherein a concentration of 0.5~1wt%, SiO of acetum2The 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.
5. such as the treatment process of claims 1 to 3 any one of them catalytic ozonation degradation dyeing waste water, feature exists
In the preparation method of, nitrogen, cobalt codope Cerium Oxide Nanotubes magnetic catalyst further include following steps：Five, catalysis ozone is degraded
The preparation of dyeing waste water catalyst：By the CeO of N, Co codope2Nanotube is scattered in distilled water ultrasonic disperse into suspension,
It is then added into the chitosan substrate solution that 200mL contains step 3 preparation, ultrasound 20min under the conditions of 40 DEG C, then
It is 60 DEG C to adjust bath temperature, and system pH is 9~10, is stirred to react 2~4h to get to catalyst；Wherein N, Co codope
CeO2Nanotube and the mass ratio at chitosan-based bottom are 1：10~15.
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