CN108314214B - Process for degrading printing and dyeing wastewater through heterogeneous ozone catalysis - Google Patents
Process for degrading printing and dyeing wastewater through heterogeneous ozone catalysis Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 85
- 238000004043 dyeing Methods 0.000 title claims abstract description 57
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000000593 degrading effect Effects 0.000 title claims description 8
- 238000006555 catalytic reaction Methods 0.000 title description 5
- 239000002071 nanotube Substances 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 29
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 15
- 239000010941 cobalt Substances 0.000 claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 230000015556 catabolic process Effects 0.000 claims abstract description 13
- 238000006731 degradation reaction Methods 0.000 claims abstract description 13
- 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
- 229920001661 Chitosan Polymers 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229910001868 water Inorganic materials 0.000 claims description 20
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 19
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
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- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
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- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
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- 239000002253 acid Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 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
- 239000000047 product Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- 239000006249 magnetic particle Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical group O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- YDVGDXLABZAVCP-UHFFFAOYSA-N azanylidynecobalt Chemical compound [N].[Co] YDVGDXLABZAVCP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000010525 oxidative degradation reaction Methods 0.000 claims 3
- 239000011259 mixed solution Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000975 dye Substances 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 6
- 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 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000006385 ozonation reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process 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
- 229910052593 corundum Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 241000238557 Decapoda Species 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
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- 239000005416 organic matter Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002451 CoOx Inorganic materials 0.000 description 1
- 241000238424 Crustacea 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
- 239000000654 additive Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- -1 hydroxyl radicals Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005949 ozonolysis reaction Methods 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
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 238000005070 sampling Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a treatment process for catalyzing ozone to degrade printing and dyeing wastewater, which adopts a nitrogen and cobalt co-doped cerium oxide nanotube magnetic catalyst as a catalyst, has high catalytic ozone degradation activity due to the special nanotube-shaped structure of active components of the catalyst and the doping of nitrogen and cobalt, and has the advantages of simple operation, low cost, high degradation efficiency and the like.
Description
Technical Field
The invention relates to a treatment process for degrading printing and dyeing wastewater by using a nitrogen and cobalt co-doped cerium oxide nanotube catalyst, which adopts a nitrogen and cobalt co-doped cerium oxide nanotube magnetic chitosan catalyst, has high catalytic ozone degradation activity due to the special nanotube structure of the active component of the catalyst and the doping of non-metallic nitrogen elements and metallic cobalt elements, and has the advantages of simple operation, low cost, high degradation efficiency and the like.
Background
The dyeing wastewater is characterized by (1) high organic matter content and high chroma, the dyeing wastewater belongs to organic wastewater, natural and artificially synthesized dyes form main organic matter components in the wastewater, a large amount of dyes are generally used in the dyeing processing process, the substances cannot be completely transferred to the fabrics, the chroma of the wastewater is deepened, the dyes used in the dyeing process are different due to the difference of fiber substances, the composition of the wastewater is more complex due to the frequent use of various novel additives and sizing agents in recent years, the COD (chemical oxygen demand) can reach 2000-300 mg/L, the COD/COD (chemical oxygen demand) is less than 0.2, the biodegradability of the organic matters is lower, the treatment difficulty is higher, (2) the water quality is more difficult, the water quality of the wastewater is more variable, the water quality of the dyeing wastewater is more difficult to be treated, the water quality of various dyeing wastewater is more frequently changed in the production wastewater, the dyeing wastewater is more frequently used in the dyeing industry, the dyeing wastewater is more difficult, the water quality of various dyeing wastewater is more difficult, the dyeing wastewater is more frequently changed, the water quality of various dyeing wastewater is more difficult to be treated, the dyeing wastewater is more difficult, the water quality is more frequently changed in the dyeing production wastewater, the dyeing wastewater is more frequently discharged, the dyeing wastewater is more frequently used in the dyeing process of various production wastewater, the dyeing wastewater is more frequently discharged, the dyeing wastewater is more frequently changed, the dyeing wastewater is more frequently used in the dyeing wastewater, the dyeing wastewater is more frequently discharged, the dyeing wastewater type, the dyeing process of various production industry, the dyeing wastewater is more frequently discharged, the dyeing wastewater is more frequently.
