CN111957320B - Supported catalyst filter fiber for catalytic degradation of pollutants in water, and preparation and application thereof - Google Patents
Supported catalyst filter fiber for catalytic degradation of pollutants in water, and preparation and application thereof Download PDFInfo
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- CN111957320B CN111957320B CN202010742861.2A CN202010742861A CN111957320B CN 111957320 B CN111957320 B CN 111957320B CN 202010742861 A CN202010742861 A CN 202010742861A CN 111957320 B CN111957320 B CN 111957320B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000000835 fiber Substances 0.000 title claims abstract description 63
- 230000015556 catabolic process Effects 0.000 title claims abstract description 23
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 title abstract description 13
- 239000003344 environmental pollutant Substances 0.000 title abstract description 7
- 231100000719 pollutant Toxicity 0.000 title abstract description 7
- 239000003292 glue Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 21
- 230000000593 degrading effect Effects 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 11
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 11
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims abstract description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 claims description 10
- 239000002351 wastewater Substances 0.000 claims description 9
- 238000005273 aeration Methods 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 6
- 229940039748 oxalate Drugs 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 6
- 229940039790 sodium oxalate Drugs 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims 1
- 238000010525 oxidative degradation reaction Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 23
- 238000003756 stirring Methods 0.000 description 17
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- BQSLGJHIAGOZCD-CIUDSAMLSA-N Leu-Ala-Ser Chemical compound CC(C)C[C@H](N)C(=O)N[C@@H](C)C(=O)N[C@@H](CO)C(O)=O BQSLGJHIAGOZCD-CIUDSAMLSA-N 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- QJRVOJKLQNSNDB-UHFFFAOYSA-N 4-dodecan-3-ylbenzenesulfonic acid Chemical compound CCCCCCCCCC(CC)C1=CC=C(S(O)(=O)=O)C=C1 QJRVOJKLQNSNDB-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000002068 microbial inoculum Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000000941 radioactive substance Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
-
- 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
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
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Abstract
The invention belongs to the technical field of catalysts, and discloses a supported catalyst filter fiber for catalyzing and degrading pollutants in water, and preparation and application thereof. The method comprises the following steps: 1) preparation of the catalyst: mixing potassium permanganate, potassium ferrate, soluble oxalate metal salt and cobalt salt dissolved in water, carrying out hydrothermal reaction for 7-14 h at 100-130 ℃, and carrying out subsequent treatment to obtain a catalyst; 2) uniformly mixing a catalyst, water and glue to obtain a glue solution; and coating the glue solution on the surface of the non-woven fabric, and drying to obtain the catalyst-loaded filter fiber. The method is simple, and the prepared supported catalyst filter fiber can efficiently degrade organic pollutants in water at normal temperature, so that the organic matters in the water can be rapidly enriched on the surface of the catalyst, and the purpose of rapid catalytic degradation is achieved. The supported catalyst filter fiber is used for oxidative degradation of organic pollutants in water.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a catalyst filter fiber for catalyzing and degrading organic matters in water at normal temperature, and preparation and application thereof in degrading organic pollutants.
Background
Water is one of the important natural resources essential for human survival and development. At present, with the industrial development and the great increase of human demands, a great amount of water body pollutants are generated in industrial production, and serious threats are caused to the water environment.
