CN108217905B - 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 61
- 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 34
- 238000007639 printing Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000000593 degrading effect Effects 0.000 title claims description 9
- 238000006555 catalytic reaction Methods 0.000 title description 4
- 239000011651 chromium Substances 0.000 claims abstract description 41
- 239000002073 nanorod Substances 0.000 claims abstract description 36
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 17
- 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
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- 239000000203 mixture Substances 0.000 claims description 15
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- 238000002360 preparation method Methods 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 8
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
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- 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
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 239000004471 Glycine Substances 0.000 claims description 4
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- 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
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
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- 238000003760 magnetic stirring Methods 0.000 claims description 3
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- 239000002904 solvent Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000010525 oxidative degradation reaction Methods 0.000 claims 3
- 230000000694 effects Effects 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229910052755 nonmetal Inorganic materials 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 9
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 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
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- 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
- 150000004676 glycans Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
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- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 description 2
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
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- 241000282836 Camelus dromedarius Species 0.000 description 1
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- 239000002696 acid base indicator Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000012670 alkaline solution Substances 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
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
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- 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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- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 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
- 230000006698 induction Effects 0.000 description 1
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- 239000003999 initiator Substances 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 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
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- 239000002562 thickening agent Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
- 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
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- C02F1/78—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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (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 catalyst of a chromium and nitrogen co-doped cerium oxide nanorod magnetic catalyst, has high catalytic ozone degradation activity due to a special nanorod structure of active components of the catalyst and co-doping of metal chromium elements and non-metal nitrogen elements, and has the advantages of simplicity in 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 chromium and nitrogen co-doped cerium oxide nanorod catalyst, which adopts a chromium and nitrogen co-doped cerium oxide nanorod magnetic catalyst, has a special nanorod structure of the active component of the catalyst, and has high catalytic ozone degradation activity due to co-doping of a metal chromium element and a non-metal nitrogen element, and has the advantages of simple operation, low cost, high degradation efficiency and the like.
Background
The waste water discharged from the printing and dyeing process is a mixture of various waste waters produced by reprocessing natural and man-made fiber materials in printing and dyeing mills, spinning mills, knitting mills, silk mills, and the like. The waste water mainly contains impurities such as dye, slurry, assistant, oil agent, acid and alkali, fiber, inorganic salt and the like due to the complex types of the dye, and the chemical components of the waste water comprise benzene series, naphthalene series, anthraquinone series and the like. Therefore, the printing and dyeing wastewater has the characteristics of complex components, high content of refractory organic pollutants (up to 5 ten thousand mg/L), high chroma, high Chemical Oxygen Demand (COD), high Biochemical Oxygen Demand (BOD), high alkalinity, high toxicity, large water quantity, large water quality change and the like. If the water is drunk by animals or absorbed by plants, toxic and harmful pollutants in the water can be accumulated in the bodies of the animals and the plants and are difficult to discharge. The printing and dyeing wastewater contains various organic matters with biological toxicity or causing 'three causes' (carcinogenesis, teratogenesis and mutagenesis), is a difficult point in industrial sewage treatment and is a big problem to be continuously solved for controlling water pollution at home and abroad at present.
At present, the printing and dyeing wastewater is usually treated by adsorption, biological method, chemical method, and the like. 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 chain reaction can be initiated or terminated by the presence of many substances in water, and different actions are takenThey are classified into initiators, accelerators and inhibitors of free radicals.
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, CTS) is a derivative of the natural polysaccharide chitin, chitin reserves in nature are second only to cellulose, which is widely present in crabs, shrimps, and shrimpsThe outer shell of crustaceans such as insects and the cell wall of phycomycetes. The chitosan is obtained after the chitin is hydrolyzed under the alkaline condition and partial acetyl is removed. Free amino groups on the molecular chain of chitosan make the chitosan appear weak alkaline, and the chitosan is the only alkaline polysaccharide existing in nature. The chitosan is insoluble in water and alkaline solution, and soluble in most organic acids and part of inorganic acids such as dilute HCl and HNO3And 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. Chitosan also has an extremely important application in water treatment, and can be used as an adsorbent, an ion exchanger, a flocculant, a membrane preparation and the like, and can be used for camel color of dye wastewater, recovery of heavy metal ions, purification of drinking water, softening of hard water and the like. Chitosan is a novel water treatment material with excellent performance, and the performance of chitosan is more and more concerned by researchers.
However, the problems of high wastewater treatment difficulty caused by high water quality fluctuation, low speed, low efficiency and unstable treatment effect of the catalyst for catalyzing ozone to generate free radicals generally exist in the prior art, and the conventional heterogeneous catalyst is not easy to recover and is easy to cause secondary pollution.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a printing and dyeing wastewater treatment process with high ozone utilization rate and high catalytic efficiency.
