CN115282977A - Preparation method and application of heterogeneous Fenton catalyst - Google Patents
Preparation method and application of heterogeneous Fenton catalyst Download PDFInfo
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Abstract
The application relates to a preparation method and application of a heterogeneous Fenton catalyst, wherein the method comprises the following steps: the preparation method comprises the steps of carrying out coprecipitation reaction on reducing 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 the nano ferroferric oxide, a 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 iron ions from generating precipitate, reduce the dosage of the medicament and the generation amount of the iron-containing sludge, realize catalysis under the neutral condition, realize effective recovery of the catalyst and reduce the cost.
Description
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 ecosystem and the human health, gradually increases the discharge requirement of sewage treatment along with the gradual promotion of the water pollution prevention work in China, adopts proper measures to stably control the Chemical Oxygen Demand (COD) in the discharge range below 30mg/L, and becomes a problem which needs to be solved urgently in the industry.
In the design of water treatment process, in order to ensure that the effluent COD is stable and reaches the standard, advanced oxidation advanced treatment procedures such as a Fenton oxidation process and the like are generally required to be arranged after secondary biochemical treatment. The Fenton oxidation method is to add H into wastewater under acidic condition 2 O 2 And catalyst Fe 2+ The organic free radicals are generated in the water solution with refractory organic matters to destroy the structure of the organic free radicals, so that the organic free radicals are oxidized and decomposed to effectively remove the refractory organic matters in the traditional wastewater treatment technology.
At present, the Fenton oxidation process is widely applied to the advanced treatment of industrial wastewater, but the traditional Fenton oxidation method also has some defects: (1) Treatment of high concentrations of contaminants H 2 O 2 The consumption of the waste water is large, and the waste water treatment cost is high. (2) The applicable pH value range is small, the pH value is required to be carried out under the condition that the pH value is about 3, and the treated water is still in strong acidity. (3) The conventional Fenton reagent belongs to a homogeneous catalysis system, effluent contains a large amount of iron ions, and subsequent treatment generates a large amount of iron-containing sludge, so that secondary pollution is easily caused. In recent years, heterogeneous Fenton has received high attention due to wide pH value application range, small sludge yield and good treatment effect. Patent numbers:CN201210388172.1 proposes "a preparation method and application of a heterogeneous fenton-like catalyst", but the problems that the stability of a complexing agent is poor and grafted metal ions are easy to run off still exist. CN202110374731.2 proposes a method for regulating and controlling the selective generation of oxidation active matters of an iron-based Fenton catalyst, but has the problems that the catalytic efficiency of the catalyst is low and the catalyst can not be recycled under the condition of neutral pH value. Therefore, it is necessary to develop a heterogeneous fenton catalyst having high catalytic activity, a 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, wherein a tartrate-EDTA-Fe complex system is constructed in the catalyst, so that the stability of iron is improved, iron hydroxide precipitation generated by iron ions is avoided, and the pH value range of the fenton reaction is widened. Takes zero-valent reducing iron powder as a matrix to form Fe in a catalyst 0 And Fe 3+ The oxidation-reduction reaction of (2) promotes the circulation of ferric ions, and increases the use efficiency of the catalyst. 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 lose, and the stability and the catalytic efficiency of the catalyst are improved.
In order to solve the above technical problem, one technical solution adopted by the embodiment of the present application is:
in a first aspect, an embodiment of the present application provides a method for preparing a heterogeneous fenton catalyst, including the following steps: carrying out coprecipitation reaction on reducing iron powder, ferrous chloride, ferric chloride, a complexing agent and a first solvent to obtain 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 the nano ferroferric oxide; and preparing the nano ferroferric oxide supported iron-based material, 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-ethylenediaminetetraacetic acid, tartrate-diethylenetriaminepentaacetic acid.
Preferably, when the complexing agent comprises tartrate-ethylene diamine tetraacetic acid, the molar ratio of the tartrate to the ethylene diamine tetraacetic acid is 1-100; when the complexing agent comprises tartrate-diethylenetriamine pentaacetic acid, the molar ratio of the tartrate to the diethylenetriamine pentaacetic acid is 1-100.
Preferably, the transition metal salt includes 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 nano ferroferric oxide-loaded iron-based material is 0.1.