The pollutants in the water resource are heavy metals and pathogenicBacteria, radioactive substances and organic pollutants. Wherein the organic pollutants have the largest pollution to the environment and human health, and the organic pollutants have the characteristics of large discharge amount and difficult degradation. The existing methods for treating organic pollutants mainly comprise biological methods, physical methods and chemical methods. The microbial treatment method has long treatment period, large occupied area of treatment equipment and high requirement on the activity of the microbes. Physical treatment methods such as adsorption, extraction and the like do not essentially eliminate organic pollutants, and have the risk of secondary pollution. The advanced oxidation technology in the chemical method is based on the utilization of radicals with strong oxidation capacity in a system, such as hydroxyl radicals (. OH), sulfate radicals and the like, to carry out oxidative decomposition on pollutants in a water body. At present, the advanced oxidation technology mainly comprises Fenton (Fenton) and Fenton-like methods, photocatalysis, electrochemical oxidation methods, ozone oxidation methods and the like. The Fenton oxidation method uses a Fenton reagent (H)2O2And Fe2+) OH generated by catalytic decomposition attacks organic molecules, and the organic substances are gradually oxidized into inorganic substances such as carbon dioxide and water. The Fenton oxidation method has the advantages of mild reaction conditions, simplicity in operation, no secondary pollution caused by reaction and the like, the Fenton oxidation method has high reaction speed, so that the degradation persistence of the Fenton oxidation method on pollutants is low, and H is low2O2The effective utilization rate of the organic matters is low, so that the organic matters are not completely degraded. The cost of treating wastewater completely by means of the Fenton method is very high, and the method is not beneficial to practical application. The photocatalytic oxidation method is characterized in that a photocatalyst generates strong oxidizing free radicals under the action of light to degrade organic matters. Widely used photocatalysts are mainly n-type semiconductors with wide forbidden bands, such as TiO2The mechanism may be that OH, which is more oxidizing, is generated by reaction with hydroxyl groups or chemically adsorbed water on the surface. The photocatalyst has the advantages of stable chemical property, mild reaction condition, easy control of operation and the like. The defects of high recombination probability of electron-hole pairs, low quantum yield and the like limit TiO due to insufficient absorption wavelength range, low sunlight utilization rate and catalytic degradation only under the irradiation of limited light waves2And other photocatalysts are used on a large scale in water treatment.
At present, common surfactants in wastewater, such as linear alkyl benzene sulfonic acid sodium (LAS), potassium hydrogen phthalate, Dimethylacetamide (DMAC), cause serious harm to the water environment, and the degradation difficulty is high. Domestic and foreign methods for treating LAS wastewater include adsorption method, coagulation method, biodegradation method, membrane separation method and the like, and in the patent application CN 106754532A, the composite microbial inoculum is adopted to treat the wastewater containing the surfactant, so that the LAS treatment system is difficult to operate and the investment cost is high.
Patent application CN 109096140A adopts rectification purification technology to retrieve the DMAC, but in actual technology recovery process, the long-time heating of DMAC solution that contains acid or alkali is easily decomposed to dimethylamine, and simple rectification and decompression rectification are all difficult to avoid the condition of DMAC pyrolysis to it is big to consume energy. Currently, there are few reports on the removal of potassium hydrogen phthalate from water.
Disclosure of Invention
Aiming at the problem of water pollution at present and the problem that organic matters which are difficult to degrade are difficult to effectively remove by adopting the traditional wastewater treatment process, the invention aims to provide a supported catalyst filter fiber for catalyzing and degrading organic pollutants in water and a preparation method thereof. According to the invention, the transition metal manganese-based hybrid catalyst is loaded on the non-woven fabric fibers, and the obtained product can efficiently degrade LAS, DMAC and potassium hydrogen phthalate under the normal temperature condition, so that the wastewater can be efficiently treated.
The invention also aims to provide application of the supported catalyst filter fiber. The supported catalyst filter fiber is used for oxidative degradation of organic pollutants in water. The organic pollutants are more than one of LAS, DMAC and potassium hydrogen phthalate.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a catalyst-loaded filter fiber comprises the following steps:
(1) preparation of the catalyst: mixing potassium permanganate, potassium ferrate, soluble oxalate metal salt and cobalt salt dissolved in water, carrying out hydrothermal reaction for 7-14 h at 100-130 ℃, and carrying out subsequent treatment to obtain a catalyst;
(2) preparation of the supported catalyst filter fiber: uniformly mixing a catalyst, water and glue to obtain a glue solution; and coating the glue solution on the surface of the non-woven fabric, and drying to obtain the catalyst-loaded filter fiber.
The soluble oxalate metal salt is more than one of sodium oxalate or potassium oxalate;
the cobalt salt dissolved in water is more than one of cobalt chloride or cobalt nitrate.
The mass ratio of the potassium permanganate to the potassium ferrate to the soluble oxalate metal salt to the water-soluble cobalt salt is (1-5): (1-5): (1-5): (1-5).
The mass volume ratio of the potassium permanganate to the water is (1-5) kg: (20-100) L; the water here is the water in the "mixing in water" in step (1).
