CN114618592A - Preparation method of efficient heterogeneous Fenton catalyst and application of efficient heterogeneous Fenton catalyst in printing and dyeing wastewater treatment - Google Patents
Preparation method of efficient heterogeneous Fenton catalyst and application of efficient heterogeneous Fenton catalyst in printing and dyeing wastewater treatment Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000004043 dyeing Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000004065 wastewater treatment Methods 0.000 title abstract description 7
- 239000002351 wastewater Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000002135 nanosheet Substances 0.000 claims abstract description 19
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 16
- 238000004729 solvothermal method Methods 0.000 claims abstract description 15
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000013110 organic ligand Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 229920000742 Cotton Polymers 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- 239000004744 fabric Substances 0.000 claims description 19
- 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 13
- 238000000926 separation method Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 150000002505 iron Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 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
- 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 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000000975 dye Substances 0.000 claims 1
- 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
- -1 and meanwhile Substances 0.000 abstract description 7
- 239000013082 iron-based metal-organic framework Substances 0.000 abstract description 7
- 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010525 oxidative degradation reaction Methods 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000007788 liquid Substances 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
- 239000007789 gas Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000009826 distribution Methods 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
- 238000012545 processing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 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
- 229940032296 ferric chloride Drugs 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002841 Lewis acid Substances 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
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052742 iron 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
- 238000010907 mechanical stirring Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 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
- 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]
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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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
- B01J35/612—Surface area less than 10 m2/g
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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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- 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
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- B01J2531/84—Metals of the iron group
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- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- 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
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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Abstract
The invention provides a preparation method of an efficient heterogeneous Fenton catalyst and application of the efficient heterogeneous Fenton catalyst in printing and dyeing wastewater treatment. The preparation method comprises the following steps: preparing FeOCl nanosheets from anhydrous ferric trichloride by adopting a partial thermal decomposition method, adding the FeOCl nanosheets, a metallic ferric salt and an organic ligand into a solvent to perform solvothermal reaction, and after the reaction is finished, performing post-treatment to obtain the high-efficiency heterogeneous Fenton catalyst FeOCl @ Fe-MOFs. The preparation method of the invention adoptsThe FeOCl @ Fe-MOFs heterogeneous Fenton catalyst with a core-shell structure is prepared by a solvothermal method, organic pollutants in wastewater are adsorbed to the surface of the catalyst by utilizing the strong adsorption performance of Fe-MOFs, and meanwhile, Fe active sites and H are enhanced2O2Acceleration H of2O2The electrons are transferred to Fe (III), and the conversion of Fe (III) to Fe (II) is accelerated, thereby catalyzing H2O2Fast decomposing to generate more hydroxyl free radicals, enhancing the oxidative degradation of organic pollutants in water, obviously reducing the COD of the wastewater and improving the BOD5The COD value, the biodegradability of the printing and dyeing wastewater is improved.
Description
Technical Field
The invention belongs to the technical field of printing and dyeing wastewater treatment, and particularly relates to an efficient heterogeneous Fenton catalyst FeOCl @ Fe-MOFs, a preparation method thereof and application thereof in printing and dyeing wastewater treatment.
Background
With the pursuit of people on living quality, the demand on textiles is continuously improved, and polyester-cotton fabrics have the characteristics of polyester and cotton fabrics, have the characteristics of skin friendliness, comfort, wear resistance, stable size and the like, and are widely applied to the manufacture of various clothes.
The printing and dyeing processing is a key technical link for ensuring the quality of textiles and improving the added value of the textiles, the printing and dyeing characteristics of polyester fibers and cotton fibers are required to be considered in the printing and dyeing processing of polyester cotton fabrics, reactive dyes and disperse dyes are generally selected for dyeing, and a large amount of printing and dyeing auxiliaries such as salt, alkali, surfactants and the like are required to be added in the printing and dyeing processing process. The water content of the polyester-cotton fabric printing and dyeing wastewater is large, the components are complex, and especially some dye intermediates such as some difficultly-degraded aromatic hydrocarbon derivatives cause the COD (chemical oxygen demand) of the polyester-cotton fabric printing and dyeing wastewater to be high and BOD (biochemical oxygen demand) of the polyester-cotton fabric printing and dyeing wastewater5Low COD and poor biodegradability, and the direct discharge of the pollutants into the natural water body causes serious harm.