Preferably, the mass ratio of the transition metal salt to the iron-based material loaded with nano ferroferric oxide is 0.01.
Preferably, the coprecipitation reaction of the reduced iron powder, the ferrous chloride, the ferric chloride, the complexing agent and the first solvent comprises: dispersing the reducing 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 solution; and adding a first solvent into the mixed solution under the protection of constant-temperature gas to obtain the iron-based precipitate loaded with ferroferric oxide.
Preferably, the nano ferroferric oxide supported iron-based material, the transition metal salt, tetrabutyl titanate and the second solvent are prepared by a sol-gel method to obtain the heterogeneous fenton catalyst, and the method comprises the following steps: dispersing the iron-based material loaded with the nano ferroferric oxide in the second solvent to obtain a second dispersion liquid; and adding the tetrabutyl titanate into the second dispersion liquid, then adding the transition metal salt to form gel, standing and aging, drying, and grinding to obtain the heterogeneous Fenton catalyst.
In a second aspect, embodiments of the present application provide a use of the above-described heterogeneous fenton catalyst in degradation of organic pollutants in industrial wastewater treatment.
Different from the related technology, the preparation method of the heterogeneous Fenton catalyst provided by the application has the beneficial effects that: the preparation method comprises the steps of carrying out coprecipitation reaction on reducing 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 the nano ferroferric oxide, a 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 iron ions from generating precipitates, reduce the dosage of the medicament and the generation amount of the iron-containing sludge, realize catalysis under the neutral condition, realize the effective recovery of the catalyst and reduce the cost.
Drawings
One or more embodiments are illustrated in drawings corresponding to, and not limiting to, the embodiments, in which elements having the same reference number designation may be represented as similar elements, unless specifically noted, the drawings in the figures are not to scale.
Fig. 1 is a flow chart of a method for preparing a heterogeneous fenton catalyst according to an embodiment of the present disclosure;
FIG. 2 is a schematic view of a sub-process S1 in FIG. 1 according to an embodiment of the present application;
fig. 3 is a schematic view of the S3 sub-flow in fig. 1 according to the 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 is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
It should be noted that, if not conflicted, the individual features of the embodiments of the present application can be combined with one another within the scope of protection of the present application. Additionally, a logical order is shown in the flowcharts, but in some cases, the steps shown or described may be performed in the order in the flowcharts.
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. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
As shown in fig. 1, fig. 1 is a flow chart of a method for preparing a heterogeneous fenton catalyst, which is provided in an embodiment of the present application, and the method includes:
step S1: and carrying out coprecipitation reaction on the reducing 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.
And step S3: and preparing the nano ferroferric oxide supported iron-based material, 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, reducing iron powder, ferrous chloride and ferric chloride are dispersed by a coprecipitation method, then a complexing agent is added into a dispersion liquid, the complexing agent and iron ions in the solution form a complexing system, then a first solvent is added, wherein the first solvent can be ammonia water to obtain iron-based precipitates loaded with ferroferric oxide, the iron-based precipitates loaded with ferroferric oxide are cured, cooled, filtered, washed and dried to obtain iron-based materials loaded with nano ferroferric oxide, and then the iron-based materials loaded with nano ferroferric oxide are dispersed in a second solvent, wherein the second solvent can be a mixture of anhydrous ethanol and glacial acetic acid, specifically, the volume ratio of the anhydrous ethanol to the glacial acetic acid is 3.
In some embodiments, the first solvent may also be sodium hydroxide, the sodium hydroxide is a strong base, and in the process of forming the ferroferric oxide by using the sodium hydroxide as the solvent, the forming rate of the ferroferric oxide nanoparticles is too fast, so that the ferroferric oxide nanoparticles are easy to agglomerate on the surface of the reducing iron powder, and the specific surface area of the material is reduced.
In the examples of the present application, reduced iron powder was used as a base material to form Fe in a catalyst 0 And Fe 3+ The redox reaction of the method promotes the circulation of ferric ions, increases the service efficiency of the catalyst, adds a complexing agent in the coprecipitation process, enables the complexing agent and the ferric ions in the solution to form a complexing system, avoids the ferric ions from precipitating, and the coprecipitation method is easy to prepare nano powder materials with small particle size and uniform distribution.