The subsequent treatment is water washing and drying treatment. The drying condition is drying for 1-10h at 50-150 ℃.
The glue in the step (2) is polyurethane glue.
In the step (2), the mass ratio of the catalyst to the water to the glue is (1-3): (0.5-2): (1-3).
The step (2) of uniformly mixing refers to that the catalyst and water are uniformly mixed firstly, and then the glue is added to continuously and uniformly mix.
Firstly, uniformly mixing refers to ultrasonic dispersion for 5-30 min; and the step of continuously mixing the materials is to stir the materials for 3 to 20 min.
The coating includes spraying, spin coating, dipping and the like.
The coating amount of the glue solution meets the condition that the thickness of the single-side coating is 400-500 mu m, and the glue solution is fully coated on the two surfaces of the non-woven fabric.
In the step (2), the drying temperature is 100-130 ℃, and the drying time is 1-3 h.
The supported catalyst filter fiber is used for oxidative degradation of organic pollutants in water. The organic pollutants are more than one of LAS, DMAC and potassium hydrogen phthalate.
The application specifically comprises the following steps:
adding the supported catalyst filter fibers into the wastewater containing the organic pollutants, aerating (introducing oxygen or air), reacting, and finishing the degradation of the organic pollutants.
The aeration rate is 5-10L/min.
The invention is applied to the reaction at normal temperature and normal pressure.
The addition amount of the supported catalyst filter fibers meets the following requirements: every 1g of organic pollutants needs to be added with 5g or more of supported catalyst filter fibers, namely the mass ratio of the supported catalyst filter fibers to the organic pollutants in the wastewater is not less than 5, preferably 5-20.
Compared with the prior art, the invention has the advantages that:
(1) the load catalyst fiber for catalyzing and degrading organic matters in water at normal temperature loads a catalyst for degrading the organic matters at room temperature, and the catalyst has a loose and porous space structure and a large specific surface area, so that the organic matters in water can be rapidly enriched on the surface of the catalyst fiber, and the aim of rapid catalytic degradation is fulfilled.
(2) The load catalyst fiber for catalyzing and degrading organic matters in water at normal temperature can be repeatedly used and can also be repeatedly used after being dried in the sun.
(3) The invention synthesizes the transition metal manganese, iron and cobalt mixed catalyst by nano synthesis and doping technology, so that the electron transfer efficiency of the supported catalyst fiber is improved in the catalytic degradation, the conditions required by the catalytic degradation are reduced, and the catalytic degradation of organic substances in water at normal temperature is finally realized. For normal-temperature catalytic degradation of potassium hydrogen phthalate, the COD value of a 2L initial water sample is 547, after 10 days of treatment, the COD value of the water sample is reduced to 15, and the degradation rate of LAS reaches 97.3%.
(4) The catalyst for catalyzing and degrading organic matters in water at normal temperature, which is prepared by the invention, can be tightly loaded on non-woven fabric fibers, does not remove powder, and is safe, nontoxic and free of any peculiar smell.
(5) The load catalyst fiber for catalyzing and degrading organic matters in water at normal temperature prepared by the invention has rich source of production raw materials and low price, and can be produced in large scale.
(6) Compared with the traditional method for treating the organic matters in the water, the supported catalyst fiber for catalyzing and degrading the organic matters in the water at the normal temperature, which is prepared by the invention, is more energy-saving and has lower cost.
Drawings
FIG. 1 is an SEM image of the catalyst on the supported fiber of example 1;
FIG. 2 is an SEM image of the catalyst-supporting fiber in example 2;
FIG. 3 is an SEM image of the catalyst on supported fibers of example 3;
fig. 4 is an SEM image of the catalyst on the supported fiber in example 4.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example 1
(1) Weighing 5.0kg of potassium permanganate, 4.0kg of potassium ferrate, 4.0kg of sodium oxalate and 2kg of cobalt chloride into a reaction kettle, adding 100L of distilled water, and stirring and mixing uniformly; then carrying out hydrothermal reaction for 7h at 120 ℃, naturally cooling to room temperature after the reaction is finished, soaking in distilled water and stirring for 10-30min, pouring out the water on the upper layer after the materials are slowly settled, repeating the operation for 3-5 times until the water after cleaning is colorless, and drying the cleaned materials for 3h at 110 ℃ to obtain the catalyst;
(2) according to the catalyst: water: the mass ratio of the glue (polyurethane glue, model PU800, produced by Guangzhou De Gong Mingxin environmental protection technology Co., Ltd.) is 2: 1: 1.5, adding a catalyst into water, performing ultrasonic treatment for 15min until a catalytic material forms a uniform colloidal solution in the aqueous solution, adding glue into the solution, stirring for 10min, and fully dispersing to obtain a glue solution; spraying the prepared glue solution on the front side and the back side of the non-woven fabric to form the fiber loaded with the catalyst, controlling the thickness of the single-side coating to be 400-500 mu m, and placing the fiber loaded with the catalyst at 120 ℃ for drying for 1h to obtain the fiber loaded with the catalyst for catalytically degrading the organic matters in the water. The supported catalyst fibers were cut to different sizes with scissors.