The invention provides a treatment process for degrading printing and dyeing wastewater by catalyzing ozone, which adopts a chromium and nitrogen co-doped cerium oxide nanorod 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 therein, and addingPutting the wastewater into a 1L flask, adjusting the pH of the wastewater to 6-9 by adding acid or alkali, and then introducing N into the wastewater2Until no residual oxygen exists in the wastewater, then adding a certain amount of chromium and nitrogen co-doped cerium oxide nanorod magnetic catalyst, introducing stable ozone airflow into the wastewater at room temperature, and controlling the ozone flow to be 12-24 mg.L by adjusting the current of an ozone generator-1H, catalyzing ozone to react for a period of time to complete the degradation of the printing and dyeing wastewater.
Wherein the mass-to-volume ratio of the chromium and nitrogen co-doped cerium oxide nanorod magnetic catalyst to the printing and dyeing wastewater is 5-10 g: 1L, and the time for catalyzing the ozone reaction is 0.2-2 h.
The chromium and nitrogen codoped cerium oxide nanorod 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 Cr and N codoped CeO2Nanorods of CeO doped with Cr and N2The nano-rod is deposited on the pore and the surface of the substrate, and the preparation method comprises the following specific steps:
one, magnetic Fe3O4Preparing nano particles: preparation of Fe by chemical coprecipitation method3O4Nano-particles: in N2Under protection, FeCl is added2·4H2O and FeCl3·6H2Dissolving O in distilled water, and fully mixing under the action of magnetic stirring; heating the solution to 85-95 ℃, dropwise adding ammonia water, reacting at the rotating speed of 500-700 rpm for 1-2 h, separating by using a magnet after the reaction is finished, repeatedly washing by using distilled water until the solution is neutral, and then drying in vacuum to obtain magnetic Fe3O4And (3) nanoparticles.
Wherein FeCl2·4H2O and FeCl3·6H2The molar ratio of O is 1 (1.7-2); FeCl2·4H2O and NH in ammonia3The molar ratio of (1), (10-15), and magnetic Fe3O4The particle size of the nanoparticles is 20-50 nm.
II, SiO2Coated magnetic Fe3O4Preparing nano particles: to avoid magnetic Fe3O4The nanoparticles are dissolved in the process of loading on chitosan due to the existence of an acidic solvent, and a thin layer of SiO is coated on the surface of the nanoparticles2. Taking the Fe prepared in the step one3O4Placing the nano particles into a three-neck flask, sequentially adding 20-50% by volume of ethanol aqueous solution, ammonia water and tetraethyl orthosilicate, and reacting for 22-25 h at the temperature of 30-40 ℃ and the rotating speed of 200-300 rpm; after the reaction is finished, separating the product by using a magnet, repeatedly washing the product by using distilled water until the filtrate is neutral, and drying the filtrate in vacuum to obtain SiO2Coated magnetic Fe3O4A nanoparticle;
wherein Fe3O4The volume ratio of the ethanol water solution with the mass and volume fraction of 20-50% (0.1-1 g) is 100 mL; the volume ratio of the ammonia water to the tetraethyl orthosilicate to the ethanol water solution with the volume fraction of 20% -50% is 1: 3-5: 150 to 200 of SiO2The thickness of the thin layer is 5-10 nm.
Thirdly, preparing a substrate: dissolving chitosan in acetic acid solution, adding the above SiO2Encapsulated magnetic Fe3O4Uniformly stirring the nano particles, and then adding a cross-linking agent to obtain a gel substance, namely the chitosan substrate loaded with the magnetic particles;
wherein the concentration of the acetic acid solution is 0.5-1 wt%, and SiO2Encapsulated magnetic Fe3O4The mass ratio of the nano particles to the chitosan is 1: 5-8, the cross-linking agent is glutaraldehyde, and the addition amount of the cross-linking agent is 20-65 wt% of the mass of the chitosan;
four, Cr, N codoped CeO2Preparing the nano-rods: weighing 0.73-1.25 g Ce (NO)3)3·6H2Dissolving O and 5.8-10.2 g NaOH in 5mL and 35mL of deionized water respectively, mixing the two solutions, adding 0.1-0.2 g of chromium glycine into the mixed solution, stirring the mixture uniformly, transferring the mixture into a 100mL hydrothermal reaction kettle, reacting the mixture for 10-12 h at 100 ℃, cooling the mixture, filtering the mixture, washing the mixture for three times by using absolute ethyl alcohol and deionized water, and drying the mixture for 8-12 h at 40-80 ℃ to obtain yellow powder, namely Cr and N co-doped CeO2And (4) nanorods.