At present, the printing and dyeing wastewater is usually treated by adsorption, biological method, chemical method, and the like. Common advanced oxidation techniques are Fenton-type oxidation, photocatalytic oxidation, ozone oxidation, and catalytic ozonation.
The principle of catalytic ozonation is as follows: ozone reacts with organic substances in water mainly through two modes of direct oxidation and free radical reaction. OH in Water-Under the induction action of (2), the chain reaction of ozonolysis is initiated, and comprises three stages of chain initiation, chain proliferation and chain termination. In fact, the presence of many substances in water can initiate or terminate this chain reaction, which we have classified into radical initiators, accelerators and inhibitors, depending on the action. The main objective of catalytic ozonation is to initiate the ozone chain reaction under the action of catalysis to produce more hydroxyl radicals, and simultaneously reduce the intermediate products which can become radical inhibitors to obtain complete removal of organic matters, because the gun-shot radicals have higher electrode potential, stronger oxidizing ability and no selectivity than ozone and other oxidants, and almost all organic matters in the wastewater can be indiscriminately degraded into CO2And H2O, is particularly suitable for the treatment of organic wastewater which is difficult to degrade.
The homogeneous catalysis ozone technology causes new problems while removing organic matters in wastewater, namely, the secondary pollution is increased by excessive metal ions added in water, other treatment processes must be added to remove the metal ions after the organic matters are degraded, so that the process cost is increased, and the concentration of ions in the wastewater is gradually reduced along with the discharge of the wastewater, so that the catalytic efficiency is reduced. In addition, the metal ions used for catalysis are often toxic, which reduces the difficulty of recycling the treated wastewater, and due to the defects, heterogeneous catalysis which is easier to separate, recycle and recycle is gradually developed for treating wastewater by using a catalytic ozonation technology.
The heterogeneous catalytic ozonation technology mainly utilizes a solid catalyst to be combined with an ozone technology to achieve the purpose of more thoroughly removing organic matters. Common catalysts comprise noble metal simple substances Au, Ru and the like, and metal oxide MnO2、Al2O3、TiO2、CeO2、Co3O4、Ni2O3Active carbon, supported composite catalyst TiO2/Al2O3、CuO/ Al2O3、CoOx/ZrO2、Co/AC、TiO2and/AC, etc.
Chitosan ((1, 4) -2-amino-2-deoxy- β -D-glucose, chitosan, CTS) is a derivative of natural polysaccharide chitin, the storage amount of chitin in nature is second to cellulose, and the chitin is widely present in shells of crustaceans such as crabs, shrimps and insects and cell walls of phycomycetes3And the like. The chitosan backbone will slowly hydrolyze in dilute acid solutions. The molecular chain of the chitosan is distributed with a large number of hydroxyl and amino groups and a small number of acetyl groups, and the chitosan shows a plurality of unique chemical properties due to the groups. Chitosan has film forming and bacteriostatic properties, can be used as a thickener, an emulsifier and a stabilizer, and is widely applied in the food industry. The chitosan also has extremely important application in the aspect of water treatment, and can be used as an adsorbent, an ion exchanger, a flocculant, a membrane preparation and the like, and can be used for decoloring dye wastewater, recovering heavy metal ions,Purification of drinking water and softening of hard water, etc. Chitosan is a novel water treatment material with excellent performance, and the performance of chitosan is more and more concerned by researchers.
However, the problems of high wastewater treatment difficulty caused by high water quality fluctuation, low speed, low efficiency and unstable treatment effect of the catalyst for catalyzing ozone to generate free radicals generally exist in the prior art, and the conventional heterogeneous catalyst is not easy to recover and is easy to cause secondary pollution.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a printing and dyeing wastewater treatment process with high ozone utilization rate and high purification efficiency.