Weighing 5g of supported catalyst fiber capable of catalyzing and degrading organic matters in water, weighing 2L of distilled water, adding potassium hydrogen phthalate, mixing and stirring uniformly, measuring COD value again after 0 day, 2 days, 7 days and 10 days respectively at aeration rate of 6L/min, and measuring the unit mg/L. The control group was not provided with a filter cloth and the other conditions were the same. Table 1 is a data table of degradation data of potassium hydrogen phthalate in example 1, and "water sample COD" is an experimental group to which the supported catalyst fiber prepared in example 1 was added; "blank COD" indicates the control without nonwoven and catalyst.
TABLE 1 degradation data for potassium hydrogen phthalate in example 1
Example 2
(1) Weighing 5.0kg of potassium permanganate, 4.0kg of potassium ferrate, 4.0kg of sodium oxalate and 2kg of cobalt chloride into a reaction kettle, adding 100L of distilled water, uniformly stirring and mixing, then carrying out hydrothermal reaction for 7h at 120 ℃, naturally cooling to room temperature after the reaction is finished, soaking in distilled water and stirring for 10-30min, pouring out the water on the upper layer after the materials are slowly settled, repeatedly operating for 3-5 times until the water after cleaning has no color, and drying the cleaned materials for 3h at 110 ℃ to obtain a catalyst;
(2) catalyst: water: the mass ratio of the glue (polyurethane glue, model PU800, produced by Guangzhou De Gong Mingxin environmental protection technology Co., Ltd.) is 2: 1: 1.5, adding a catalyst into pure water, performing ultrasonic treatment for 15min until a catalytic material forms a uniform colloidal solution in an aqueous solution, adding glue into the solution, stirring for 10min, and fully dispersing to obtain a glue solution; spraying the prepared glue solution on the front surface and the back surface of the non-woven fabric to form the fiber loaded with the catalyst, controlling the thickness of the single-side coating to be 400-500 mu m, and placing the fiber loaded with the catalyst at 120 ℃ for drying for 1h to obtain the fiber loaded with the catalyst for catalytically degrading the organic matters in the water. Cut it into different sizes with scissors.
Weighing 5g of supported catalyst fiber capable of catalyzing and degrading organic matters in water, weighing 2L of distilled water, adding different amounts of LAS, mixing and stirring uniformly, and measuring COD values in mg/L in 0 day, 3 days and 5 days respectively at an aeration rate of 6L/min. The control was carried out without the addition of the supported catalyst fibers under the same conditions. Table 2 is a table of degradation data for LAS in example 2.