NaOH is CeO in hydrothermal process2Nucleation, crimping provision of nanorodsIn strong alkaline environment, chromium glycine is used as both nitrogen source and chromium source in CeO2N, Cr in-situ co-doping in nano-rod, and performing Cr in CeO after hydrothermal reaction2The content of the nano-rods is 1.1-2.3 wt%, and N is in CeO2The content of the nano-rods is 0.6-2.1 wt%.
Fifthly, preparing a catalyst for catalyzing ozone to degrade printing and dyeing wastewater: co-doped CeO of Cr and N2Dispersing the nano rods in distilled water, performing ultrasonic dispersion to obtain a suspension, adding the suspension into 200mL of chitosan substrate solution containing the chitosan prepared in the step three, performing ultrasonic treatment for 20min at 40 ℃, then adjusting the water bath temperature to 60 ℃, adjusting the pH of the system to 9-10, and performing stirring reaction for 2-4 h to obtain the catalyst;
wherein Cr and N are codoped with CeO2The mass ratio of the nano rod to the chitosan substrate is 1:10 to 15.
Congo red is brownish red powder, is yellow red when dissolved in water and orange when dissolved in alcohol, is used as an acid-base indicator and in the paper industry, and can cause water pollution if existing in water, so Congo red is selected as a target pollutant to simulate and evaluate the catalytic efficiency of a 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. NaOH is CeO in hydrothermal process2The nucleation and the curling of the nano-rod provide a strong alkaline environment, and the chromium glycinate is used as the chromium glycinateAs nitrogen source and chromium source in CeO2N, Cr in-situ co-doping is carried out in the nano-rods, and the co-doping of Cr and N elements 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 1:22·4H2O and FeCl3·6H2Dissolving O in distilled water, and fully mixing under the action of magnetic stirring; heating the solution to 90 deg.C according to FeCl2·4H2O and NH3Adding ammonia water dropwise at a molar ratio of 1:10, reacting at 600rpm for 1h, separating with magnet after reaction, washing with distilled water repeatedly until the solution is neutral, and vacuum drying to obtain magnetic Fe with average particle diameter of 35nm3O4And (3) nanoparticles.
II, SiO2Coated magnetic Fe3O4Preparing nano particles: to avoid magnetic Fe3O4The nanoparticles are dissolved in the process of loading on chitosan due to the existence of an acidic solvent, and a thin layer of SiO is coated on the surface of the nanoparticles2. 0.2g of Fe obtained in step one3O4Placing the nano particles into a three-neck flask, sequentially adding 200mL of ethanol aqueous solution with the volume fraction of 20%, 1mL of ammonia water and 3mL of tetraethyl orthosilicate, and reacting for 22h at the temperature of 30 ℃ and the rotating speed of 20 rpm; after the reaction is finished, separating the product by using a magnet, repeatedly washing the product by using distilled water until the filtrate is neutral, and drying the filtrate in vacuum to obtain SiO2Coated magnetic Fe3O4A nanoparticle; wherein SiO is2The thickness of the thin layer was 5 nm.
Thirdly, preparing the magnetic chitosan substrate: dissolving 8g of chitosan in 0.5wt% acetic acid solution, addingTo 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 Co-doping of CeO with chromium and Nitrogen2Preparation of nanorods
0.95g of Ce (NO) is weighed out3)3·6H2Dissolving O and 8.2g NaOH in 5mL and 35mL of deionized water respectively, mixing the two solutions, adding 0.18g of chromium glycinate, stirring uniformly, transferring into a 100mL hydrothermal reaction kettle, reacting for 12h at 100 ℃, cooling, filtering, washing with absolute ethyl alcohol and deionized water for three times, and drying for 12h at 80 ℃ to obtain yellow powder, namely Cr and N codoped CeO2And (4) nanorods.
EXAMPLE 3 preparation of catalyst for catalyzing ozone degradation of printing and dyeing wastewater
Cr and N-codoped CeO prepared in example 22Dispersing nanorods in distilled water, performing ultrasonic dispersion to obtain a suspension, adding the suspension into 200mL of chitosan substrate solution containing the chitosan prepared in example 1, performing ultrasonic treatment at 40 ℃ for 20min, adjusting the water bath temperature to 60 ℃, adjusting the pH of the system to 9, and stirring for reaction for 4h to obtain a catalyst; wherein Cr and N are codoped with CeO2The mass ratio of the nano rod to the chitosan substrate is 1: 14.
comparative example 1 conventional CeO2Preparation of nanoparticle-supported catalyst
Selecting commercially available CeO with average particle size of 25nm2Nanoparticles, loaded on a magnetic chitosan substrate according to the method of example 3, with CeO2The mass ratio of the nanoparticles to the chitosan substrate was 1: 14.
