CN115282977B - Preparation method and application of heterogeneous Fenton catalyst - Google Patents

Preparation method and application of heterogeneous Fenton catalyst Download PDF

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CN115282977B
CN115282977B CN202210918029.2A CN202210918029A CN115282977B CN 115282977 B CN115282977 B CN 115282977B CN 202210918029 A CN202210918029 A CN 202210918029A CN 115282977 B CN115282977 B CN 115282977B
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iron
ferroferric oxide
heterogeneous fenton
fenton catalyst
based material
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CN115282977A (en
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林娜
王胜凡
欧阳清华
张彬彬
李海波
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Hynar Water Group Corp
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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
    • B01J23/8898—Manganese, technetium or rhenium containing also molybdenum
    • 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
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8878—Chromium
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • 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
    • 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
    • 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
    • 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
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The application relates to a preparation method and application of a heterogeneous Fenton catalyst, wherein the method comprises the following steps: performing coprecipitation reaction on reducing iron powder, ferrous chloride, ferric chloride, a complexing agent and a first solvent to obtain an iron-based precipitate carrying ferroferric oxide, curing, cooling, filtering, washing and drying the iron-based precipitate carrying ferroferric oxide to obtain an iron-based material carrying nano ferroferric oxide, and preparing the iron-based material carrying nano ferroferric oxide, transition metal salt, tetrabutyl titanate and a second solvent by a sol-gel method to obtain the heterogeneous Fenton catalyst. The method can improve the stability of iron ions in the solution, avoid the precipitation of the iron ions, reduce the dosage of the medicament and the generation amount of the iron-containing sludge, realize catalysis under neutral conditions, realize the effective recovery of the catalyst and reduce the cost.

Description

Preparation method and application of heterogeneous Fenton catalyst
Technical Field
The application relates to the field of wastewater treatment, in particular to a preparation method and application of a heterogeneous Fenton catalyst.
Background
The industrial wastewater has the characteristics of high pollutant concentration, high toxicity, difficult biodegradation and the like, seriously threatens the safety of an ecological system and the health of human beings, gradually increases the wastewater treatment and emission requirements along with the gradual promotion of water pollution control work in China, and adopts proper measures to stably control the chemical quantity (COD) within the emission range of below 30mg/L, thus becoming the problem to be solved urgently in the industry.
In the design of water treatment process, in order to ensure that the COD of the effluent reaches the standard, the effluent is usually required to be subjected to secondary biochemical treatmentAdvanced oxidation advanced treatment procedures such as Fenton oxidation technology are set. Fenton oxidation is to add H into waste water under acidic condition 2 O 2 And catalyst Fe 2+ The oxidation system is formed to generate hydroxyl free radicals with strong oxidizing ability, and organic free radicals are generated with refractory organic matters in aqueous solution to destroy the structure of the organic free radicals, so that the organic radicals are oxidized and decomposed, and refractory organic matters in the traditional wastewater treatment technology are effectively removed.
At present, the Fenton oxidation technology is widely applied to the advanced treatment of industrial wastewater, but the traditional Fenton oxidation method also has some disadvantages: (1) H in the treatment of high concentration contaminants 2 O 2 The consumption of (2) is large, resulting in higher wastewater treatment cost. (2) The applicable pH value range is small, the treatment is carried out under the condition that the pH value is about 3, and the treated water still has stronger acidity. (3) The conventional Fenton reagent belongs to a homogeneous catalysis system, and effluent contains a large amount of iron ions, and subsequent treatment generates a large amount of iron-containing sludge, so that secondary pollution is easy to cause. In recent years, heterogeneous Fenton has received high attention due to wide pH value application range, small sludge yield and good treatment effect. Patent number: CN201210388172.1 proposes a "preparation method and application of heterogeneous Fenton-like catalyst", but the problem of poor stability of complexing agent and easy loss of grafted metal ions still exists. CN202110374731.2 proposes a method for controlling selective generation of oxidation active matter of iron-based Fenton catalyst, but the problems of low catalytic efficiency and incapability of realizing cyclic utilization of the catalyst under neutral pH condition exist. Therefore, it is necessary to develop a heterogeneous Fenton catalyst that has high catalytic activity, wide application range and stability.
Disclosure of Invention
In order to overcome the defects of the traditional Fenton oxidation process, the embodiment of the application provides a preparation method of a novel heterogeneous Fenton catalyst, a tartrate-EDTA-Fe complex system is constructed in the catalyst, so that the stability of iron is improved, iron ions are prevented from generating ferric hydroxide precipitation, and the pH value range suitable for Fenton reaction is widened. The zero-valent reducing iron powder is used as a matrix to form Fe in the catalyst 0 And Fe (Fe) 3+ Promotes the oxidation-reduction reaction of ferric ionsAnd the catalyst is circulated, so that the use efficiency of the catalyst is increased. The transition metal ions are grafted by a solution gel method, the transition metal ions are tightly combined with the iron-based carrier and are not easy to run off, and the stability and the catalytic efficiency of the catalyst are improved.
In order to solve the technical problems, one technical scheme adopted by the embodiment of the application is as follows:
in a first aspect, embodiments of the present application provide a method for preparing a heterogeneous Fenton catalyst, including the steps of: performing coprecipitation reaction on reduced iron powder, ferrous chloride, ferric chloride, a complexing agent and a first solvent to obtain an iron-based precipitate loaded with ferroferric oxide; curing, cooling, filtering, washing and drying the iron-based precipitate loaded with the ferroferric oxide to obtain an iron-based material loaded with nano ferroferric oxide; and preparing the iron-based material loaded with nano ferroferric oxide, transition metal salt, tetrabutyl titanate and a second solvent by a sol-gel method to obtain the heterogeneous Fenton catalyst.