The invention provides a treatment process for degrading printing and dyeing wastewater by ozone catalysis, which adopts a nitrogen and cobalt co-doped cerium oxide nanotube magnetic catalyst as a heterogeneous catalyst to catalyze ozone to generate OH active free radicals, thereby realizing the efficient removal of various dyes in the printing and dyeing wastewater.
The treatment process for degrading printing and dyeing wastewater by catalytic ozone comprises the following steps:
filtering a certain amount of printing and dyeing wastewater to remove particles in the wastewater, adding the wastewater into a 1L flask, adjusting the pH of the wastewater to 4.5-8.5 by adding acid or alkali, and introducing N into the wastewater2Until no residual oxygen exists in the wastewater, adding a certain amount of nitrogen and cobalt co-doped cerium oxide nanotube magnetic catalyst, introducing stable ozone airflow into the wastewater at room temperature, and controlling the flow of ozone to be 10-40 mg-L by adjusting the current of an ozone generator-1H, catalyzing ozone to react for a period of time to complete the degradation of the printing and dyeing wastewater.
The mass volume ratio of the nitrogen-cobalt co-doped cerium oxide nanotube magnetic catalyst to the printing and dyeing wastewater is 5-15 g: 1L, and the time for catalyzing the ozone reaction is 0.1-2.5 h.
The nitrogen and cobalt co-doped cerium oxide nanotube magnetic catalyst for catalyzing ozone degradation of printing and dyeing wastewater takes magnetic chitosan as a substrate, enhances the stability of the chitosan in an acid environment through crosslinking, and then loads N, Co co-doped CeO2Nanotubes of which N, Co is co-doped with CeO2The nanotube is deposited on the pore channel and the surface position of the substrate, and the specific preparation steps are as follows:
one, magnetic Fe3O4Preparing nano particles: preparation of Fe by chemical coprecipitation method3O4Nano-particles: in N2Under protection, FeCl is added2·4H2O and FeCl3·6H2Dissolving O in distilled water, and fully mixing under the action of magnetic stirring; heating the solution to 85-95 ℃, dropwise adding ammonia water, reacting at the rotating speed of 500-700 rpm for 1-2 h, separating by using a magnet after the reaction is finished, repeatedly washing by using distilled water until the solution is neutral, and then drying in vacuum to obtain magnetic Fe3O4And (3) nanoparticles.
Wherein FeCl2·4H2O and FeCl3·6H2The molar ratio of O is 1 (1.7-2); FeCl2·4H2O and NH in ammonia3The molar ratio of (1), (10-15), and magnetic Fe3O4The particle size of the nanoparticles is 20-50 nm.
II, SiO2Coated magnetic Fe3O4Preparing nano particles: to avoid magnetic Fe3O4The nanoparticles are dissolved in the process of loading on chitosan due to the existence of an acidic solvent, and a thin layer of SiO is coated on the surface of the nanoparticles2. Taking the Fe prepared in the step one3O4Placing the nano particles into a three-neck flask, sequentially adding 20-50% by volume of ethanol aqueous solution, ammonia water and tetraethyl orthosilicate, and reacting for 22-25 h at the temperature of 30-40 ℃ and the rotating speed of 200-300 rpm; after the reaction is finished, separating the product by using a magnet, repeatedly washing the product by using distilled water until the filtrate is neutral, and drying the filtrate in vacuum to obtain SiO2Coated magnetic Fe3O4A nanoparticle;
wherein Fe3O4The volume ratio of the ethanol aqueous solution with the mass and volume fraction of 20-50% (0.1 g-1 g) is 100m L, the volume ratio of the ammonia water, the tetraethyl orthosilicate and the ethanol aqueous solution with the volume fraction of 20-50% is 1: 3-5: 150-200, and the SiO is2The thickness of the thin layer is 5-10 nm。
Thirdly, preparing a substrate: dissolving chitosan in acetic acid solution, adding the above SiO2Encapsulated magnetic Fe3O4Uniformly stirring the nano particles, and then adding a cross-linking agent to obtain a gel substance, namely the chitosan substrate loaded with the magnetic particles;