The current methods for treating the printing and dyeing wastewater mainly comprise an adsorption method, a membrane separation method, a coagulation method, an oxidation method, a biological method and the like. The physical methods such as adsorption method, membrane separation method, coagulation method and the like can not thoroughly remove organic pollutants, which is easy to cause secondary pollution and has higher cost. The biological method has low operation cost and is not easy to cause secondary pollution, but the microorganism has higher requirement on the storage environment and has low removal efficiency on some dye intermediates which are difficult to degrade.
The advanced oxidation method can efficiently mineralize and degrade refractory organic pollutants in the printing and dyeing wastewater of the polyester-cotton fabrics by generating active oxygen species with strong oxidizing property in a reaction system, thereby improving the biodegradability of the wastewater. Wherein the heterogeneous Fenton oxidation technology is used for catalyzing hydrogen peroxide to be effectively decomposed into hydroxyl radicals through the iron-based catalyst, so that organic pollutants are degraded by oxidation, the COD of the sewage is reduced, and the BOD is improved5COD, increased wastewater productivityAnd (4) performing chemical treatment. The existing heterogeneous Fenton catalyst has the defects of low catalytic efficiency, poor stability, narrow pH application range and the like.
Therefore, an economical, stable heterogeneous Fenton catalyst with high activity over a wide pH range was developed for reducing COD and increasing BOD5COD, the improvement of biodegradability is particularly important.
Disclosure of Invention
Aiming at the defects of the prior heterogeneous Fenton oxidation treatment technology of polyester-cotton fabric printing and dyeing wastewater, 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 purpose of the invention is realized by the following scheme:
a preparation method of an efficient heterogeneous Fenton catalyst FeOCl @ Fe-MOFs comprises the following steps:
(1) fully grinding anhydrous ferric trichloride into powder, and obtaining FeOCl nanosheets by adopting a partial thermal decomposition method;
(2) adding FeOCl nanosheets, metallic iron salt and organic ligand into a solvent, and fully mixing to obtain a FeOCl @ Fe-MOFs precursor mixed solution;
(3) and carrying out solvothermal reaction on the precursor mixed solution, and after the reaction is finished, carrying out centrifugal separation and vacuum drying to obtain the high-efficiency heterogeneous Fenton catalyst FeOCl @ Fe-MOFs.
In the step (1), the anhydrous ferric trichloride is preferably 200-300 ℃, and is preferably 2-3 h; the heating temperature for partial thermal decomposition is further preferably 220 ℃ and the heating time is preferably 2 hours.
In the step (2), the metal salt 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 metallic iron salt to the FeOCl nanosheet is preferably 1: (1 to 2.5), more preferably 1: 2; the molar optimal ratio of the metal iron salt to the organic ligand is 1: (0.5 to 1.5), and more preferably 1: 1; the mass-volume ratio of the metal iron salt to the solvent is optimized to be 1: (20-60), more preferably 1: 50. and (2) uniformly mixing by adopting magnetic stirring or mechanical stirring.
The solvothermal reaction in step (3) may be carried out in a stainless steel reactor containing a polytetrafluoroethylene lining.
Preferably, the reaction temperature is 60-120 ℃, the reaction time is 3-10 h, more preferably 150 ℃, and the reaction time is 3 h
Preferably, the following post-treatment is carried out after the solvothermal reaction is completed:
and centrifuging the reaction liquid to separate solid from liquid, and further vacuum drying the obtained solid to obtain the high-efficiency heterogeneous Fenton catalyst FeOCl @ Fe-MOFs.
Preferably, the vacuum drying temperature is 60-100 ℃, the vacuum drying time is 5-10 h, and further preferably, the vacuum drying temperature is 100 ℃, and the vacuum drying time is 10 h.
A high-efficiency neutral heterogeneous Fenton catalyst FeOOF is prepared by the preparation method.