Preferably, the reduced iron powder includes at least one of sponge iron powder, zero-valent iron powder, and ferrous sulfide.
Preferably, the complexing agent comprises at least one of tartrate-ethylenediamine tetraacetic acid, tartrate-diethylenetriamine pentaacetic acid.
Preferably, when the complexing agent comprises tartrate-ethylenediamine tetraacetic acid, the molar ratio of tartrate to ethylenediamine tetraacetic acid is 1:100-100:100; when the complexing agent comprises tartrate-diethylenetriamine pentaacetic acid, the molar ratio of the tartrate to the diethylenetriamine pentaacetic acid is 1:100-100:100.
Preferably, the transition metal salt comprises at least one of manganese, zinc, cobalt, copper, molybdenum, nickel, vanadium, and chromium metal salts.
Preferably, the mass ratio of the complexing agent to the iron-based material loaded with nano ferroferric oxide is 0.1:100-10:100.
Preferably, the mass ratio of the transition metal salt to the iron-based material loaded with nano ferroferric oxide is 0.01:100-50:100.
Preferably, the co-precipitation reaction of the reduced iron powder, the ferrous chloride, the ferric chloride, the complexing agent and the first solvent comprises: dispersing the reduced iron powder in ultrapure water to obtain a first dispersion liquid; adding the ferrous chloride and the ferric chloride into the first dispersion liquid, and then adding a complexing agent to obtain a mixed liquid; and adding the first solvent into the mixed solution under the protection of constant temperature gas to obtain the iron-based precipitate loaded with the ferroferric oxide.
Preferably, the preparing the iron-based material loaded with nano ferroferric oxide, transition metal salt, tetrabutyl titanate and a second solvent by a sol-gel method to obtain a heterogeneous Fenton catalyst comprises the following steps: dispersing the iron-based material loaded with nano ferroferric oxide in the second solvent to obtain second dispersion liquid; and adding tetrabutyl titanate into the second dispersion liquid, adding the transition metal salt to form gel, standing for aging, drying and grinding to obtain the heterogeneous Fenton catalyst.
In a second aspect, embodiments of the present application provide for the use of the heterogeneous Fenton catalyst described above for degrading organic contaminants in industrial wastewater treatment.
Different from the related art, the preparation method of the heterogeneous Fenton catalyst has the beneficial effects that: performing coprecipitation reaction on reducing iron powder, ferrous chloride, ferric chloride, a complexing agent and a first solvent to obtain an iron-based precipitate carrying ferroferric oxide, curing, cooling, filtering, washing and drying the iron-based precipitate carrying ferroferric oxide to obtain an iron-based material carrying nano ferroferric oxide, and preparing the iron-based material carrying nano ferroferric oxide, transition metal salt, tetrabutyl titanate and a second solvent by a sol-gel method to obtain the heterogeneous Fenton catalyst. The method can improve the stability of iron ions in the solution, avoid the precipitation of the iron ions, reduce the dosage of the medicament and the generation amount of the iron-containing sludge, realize catalysis under neutral conditions, realize the effective recovery of the catalyst and reduce the cost.
Drawings
One or more embodiments are illustrated by way of example and not limitation in the figures of the accompanying drawings, in which like references indicate similar elements, and in which the figures of the drawings are not to scale, unless expressly stated otherwise.
FIG. 1 is a flow chart of a method for preparing a heterogeneous Fenton catalyst according to an embodiment of the present application;
FIG. 2 is a schematic diagram of the S1 sub-process in FIG. 1 according to an embodiment of the present application;
fig. 3 is a schematic diagram of the S3 sub-flow in fig. 1 according to an embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be further described in detail with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
It should be noted that, if not conflicting, the various features in the embodiments of the present application may be combined with each other, which are all within the protection scope of the present application. Additionally, logical orders are illustrated in the flow chart, but in some cases, the steps illustrated or described may be performed in the order in the flow chart.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used in this specification includes any and all combinations of one or more of the associated listed items.
As shown in fig. 1, fig. 1 is a flowchart of a preparation method of a heterogeneous fenton catalyst provided in an embodiment of the present application, where the method includes:
step S1: and performing coprecipitation reaction on the reductive iron powder, ferrous chloride, ferric chloride, a complexing agent and a first solvent to obtain an iron-based precipitate loaded with ferroferric oxide.
Step S2: and curing, cooling, filtering, washing and drying the iron-based precipitate loaded with the ferroferric oxide to obtain the iron-based material loaded with the nano ferroferric oxide.
Step S3: and preparing the iron-based material loaded with nano ferroferric oxide, transition metal salt, tetrabutyl titanate and a second solvent by a sol-gel method to obtain the heterogeneous Fenton catalyst.
In the embodiment of the application, the reducing iron powder, the ferrous chloride and the ferric chloride are dispersed by a coprecipitation method, then the complexing agent is added into the dispersion liquid, the complexing agent and iron ions in the solution form a complexing system, then the first solvent is added, wherein the first solvent can be ammonia water to obtain iron-based precipitate loaded with the ferroferric oxide, the iron-based precipitate loaded with the ferroferric oxide can be cured, cooled, filtered, washed and dried to obtain the iron-based material loaded with the nano ferroferric oxide, and then the iron-based material loaded with the nano ferroferric oxide is dispersed in the second solvent, wherein the second solvent can be a mixture of absolute ethyl alcohol and glacial acetic acid, specifically, the volume ratio of the absolute ethyl alcohol to the glacial acetic acid is 3:1, tetrabutyl titanate and transition metal salt are added, and the heterogeneous Fenton catalyst is prepared by a sol-gel method.