wherein the concentration of the acetic acid solution is 0.5-1 wt%, and SiO2Encapsulated magnetic Fe3O4The mass ratio of the nano particles to the chitosan is 1: 5-8, the cross-linking agent is glutaraldehyde, and the addition amount of the cross-linking agent is 20-65 wt% of the mass of the chitosan;
tetra, N, Co codoped CeO2Preparing the nanotube: weighing 0.5-0.9 g Ce (NO)3)3·6H2Dissolving O and 1.5-2.0 g of urea in 80-100 m L deionized water, stirring for 30-60 min, transferring the solution into a 200-250 m L round-bottom flask, stirring for 24-48 h in an oil bath at 80-90 ℃, cooling, and centrifugally drying to obtain Ce (OH) CO3. Weighing 0.2-0.4 g Ce (OH) CO3Dispersing the solid in 40-80 m L deionized water, adding 0.05-0.1 g Co (NH)2)6Cl3Stirring with 4.5-5 g of NaOH for 30-45 min, transferring to a reaction kettle of 100-150 m L, reacting for 24-36 h at 120-130 ℃, cooling to room temperature, filtering, respectively cleaning with absolute ethyl alcohol and deionized water for 3 times, drying the obtained solid at 120 ℃ for 20h to obtain N, Co yellow powder co-doped with CeO2A nanotube.
NaOH is CeO in hydrothermal process2Nucleation of nanotubes, tubular curling provides a strong alkaline environment, while Co (NH)2)6Cl3Then the CeO is simultaneously used as a nitrogen source and a cobalt source2In-situ doping the nanotube, carrying out hydrothermal reaction, and adding N into CeO2The content of the nano tube is 4.5-6.5 wt%, and Co is in CeO2The content of the nano-tube is 3.5-5.2 wt%.
Fifthly, preparing a catalyst for catalyzing ozone to degrade printing and dyeing wastewater: n, Co codoped CeO2Dispersing the nanotubes in distilled water by ultrasonic dispersion to obtain suspension, adding into 200m L chitosan base solution prepared in step three, performing ultrasonic treatment at 40 deg.C for 20min, and adjusting water bath temperature to 60 deg.CThe pH value is 9-10, and the mixture is stirred and reacted for 2-4 hours to obtain the catalyst;
CeO codoped with N, Co therein2The mass ratio of the nanotube to the chitosan substrate is 1:10 to 15.
The reactive orange 14 is orange powder, is easy to dissolve in water, has the solubility of 60 g/L in water at 20 ℃, is 130 g/L at 50 ℃, contains a plurality of benzene rings, N-containing heterocyclic rings, ketone groups and the like in the structure, is difficult to degrade, and can cause water pollution if existing in water, so the reactive orange 14 is selected as a target pollutant to simulate and evaluate the catalytic efficiency of the catalytic material.
Compared with the prior art, the invention has the following advantages:
1. compared with the prior art, the method for treating printing and dyeing wastewater by catalytic ozone has the advantages of simple operation, easily controlled reaction conditions, low cost and potential industrial application prospect;
2. the chitosan has stronger adsorption performance, can be used as a substrate of a catalyst for catalyzing ozone degradation of printing and dyeing wastewater, can realize the enrichment of dye by utilizing the adsorption of the chitosan on the dye in the wastewater, is beneficial to the reaction between the generated OH and dye molecules, reduces the resistance of the diffusion and reaction between active groups OH and the dye molecules, and improves the degradation efficiency of the printing and dyeing wastewater;
3. the introduction of the magnetic particles can improve the recyclability of the catalyst, reduce the loss of the catalyst and reduce the cost of the degradation of the printing and dyeing wastewater;
4. in the catalyst for catalyzing ozone to degrade printing and dyeing wastewater, NaOH is CeO2Nucleation of nanotubes provides a suitably strongly alkaline environment, while Co (NH)2)6Cl3Then the CeO is simultaneously used as a nitrogen source and a cobalt source2The nano tube is doped in situ, and the co-doping of N, Co element can obviously improve the speed of the catalyst for catalyzing ozone to generate OH active groups, thereby improving the efficiency of catalyzing ozone to degrade printing and dyeing wastewater.
