CN114618592B - Preparation method of efficient heterogeneous Fenton catalyst and application of catalyst in treatment of printing and dyeing wastewater - Google Patents
Preparation method of efficient heterogeneous Fenton catalyst and application of catalyst in treatment of printing and dyeing wastewater Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 239000002351 wastewater Substances 0.000 title claims abstract description 46
- 238000004043 dyeing Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000002135 nanosheet Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000004729 solvothermal method Methods 0.000 claims abstract description 13
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 239000013110 organic ligand Substances 0.000 claims abstract description 7
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 229920000742 Cotton Polymers 0.000 claims description 19
- 239000004744 fabric Substances 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims 1
- 239000012046 mixed solvent Substances 0.000 claims 1
- 239000002064 nanoplatelet Substances 0.000 claims 1
- 239000013082 iron-based metal-organic framework Substances 0.000 abstract description 8
- 238000004065 wastewater treatment Methods 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011258 core-shell material Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 2
- 238000010525 oxidative degradation reaction Methods 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910015182 FeOF Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001492 aromatic hydrocarbon derivatives Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
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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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/612—Surface area less than 10 m2/g
-
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
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- Chemical & Material Sciences (AREA)
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Abstract
The invention provides a preparation method of a high-efficiency heterogeneous Fenton catalyst and application thereof in printing and dyeing wastewater treatment. The preparation method comprises the following steps: and preparing FeOCl nano-sheets from anhydrous ferric trichloride by adopting a partial thermal decomposition method, adding the FeOCl nano-sheets, metallic ferric salt and organic ligands into a solvent for solvothermal reaction, and after the reaction is finished, performing aftertreatment to obtain the Gao Xiaofei homogeneous Fenton catalyst FeOCl@Fe-MOFs. The preparation method adopts a solvothermal method to prepare the FeOCl@Fe-MOFs heterogeneous Fenton catalyst with a core-shell structure, and utilizes the stronger adsorption performance of the Fe-MOFs to adsorb organic pollutants in wastewater on the surface of the catalyst, and simultaneously strengthen Fe active sites and H 2 O 2 Accelerating H by interaction of 2 O 2 Electrons are transferred into Fe (III), and the conversion of Fe (III) to Fe (II) is accelerated, thereby catalyzing H 2 O 2 The method can quickly decompose to generate more hydroxyl radicals, enhance the oxidative degradation of organic pollutants in water, obviously reduce the COD of the wastewater and improve the BOD 5 The COD value improves the biodegradability of the printing and dyeing wastewater.
Description
Technical Field
The invention belongs to the technical field of printing and dyeing wastewater treatment, and particularly relates to a high-efficiency heterogeneous Fenton catalyst FeOCl@Fe-MOFs, a preparation method thereof and application thereof in printing and dyeing wastewater treatment.
Background
Along with the pursuit of people on life quality, the demand for textiles is continuously improved, and polyester cotton fabrics have the characteristics of terylene and cotton fabrics, and have the characteristics of skin friendliness, comfort, wearing resistance, dimensional stability and the like, so that the polyester cotton fabrics are widely applied to manufacturing various garments.
The dyeing process is a key technical link for ensuring the quality of textiles and improving the added value of the textiles, the dyeing characteristics of polyester fibers and cotton fibers are considered in the dyeing process of polyester cotton fabrics, reactive dyes and disperse dyes are generally selected for dyeing, and a large amount of dyeing auxiliary agents such as salt, alkali, surfactant and the like are required to be added in the dyeing process. Polyester-cotton fabric printing and dyeing wastewater with large water quantityComplex composition, especially some dye intermediates, such as some refractory aromatic hydrocarbon derivatives, so that the COD and BOD of the printing and dyeing wastewater of the polyester-cotton fabric are high 5 Low COD and poor biodegradability, and the pollutants are directly discharged into natural water bodies to cause serious harm.
The current printing and dyeing wastewater treatment methods mainly comprise an adsorption method, a membrane separation method, a coagulation method, an oxidation method, a biological method and the like. Physical methods such as an adsorption method, a membrane separation method, a coagulation method and the like cannot thoroughly remove organic pollutants, secondary pollution is easy to cause, and the cost is high. The biological method has low running cost and is not easy to cause secondary pollution, but the microorganism has higher requirements on living environment and has low removal efficiency on some nondegradable dye intermediates.