In some embodiments, the first solvent may be sodium hydroxide, sodium hydroxide is strong alkali, and in the process of forming ferroferric oxide by using sodium hydroxide as a solvent, the formation rate of ferroferric oxide nano particles is too fast, and the ferroferric oxide nano particles are easy to agglomerate on the surface of the reducible iron powder, so that the specific surface area of the material is reduced, and therefore, a complexing agent is added in the coprecipitation process, and forms a complex with iron ions in the solution, thereby improving the stability of the iron ions, avoiding the precipitation of the iron ions, and reducing the agglomeration phenomenon.
In the embodiment of the application, the reduced iron powder is used as a base material to form Fe in the catalyst 0 And Fe (Fe) 3+ The redox reaction of (2) promotes ferric ion circulation, increases the use efficiency of the catalyst, adds complexing agent in the coprecipitation process, so that the complexing agent and ferric ions in the solution form a complexing system, the precipitation of the ferric ions is avoided, the coprecipitation method is easy to prepare nano powder materials with small granularity and uniform distribution, and the heterogeneous Fenton catalyst prepared by the sol-gel method has the following characteristics thatThe surface area is larger, the transition metal ions can be fixed on the surface of the iron-based material carrying nano ferroferric oxide, so that the transition metal elements are not easy to run off, and the transition metal ions and the iron-based material carrying nano ferroferric oxide have synergistic catalysis, so that the catalysis performance of the iron ions is enhanced, and the degradation efficiency of refractory organic matters in sewage is improved.
In some embodiments, the reducing iron powder comprises at least one of sponge iron powder, zero-valent iron powder and ferrous sulfide, further, the iron mass ratio of the reducing iron powder to ferrous chloride to ferric chloride is 10:10-10:1, and the reducing iron powder with 200 meshes is usually selected.
In some embodiments, the mass ratio of complexing agent to the iron-based material loaded with nano-ferroferric oxide is 0.1:100 to 10:100.
In some embodiments, the complexing agent comprises at least one of tartrate-ethylenediamine tetraacetic acid and tartrate-diethylenetriamine pentaacetic acid, wherein when the complexing agent comprises tartrate-ethylenediamine tetraacetic acid, the molar ratio of tartrate to ethylenediamine tetraacetic acid is 1:100-100:100; when the complexing agent comprises tartrate-diethylenetriamine pentaacetic acid, the molar ratio of the tartrate to the diethylenetriamine pentaacetic acid is 1:100-100:100, and when the complex is lithonate-ethylenediamine tetraacetic acid, the lithonate-ethylenediamine tetraacetic acid is added in the coprecipitation process, a tartrate-EDTA-Fe complex system can be constructed, the stability of iron ions can be improved, precipitation caused by the iron ions is avoided, and the catalytic efficiency is reduced; when the complex is tartrate-diethylenetriamine pentaacetic acid, tartrate-diethylenetriamine pentaacetic acid is added in the coprecipitation process, a tartrate-DTPA-Fe complex system can be constructed, the stability of iron ions can be improved, precipitation caused by the iron ions is avoided, and the catalytic efficiency is reduced.
In some embodiments, the transition metal salt includes at least one of manganese, zinc, cobalt, copper, molybdenum, nickel, vanadium, and chromium metal salts, in particular, manganese (Mn) element is manganese sulfate (MnSO 4 ) Manganese chloride (MnCl) 2 ) Adding in an equal form; the zinc (Zn) element is zinc sulfate (ZnSO) 4 ) Zinc chloride (ZnCl) 2 ) Equal form additionAdding; cobalt (Co) element is chloridized in a cobalt (CoCl) 2 ) Is added in the form of (2); the copper (Cu) element is copper sulfate ((CuSO) 4 ) Copper chloride (CuCl) 2 ) Adding in an equal form; molybdenum (Mo) element is molybdenum trioxide (MoO) 3 ) Is added in the form of (2); the nickel (Ni) element is nickel sulfate (NiSO) 4 ) Is added in the form of (2); the vanadium (V) element is sodium vanadate (NaVO) 3 ) Ammonium vanadate (NH) 4 VO 3 ) Is added in the form of (2); chromium (Cr) element is chromium potassium sulfate [ CrK (SO) 4 ) 2 ]Is added in the form of (c).
In some embodiments, the mass ratio of the transition metal salt to the iron-based material loaded with nano ferroferric oxide is 0.01:100-50:100, if the addition amount of the transition metal salt is too small, the content of the transition metal salt loaded on the surface of the iron-based material loaded with nano ferroferric oxide is small, and the catalytic efficiency of the catalyst is reduced due to the synergistic catalysis of the transition metal ion and the iron-based material loaded with nano ferroferric oxide; if the transition metal salt is excessively added, the content of the transition metal salt loaded on the iron-based material of the nano ferroferric oxide is also certain because the content of the iron-based material of the nano ferroferric oxide is certain, the excessive metal salt can cause raw material waste, and meanwhile, the excessive transition metal salt can also cause pollution to water.
In some embodiments, as shown in fig. 2, co-precipitation of the reduced iron powder, ferrous chloride, ferric chloride, complexing agent, and first solvent comprises:
step S11: dispersing the reduced iron powder in ultrapure water to obtain a first dispersion liquid;
step S12: adding the ferrous chloride and the ferric chloride into the first dispersion liquid, and then adding a complexing agent to obtain a mixed liquid;
step S13: and adding the first solvent into the mixed solution under the protection of constant temperature gas to obtain the iron-based precipitate loaded with the ferroferric oxide.