Detailed Description
The invention will now be further illustrated by reference to specific examples.
Example 1 preparation of magnetic Chitosan substrate
One, magnetic Fe3O4Preparing nano particles: preparation of Fe by chemical coprecipitation method3O4Nano-particles: in N2Under protection, FeCl is added according to a molar ratio of 1:1.92·4H2O and FeCl3·6H2Dissolving O in distilled water, and fully mixing under the action of magnetic stirring; heating the solution to 90 deg.C according to FeCl2·4H2O and NH3Adding ammonia water dropwise at a molar ratio of 1:10, reacting at 600rpm for 1h, separating with magnet after reaction, washing with distilled water repeatedly until the solution is neutral, and vacuum drying to obtain magnetic Fe with average particle diameter of 30nm3O4And (3) nanoparticles.
II, SiO2Coated magnetic Fe3O4Preparing nano particles: to avoid magnetic Fe3O4The nanoparticles are dissolved in the process of loading on chitosan due to the existence of an acidic solvent, and a thin layer of SiO is coated on the surface of the nanoparticles2. 0.2g of Fe obtained in step one3O4Placing the nanoparticles in a three-neck flask, sequentially adding 200m L volume percent 20% ethanol water solution, 1m L ammonia water and 3m L tetraethyl orthosilicate, reacting at 30 ℃ and 20rpm for 22h, separating the product by using a magnet after the reaction is finished, repeatedly washing the product by using distilled water until the filtrate is neutral, and drying in vacuum to obtain SiO2Coated magnetic Fe3O4A nanoparticle; wherein SiO is2The thickness of the thin layer was 5 nm.
Thirdly, preparing the magnetic chitosan substrate: 8g of chitosan was dissolved in 0.5wt% acetic acid solution, to which the above 1g of SiO was added2Encapsulated magnetic Fe3O4Uniformly stirring the nano particles, and then adding 10wt% of glutaraldehyde to obtain a gel substance, namely the chitosan substrate loaded with the magnetic particles;
EXAMPLE 2 Nitrogen, cobalt codoped CeO2Preparation of nanotubes
0.7g of Ce (NO) is weighed3)3·6H2Dissolving O and 1.8g urea in 80m L deionized water, stirring for 40min, and transferring the solution toTransferring into 200m L round bottom flask, stirring in 80 deg.C oil bath for 24 hr, cooling, centrifuging, and drying to obtain Ce (OH) CO3. Weighing 0.3g of Ce (OH) CO3The solid was dispersed in 50m L deionized water, and 0.08g Co (NH) was added2)6Cl3Stirring with 5g NaOH for 30min, transferring into a 100m L reaction kettle, reacting at 120 deg.C for 24h, cooling to room temperature, filtering, washing with anhydrous ethanol and deionized water for 3 times, drying the solid at 120 deg.C for 20h to obtain N, Co yellow powder co-doped with CeO2A nanotube.
EXAMPLE 3 preparation of catalyst for catalyzing ozone degradation of printing and dyeing wastewater
N, Co codoped CeO prepared in example 22Dispersing the nano-tube in distilled water, performing ultrasonic dispersion to obtain a suspension, adding the suspension into 200m L chitosan substrate solution containing the chitosan prepared in the example 1, performing ultrasonic treatment at 40 ℃ for 20min, adjusting the water bath temperature to 60 ℃ and the system pH to 9, and stirring for reaction for 4h to obtain the catalyst, wherein N, Co codoped CeO is N, Co2The mass ratio of the nanotube to the chitosan substrate is 1: 11.
comparative example 1 conventional CeO2Preparation of nanoparticle-supported catalyst
Selecting commercially available CeO with average particle size of 30nm2Nanoparticles, loaded on a magnetic chitosan substrate according to the method of example 3, with CeO2The mass ratio of the nanoparticles to the chitosan substrate was 1: 11.