The advanced oxidation method can efficiently mineralize and degrade refractory organic pollutants in the polyester-cotton fabric printing and dyeing wastewater by generating active oxygen species with strong oxidability in a reaction system, so that the biodegradability of the wastewater is improved. Wherein the heterogeneous Fenton oxidation technology is that hydrogen peroxide is catalyzed by an iron-based catalyst to be effectively decomposed into hydroxyl free radicals, organic pollutants are oxidized and degraded, COD of sewage is reduced, and BOD is improved 5 COD, improves the biodegradability of the wastewater. The existing heterogeneous Fenton catalyst has the defects of low catalytic efficiency, poor stability, narrow applicable pH range and the like.
Thus, a heterogeneous Fenton catalyst is developed which is economical, stable and has high activity under a wide pH condition, and can reduce COD and increase BOD 5 COD, it is particularly important to improve the biodegradability.
Disclosure of Invention
Aiming at the defects existing in the current polyester-cotton fabric printing and dyeing wastewater heterogeneous Fenton oxidation treatment technology, the invention aims to provide a preparation method of a high-efficiency heterogeneous Fenton catalyst and application of the high-efficiency heterogeneous Fenton catalyst in printing and dyeing wastewater treatment
The invention aims at realizing the following scheme:
a preparation method of a high-efficiency heterogeneous Fenton catalyst FeOCl@Fe-MOFs comprises the following steps:
(1) Fully grinding anhydrous ferric trichloride into powder, and obtaining FeOCl nano-sheets by adopting a partial thermal decomposition method;
(2) Adding FeOCl nanosheets, metallic ferric salt and organic ligands into a solvent, and fully mixing to obtain FeOCl@Fe-MOFs precursor mixed solution;
(3) And carrying out solvothermal reaction on the precursor mixed solution, and carrying out centrifugal separation and vacuum drying after the reaction is finished to obtain the Gao Xiaofei homogeneous Fenton catalyst FeOCl@Fe-MOFs.
In the step (1), the temperature of the anhydrous ferric trichloride is preferably 200-300 ℃, and the time is preferably 2-3 hours; the heating temperature for partial thermal decomposition is further preferably 220℃and the heating time is preferably 2 h.
The metal salt in the step (2) is preferably one or two of ferric nitrate and ferric chloride, and is further preferably ferric chloride; the organic ligand is preferably terephthalic acid; the solvent is preferably N, N-dimethylformamide.
The molar ratio of the metal ferric salt to the FeOCl nano-sheet is preferably 1: (1 to 2.5), more preferably 1:2; the molar ratio of the metal ferric salt to the organic ligand is preferably 1: (0.5 to 1.5), more preferably 1:1, a step of; the mass volume ratio of the metal ferric salt to the solvent is optimized to be 1: (20 to 60), more preferably 1:50. and (2) uniformly mixing the materials in the step (2) in a magnetic stirring mode or a mechanical stirring mode.
The solvothermal reaction in step (3) may be carried out in a stainless steel reactor containing a polytetrafluoroethylene liner.
Preferably, the reaction temperature is 60-120 ℃, the reaction time is 3-10 h, more preferably, the reaction temperature is 150 ℃, and the reaction time is 3 h
Preferably, the solvent thermal reaction is finished and then the following post-treatment is performed:
and centrifuging the reaction solution to separate solid from liquid, and further carrying out vacuum drying on the obtained solid to obtain the Gao Xiaofei homogeneous Fenton catalyst FeOCl@Fe-MOFs.
Preferably, the vacuum drying temperature is 60-100 ℃, the vacuum drying time is 5-10 h, more preferably, the vacuum drying temperature is 100 ℃, and the vacuum drying time is 10 h.
An efficient neutral heterogeneous Fenton catalyst FeOF, prepared by the preparation method of any one of the above.
The application of the efficient heterogeneous Fenton catalyst FeOCl@Fe-MOFs in degrading organic pollutants in printing and dyeing wastewater.