In some embodiments, 200 mesh sponge iron powder is dispersed in ultrapure water to obtain a first dispersion liquid, and ferrous chloride and ferric chloride solution are added into the first dispersion liquid under the condition of continuous stirring, wherein the iron weight ratio of the sponge iron powder to the ferrous chloride and the ferric chloride is 10:10-10:1, and tartrate-ethylenediamine tetraacetic acid is further added, and specifically, the molar ratio of tartrate to ethylenediamine tetraacetic acid is 1:1, obtaining a mixed solution, dropwise adding first solvent ammonia water into the mixed solution under the protection of constant-temperature water bath nitrogen at 60-80 ℃ and continuously and mechanically stirring to obtain an iron-based precipitate loaded with ferroferric oxide, curing the iron-based precipitate loaded with ferroferric oxide for 30-60 min, cooling to room temperature, filtering and washing, and then vacuum drying at 40-60 ℃ for 8-24 h to obtain the iron-based material loaded with nano ferroferric oxide, wherein the mass ratio of tartrate-ethylenediamine tetraacetic acid to the iron-based material loaded with nano ferroferric oxide is 0.1:100-10:100.
In the embodiment of the application, the zero-valent reducing sponge iron powder is taken as a matrix to form Fe in the catalyst 0 And Fe (Fe) 3+ The oxidation-reduction reaction of the ferric ions is promoted, the use efficiency of the catalyst is improved, the tartrate-ethylenediamine tetraacetic acid in the solution and the ferric ions in the solution form a tartrate-EDTA-Fe complex system, the stability of the ferric ions is improved, the ferric ions are prevented from generating precipitation, the oxidation-reduction reaction of the ferric ions and the reducible zero-valent iron in the prepared iron-based material loaded with the nano ferroferric oxide can be generated in the catalytic process, the ferrous ions required by Fenton catalytic oxidation are generated, and the reaction rate of Fenton catalytic oxidation is effectively improved.
In some embodiments, as shown in fig. 3, the nano ferroferric oxide loaded iron-based material, transition metal salt, tetrabutyl titanate and a second solvent are prepared by a sol-gel method to obtain a heterogeneous Fenton catalyst, which comprises:
step S31: dispersing the iron-based material loaded with nano ferroferric oxide in the second solvent to obtain second dispersion liquid;
step S32: and adding tetrabutyl titanate into the second dispersion liquid, adding the transition metal salt to form gel, standing for aging, drying and grinding to obtain the heterogeneous Fenton catalyst.
Specifically, the mass ratio of tetrabutyl titanate to the iron-based material loaded with nano ferroferric oxide is 1:10-10:10, and the second solvent is a mixed solution of anhydrous ethanol and glacial acetic acid, wherein the volume ratio of the anhydrous ethanol to the glacial acetic acid is 3:1.
In some embodiments, mixing absolute ethyl alcohol and glacial acetic acid in a volume of 3:1 to obtain a mixed solution A, dispersing an iron-based material loaded with nano ferroferric oxide in the mixed solution A to obtain a second dispersion, dropwise adding tetrabutyl titanate under the condition of continuous stirring, wherein the mass ratio of the tetrabutyl titanate to the iron-based material loaded with nano ferroferric oxide is 1:10-10:10, adding a transition metal salt solution, wherein the mass ratio of the transition metal salt to the iron-based material loaded with nano ferroferric oxide is 0.01:100-50:100, mixing and stirring until a gel state is formed, standing and aging, vacuum drying for 8-24 hours at 40-60 ℃, and grinding to obtain the heterogeneous Fenton catalyst.
In the embodiment, the heterogeneous Fenton catalyst prepared by the sol-gel method has a larger surface area, and the transition metal salt can be well loaded on the surface of the iron-based material of the nano ferroferric oxide, so that the transition metal element is not easy to run off, and the heterogeneous Fenton catalyst has a synergistic effect with the iron-based material of the nano ferroferric oxide, so that the heterogeneous Fenton catalyst has a better catalytic performance.
The heterogeneous Fenton catalyst prepared by the method has small particles, good affinity with water and good dispersibility, and the heterogeneous Fenton catalyst can be separated from a solution by a magnet after the Fenton catalytic reaction is finished, so that the heterogeneous Fenton catalyst is recovered.
In some embodiments, the heterogeneous Fenton catalyst prepared by the method can be applied to industrial sewage treatment, and organic pollutants in water can be effectively degraded.
The following description is made in connection with specific embodiments:
example 1
The preparation process of the heterogeneous Fenton catalyst A specifically comprises the following steps:
(1) 10g of 200 mesh sponge iron powder was dispersed in 100ml of ultrapure water to obtain a dispersion;
(2) Adding a solution containing 2.0g of ferrous chloride and 5.2g of ferric chloride to the dispersion with continuous stirring;
(3) After 1.0g of tartrate-ethylenediamine tetraacetic acid complexing agent is added, 100ml of concentrated ammonia water is dropwise added into the mixed solution under the protection of water bath nitrogen at the constant temperature of 60-80 ℃ and is continuously and mechanically stirred, so as to obtain an iron-based precipitate loaded with ferroferric oxide;
(4) Curing the iron-based precipitate loaded with the ferroferric oxide for 30-60 min, cooling to room temperature, filtering and washing, and vacuum drying at 40-60 ℃ for 8-24 h to obtain the iron-based material loaded with the nano ferroferric oxide;
(5) Performing ultrasonic dispersion on 10g of iron-based material loaded with nano ferroferric oxide in 100ml of mixed solution of absolute ethyl alcohol and glacial acetic acid, dropwise adding 10ml of tetrabutyl titanate under the condition of continuous stirring, adding 10ml of salt solution containing transition metals of manganese, zinc, cobalt, copper, molybdenum, nickel, vanadium and chromium, mixing, stirring until gel is formed, standing for aging, vacuum drying at 40-60 ℃ for 8-24 h, and grinding to obtain the iron-based heterogeneous Fenton catalyst precursor material;
(6) And grinding the iron-based heterogeneous Fenton catalyst precursor material to obtain the heterogeneous Fenton catalyst A.