TABLE 2 degradation data for LAS in example 2
| Time/day | 0 | 3 | 5 |
| Water sample COD | 350 | 83 | Less than the lowest detection value |
| Blank COD | 350 | 312 | 284 |
| Time/day | 0 | 3 | 5 |
| Water sample COD | 650 | 156 | Less than the lowest detection value |
| Blank COD | 650 | 603 | 578 |
Example 3
(1) Weighing 5.0kg of potassium permanganate, 4.0kg of potassium ferrate, 4.0kg of sodium oxalate and 2kg of cobalt chloride into a reaction kettle, adding 100L of distilled water, uniformly stirring and mixing, then carrying out hydrothermal reaction for 7h at 120 ℃, naturally cooling to room temperature after the reaction is finished, soaking in distilled water and stirring for 10-30min, pouring out the water on the upper layer after the materials are slowly settled, repeatedly operating for 3-5 times until the water after cleaning has no color, drying the cleaned materials for 3h at 110 ℃, and drying for 3h at 110 ℃ to obtain the catalyst;
(2) catalyst: water: the mass ratio of the glue (polyurethane glue, model PU800, produced by Guangzhou De Gong Mingxin environmental protection technology Co., Ltd.) is 2: 1: 1.5, adding a catalyst into pure water, performing ultrasonic treatment until a catalytic material forms a uniform colloidal solution in an aqueous solution, adding a glue solution into the solution, stirring for 10min, and fully dispersing to obtain a glue solution; spraying the prepared glue solution on the front side and the back side of the non-woven fabric to form the fiber loaded with the catalyst, controlling the thickness of the single-side coating to be 400-500 mu m, and placing the fiber loaded with the catalyst at 120 ℃ for drying for 1h to obtain the fiber loaded with the catalyst for catalytically degrading the organic matters in the water. The supported catalyst fibers were cut to different sizes with scissors.
Weighing 5g of supported catalyst fiber capable of catalyzing and degrading organic matters in water, weighing 2L of distilled water, adding DMAC (dimethylacetamide), uniformly mixing and stirring, and measuring COD (chemical oxygen demand) values of water samples in units of mg/L in 0 day, 1 day and 8 days respectively at an aeration rate of 6L/min. Table 3 is a table of the degradation data for DMAC in example 3.
Table 3 degradation data for DMAC in example 3
Example 4
(1) Weighing 5.0kg of potassium permanganate, 4.0kg of potassium ferrate, 4.0kg of sodium oxalate and 2kg of cobalt chloride into a reaction kettle, adding 100L of distilled water, uniformly stirring and mixing, then carrying out hydrothermal reaction for 7h at 120 ℃, naturally cooling to room temperature after the reaction is finished, soaking in distilled water and stirring for 10-30min, pouring out the water on the upper layer after the materials are slowly settled, repeatedly operating for 3-5 times until the water after cleaning has no color, drying the cleaned materials for 3h at 110 ℃, and drying for 3h at 110 ℃ to obtain the catalyst;
(2) catalyst: water: the mass ratio of the glue (polyurethane glue, model PU800, produced by Guangzhou De Gong Mingxin environmental protection technology Co., Ltd.) is 2: 1: 1.5, adding a catalyst into pure water, performing ultrasonic treatment until a catalytic material forms a uniform colloidal solution in an aqueous solution, adding a glue solution into the solution, stirring for 10min, and fully dispersing to obtain a glue solution; spraying the prepared glue solution on the front side and the back side of the non-woven fabric to form the fiber loaded with the catalyst, controlling the thickness of the single-side coating to be 400-500 mu m, and placing the fiber loaded with the catalyst at 120 ℃ for drying for 1h to obtain the fiber loaded with the catalyst for catalytically degrading the organic matters in the water. Cut it into different sizes with scissors.
Weighing 5g of supported catalyst fiber capable of catalyzing and degrading organic matters in water, weighing 2L of distilled water, adding DMAC (dimethylacetamide), uniformly mixing and stirring, and respectively measuring COD (chemical oxygen demand) values of water samples in units of mg/L at 6L/min aeration rate and at 0 day, 3 day, 9 day, 16 day and 23 day, wherein ultraviolet lamps are used for irradiating from the third day (the illumination intensity is 3W, and the length is 7 cm). Table 4 is a table of the degradation data for DMAC in example 4.
Table 4 is the degradation data for DMAC in example 4
FIG. 1 is an SEM image of the catalyst on the supported fiber of example 1; FIG. 2 is an SEM image of the catalyst-supporting fiber in example 2; FIG. 3 is an SEM image of the catalyst on supported fibers of example 3; fig. 4 is an SEM image of the catalyst on the supported fiber in example 4. FIGS. 1-4 are SEM images at different magnifications.