In some embodiments, the reducing iron powder includes 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 the ferrous chloride and the ferric chloride is 10-10, and the particle size is generally 200 mesh.
In some embodiments, the mass ratio of the complexing agent to the nano ferroferric oxide-loaded iron-based material is 0.1.
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 to 100; when the complexing agent comprises tartrate-diethylenetriamine pentaacetic acid, the molar ratio of tartrate to diethylenetriamine pentaacetic acid is 1-100, and when the complex is tartrate-ethylenediamine tetraacetic acid, the tartrate-ethylenediamine tetraacetic acid is added in the coprecipitation process, a tartrate-EDTA-Fe complex system can be constructed, and the system can improve the stability of iron ions, avoid the generation of precipitates due to the iron ions and reduce the catalytic efficiency; when the complex is tartrate-diethylenetriamine pentaacetic acid, the tartrate-diethylenetriamine pentaacetic acid is added in the coprecipitation process, so that a tartrate-DTPA-Fe complex system can be constructed, the stability of iron ions can be improved, the precipitation caused by the iron ions is avoided, and the catalytic efficiency is reduced.
In some embodiments, the transition metal salt comprises at least one of manganese, zinc, cobalt, copper, molybdenum, nickel, vanadium, and chromium metal salts, specifically, manganese (Mn) as manganese sulfate (MnSO) 4 ) Manganese chloride (MnCl) 2 ) Adding in the form of equal parts; zinc (Zn) element as zinc sulfate (ZnSO) 4 ) Zinc chloride (ZnCl) 2 ) Adding in the form of equal parts; cobalt (Co) element as cobalt chloride (CoCl) 2 ) Is added in the form of (1); copper (Cu) element as copper sulfate ((CuSO) 4 ) Copper chloride (CuCl) 2 ) Adding in the form of equal parts; molybdenum (Mo) element as molybdenum trioxide (MoO) 3 ) Is added in the form of (1); nickel (Ni) element is nickel sulfate (NiSO) 4 ) Is added in the form of (1); vanadium (V) element selected from sodium vanadate (NaVO) 3 ) Ammonium vanadate (NH) 4 VO 3 ) Is added in the form of (1); chromium (Cr) element is chromium potassium sulfate [ CrK (SO) 4 ) 2 ]Is added in the form of (1).
In some embodiments, the mass ratio of the transition metal salt to the iron-based material loaded with nano ferroferric oxide is 0.01-50, wherein 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 because the transition metal ion and the iron-based material loaded with nano ferroferric oxide have a synergistic catalytic effect; if the transition metal salt is added excessively, the content of the transition metal salt loaded on the iron-based material of the nano ferroferric oxide is also constant because the content of the iron-based material of the nano ferroferric oxide is constant, the excessive metal salt can cause raw material waste, and meanwhile, the excessive transition metal salt can cause pollution to water.
In some embodiments, as shown in fig. 2, subjecting the reduced iron powder, ferrous chloride, ferric chloride, complexing agent, and first solvent to a co-precipitation reaction comprises:
step S11: dispersing the reducing 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 solution;
step S13: and adding a first solvent into the mixed solution under the protection of constant-temperature gas to obtain the iron-based precipitate loaded with ferroferric oxide.
In some examples, a 200 mesh sponge iron powder is dispersed in ultra pure water to obtain a first dispersion, and under continuous stirring, ferrous chloride and ferric chloride solution are added to the first dispersion, wherein the iron mass ratio of the sponge iron powder to the ferrous chloride and the ferric chloride is 10 to 10:1, obtaining a mixed solution, dropwise adding ammonia water serving as a first solvent into the mixed solution under the protection of nitrogen in a constant-temperature water bath 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 performing vacuum drying at 40-60 ℃ for 8-24 h to obtain an 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.