Example 2
The preparation process of the heterogeneous Fenton catalyst B specifically comprises the following steps:
(1) 10g of 200 mesh zero-valent iron powder was dispersed in 100ml of ultrapure water to obtain a dispersion;
(2) Adding a solution containing 2.0g of ferrous chloride and 5.2g of ferric chloride to the dispersion with continuous stirring;
(3) After 1.0g of tartrate-ethylenediamine tetraacetic acid complexing agent is added, 100ml of concentrated ammonia water is dropwise added into the mixed solution under the protection of water bath nitrogen at the constant temperature of 60-80 ℃ and is continuously and mechanically stirred, so as to obtain an iron-based precipitate loaded with ferroferric oxide;
(4) Curing the iron-based precipitate loaded with the ferroferric oxide for 30-60 min, cooling to room temperature, filtering and washing, and vacuum drying at 40-60 ℃ for 8-24 h to obtain the iron-based material loaded with the nano ferroferric oxide;
(5) Ultrasonically dispersing 10g of iron-based material loaded with nano ferroferric oxide in 100ml of mixed solution of absolute ethyl alcohol and glacial acetic acid, wherein the volume ratio of the absolute ethyl alcohol to the glacial acetic acid is 3:1, dropwise adding 10ml of tetrabutyl titanate under the condition of continuous stirring, adding 10ml of salt solution containing transition metals of manganese, zinc, cobalt, copper, molybdenum, nickel, vanadium and chromium, mixing, stirring until gel is formed, standing for aging, vacuum drying at 40-60 ℃ for 8-24 h, and grinding to obtain the iron-based heterogeneous Fenton catalyst precursor material;
(6) And grinding the iron-based heterogeneous Fenton catalyst precursor material to obtain the heterogeneous Fenton catalyst B.
Example 3
The preparation process of the heterogeneous Fenton catalyst C comprises the following steps:
(1) 10g of 200 mesh pyrite iron powder was dispersed in 100ml of ultrapure water to obtain a dispersion;
(2) Adding a solution containing 2.0g of ferrous chloride and 5.2g of ferric chloride to the dispersion with continuous stirring;
(3) After 1.0g of tartrate-ethylenediamine tetraacetic acid complexing agent is added, 100ml of concentrated ammonia water is dropwise added into the mixed solution under the protection of water bath nitrogen at the constant temperature of 60-80 ℃ and is continuously and mechanically stirred, so as to obtain an iron-based precipitate loaded with ferroferric oxide;
(4) Curing the iron-based precipitate loaded with the ferroferric oxide for 30-60 min, cooling to room temperature, filtering and washing, and vacuum drying at 40-60 ℃ for 8-24 h to obtain the iron-based material loaded with the nano ferroferric oxide;
(5) Ultrasonically dispersing 10g of iron-based material loaded with nano ferroferric oxide in 100ml of mixed solution of absolute ethyl alcohol and glacial acetic acid, wherein the volume ratio of the absolute ethyl alcohol to the glacial acetic acid is 3:1, dropwise adding 10ml of tetrabutyl titanate under the condition of continuous stirring, adding 10ml of salt solution containing transition metals of manganese, zinc, cobalt, copper, molybdenum, nickel, vanadium and chromium, mixing, stirring until gel is formed, standing for aging, vacuum drying at 40-60 ℃ for 8-24 h, and grinding to obtain the iron-based heterogeneous Fenton catalyst precursor material;
(6) And grinding the iron-based heterogeneous Fenton catalyst precursor material to obtain the heterogeneous Fenton catalyst C.
Example 4
The preparation process of the heterogeneous Fenton catalyst D comprises the following steps:
(1) 10g of 200 mesh sponge iron powder was dispersed in 100ml of ultrapure water to obtain a dispersion;
(2) Adding a solution containing 2.0g of ferrous chloride and 5.2g of ferric chloride to the dispersion with continuous stirring;
(3) After 1.0g of tartrate-ethylenediamine tetraacetic acid complexing agent is added, 100ml of concentrated ammonia water is dropwise added into the mixed solution under the protection of water bath nitrogen at the constant temperature of 60-80 ℃ and is continuously and mechanically stirred, so as to obtain an iron-based precipitate loaded with ferroferric oxide;
(4) Curing the iron-based precipitate loaded with the ferroferric oxide for 30-60 min, cooling to room temperature, filtering and washing, and vacuum drying at 40-60 ℃ for 8-24 h to obtain the iron-based material loaded with the nano ferroferric oxide;
(5) Ultrasonically dispersing 10g of iron-based material loaded with nano ferroferric oxide in 100ml of mixed solution of absolute ethyl alcohol and glacial acetic acid, wherein the volume ratio of the absolute ethyl alcohol to the glacial acetic acid is 3:1, dropwise adding 10ml of tetrabutyl titanate under the condition of continuous stirring, adding 10ml of salt solution containing transition metals of copper, molybdenum, nickel, vanadium and chromium, mixing, stirring until gel is formed, standing for aging, vacuum drying at 40-60 ℃ for 8-24 h, and grinding to obtain the iron-based heterogeneous Fenton catalyst precursor material;
(6) And grinding the iron-based heterogeneous Fenton catalyst precursor material to obtain the heterogeneous Fenton catalyst D.