Comparative example 2 preparation of catalyst for degrading printing and dyeing wastewater by catalyzing ozone through co-doping of nitrogen and cobalt
Nitrogen-free, cobalt-codoped CeO was prepared as in example 22Nanotubes, with the difference that no Co (NH) is added during the preparation2)6Cl3The nitrogen-free, cobalt-codoped CeO was then subjected to the procedure of example 32The nanotube is loaded on a magnetic chitosan substrate, wherein nitrogen and cobalt co-doped CeO are not contained2The mass ratio of the nanotube to the chitosan substrate is 1: 11.
Example 4 method for degrading reactive orange 14 wastewater
Dye molecule investigation catalyst with reactive orange 14 as modelActivity of catalyst for catalyzing ozone degradation, namely preparing 3 parts of active orange 14 solution with the concentration of 1 mol/L, each 600m L, adding the solution into a 1L flask respectively, adjusting the pH of wastewater to 7.5 by adding acid or alkali, and introducing N into the solution respectively2Until no residual oxygen exists in the wastewater, 4g of the catalysts prepared in example 3, comparative example 1 and comparative example 2 are added into the wastewater respectively, a stable ozone gas flow is introduced into the wastewater at room temperature, and the flow rate of the ozone is controlled to be 15 mg-L by adjusting the current of an ozone generator-1H, catalyzing ozone reaction, sampling 5m L every 10min to analyze the purification degree of wastewater by different catalysts, and the specific data are shown in the following table 1:
TABLE 1 degradation Activity of different samples on reactive orange 14
As can be seen from the data analysis in Table 1, compared with ordinary CeO2Catalyst is loaded on nano particles, CeO is added2Is adjusted into a nano tube, and further is used for CeO2N, Co, the catalyst has significant improvement on the activity of inducing ozone to generate active groups OH, because the nano tube is formed by curling and shrinking a nano sheet in a strong alkaline environment, the specific surface area of the nano sheet is larger relative to the nano particle under the same mass, and the exposed active surface is relatively more, and the doping of N, Co can further improve the activity of catalyzing ozone to generate active groups, so that the printing and dyeing wastewater can be efficiently and completely degraded.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (4)
1. A treatment process for degrading printing and dyeing wastewater by catalytic oxidation of ozone is characterized by comprising the following steps:
filtering a certain amount of printing and dyeing wastewater to remove particles in the wastewater, adding the wastewater into a 1L flask, adjusting the pH of the wastewater to 4.5-8.5 by adding acid or alkali, and introducing N into the wastewater2Until no residual oxygen exists in the wastewater, adding a certain amount of nitrogen and cobalt co-doped cerium oxide nanotube magnetic catalyst, introducing stable ozone airflow into the wastewater at room temperature, and controlling the flow of ozone to be 10-40 mg-L by adjusting the current of an ozone generator-1H, catalyzing ozone to react for a period of time and then finishing degradation of the printing and dyeing wastewater;
the mass volume ratio of the nitrogen-cobalt co-doped cerium oxide nanotube magnetic catalyst to the printing and dyeing wastewater is 5-15 g: 1L, and the time for catalyzing the ozone reaction is 0.1-2.5 h;
the preparation method of the nitrogen and cobalt co-doped cerium oxide nanotube magnetic catalyst comprises the following steps:
one, magnetic Fe3O4Preparing nano particles: preparation of Fe by chemical coprecipitation method3O4Nano-particles: in N2Under protection, FeCl is added2·4H2O and FeCl3·6H2Dissolving O in distilled water, and fully mixing under the action of magnetic stirring; heating the mixed solution to 85-95 ℃, dropwise adding ammonia water, reacting at the rotating speed of 500-700 rpm for 1-2 h, separating by using a magnet after the reaction is finished, repeatedly washing by using distilled water until the solution is neutral, and then drying in vacuum to obtain magnetic Fe3O4A nanoparticle;