In the embodiment of the application, zero-valent reducing sponge iron powder is used as a matrix, and Fe is formed in the catalyst 0 And Fe 3+ The redox reaction of the catalyst promotes the circulation of ferric ions and increases the use efficiency of the catalyst, the complexing agent is tartrate-ethylene diamine tetraacetic acid, and tartrate-ethylene diamine tetraacetic acid and ferric ions in the solution can construct a tartrate-EDTA-Fe complex systemThe stability of iron ions is improved, the iron ions are prevented from precipitating, ferric iron and reductive zero-valent iron in the prepared nano ferroferric oxide loaded iron-based material can undergo redox reaction in the catalysis process to generate ferrous ions required by Fenton catalytic oxidation, and the reaction rate of the Fenton catalytic oxidation is effectively improved.
In some embodiments, as shown in fig. 3, the nano ferroferric oxide supported iron-based material, the transition metal salt, tetrabutyl titanate and the second solvent are prepared by a sol-gel method to obtain a heterogeneous fenton catalyst, including:
step S31: dispersing the iron-based material loaded with the nano ferroferric oxide in the second solvent to obtain a second dispersion liquid;
step S32: and adding the tetrabutyl titanate into the second dispersion liquid, then adding the transition metal salt to form gel, standing and 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.
In some embodiments, anhydrous ethanol and glacial acetic acid are mixed in a volume ratio of 3.
In this embodiment, the heterogeneous fenton catalyst prepared by the sol-gel method has a large surface area, and the transition metal salt can be better loaded on the surface of the iron-based material of the nano ferroferric oxide, so that the transition metal element is not easy to lose, and the heterogeneous fenton catalyst and the iron-based material of the nano ferroferric oxide have a synergistic effect, 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 better 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 to effectively degrade organic pollutants in water.
The following description is given with reference to specific examples:
example 1
The preparation process of the heterogeneous Fenton catalyst A is as follows:
(1) Dispersing 10g of 200-mesh sponge iron powder in 100ml of ultrapure water to obtain a dispersion liquid;
(2) Adding a solution containing 2.0g of ferrous chloride and 5.2g of ferric chloride to the dispersion under continuous stirring;
(3) After 1.0g of tartrate-ethylene diamine tetraacetic 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 the temperature of 60-80 ℃, and the mixed solution is continuously and mechanically stirred to obtain 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 drying in vacuum 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 into 100ml of mixed solution of anhydrous ethanol and glacial acetic acid, wherein the volume ratio of the anhydrous ethanol to the glacial acetic acid is 3;
(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 is as follows:
(1) 1, dispersing 10g of 200-mesh zero-valent ferroiron powder in 100ml of ultrapure water to obtain a dispersion liquid;
(2) Adding a solution containing 2.0g of ferrous chloride and 5.2g of ferric chloride to the dispersion under continuous stirring;
(3) After 1.0g of tartrate-ethylene diamine tetraacetic 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 the temperature of 60-80 ℃, and the mixed solution is continuously and mechanically stirred to obtain 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 drying in vacuum 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 anhydrous ethanol and glacial acetic acid, wherein the volume ratio of the anhydrous ethanol to the glacial acetic acid is 3;
(6) And grinding the precursor material of the iron-based heterogeneous Fenton catalyst to obtain a heterogeneous Fenton catalyst B.
Example 3
The preparation process of the heterogeneous fenton catalyst C is specifically as follows:
(1) 1, dispersing 10g of 200-mesh pyrite iron powder in 100ml of ultrapure water to obtain a dispersion liquid;
(2) Adding a solution containing 2.0g of ferrous chloride and 5.2g of ferric chloride to the dispersion with constant stirring;
(3) After 1.0g of tartrate-ethylene diamine tetraacetic 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 the temperature of 60-80 ℃, and the mixed solution is continuously and mechanically stirred to obtain 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) Ultrasonically dispersing 10g of iron-based material loaded with nano ferroferric oxide in 100ml of mixed solution of anhydrous ethanol and glacial acetic acid, wherein the volume ratio of the anhydrous ethanol to the glacial acetic acid is 3;
(6) And grinding the precursor material of the iron-based heterogeneous Fenton catalyst to obtain the heterogeneous Fenton catalyst C.