Example 5
The preparation process of the heterogeneous Fenton catalyst E is specifically as follows:
(1) 10g of 200 mesh sponge iron powder was dispersed in 100ml of ultrapure water to obtain a dispersion;
(2) Adding a solution containing 2.0g of ferrous chloride and 5.2g of ferric chloride to the dispersion with continuous stirring;
(3) After 1.0g of tartrate-diethylenetriamine pentaacetic acid complexing agent is added, 100ml of concentrated ammonia water is dropwise added into the mixed solution under the protection of nitrogen in a constant-temperature water bath at 60-80 ℃ and is continuously and mechanically stirred, so that an iron-based precipitate carrying ferroferric oxide is obtained;
(4) Curing the iron-based precipitate loaded with the ferroferric oxide for 30-60 min, cooling to room temperature, filtering and washing, and vacuum drying at 40-60 ℃ for 8-24 h to obtain the iron-based material loaded with the nano ferroferric oxide;
(5) Ultrasonically dispersing 10g of iron-based material loaded with nano ferroferric oxide in 100ml of mixed solution of absolute ethyl alcohol and glacial acetic acid, wherein the volume ratio of the absolute ethyl alcohol to the glacial acetic acid is 3:1, dropwise adding 10ml of tetrabutyl titanate under the condition of continuous stirring, adding 10ml of salt solution containing transition metals of manganese, zinc, cobalt, copper, molybdenum, nickel, vanadium and chromium, mixing, stirring until gel is formed, standing for aging, vacuum drying at 40-60 ℃ for 8-24 h, and grinding to obtain the iron-based heterogeneous Fenton catalyst precursor material;
(6) And grinding the iron-based heterogeneous Fenton catalyst precursor material to obtain the heterogeneous Fenton catalyst E.
Example 6
The preparation process of the heterogeneous Fenton catalyst F is specifically as follows:
(1) 10g of 200 mesh sponge iron powder was dispersed in 100ml of ultrapure water to obtain a dispersion;
(2) Adding a solution containing 2.0g of ferrous chloride and 5.2g of ferric chloride to the dispersion with continuous stirring;
(3) After 1.0g of tartrate-ethylenediamine tetraacetic acid complexing agent is added, 100ml of concentrated ammonia water is dropwise added into the mixed solution under the protection of water bath nitrogen at the constant temperature of 60-80 ℃ and is continuously and mechanically stirred, so as to obtain an iron-based precipitate loaded with ferroferric oxide;
(4) Curing the iron-based precipitate loaded with the ferroferric oxide for 30-60 min, cooling to room temperature, filtering and washing, and vacuum drying at 40-60 ℃ for 8-24 h to obtain the iron-based material loaded with the nano ferroferric oxide;
(5) Ultrasonically dispersing 10g of iron-based material loaded with nano ferroferric oxide in 100ml of mixed solution of absolute ethyl alcohol and glacial acetic acid, wherein the volume ratio of the absolute ethyl alcohol to the glacial acetic acid is 3:1, dropwise adding 10ml of tetrabutyl titanate under the condition of continuous stirring, adding 10ml of salt solution containing transition metals of manganese, zinc, cobalt, copper, molybdenum, nickel, vanadium and chromium, mixing, stirring until gel is formed, standing for aging, vacuum drying at 40-60 ℃ for 8-24 h, and grinding to obtain the iron-based heterogeneous Fenton catalyst precursor material;
(6) And grinding the iron-based heterogeneous Fenton catalyst precursor material to obtain the heterogeneous Fenton catalyst F.
Example 7
The preparation process of the heterogeneous Fenton catalyst G is specifically as follows:
(1) 10g of 200 mesh sponge iron powder was dispersed in 100ml of ultrapure water to obtain a dispersion;
(2) Adding a solution containing 2.0g of ferrous chloride and 5.2g of ferric chloride to the dispersion with continuous stirring;
(3) After adding 2.0g of tartrate-ethylenediamine tetraacetic acid complexing agent, dropwise adding 100ml of concentrated ammonia water into the mixed solution under the protection of water bath nitrogen at the constant temperature of 60-80 ℃ and continuously mechanically stirring to obtain an iron-based precipitate loaded with ferroferric oxide;
(4) Curing the iron-based precipitate loaded with the ferroferric oxide for 30-60 min, cooling to room temperature, filtering and washing, and vacuum drying at 40-60 ℃ for 8-24 h to obtain the iron-based material loaded with the nano ferroferric oxide;
(5) Ultrasonically dispersing 10g of iron-based material loaded with nano ferroferric oxide in 100ml of mixed solution of absolute ethyl alcohol and glacial acetic acid, wherein the volume ratio of the absolute ethyl alcohol to the glacial acetic acid is 3:1, dropwise adding 10ml of tetrabutyl titanate under the condition of continuous stirring, adding 10ml of salt solution containing transition metals of manganese, zinc, cobalt, copper, molybdenum, nickel, vanadium and chromium, mixing, stirring until gel is formed, standing for aging, vacuum drying at 40-60 ℃ for 8-24 h, and grinding to obtain the iron-based heterogeneous Fenton catalyst precursor material;
(6) And grinding the iron-based heterogeneous Fenton catalyst precursor material to obtain the heterogeneous Fenton catalyst G.