Comparative example 2 preparation of catalyst for degrading printing and dyeing wastewater by using chromium-free and nitrogen-doped catalytic ozone
Chromium-free, Nitrogen-free CeO was prepared as in example 22Nanorods, except that no chromium glycine was added during the preparation, and then the chromium-free, nitrogen-doped CeO was added according to the method of example 32The nano-rod is loaded on a magnetic chitosan substrate, wherein, CeO is doped without chromium and nitrogen2Nanorods and shellsThe mass ratio of the glycan substrate was 1: 14.
Example 4 method for degrading Congo Red wastewater
The Congo red is used as a model dye molecule to investigate the catalytic activity of the catalyst on ozone degradation: preparing 600mL of 3 Congo red solutions with the concentration of 1mol/L, adding the solutions into a 1L flask respectively, adjusting the pH of the wastewater to 6 by adding acid or alkali, and introducing N into the solutions respectively2Until no residual oxygen exists in the wastewater, 5g of the catalysts prepared in example 3, comparative example 1 and comparative example 2 are added into the wastewater respectively, a stable ozone gas flow is introduced into the wastewater at room temperature, and the flow rate of the ozone is controlled to be 15 mg.L by adjusting the current of an ozone generator-1H, catalyzing ozone reaction, sampling 5mL every 10min to analyze the purification degree of wastewater by different catalysts, and the specific data are shown in the following table 1:
TABLE 1 Congo Red degrading Activity of different samples
As can be seen from the data analysis in Table 1, compared with ordinary CeO2Catalyst is loaded on nano particles, CeO is added2The morphology of the CeO is adjusted to be a nano rod, and further the CeO is added2After the co-doping of Cr and N is carried out, the activity of the catalyst for inducing ozone to generate active groups OH is remarkably improved, the nano rod is formed by curling, shrinking and nucleating the nano sheet in a strong alkaline environment, the specific surface area of the nano sheet is larger relative to that of nano particles under the same quality, the exposed active surface is relatively more, and the co-doping of N, Cr can further improve the activity of the catalyst, so that the efficient and complete degradation of printing and dyeing wastewater can be realized.
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 6-9 by adding acid or alkali, and introducing N into the wastewater2Until no residual oxygen exists in the wastewater, then adding a certain amount of chromium and nitrogen co-doped cerium oxide nanorod magnetic catalyst, introducing stable ozone airflow into the wastewater at room temperature, and controlling the ozone flow to be 12-24 mg.L by adjusting the current of an ozone generator-1H, catalyzing ozone to react for a period of time and then finishing degradation of the printing and dyeing wastewater; wherein the mass-to-volume ratio of the chromium and nitrogen co-doped cerium oxide nanorod magnetic catalyst to the printing and dyeing wastewater is 5-10 g: 1L, the time for catalyzing the ozone reaction is 0.2-2 h, and the preparation method of the chromium and nitrogen co-doped cerium oxide nanorod 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 finished, separating the product by using a magnet, and repeatedly washing the product by using distilled water until filtrate is obtainedNeutral, 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;
four, Cr, N codoped CeO2Preparing the nano-rods: weighing 0.73-1.25 g Ce (NO)3)3·6H2Dissolving O and 5.8-10.2 g of NaOH in 5mL and 35mL of deionized water respectively, mixing the two solutions, adding 0.1-0.2 g of chromium glycine into the mixed solution, stirring the mixture uniformly, transferring the mixture into a 100mL hydrothermal reaction kettle, reacting the mixture for 10-12 h at 100 ℃, cooling the mixture, filtering the mixture, washing the mixture for three times by using absolute ethyl alcohol and deionized water, and drying the mixture for 8-12 h at 40-80 ℃ to obtain yellow powder, namely Cr and N co-doped CeO2A nanorod;
fifthly, preparing a catalyst for catalyzing ozone to degrade printing and dyeing wastewater: CeO doped with Cr and N2Dispersing the nano rods in distilled water, performing ultrasonic dispersion to obtain a suspension, adding the suspension into 200mL of chitosan substrate solution containing the chitosan prepared in the step three, performing ultrasonic treatment for 20min at 40 ℃, then adjusting the water bath temperature to 60 ℃, adjusting the pH of the system to 9-10, and performing stirring reaction for 2-4 h to obtain the catalyst; wherein Cr and N are codoped with CeO2The mass ratio of the nano rod 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 water solution with the mass and volume fraction of 20-50% (0.1-1 g) is 100 mL; the volume ratio of the ammonia water to the tetraethyl orthosilicate to the ethanol water solution with the volume fraction of 20% -50% is 1: 3-5: 150 to 200 of SiO2The thickness of the thin layer is 5-10 nm.
4. The process for treating printing and dyeing wastewater by catalytic oxidative degradation by ozone as claimed in claim 1, wherein the concentration of the acetic acid solution is 0.5 to 1wt%, 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.
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