II, SiO2Coated magnetic Fe3O4Preparing nano particles: to avoid magnetic Fe3O4The nanoparticles are dissolved in the process of loading on chitosan due to the existence of an acidic solvent, and a thin layer of SiO is coated on the surface of the nanoparticles2Taking the Fe prepared in the step one3O4Placing the nano particles into a three-neck flask, sequentially adding 20-50% by volume of ethanol aqueous solution, ammonia water and tetraethyl orthosilicate, and reacting for 22-25 h at the temperature of 30-40 ℃ and the rotating speed of 200-300 rpm; after the reaction is completed, the product is separated by using a magnet and is repeatedly used with distilled waterWashing until the filtrate is neutral, and vacuum drying to obtain SiO2Coated magnetic Fe3O4A nanoparticle;
thirdly, preparing a substrate: dissolving chitosan in acetic acid solution, adding the above SiO2Encapsulated magnetic Fe3O4Uniformly stirring the nano particles, and then adding a cross-linking agent to obtain a gel substance, namely the chitosan substrate loaded with the magnetic particles;
tetra, N, Co codoped CeO2Preparing the nanotube: weighing 0.5-0.9 g Ce (NO)3)3·6H2Dissolving O and 1.5-2.0 g of urea in 80-100 m L deionized water, stirring for 30-60 min, transferring the solution into a 200-250 m L round-bottom flask, stirring for 24-48 h in an oil bath at 80-90 ℃, cooling, and centrifugally drying to obtain Ce (OH) CO3Weighing 0.2-0.4 g Ce (OH) CO3Dispersing the solid in 40-80 m L deionized water, adding 0.05-0.1 g Co (NH)2)6Cl3Stirring with 4.5-5 g of NaOH for 30-45 min, transferring to a reaction kettle of 100-150 m L, reacting for 24-36 h at 120-130 ℃, cooling to room temperature, filtering, respectively cleaning with absolute ethyl alcohol and deionized water for 3 times, drying the obtained solid at 120 ℃ for 20h to obtain N, Co yellow powder co-doped with CeO2Nanotube, N in CeO after hydrothermal reaction2The content of the nano tube is 4.5-6.5 wt%, and Co is in CeO2The content of the nano tube is 3.5-5.2 wt%;
fifthly, preparing a catalyst for catalyzing ozone to degrade printing and dyeing wastewater: n, Co codoped CeO2Dispersing the nanotubes in distilled water, performing ultrasonic dispersion to obtain a suspension, adding the suspension into 200m L chitosan substrate solution containing the chitosan prepared in the third step, performing ultrasonic treatment at 40 ℃ for 20min, adjusting the water bath temperature to 60 ℃, adjusting the pH of the system to 9-10, and stirring for reaction for 2-4 h to obtain the catalyst, wherein N, Co codoped CeO is used as the catalyst2The mass ratio of the nanotube to the chitosan substrate is 1:10 to 15.
2. The process for treating printing and dyeing wastewater by ozone-catalyzed oxidative degradation according to claim 1, wherein FeCl is added in the first step2·4H2O and FeCl3·6H2The molar ratio of O is 1 (1.7-2); FeCl2·4H2O and NH in ammonia3The molar ratio of (1), (10-15), and magnetic Fe3O4The particle size of the nanoparticles is 20-50 nm.
3. The process for treating printing and dyeing wastewater by ozone-catalyzed oxidative degradation as claimed in claim 1, wherein in the second step, Fe3O4The volume ratio of the ethanol aqueous solution with the mass and volume fraction of 20-50% (0.1 g-1 g) is 100m L, the volume ratio of the ammonia water, the tetraethyl orthosilicate and the ethanol aqueous solution with the volume fraction of 20-50% is 1: 3-5: 150-200, and the SiO is2The thickness of the thin layer is 5-10 nm.
4. The process for treating printing and dyeing wastewater by catalytic oxidative degradation by ozone as claimed in any of claims 1 to 3, wherein the concentration of the acetic acid solution is 0.5 to 1wt%, and SiO is used as the catalyst2Encapsulated magnetic Fe3O4The mass ratio of the nano particles to the chitosan is 1: 5-8, the cross-linking agent is glutaraldehyde, and the addition amount of the cross-linking agent is 20-65 wt% of the mass of the chitosan.
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