Example 4
The preparation process of the heterogeneous fenton catalyst D is specifically as follows:
(1) Dispersing 10g of 200-mesh sponge iron powder in 100ml of ultrapure water to obtain a dispersion liquid;
(2) Adding a solution containing 2.0g of ferrous chloride and 5.2g of ferric chloride to the dispersion with constant stirring;
(3) After 1.0g of tartrate-ethylene diamine tetraacetic 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 the temperature of 60-80 ℃, and the mixed solution is continuously and mechanically stirred to obtain 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) Ultrasonically dispersing 10g of iron-based material loaded with nano ferroferric oxide in 100ml of mixed solution of anhydrous ethanol and glacial acetic acid, wherein the volume ratio of the anhydrous ethanol to the glacial acetic acid is 3;
(6) And grinding the precursor material of the iron-based heterogeneous Fenton catalyst to obtain a heterogeneous Fenton catalyst D.
Example 5
The preparation process of the heterogeneous Fenton catalyst E is as follows:
(1) Dispersing 10g of 200-mesh sponge iron powder in 100ml of ultrapure water to obtain a dispersion liquid;
(2) Adding a solution containing 2.0g of ferrous chloride and 5.2g of ferric chloride to the dispersion with constant stirring;
(3) After 1.0g of tartrate-diethylenetriamine pentaacetic acid complexing agent is added, 100ml of strong ammonia water is dripped into the mixed solution drop by drop under the protection of nitrogen in constant-temperature water bath at 60-80 ℃ and is continuously and mechanically stirred to obtain iron-based sediment 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 drying in vacuum 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 anhydrous ethanol and glacial acetic acid, wherein the volume ratio of the anhydrous ethanol to the glacial acetic acid is 3;
(6) And grinding the precursor material of the iron-based heterogeneous Fenton catalyst to obtain the heterogeneous Fenton catalyst E.
Example 6
The preparation process of the heterogeneous Fenton catalyst F is as follows:
(1) Dispersing 10g of 200-mesh sponge iron powder in 100ml of ultrapure water to obtain a dispersion liquid;
(2) Adding a solution containing 2.0g of ferrous chloride and 5.2g of ferric chloride to the dispersion with constant stirring;
(3) After 1.0g of tartrate-ethylene diamine tetraacetic acid complexing agent is added, 100ml of strong ammonia water is dropwise added into the mixed solution under the protection of nitrogen in constant-temperature water bath at 60-80 ℃ and continuously and mechanically stirred, so as to obtain 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 drying in vacuum 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 anhydrous ethanol and glacial acetic acid, wherein the volume ratio of the anhydrous ethanol to the glacial acetic acid is 3;
(6) And grinding the precursor material of the iron-based heterogeneous Fenton catalyst to obtain the heterogeneous Fenton catalyst F.
Example 7
The preparation process of the heterogeneous Fenton catalyst G is as follows:
(1) Dispersing 10g of 200-mesh sponge iron powder in 100ml of ultrapure water to obtain a dispersion liquid;
(2) Adding a solution containing 2.0g of ferrous chloride and 5.2g of ferric chloride to the dispersion with constant stirring;
(3) After 2.0g of tartrate-ethylene diamine tetraacetic 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 the temperature of 60-80 ℃, and the mixed solution is continuously and mechanically stirred to obtain 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 drying in vacuum 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 anhydrous ethanol and glacial acetic acid, wherein the volume ratio of the anhydrous ethanol to the glacial acetic acid is 3;
(6) And grinding the precursor material of the iron-based heterogeneous Fenton catalyst to obtain a heterogeneous Fenton catalyst G.
Example 8
The preparation process of the heterogeneous fenton catalyst H is specifically as follows:
(1) Dispersing 10g of 200-mesh sponge iron powder in 100ml of ultrapure water to obtain a dispersion liquid;
(2) Adding a solution containing 2.0g ferrous chloride and 5.2g ferric chloride to the dispersion with constant stirring;
(3) After 1.0g of tartrate-ethylene diamine tetraacetic 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 the temperature of 60-80 ℃, and the mixed solution is continuously and mechanically stirred to obtain 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 drying in vacuum 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 anhydrous ethanol and glacial acetic acid, wherein the volume ratio of the anhydrous ethanol to the glacial acetic acid is 3;
(6) And grinding the precursor material of the iron-based heterogeneous Fenton catalyst to obtain the heterogeneous Fenton catalyst H.