Example 8
The preparation process of the heterogeneous Fenton catalyst H comprises the following steps:
(1) 10g of 200 mesh sponge iron powder was dispersed in 100ml of ultrapure water to obtain a dispersion;
(2) Adding a solution containing 2.0g of ferrous chloride and 5.2g of ferric chloride to the dispersion with continuous stirring;
(3) After 1.0g of tartrate-ethylenediamine tetraacetic acid complexing agent is added, 100ml of concentrated ammonia water is dropwise added into the mixed solution under the protection of water bath nitrogen at the constant temperature of 60-80 ℃ and is continuously and mechanically stirred, so as to obtain an iron-based precipitate loaded with ferroferric oxide;
(4) Curing the iron-based precipitate loaded with the ferroferric oxide for 30-60 min, cooling to room temperature, filtering, washing, and vacuum drying at 40-60 ℃ for 8-24 h to obtain the iron-based material loaded with the nano ferroferric oxide;
(5) Dispersing 10g of iron-based material loaded with nano ferroferric oxide in 100ml of mixed solution of absolute ethyl alcohol and glacial acetic acid in a volume ratio of 3:1, dropwise adding 20ml of tetrabutyl titanate under the condition of continuous stirring, adding 10ml of salt solution containing transition metals of manganese, zinc, cobalt, copper, molybdenum, nickel, vanadium and chromium, mixing, stirring until gel is formed, standing for aging, vacuum drying at 40-60 ℃ for 8-24 h, and grinding to obtain the iron-based heterogeneous Fenton catalyst precursor material;
(6) And grinding the iron-based heterogeneous Fenton catalyst precursor material to obtain the heterogeneous Fenton catalyst H.
Comparative example 1
Other process conditions and experimental steps of this comparative example 1 are the same as those of example 1, except that the biochar powder in step (1) replaces sponge iron powder, and the tartrate-ethylenediamine tetraacetic acid complexing agent is not added in step (3). The preparation process of the heterogeneous Fenton catalyst M is specifically as follows:
(1) 10g of 200 mesh charcoal powder was dispersed in 100ml of ultrapure water to obtain a dispersion;
(2) Adding a solution containing 2.0g of ferrous chloride and 5.2g of ferric chloride to the dispersion with continuous stirring;
(3) Dropwise adding 100ml of concentrated ammonia water into the dispersion liquid under the protection of nitrogen in a constant-temperature water bath at 60-80 ℃ and continuously and mechanically stirring to obtain a precipitate;
(4) Aging the precipitate for 30-60 min, cooling to room temperature, filtering, washing, and vacuum drying at 40-60 ℃ for 8-24 h to obtain an iron-based material;
(5) Performing ultrasonic dispersion on 10g of iron-based material in 100ml of mixed solution of absolute ethyl alcohol and glacial acetic acid, wherein the volume ratio of the absolute ethyl alcohol to the glacial acetic acid is 3:1, dropwise adding 10ml of tetrabutyl titanate under the condition of continuous stirring, adding 10ml of salt solution containing transition metals of manganese, zinc, cobalt, copper, molybdenum, nickel, vanadium and chromium, mixing, stirring until gel is formed, standing for aging, vacuum drying at 40-60 ℃ for 8-24 h, and grinding to obtain a precursor material of the heterogeneous Fenton catalyst M;
(6) And grinding the precursor material of the heterogeneous Fenton catalyst M to obtain the heterogeneous Fenton catalyst M.
Comparative example 2
Other process conditions and experimental procedures of this comparative example 2 were the same as in example 1, except that the zeolite powder was used in place of the sponge iron powder in step (1), and the salt solutions of the transition metals manganese, zinc, cobalt, copper, molybdenum, nickel, vanadium, and chromium were not added in step (5). The preparation process of the heterogeneous Fenton catalyst N specifically comprises the following steps:
(1) 10g of 200 mesh zeolite powder was dispersed in 100ml of ultrapure water to obtain a dispersion;
(2) Adding a solution containing 2.0g of ferrous chloride and 5.2g of ferric chloride to the dispersion with continuous stirring;
(3) After 1.0g of tartrate-ethylenediamine tetraacetic acid complexing agent is added, 100ml of concentrated ammonia water is dropwise added into the mixed solution under the protection of water bath nitrogen at the constant temperature of 60-80 ℃ and is continuously and mechanically stirred, so as to obtain an iron-based precipitate loaded with ferroferric oxide;
(4) Curing the iron-based precipitate loaded with the ferroferric oxide for 30-60 min, cooling to room temperature, filtering and washing, and vacuum drying at 40-60 ℃ for 8-24 h to obtain the iron-based material loaded with the nano ferroferric oxide;
(5) Performing ultrasonic dispersion on 10g of iron-based material loaded with nano ferroferric oxide in 100ml of mixed solution of absolute ethyl alcohol and glacial acetic acid, dropwise adding 10ml of tetrabutyl titanate under the condition of continuous stirring, mixing, stirring, standing and ageing, vacuum drying at 40-60 ℃ for 8-24 h, and grinding to obtain a precursor material of a heterogeneous Fenton catalyst N;
(6) And grinding the precursor material of the heterogeneous Fenton catalyst N to obtain the heterogeneous Fenton catalyst N.
The heterogeneous Fenton catalysts prepared in examples 1 to 8, comparative example 1 and comparative example 2 were subjected to an organic pollutant removal effect test, and the test method comprises:
10 groups of 1L wastewater to be treated with COD of 300mg/L are prepared, the pH=7.0 of the wastewater is adjusted, and 10g of heterogeneous Fenton catalysts prepared in examples 1 to 8, comparative example 1 and comparative example 2 are respectively added according to the COD: h 2 O 2 H is added in a ratio of 1:1 2 O 2 After that, the reaction was stirred for 30 minutes, the COD value of each group was detected, and the removal rate of COD of each group was calculated.
The test results were as follows:
table 1: removal rate of COD by heterogeneous fenton catalyst prepared in different examples.