Preferably, adding a high-efficiency heterogeneous Fenton catalyst FeOCl@Fe-MOFs into the wastewater containing the organic pollutants, and adding hydrogen peroxide; wherein the pH is 3-7, the COD is 10-2000 mg/L, and the BOD 5 The COD is 0.2-0.5, and the mass ratio of the catalyst to the hydrogen peroxide is 1:10.
specifically, the test of the catalytic activity of the efficient heterogeneous Fenton catalyst FeOCl@Fe-MOFs can be performed in a constant-temperature air bath shaking table, the efficient heterogeneous Fenton catalyst FeOCl@Fe-MOFs is added into organic wastewater with COD of 10-2000 mg/L, and then hydrogen peroxide is added into the organic wastewater to react for 5-30 min in the constant-temperature air bath shaking table. Determination of COD and BOD of wastewater before and after treatment 5 /COD。
The invention adopts a solvothermal method to prepare the high-efficiency heterogeneous Fenton catalyst FeOCl@Fe-MOFs, the Fe-MOFs is coated on the surface of the FeOCl nanosheet to form a core-shell structure, the organic pollutants in the wastewater are adsorbed on the surface of the catalyst by utilizing the larger specific surface area and the stronger adsorption property of the Fe-MOFs, and meanwhile, the high-efficiency catalytic activation performance of FeOCl under the wide pH condition is utilized to catalyze hydrogen peroxide to effectively decompose into hydroxyl free radicals to oxidize and mineralize organic pollutants which are difficult to degrade in the wastewater, reduce the COD of the wastewater and improve BOD 5 COD, improves biodegradability.
The catalyst of the invention can improve the heterogeneous Fenton reaction in catalyzing H 2 O 2 The capability of effectively decomposing into hydroxyl free radicals and the utilization rate of the hydroxyl free radicals are improved, the application range of the heterogeneous Fenton reaction can be widened, and the method can be applied to the fields of dyeing wastewater treatment of polyester-cotton fabrics with complex components, high COD and poor biodegradability.
Compared with the prior art, the invention has the following advantages:
(1) The preparation and application of the efficient heterogeneous Fenton catalyst FeOCl@Fe-MOFs provided by the invention adopt a solvothermal method to prepare the heterogeneous Fenton catalyst FeOCl@Fe-MOFs, and adopt a core-shell structure design to coat the Fe-MOFs on the surface of the FeOCl, so that the strong adsorption performance of the Fe-MOFs is utilized to adsorb organic pollutants in wastewater on the surface of the catalyst, the effective decomposition of hydrogen peroxide into hydroxyl free radicals is accelerated, and the utilization rate of the hydroxyl free radicals is improved, thereby enhancing the mineralization degradation capability of the system on the organic pollutants in wastewater.
(2) FeOCl and Fe-MOFs components in the catalyst FeOCl@Fe-MOFs have higher Lewis acid sites, so that Fe and H can be strengthened 2 O 2 Accelerating H by interaction of 2 O 2 Electrons are transferred into Fe (III), and the conversion of Fe (III) to Fe (II) is accelerated, thereby catalyzing H 2 O 2 More hydroxyl radicals are generated by rapid decomposition, so that the oxidative degradation of organic pollutants in water is enhanced, the COD of the wastewater is obviously reduced, and the biodegradability of the wastewater is improved.
Drawings
FIG. 1 is an SEM photograph of a highly heterogeneous Fenton catalyst FeOCl@Fe-MOFs prepared in example 1.
Detailed Description
The technical scheme of the present invention will be further described by the following examples.
Example 1
A preparation method of a high-efficiency heterogeneous Fenton catalyst FeOCl@Fe-MOFs comprises the following steps:
(1) Fully grinding anhydrous ferric trichloride into powder, and heating at 220 ℃ for 2 h to obtain FeOCl nano-sheets;
(2) Adding 2.0 g FeOCl nano-sheets, 2.5192 g ferric trichloride hexahydrate and 1.5484 g terephthalic acid into 125 mL DMF solvent, and fully mixing to obtain FeOCl@Fe-MOFs precursor mixed solution;
(3) Transferring the precursor mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining for solvothermal reaction, reacting at 150 ℃ for 3 h, performing solid-liquid separation, and vacuum drying the obtained solid at 100 ℃ for 10 h to obtain the Gao Xiaofei homogeneous Fenton catalyst FeOCl@Fe-MOFs.