Comparative example 1
Other process conditions and experimental procedures of the comparative example 1 are the same as those of the example 1, except that the charcoal powder in the step (1) replaces the sponge iron powder, and the tartrate-ethylenediaminetetraacetic acid complexing agent is not added in the step (3). The preparation process of the heterogeneous Fenton catalyst M is as follows:
(1) Dispersing 10g of 200 mesh charcoal powder in 100ml of ultrapure water to obtain a dispersion liquid;
(2) Adding a solution containing 2.0g of ferrous chloride and 5.2g of ferric chloride to the dispersion under continuous stirring;
(3) Under the protection of nitrogen in a constant-temperature water bath at 60-80 ℃, dropwise adding 100ml of strong ammonia water into the dispersion liquid and continuously mechanically stirring to obtain a precipitate;
(4) Curing the precipitate for 30-60 min, cooling to room temperature, filtering, washing, and vacuum drying at 40-60 deg.c for 8-24 hr to obtain iron-base material;
(5) Ultrasonically dispersing 10g of iron-based material in 100ml of mixed solution of anhydrous ethanol and glacial acetic acid, wherein the volume ratio of the anhydrous ethanol to the glacial acetic acid is 3;
(6) And grinding the precursor material of the heterogeneous Fenton catalyst M to obtain the heterogeneous Fenton catalyst M.
Comparative example 2
The other process conditions and experimental procedures of this comparative example 2 were the same as those of example 1 except that the zeolite powder was used instead of the sponge iron powder in step (1) and the salt solution of transition metals manganese, zinc, cobalt, copper, molybdenum, nickel, vanadium, and chromium was not added in step (5). The preparation process of the heterogeneous Fenton catalyst N is as follows:
(1) 1, 10g of 200-mesh zeolite powder is dispersed in 100ml of ultrapure water to obtain a dispersion liquid;
(2) Adding a solution containing 2.0g of ferrous chloride and 5.2g of ferric chloride to the dispersion under continuous stirring;
(3) After 1.0g of tartrate-ethylene diamine tetraacetic acid complexing agent is added, 100ml of strong ammonia water is dropwise added into the mixed solution under the protection of nitrogen in constant-temperature water bath at 60-80 ℃ and continuously and mechanically stirred, so as to obtain 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 drying in vacuum 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 into 100ml of mixed solution of anhydrous ethanol and glacial acetic acid, wherein the volume ratio of the anhydrous ethanol to the glacial acetic acid is 3;
(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 1-8, comparative example 1 and comparative example 2 were tested for organic contaminant removal efficiency, and the test method included:
preparing 10 groups of 1L wastewater to be treated with COD of 300mg/L, adjusting the pH of the wastewater to be treated to be =7.0, and respectively adding 10g of heterogeneous Fenton catalysts prepared in examples 1-8, comparative example 1 and comparative example 2 according to the ratio of COD: h 2 O 2 Adding H in a proportion of 1 2 O 2 And then, stirring and reacting for 30min, detecting the COD value of each group, and calculating the removal rate of each group of COD.
The test results were as follows:
table 1: the heterogeneous Fenton catalysts prepared in different examples have COD removal rate.
As can be seen from table 1, the heterogeneous fenton catalysts obtained in examples 1 to 8 all have COD removal rates of 85% or more, and particularly, the heterogeneous fenton catalyst a obtained in example 1 has a COD removal rate as high as 92.9%, while the heterogeneous fenton catalysts obtained in comparative examples 1 and 2 have COD removal rates of 34.0% and 42.0%, respectively, and the heterogeneous fenton catalysts obtained in examples 1 to 8 have COD removal rates significantly higher than those of the heterogeneous fenton catalysts obtained in comparative examples 1 and 2. As can be seen from table 2, in comparative example 1 and comparative example 1, the reducing iron provides iron ions required for the fenton reaction during the catalytic reaction, and the tartrate-ethylenediaminetetraacetic acid complexing agent improves the stability of the iron ions under neutral conditions, so that the removal effect of COD is significantly improved. In comparative example 1 and comparative example 2, the addition of the transition metal element can promote the catalytic effect of the heterogeneous fenton catalyst, and in comparative example 1 and examples 2 to 3, the removal effect of COD is the best when the reducing iron is sponge iron powder, the removal effect of COD is the best when the transition metal is manganese, zinc, cobalt, copper, molybdenum, nickel, vanadium, and chromium in comparative example 1 and example 4, the removal effect of COD is the best when the complexing agent is tartrate-ethylenediaminetetraacetic acid, and the removal effect of COD is the best in comparative example 1 and examples 6 to 8 when the mass ratio of the transition metal element to the reducing iron powder is 1.