The application of the high-efficiency 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 and adding hydrogen peroxide into the wastewater containing the organic pollutants; wherein the pH is 3-7, the COD is 10-2000 mg/L, BOD5The 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 high-efficiency heterogeneous Fenton catalyst FeOCl @ Fe-MOFs can be carried out in a constant-temperature gas bath shaking table, the high-efficiency heterogeneous Fenton catalyst FeOCl @ Fe-MOFs is added into organic wastewater with COD of 10-2000 mg/L, and then hydrogen peroxide is added to react for 5-30 min in the constant-temperature gas bath shaking table. Measuring COD and BOD of the wastewater before and after treatment5/COD。
The invention adopts a solvothermal method to prepare an efficient heterogeneous Fenton catalyst FeOCl @ Fe-MOFs, the Fe-MOFs is coated on the surface of a FeOCl nanosheet to form a core-shell structure, and organic pollution in wastewater is caused by utilizing the larger specific surface area and the stronger adsorption property of the Fe-MOFsThe substances are adsorbed on the surface of the catalyst, and simultaneously, the high-efficiency catalytic activation performance of FeOCl under the wide pH condition is utilized to catalyze hydrogen peroxide to be effectively decomposed into hydroxyl radicals, oxidize and mineralize organic pollutants which are difficult to degrade in the wastewater, reduce the COD of the wastewater, and improve the BOD5COD, increased biodegradability.
The catalyst of the invention can improve the heterogeneous Fenton reaction in catalyzing H2O2The ability of effectively decomposing into hydroxyl free radicals improves the utilization ratio of the hydroxyl free radicals, can widen the application range of heterogeneous Fenton reaction, and can be applied to the field of polyester-cotton fabric printing and dyeing wastewater treatment with complex components, high COD and poor biodegradability.
Compared with the prior art, the invention has the following advantages:
(1) the invention provides a preparation method and application of an efficient heterogeneous Fenton catalyst FeOCl @ Fe-MOFs, wherein the FeOCl @ Fe-MOFs heterogeneous Fenton catalyst is prepared by a solvothermal method, the Fe-MOFs is coated on the surface of the FeOCl by adopting the design of a core-shell structure, and organic pollutants in wastewater are adsorbed to the surface of the catalyst by utilizing the strong adsorption performance of the Fe-MOFs, so that the effective decomposition of hydrogen peroxide into hydroxyl radicals is accelerated, and the utilization rate of the hydroxyl radicals is improved, so that the capability of the system for mineralizing and degrading the organic pollutants in the wastewater is enhanced.
(2) FeOCl and Fe-MOFs in the catalyst FeOCl @ Fe-MOFs have higher Lewis acid sites, and can strengthen Fe and H2O2Acceleration H of2O2The electrons are transferred to Fe (III), and the conversion of Fe (III) to Fe (II) is accelerated, thereby catalyzing H2O2The fast decomposition produces more hydroxyl free radicals, strengthens the oxidative degradation of organic pollutants in water, obviously reduces the COD of the waste water, and improves the biodegradability of the waste water.
Drawings
FIG. 1 is an SEM picture of the high-efficiency heterogeneous Fenton catalyst FeOCl @ Fe-MOFs prepared in example 1.
Detailed Description
The technical solution of the present invention will be further illustrated by the following examples.
Example 1
A preparation method of an efficient heterogeneous Fenton catalyst FeOCl @ Fe-MOFs comprises the following steps:
(1) fully grinding anhydrous ferric trichloride into powder, and heating at 220 ℃ for 2 hours to obtain FeOCl nanosheets;
(2) adding 2.0 g of FeOCl nanosheet, 2.5192 g of ferric trichloride hexahydrate and 1.5484 g of terephthalic acid into 125 mL of DMF solvent, and fully mixing to obtain a FeOCl @ Fe-MOFs precursor mixed solution;
(3) and transferring the precursor mixed solution into a stainless steel reaction kettle containing a polytetrafluoroethylene lining for solvothermal reaction, reacting for 3 h at 150 ℃, carrying out solid-liquid separation after the reaction is finished, and carrying out vacuum drying on the obtained solid for 10 h at 100 ℃ to obtain the high-efficiency heterogeneous Fenton catalyst FeOCl @ Fe-MOFs.