The prepared high-efficiency heterogeneous Fenton catalyst FeOCl@Fe-MOFs is prepared by covering a layer of Fe-MOFs on the surface of FeOCl and exists in a sampleRegular octahedral Fe-MOFs crystals (as shown in FIG. 1). The heterogeneous Fenton catalyst has rich pore structure (pore diameter distribution is 2-80 nm) and large specific surface area (8.74 m) 2 g -1 ）。
Application Performance test
Experiments are carried out by selecting the dyeing wastewater of the polyester-cotton blended fabric in a printing and dyeing factory in Zhejiang Shaoxing, and the pH value is 6.18, the COD is 628 mg/L and the BOD is measured 5 176 mg/L BOD 5 COD was 0.28. 50mL of the wastewater was measured in a beaker, the pH of the wastewater was adjusted to 4, and 5 mg of the FeOCl@Fe-MOFs was added to the solution to be sufficiently dispersed. Fixing the beaker with the reaction liquid on a constant temperature gas bath table, adding 75 mu L of hydrogen peroxide (with the mass concentration of 30% and the density of 1.11 g/mL) into the beaker after the temperature is constant at 25 ℃, triggering Fenton reaction, sampling after 30min, and testing the COD and BOD of the treated wastewater 5 /COD。
The result shows that after heterogeneous Fenton oxidation treatment, the COD is from 628 mg/L to 301 mg/L, the COD removal rate is up to 52%, and the BOD is 5 Reduced to 126 mg/L BOD 5 COD is 0.418, and the biodegradability is improved remarkably.
The heterogeneous Fenton catalyst FeOCl@Fe-MOFs with a core-shell structure is prepared by using a solvothermal method. The catalyst has higher Fenton activity, the effective decomposition efficiency of catalytic hydrogen peroxide is remarkable, and the preparation method of the high-efficiency heterogeneous Fenton catalyst FeOCl@Fe-MOFs provides a more practical new scheme for treating multi-component fabric printing and dyeing wastewater such as polyester-cotton blending.
Example 2
A preparation method of a high-efficiency heterogeneous Fenton catalyst FeOCl@Fe-MOFs comprises the following steps:
(1) Fully grinding anhydrous ferric trichloride into powder, and heating at 250 ℃ for 2 h to obtain FeOCl nano-sheets;
(2) Adding 2.0 g FeOCl nano-sheets, 2.5192 g ferric trichloride hexahydrate and 1.5484 g terephthalic acid into 125 mL DMF solvent, and fully mixing to obtain FeOCl@Fe-MOFs precursor mixed solution;
(3) Transferring the precursor mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining for solvothermal reaction, reacting at 150 ℃ for 3 h, performing solid-liquid separation, and vacuum drying the obtained solid at 100 ℃ for 10 h to obtain the Gao Xiaofei homogeneous Fenton catalyst FeOCl@Fe-MOFs.
The prepared efficient heterogeneous Fenton catalyst FeOCl@Fe-MOFs has the pore diameter distribution of 2-120 nm and larger specific surface area (8.82 m) 2 g -1 ）。
Application Performance test
Experiments are carried out by selecting the dyeing wastewater of the polyester-cotton blended fabric in a printing and dyeing factory in Zhejiang Shaoxing, and the pH value is 6.18, the COD is 628 mg/L and the BOD is measured 5 176 mg/L BOD 5 COD was 0.28. The test method was the same as in example 1.
The result shows that after heterogeneous Fenton oxidation treatment, COD is 342 mg/L from 628 mg/L, COD removal rate is 45.5%, BOD 5 Reduced to 138.5 mg/L, BOD 5 COD is 0.405, which can improve the biodegradability of the wastewater.
Example 3
A preparation method of a high-efficiency heterogeneous Fenton catalyst FeOCl@Fe-MOFs comprises the following steps:
(1) Fully grinding anhydrous ferric trichloride into powder, and heating at 250 ℃ for 2 h to obtain FeOCl nano-sheets;
(2) Adding 2.0 g FeOCl nano-sheets, 3.3589 g ferric trichloride hexahydrate and 2.0645 g terephthalic acid into 160 mL DMF solvent, and fully mixing to obtain FeOCl@Fe-MOFs precursor mixed solution;
(3) Transferring the precursor mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining for solvothermal reaction, reacting at 150 ℃ for 3 h, performing solid-liquid separation, and vacuum drying the obtained solid at 100 ℃ for 10 h to obtain the Gao Xiaofei homogeneous Fenton catalyst FeOCl@Fe-MOFs.