Figure BDA0003776572020000151
As can be seen from Table 1, the removal rates of the heterogeneous Fenton catalysts prepared in examples 1 to 8 were all above 85%, and in particular, the removal rates of the heterogeneous Fenton catalyst A prepared in example 1 were as high as 92.9%, whereas the removal rates of the heterogeneous Fenton catalysts prepared in comparative examples 1 and 2 were 34.0% and 42.0%, respectively, and the removal rates of the heterogeneous Fenton catalysts prepared in examples 1 to 8 were significantly improved as compared with the heterogeneous Fenton catalysts prepared in comparative examples 1 and 2. As can be seen from table 2, in comparative example 1 and comparative example 1, the reduced iron provides iron ions required for the Fenton reaction during the catalytic reaction, and the tartrate-ethylenediamine tetraacetic acid complexing agent improves the stability of the iron ions under neutral conditions, so that the removal effect of COD is significantly improved. The addition of transition metal elements of comparative examples 1 and 2 promotes the catalytic effect of heterogeneous Fenton catalyst, comparative examples 1 and 2 to 3 have the best COD removing effect when the reduced iron is sponge iron powder, and comparative examples 1 and 4 have the best COD removing effect when the transition metal is manganese, zinc, cobalt, copper, molybdenum, nickel, vanadium, and chromium, comparative examples 1 and 5, the removal effect of COD was optimal when the complexing agent was tartrate-ethylenediamine tetraacetic acid, and comparative examples 1 and examples 6 to 8, the removal effect of COD was optimal when the mass ratio of the transition metal element to the reduced iron powder was 1:5, the mass ratio of the complexing agent to the reduced iron powder was 1:10, and the mass ratio of tetrabutyl titanate to the reduced iron powder was 1:1.
Table 2: different examples are prepared of heterogeneous Fenton catalyst raw material types and proportions.
Figure BDA0003776572020000161
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Figure BDA0003776572020000171
Note that: a: mass of the reductive iron powder, B: transition metal element mass, C: complexing agent mass, D: tetrabutyl titanate mass
In summary, the removal rate of the heterogeneous Fenton catalyst prepared in the embodiment of the application to COD is above 85%, particularly, the heterogeneous Fenton catalyst A prepared in the embodiment 1 reaches 92.9%, and the heterogeneous Fenton catalyst prepared in the embodiment of the application can realize catalysis under neutral conditions, so that the dosage of the medicament and the generation amount of the iron-containing sludge are reduced, the catalyst is effectively recovered, and the cost is reduced.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and are not limiting thereof; the technical features of the above embodiments or in the different embodiments may also be combined under the idea of the present application, the steps may be implemented in any order, and there are many other variations of the different aspects of the present application as described above, which are not provided in details for the sake of brevity; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.

Claims (7)

1. A method for preparing a heterogeneous Fenton catalyst, comprising the steps of:
performing coprecipitation reaction on reduced iron powder, ferrous chloride, ferric chloride, a complexing agent and a first solvent to obtain an iron-based precipitate loaded with ferroferric oxide;
curing, cooling, filtering, washing and drying the iron-based precipitate loaded with the ferroferric oxide to obtain an iron-based material loaded with nano ferroferric oxide;
preparing the iron-based material loaded with nano ferroferric oxide, transition metal salt, tetrabutyl titanate and a second solvent by a sol-gel method to obtain a heterogeneous Fenton catalyst;
the complexing agent comprises at least one of tartrate-ethylenediamine tetraacetic acid and tartrate-diethylenetriamine pentaacetic acid;
when the complexing agent comprises tartrate-ethylenediamine tetraacetic acid, the molar ratio of the tartrate to the ethylenediamine tetraacetic acid is 1:100-100:100;
when the complexing agent comprises tartrate-diethylenetriamine pentaacetic acid, the molar ratio of the tartrate to the diethylenetriamine pentaacetic acid is 1:100-100:100;
wherein the reduced iron powder comprises sponge iron powder.
2. The method of preparing a heterogeneous Fenton catalyst according to claim 1, wherein said transition metal salt comprises at least one of manganese, zinc, cobalt, copper, molybdenum, nickel, vanadium, and chromium metal salts.
3. The method for preparing the heterogeneous Fenton catalyst according to claim 1, wherein the mass ratio of the complexing agent to the iron-based material loaded with nano ferroferric oxide is 0.1:100-10:100.
4. The method for preparing the heterogeneous Fenton catalyst according to claim 2, wherein the mass ratio of the transition metal salt to the iron-based material loaded with nano ferroferric oxide is 0.01:100-50:100.
5. The method for preparing a heterogeneous Fenton catalyst according to claim 1, wherein the co-precipitation reaction of the reduced iron powder, ferrous chloride, ferric chloride, a complexing agent and a first solvent comprises:
dispersing the reduced iron powder in ultrapure water to obtain a first dispersion liquid;
adding the ferrous chloride and the ferric chloride into the first dispersion liquid, and then adding a complexing agent to obtain a mixed liquid;
and adding the first solvent into the mixed solution under the protection of constant temperature gas to obtain the iron-based precipitate loaded with the ferroferric oxide.
6. The method for preparing a heterogeneous Fenton catalyst according to claim 1, wherein the preparing the iron-based material loaded with nano ferroferric oxide, the transition metal salt, the tetrabutyl titanate and the second solvent by a sol-gel method to obtain the heterogeneous Fenton catalyst comprises the following steps:
dispersing the iron-based material loaded with nano ferroferric oxide in the second solvent to obtain second dispersion liquid;
and adding tetrabutyl titanate into the second dispersion liquid, adding the transition metal salt to form gel, standing for aging, drying and grinding to obtain the heterogeneous Fenton catalyst.
7. Use of a heterogeneous Fenton catalyst according to any of claims 1-6 for degrading organic pollutants in industrial wastewater treatment.
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