The prepared high-efficiency heterogeneous Fenton catalyst FeOCl @ Fe-MOFs is characterized in that a layer of Fe-MOFs is covered on the surface of FeOCl, and octahedral Fe-MOFs crystals exist in a sample (as shown in figure 1). The heterogeneous Fenton catalyst has rich pore structure (the pore diameter is distributed at 2-80 nm) and large specific surface area (8.74 m)2g-1）。
Application performance testing
Experiments are carried out by selecting the dyeing wastewater of polyester-cotton blended fabrics in a Shaoxing printing and dyeing mill of Zhejiang, and the pH value is 6.18, the COD is 628 mg/L, and the BOD is measured5176 mg/L, BOD5The COD was 0.28. 50mL of the wastewater is weighed into a beaker, the pH value of the wastewater is adjusted to be 4, and 5 mg of the FeOCl @ Fe-MOFs is added to be fully dispersed. Fixing the beaker filled with the reaction solution on a constant-temperature gas bath shaking table, adding 75 mu L 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 the Fenton reaction, sampling after 30min, and testing the COD and BOD of the treated wastewater5/COD。
The results show that after heterogeneous Fenton oxidation treatment, COD is 301 mg/L from 628 mg/L, the removal rate of COD reaches 52 percent, and BOD is achieved5Reduced to 126 mg/L, BOD5The COD is 0.418, and the biodegradability is obviously improved.
The heterogeneous Fenton catalyst FeOCl @ Fe-MOFs with the core-shell structure is prepared by a solvothermal method. The catalyst has high Fenton activity, the effective decomposition efficiency of catalytic hydrogen peroxide is obvious, and the provided 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 processing wastewater such as polyester-cotton blended fabrics.
Example 2
A preparation method of an efficient heterogeneous Fenton catalyst FeOCl @ Fe-MOFs comprises the following steps:
(1) fully grinding anhydrous ferric trichloride into powder, and heating at 250 ℃ for 2 hours to obtain FeOCl nanosheets;
(2) adding 2.0 g of FeOCl nanosheet, 2.5192 g of ferric trichloride hexahydrate and 1.5484 g of terephthalic acid into 125 mL of DMF solvent, and fully mixing to obtain a FeOCl @ Fe-MOFs precursor mixed solution;
(3) and transferring the precursor mixed solution into a stainless steel reaction kettle containing a polytetrafluoroethylene lining for solvothermal reaction, reacting for 3 h at 150 ℃, carrying out solid-liquid separation after the reaction is finished, and carrying out vacuum drying on the obtained solid for 10 h at 100 ℃ to obtain the high-efficiency heterogeneous Fenton catalyst FeOCl @ Fe-MOFs.
The prepared efficient heterogeneous Fenton catalyst FeOCl @ Fe-MOFs has the pore size distribution of 2-120 nm and a large specific surface area (8.82 m)2g-1）。
Application performance testing
Experiments are carried out by selecting the dyeing wastewater of polyester-cotton blended fabrics in a Shaoxing printing and dyeing mill of Zhejiang, and the pH value is 6.18, the COD is 628 mg/L, and the BOD is measured5176 mg/L, BOD5The COD was 0.28. The test method was the same as in example 1.
The results show that after heterogeneous Fenton oxidation treatment, COD is 342 mg/L from 628 mg/L, the removal rate of COD reaches 45.5 percent, and BOD is achieved5Reduced to 138.5 mg/L, BOD5The COD is 0.405, and the biodegradability of the wastewater can be improved.
Example 3
A preparation method of an efficient heterogeneous Fenton catalyst FeOCl @ Fe-MOFs comprises the following steps:
(1) fully grinding anhydrous ferric trichloride into powder, and heating at 250 ℃ for 2 hours to obtain FeOCl nanosheets;
(2) adding 2.0 g of FeOCl nanosheet, 3.3589 g of ferric chloride hexahydrate and 2.0645 g of terephthalic acid into 160 mL of DMF solvent, and fully mixing to obtain a FeOCl @ Fe-MOFs precursor mixed solution;
(3) and transferring the precursor mixed solution into a stainless steel reaction kettle containing a polytetrafluoroethylene lining for solvothermal reaction, reacting for 3 h at 150 ℃, carrying out solid-liquid separation after the reaction is finished, and carrying out vacuum drying on the obtained solid for 10 h at 100 ℃ to obtain the high-efficiency heterogeneous 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)2g-1）。
Application performance testing
Experiments are carried out by selecting the dyeing wastewater of polyester-cotton blended fabrics in a Shaoxing printing and dyeing mill of Zhejiang, and the pH value is 6.18, the COD is 628 mg/L, and the BOD is measured5176 mg/L, BOD5The COD was 0.28. The test method was the same as in example 1.