Claims (5)
1. Use of a catalyst-loaded filter fiber, characterized in that: the supported catalyst filter fiber is used for oxidizing and degrading organic pollutants in water; the organic pollutants are more than one of LAS, DMAC and potassium hydrogen phthalate;
the preparation method of the supported catalyst filter fiber comprises the following steps:
(1) preparation of the catalyst: mixing potassium permanganate, potassium ferrate, soluble oxalate metal salt and cobalt salt dissolved in water, carrying out hydrothermal reaction for 7-14 h at 100-130 ℃, and carrying out subsequent treatment to obtain a catalyst;
(2) preparation of the supported catalyst filter fiber: uniformly mixing a catalyst, water and glue to obtain a glue solution; coating the glue solution on the surface of the non-woven fabric, and drying to obtain a catalyst-loaded filter fiber;
the soluble oxalate metal salt is more than one of sodium oxalate or potassium oxalate;
the cobalt salt dissolved in water is more than one of cobalt chloride or cobalt nitrate;
the mass ratio of the potassium permanganate to the potassium ferrate to the soluble oxalate metal salt to the water-soluble cobalt salt is (1-5): (1-5): (1-5): (1-5);
the mass volume ratio of the potassium permanganate to the water is (1-5) kg: (20-100) L.
2. Use according to claim 1, characterized in that: in the step (2), the mass ratio of the catalyst to the water to the glue is (1-3): (0.5-2): (1-3).
3. Use according to claim 1, characterized in that:
the glue in the step (2) is polyurethane glue;
the coating amount of the glue solution meets the condition that the thickness of the single-side coating is 400-500 mu m, and the glue solution is fully coated on the two surfaces of the non-woven fabric.
4. Use according to claim 1, characterized in that: the subsequent treatment in the step (1) is water cleaning and drying treatment;
the step (2) of uniformly mixing refers to that the catalyst and water are uniformly mixed firstly, and then the glue is added to continuously and uniformly mix;
the drying temperature in the step (2) is 100-130 ℃; the drying time is 1-3 h.
5. Use according to claim 1, characterized in that: the method specifically comprises the following steps:
adding the supported catalyst filter fibers into the wastewater containing the organic pollutants, aerating, reacting, and finishing the degradation of the organic pollutants;
aeration means introducing oxygen or air;
the addition amount of the supported catalyst filter fibers meets the following requirements: every 1g of organic pollutant needs to be added with 5g or more of supported catalyst filter fiber, namely the mass ratio of the supported catalyst filter fiber to the organic pollutant in the wastewater is more than or equal to 5.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919755A (en) * | 2006-09-15 | 2007-02-28 | 合肥工业大学 | Method of processing organic contaminant waste-water difficult to biochemical degradation using tetravalent manganese compounds |
| KR20170030872A (en) * | 2015-09-10 | 2017-03-20 | 한국과학기술연구원 | Catalysis for activation of persulfate, method of manufacturing the same, and method of degrading recalcitrant organic compounds using the same |
| CN107954543A (en) * | 2017-11-21 | 2018-04-24 | 东莞市联洲知识产权运营管理有限公司 | A kind of method of catalytic degradation waste water containing SDBS |
| CN110624403A (en) * | 2019-09-24 | 2019-12-31 | 华南理工大学 | Filter screen with formaldehyde and odor removing functions and preparation and application thereof |
| CN110721704A (en) * | 2019-10-30 | 2020-01-24 | 华南理工大学 | Catalytic cloth with ethylene catalytic degradation function, preparation and application |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919755A (en) * | 2006-09-15 | 2007-02-28 | 合肥工业大学 | Method of processing organic contaminant waste-water difficult to biochemical degradation using tetravalent manganese compounds |
| KR20170030872A (en) * | 2015-09-10 | 2017-03-20 | 한국과학기술연구원 | Catalysis for activation of persulfate, method of manufacturing the same, and method of degrading recalcitrant organic compounds using the same |
| CN107954543A (en) * | 2017-11-21 | 2018-04-24 | 东莞市联洲知识产权运营管理有限公司 | A kind of method of catalytic degradation waste water containing SDBS |
| CN110624403A (en) * | 2019-09-24 | 2019-12-31 | 华南理工大学 | Filter screen with formaldehyde and odor removing functions and preparation and application thereof |
| CN110721704A (en) * | 2019-10-30 | 2020-01-24 | 华南理工大学 | Catalytic cloth with ethylene catalytic degradation function, preparation and application |
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