Table 2: the raw material types and the ratios of the heterogeneous Fenton catalysts are prepared in different embodiments.
Note: a: quality of reducing iron powder, B: transition metal element mass, C: mass of complexing agent, D: mass of tetrabutyl titanate
In summary, the removal rate of the heterogeneous fenton catalyst prepared in the embodiment of the present application to COD is above 85%, and 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 present application can realize catalysis under a neutral condition, reduce the dosage of the reagent and the generation amount of the iron-containing sludge, and realize effective recovery of the catalyst, thereby reducing the cost.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application, and not to limit the same; within the context of the present application, where technical features in the above embodiments or in different embodiments may also be combined, the steps may be implemented in any order and there are many other variations of the different aspects of the present application described above which are not provided in detail 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 solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and these modifications or substitutions do not depart from the scope of the technical solutions of the embodiments of the present application.
Claims (10)
1. A preparation method of a heterogeneous Fenton catalyst is characterized by comprising the following steps:
carrying out coprecipitation reaction on reducing iron powder, ferrous chloride, ferric chloride, a complexing agent and a first solvent to obtain 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 the nano ferroferric oxide;
and preparing the nano ferroferric oxide supported iron-based material, transition metal salt, tetrabutyl titanate and a second solvent by a sol-gel method to obtain the heterogeneous Fenton catalyst.
2. The method of preparing a heterogeneous Fenton's catalyst according to claim 1, wherein the reducing iron powder comprises at least one of sponge iron powder, zero valent iron powder and ferrous sulfide.
3. A method for preparing a heterogeneous fenton catalyst according to claim 1, wherein the complexing agent comprises at least one of tartrate-ethylenediaminetetraacetic acid and tartrate-diethylenetriaminepentaacetic acid.
4. The method of preparing a heterogeneous Fenton's catalyst according to claim 3, wherein when the complexing agent comprises tartrate-ethylenediamine tetraacetic acid, the molar ratio of tartrate to ethylenediamine tetraacetic acid is 1 to 100;
when the complexing agent comprises tartrate-diethylenetriamine pentaacetic acid, the molar ratio of the tartrate to the diethylenetriamine pentaacetic acid is 1-100.
5. The method of preparing a heterogeneous Fenton's catalyst according to claim 1, wherein the transition metal salt comprises at least one of manganese, zinc, cobalt, copper, molybdenum, nickel, vanadium, and chromium metal salts.
6. The preparation method of the heterogeneous Fenton catalyst according to claim 3, wherein the mass ratio of the complexing agent to the nano ferroferric oxide-supported iron-based material is 0.1-100.
7. The preparation method of the heterogeneous Fenton catalyst according to claim 5, wherein the mass ratio of the transition metal salt to the nano ferroferric oxide supported iron-based material is 0.01-50.
8. The method of preparing a heterogeneous Fenton's catalyst according to claim 1, wherein the step of co-precipitating the reduced iron powder, the ferrous chloride, the ferric chloride, the complexing agent and the first solvent comprises:
dispersing the reducing 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 solution;
and adding a first solvent into the mixed solution under the protection of constant-temperature gas to obtain the iron-based precipitate loaded with ferroferric oxide.
9. The preparation method of the heterogeneous Fenton catalyst according to claim 1, wherein the preparation method of the nano ferroferric oxide supported iron-based material, the transition metal salt, 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 the nano ferroferric oxide in the second solvent to obtain a second dispersion liquid;
and adding the tetrabutyl titanate into the second dispersion liquid, then adding the transition metal salt to form gel, standing and aging, drying, and grinding to obtain the heterogeneous Fenton catalyst.
10. Use of a heterogeneous fenton catalyst according to any of claims 1 to 9 for degrading organic pollutants in industrial wastewater treatment.
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