The results show that after heterogeneous Fenton oxidation treatment, COD is 368 mg/L from 628 mg/L, the removal rate of COD reaches 41.1 percent, and BOD is achieved5Reduced to 151 mg/L, BOD5The COD is 0.41, and the biodegradability of the wastewater can be improved.
Example 4
A preparation method of an efficient heterogeneous Fenton catalyst FeOCl @ Fe-MOFs comprises the following steps:
(1) fully grinding anhydrous ferric trichloride into powder, and heating at 250 ℃ for 2 hours to obtain FeOCl nanosheets;
(2) adding 2.0 g of FeOCl nanosheet, 3.7655 g of ferric nitrate nonahydrate and 1.5484 g of terephthalic acid into 180 mL of DMF solvent, and fully mixing to obtain a FeOCl @ Fe-MOFs precursor mixed solution;
(3) and transferring the precursor mixed solution into a stainless steel reaction kettle containing a polytetrafluoroethylene lining for solvothermal reaction, reacting for 3 h at 150 ℃, carrying out solid-liquid separation after the reaction is finished, and carrying out vacuum drying on the obtained solid for 10 h at 100 ℃ to obtain the high-efficiency heterogeneous Fenton catalyst FeOCl @ Fe-MOFs.
PreparedThe pore size distribution of the high-efficiency heterogeneous Fenton catalyst FeOCl @ Fe-MOFs is 2-80 nm, and the specific surface area is large (8.61 m)2 g-1）。
Application performance testing
The dyeing wastewater of polyester-cotton blended fabric in a certain printing and dyeing mill from Shaoxing Zhejiang is selected for experiment, and the pH value is 6.18, the COD is 628 mg/L and the BOD is measured5176 mg/L, BOD5The COD was 0.28. The test method was the same as in example 1.
The results show that after heterogeneous Fenton oxidation treatment, COD is 315 mg/L from 628 mg/L, the removal rate of COD reaches 50.1 percent, and BOD is achieved5Reduced to 131 mg/L, BOD5The COD is 0.416, and the biodegradability of the wastewater can be improved.
Example 5
A preparation method of an efficient heterogeneous Fenton catalyst FeOCl @ Fe-MOFs comprises the following steps:
(1) fully grinding anhydrous ferric trichloride into powder, and heating at 250 ℃ for 2 hours to obtain FeOCl nanosheets;
(2) adding 2.0 g of FeOCl nanosheet, 2.5192 g of ferric trichloride hexahydrate and 1.5484 g of terephthalic acid into 125 mL of ethanol solvent, and fully mixing to obtain a FeOCl @ Fe-MOFs precursor mixed solution;
(3) and transferring the precursor mixed solution into a stainless steel reaction kettle containing a polytetrafluoroethylene lining for solvothermal reaction, reacting for 3 h at 150 ℃, carrying out solid-liquid separation after the reaction is finished, and carrying out vacuum drying on the obtained solid for 10 h at 100 ℃ to obtain the high-efficiency heterogeneous 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)2g-1）。
Application performance testing
Experiments are carried out by selecting the dyeing wastewater of polyester-cotton blended fabrics in a Shaoxing printing and dyeing mill of Zhejiang, and the pH value is 6.18, the COD is 628 mg/L, and the BOD is measured5176 mg/L, BOD5The COD was 0.28. The test method was the same as in example 1.
The result shows that after the heterogeneous Fenton oxidation treatment, the COD is 368 mg/L from 628 mg/L, the removal rate of the COD reaches 41.4 percent,BOD5reduced to 141 mg/L, BOD5The COD was 0.38.
Example 6
The printing waste water of polyester-cotton blended fabric of Shaoxing certain printing and dyeing mill of Zhejiang is selected for experiment, and the pH is 7.26, the COD is 748 mg/L, BOD is measured5270 mg/L, BOD5The COD was 0.36. 50mL of the wastewater is weighed into a beaker, the pH value of the wastewater is adjusted to 4, and 5 mg of the FeOCl @ Fe-MOFs catalyst prepared in example 1 is added to be fully dispersed. Fixing the beaker filled with the reaction solution on a constant-temperature gas bath shaking table, adding 75 mu L 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 the Fenton reaction, sampling after 30min, and testing the COD and BOD of the treated wastewater5/COD。
The results show that after heterogeneous Fenton oxidation treatment, COD is 429 mg/L from 748 mg/L, the removal rate of COD is 57 percent, and BOD is achieved5The concentration of the organic pollutants is reduced to 196 mg/L.