The prepared efficient heterogeneous Fenton catalyst FeOCl@Fe-MOFs has the pore size distribution of 2-80 nm and a large specific surface area (9.47 m) 2 g -1 ）。
Application Performance test
Experiments are carried out by selecting the dyeing wastewater of the polyester-cotton blended fabric in a printing and dyeing factory in Zhejiang Shaoxing, the pH value is 6.18, and the COD is628 mg/L，BOD 5 176 mg/L BOD 5 COD was 0.28. The test method was the same as in example 1.
The result shows that after heterogeneous Fenton oxidation treatment, COD is 368 mg/L from 628 mg/L, COD removal rate is 41.1%, BOD 5 Reduced to 151 mg/L BOD 5 COD is 0.41, and can improve the biodegradability of the wastewater.
Example 4
A preparation method of a high-efficiency heterogeneous Fenton catalyst FeOCl@Fe-MOFs comprises the following steps:
(1) Fully grinding anhydrous ferric trichloride into powder, and heating at 250 ℃ for 2 h to obtain FeOCl nano-sheets;
(2) Adding 2.0 g FeOCl nano-sheets, 3.7655 g ferric nitrate nonahydrate and 1.5484 g terephthalic acid into 180 mL DMF solvent, and fully mixing to obtain FeOCl@Fe-MOFs precursor mixed solution;
(3) Transferring the precursor mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining for solvothermal reaction, reacting at 150 ℃ for 3 h, performing solid-liquid separation, and vacuum drying the obtained solid at 100 ℃ for 10 h to obtain the Gao Xiaofei homogeneous Fenton catalyst FeOCl@Fe-MOFs.
The prepared efficient heterogeneous Fenton catalyst FeOCl@Fe-MOFs has the pore size distribution of 2-80 nm and a large specific surface area (8.61 m) 2 g -1 ）。
Application Performance test
Experiments are carried out by selecting the dyeing wastewater of the polyester-cotton blended fabric in a printing and dyeing factory in Zhejiang Shaoxing, and the pH value is 6.18, the COD is 628 mg/L and the BOD is measured 5 176 mg/L BOD 5 COD was 0.28. The test method was the same as in example 1.
The result shows that after heterogeneous Fenton oxidation treatment, COD is from 628 mg/L to 315 mg/L, COD removal rate reaches 50.1%, BOD 5 Reduced to 131 mg/L, BOD 5 COD is 0.416, which can improve the biodegradability of the wastewater.
Example 5
A preparation method of a high-efficiency heterogeneous Fenton catalyst FeOCl@Fe-MOFs comprises the following steps:
(1) Fully grinding anhydrous ferric trichloride into powder, and heating at 250 ℃ for 2 h to obtain FeOCl nano-sheets;
(2) Adding 2.0 g FeOCl nano-sheets, 2.5192 g ferric trichloride hexahydrate and 1.5484 g terephthalic acid into an ethanol solvent of 125 mL, and fully mixing to obtain a FeOCl@Fe-MOFs precursor mixed solution;
(3) Transferring the precursor mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining for solvothermal reaction, reacting at 150 ℃ for 3 h, performing solid-liquid separation, and vacuum drying the obtained solid at 100 ℃ for 10 h to obtain the Gao Xiaofei homogeneous Fenton catalyst FeOCl@Fe-MOFs.
The prepared efficient heterogeneous Fenton catalyst FeOCl@Fe-MOFs has the pore size distribution of 2-90 nm and a large specific surface area (6.14 m) 2 g -1 ）。
Application Performance test
Experiments are carried out by selecting the dyeing wastewater of the polyester-cotton blended fabric in a printing and dyeing factory in Zhejiang Shaoxing, and the pH value is 6.18, the COD is 628 mg/L and the BOD is measured 5 176 mg/L BOD 5 COD was 0.28. The test method was the same as in example 1.
The result shows that after heterogeneous Fenton oxidation treatment, COD is 368 mg/L from 628 mg/L, COD removal rate is 41.4%, BOD 5 Reduced to 141 mg/L, BOD 5 COD was 0.38.