Example 7
Experiments are carried out by selecting the dyeing wastewater of polyester-cotton blended fabrics in a Shaoxing printing and dyeing mill of Zhejiang, and the pH value is 6.18, the COD is 628 mg/L, and the BOD is measured5176 mg/L, BOD5The COD was 0.28. 50mL of the wastewater is weighed into a beaker, the pH value of the wastewater is adjusted to 4, and 5 mg of the FeOCl @ Fe-MOFs catalyst prepared in example 1 is added to be fully dispersed. Fixing the beaker filled with the reaction solution on a constant-temperature gas bath shaking table, adding 50 mu L 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 the Fenton reaction, sampling after 30min, and testing the COD and BOD of the treated wastewater5/COD。
The results show that after the heterogeneous Fenton oxidation treatment, the COD is reduced from 628 mg/L to 397 mg/L, the removal rate of the COD is 36.7 percent, and the BOD is reduced5Reduced to 135 mg/L, BOD5The COD is 0.34, and the concentration of organic pollutants is obviously reduced.
Claims (9)
1. A preparation method of an efficient heterogeneous Fenton catalyst FeOCl @ Fe-MOFs is characterized by comprising the following steps:
(1) fully grinding anhydrous ferric trichloride into powder, and obtaining FeOCl nanosheets by adopting a partial thermal decomposition method;
(2) adding FeOCl nanosheets, metallic iron salt and organic ligand into a solvent, and fully mixing to obtain a FeOCl @ Fe-MOFs precursor mixed solution;
(3) and carrying out solvothermal reaction on the precursor mixed solution, and after the reaction is finished, carrying out centrifugal separation and vacuum drying to obtain the high-efficiency heterogeneous Fenton catalyst FeOCl @ Fe-MOFs.
2. The preparation method according to claim 1, wherein the anhydrous ferric chloride is partially thermally decomposed at a heating temperature of 200 to 400 ℃ for 1 to 4 hours in the step (1).
3. The preparation method according to claim 1, wherein the metal salt in step (2) is one or more of ferric nitrate, ferric sulfate and ferric chloride; the organic ligand is one or more of terephthalic acid and 2-methylimidazole; the solvent is ethanol or N, N-Dimethylformamide (DMF) or a mixed solvent of the ethanol and the N, N-Dimethylformamide (DMF).
4. The preparation method according to claim 1, wherein the molar ratio of the metallic iron salt to FeOCl nanosheets in step (2) is 1: (0.5 to 3); the molar ratio of the metal iron salt to the organic ligand is 1: (0.5 to 2); the mass volume ratio of the metal iron salt to the solvent is 1: (10-100).
5. The preparation method according to claim 1, wherein the reaction temperature of the solvothermal reaction in the step (3) is 50-150 ℃, and the reaction time is 2-24 h; the vacuum drying temperature is 50-100 ℃, and the drying time is 5-24 h.
6. An efficient heterogeneous Fenton catalyst FeOCl @ Fe-MOFs is characterized by being prepared by the preparation method of any one of claims 1-5.
7. The use of the high-efficiency heterogeneous Fenton catalyst FeOCl @ Fe-MOFs as defined in claim 6 for degrading organic pollutants in printing and dyeing wastewater.
8. The application of claim 7, wherein the organic pollutants in the printing and dyeing wastewater are mainly one or more of residual dyes, residual auxiliaries and dye intermediates generated in the printing and dyeing process of polyester-cotton fabrics.
9. The use according to claim 8, characterized in that to the waste water containing organic pollutants is added the high efficiency heterogeneous Fenton catalyst FeOCl @ Fe-MOFs, hydrogen peroxide; wherein the pH is 3-7, the COD is 10-2000 mg/L, BOD5the/COD is 0.2-0.5, and the mass ratio of the catalyst FeOCl @ Fe-MOFs to the hydrogen peroxide is 1: (1-10).
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| CN108899494A (en) * | 2018-06-22 | 2018-11-27 | 济宁学院 | Porous nitrogen-doped carbon intercalation coated iron oxide nano-plates material and preparation method thereof |
| US20210155514A1 (en) * | 2019-11-25 | 2021-05-27 | Northeastern University | Robust flow-through platform for organic contaminants removal |
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