Example 6
Experiments are carried out by selecting the printing wastewater of the polyester-cotton blended fabric in a printing and dyeing factory in Zhejiang Shaoxing, and the pH value is 7.26, the COD is 748 mg/L and the BOD is measured 5 270 mg/L BOD 5 COD was 0.36. 50mL of the above wastewater was measured in a beaker, the pH of the wastewater was adjusted to 4, and 5 mg of the FeOCl@Fe-MOFs catalyst prepared in example 1 was added to disperse well. Fixing the beaker with the reaction liquid on a constant temperature gas bath table, adding 75 mu L of hydrogen peroxide (with the mass concentration of 30% and the density of 1.11 g/mL) into the beaker after the temperature is constant at 25 ℃, triggering Fenton reaction, sampling after 30min, and testing the COD and BOD of the treated wastewater 5 /COD。
The result shows that after heterogeneous Fenton oxidation treatment, COD is 429 mg/L from 748 mg/L, and the removal rate of COD isUp to 57%, BOD 5 The concentration of the organic pollutants is obviously reduced by being reduced to 196 mg/L.
Example 7
Experiments are carried out by selecting the dyeing wastewater of the polyester-cotton blended fabric in a printing and dyeing factory in Zhejiang Shaoxing, and the pH value is 6.18, the COD is 628 mg/L and the BOD is measured 5 176 mg/L BOD 5 COD was 0.28. 50mL of the above wastewater was measured in a beaker, the pH of the wastewater was adjusted to 4, and 5 mg of the FeOCl@Fe-MOFs catalyst prepared in example 1 was added to disperse well. Fixing the beaker with the reaction liquid on a constant temperature gas bath table, adding 50 mu L of hydrogen peroxide (with the mass concentration of 30% and the density of 1.11 g/mL) into the beaker after the temperature is constant at 25 ℃, triggering Fenton reaction, sampling after 30min, and testing the COD and BOD of the treated wastewater 5 /COD。
The result shows that after heterogeneous Fenton oxidation treatment, COD is reduced from 628 mg/L to 397 mg/L, COD removal rate is 36.7%, BOD 5 Reduced to 135 mg/L, BOD 5 The COD was 0.34 and the concentration of organic pollutants was significantly reduced.
Claims (6)
1. A preparation method of a high-efficiency heterogeneous Fenton catalyst FeOCl@Fe-MOFs is characterized by comprising the following steps:
(1) Fully grinding anhydrous ferric trichloride into powder, and obtaining FeOCl nano-sheets by adopting a partial thermal decomposition method, wherein the thermal decomposition heating temperature is 200-400 ℃, and the thermal decomposition time is 1-4 hours;
(2) Adding FeOCl nanosheets, metallic ferric salt and organic ligands into a solvent, and fully mixing to obtain FeOCl@Fe-MOFs precursor mixed solution, wherein the metallic salt is one or more of ferric nitrate, ferric sulfate and ferric chloride, the organic ligands are terephthalic acid, and the solvent is ethanol or N, N-dimethylformamide or a mixed solvent of the two;
(3) And carrying out solvothermal reaction on the precursor mixed solution, wherein the reaction temperature is 50-150 ℃, the reaction time is 2-24 hours, and after the reaction is finished, carrying out centrifugal separation and vacuum drying, wherein the drying temperature is 50-100 ℃, and the drying time is 5-24 hours, so as to obtain the Gao Xiaofei homogeneous Fenton catalyst FeOCl@Fe-MOFs.
2. The method of claim 1, wherein the molar ratio of the iron metal salt to FeOCl nanoplatelets in step (2) is 1: (0.5-3); the molar ratio of the metal ferric salt to the organic ligand is 1: (0.5-2); the mass volume ratio of the metal ferric salt to the solvent is 1: (10-100).
3. A high efficiency heterogeneous Fenton catalyst FeOCl@Fe-MOFs, characterized in that it is prepared by the preparation method of any one of claims 1-2.
4. Use of the efficient heterogeneous Fenton catalyst FeOCl@Fe-MOFs according to claim 3 for degrading organic pollutants in printing and dyeing wastewater.
5. The use according to claim 4, wherein the organic contaminants in the printing wastewater are one or more of residual dye, residual auxiliary agent and dye intermediate generated during the printing process of polyester-cotton fabric.
6. The use according to claim 5, characterized in that to the wastewater containing organic contaminants is added a highly efficient heterogeneous Fenton catalyst FeOCl@Fe-MOFs, hydrogen peroxide; wherein the pH is 3-7, the COD is 10-2000 mg/L, and the BOD 5 The mass ratio of the catalyst FeOCl@Fe-MOFs to the hydrogen peroxide is 1: (1-10).
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