CN111732181A - A kind of heterogeneous Fenton reagent and its application - Google Patents

Abstract

The invention belongs to the technical field of reagents for wastewater treatment, in particular to a heterogeneous Fenton reagent and its application. The multiphase Fenton reagent provided by the present invention includes ferrous disulfide, hydrogen peroxide and transition metal sulfide; the transition metal sulfide includes one or more of molybdenum disulfide, zinc sulfide and tungsten disulfide; The hydrogen peroxide is separately packaged. In the heterogeneous Fenton reagent provided by the present invention, transition metal sulfides are used as cocatalysts, which can reduce ferric ions to ferrous ions in time, continue to decompose hydrogen peroxide to generate hydroxyl radicals to degrade pollutants, and transition metal As a co-catalyst, sulfide itself will not be destroyed, and it can play a role of co-catalysis continuously and stably. Therefore, transition metal sulfide can improve the generation efficiency and stability of ferrous ions on the surface of ferrous disulfide, and overcome the The problem of secondary pollution caused by the ferric ions contained in the homogeneous Fenton system solution.

Description

A kind of heterogeneous Fenton reagent and its application

technical field

The invention belongs to the technical field of reagents for wastewater treatment, in particular to a heterogeneous Fenton reagent and its application.

Background technique

Fenton's reagent refers to a strong oxidizing system composed of hydrogen peroxide and ferrous ions, and has a wide range of applications in the field of wastewater treatment. The traditional homogeneous Fenton system currently used, because the conversion of Fe ³⁺ and Fe ²⁺ is seriously limited by thermodynamics, so it requires higher Fe ²⁺ concentration and H ₂ O ₂ concentration, which causes great damage to water quality and equipment; Although the conversion efficiency of Fe ³⁺ to Fe ²⁺ can be improved by combining electrochemical technology, ultrasonic technology or adding reducing reagents, the reducing reagents are easy to cause secondary pollution of the water system.

At present, the concept of using Fenton's reagent to degrade pollutants in wastewater has attracted widespread attention in the field because of its low requirement for reducing reagents, but there are still problems such as low degradation performance and expensive reagent preparation.

SUMMARY OF THE INVENTION

In view of this, the purpose of the present invention is to provide a heterogeneous Fenton reagent, which can efficiently decompose organic pollutants in wastewater; the invention also provides the application of a heterogeneous Fenton reagent.

In order to realize the purpose of the above invention, the present invention provides the following technical solutions:

The invention provides a heterogeneous Fenton reagent, comprising ferrous disulfide, hydrogen peroxide and transition metal sulfide;

The transition metal sulfide includes one or more of molybdenum disulfide, zinc sulfide and tungsten disulfide;

The hydrogen peroxide is separately packaged.

Preferably, the mass ratio of the transition metal sulfide to ferrous disulfide is (1-30):100; the hydrogen oxide is provided in the form of hydrogen peroxide, and the concentration of the hydrogen peroxide is 0.01-1 mol/L.

Preferably, the ferrous disulfide and the transition metal sulfide in the heterogeneous Fenton reagent are an independent packaging system or a composite system.

The present invention also provides the application of the heterogeneous Fenton reagent described in the above technical solution in wastewater treatment.

Preferably, the waste water includes one or more of garbage permeate, pesticide waste water, pharmaceutical waste water, papermaking waste water, dye waste liquid, electroplating industry waste water and laboratory waste water.

Preferably, the pH value of the wastewater is 1-12.

Preferably, the pollutants in the wastewater include one or more of rhodamine B, methyl orange, methylene blue and p-nitrophenol.

Preferably, the application includes the following steps:

When the ferrous disulfide and the transition metal sulfide are separately packaged, the ferrous disulfide is mixed with the waste water and adsorbed to obtain the primary treatment waste water;

Mixing the primary treatment wastewater, hydrogen peroxide and transition metal sulfide to carry out a degradation reaction;

Or, when ferrous disulfide and transition metal sulfide are composite systems, the composite system of ferrous disulfide and transition metal sulfides is mixed with wastewater, and adsorbed to obtain primary treatment wastewater;

The primary treatment wastewater is mixed with hydrogen peroxide to carry out a degradation reaction.

Preferably, the concentration of the ferrous disulfide in the wastewater is 0.01-5 g/L.

Preferably, the concentration of the hydrogen peroxide in the wastewater is 0.01 mmol/L to 1 mol/L.

The present invention provides a heterogeneous Fenton reagent, comprising ferrous disulfide, hydrogen peroxide and transition metal sulfide; the transition metal sulfide includes one or more of molybdenum disulfide, zinc sulfide and tungsten disulfide The hydrogen peroxide is separately packaged. In the multiphase Fenton reagent provided by the present invention, ferrous ions on the surface of ferrous disulfide can be used as active sites, which can promote the dissociation of hydrogen peroxide to generate hydroxyl radicals, which are used for degrading organic pollutants in the water system. After the iron ion reacts with the hydrogen peroxide, it is oxidized into a ferric ion, and the transition metal sulfide is used as a co-catalyst to promptly reduce the ferric ion to a ferrous ion and continue to decompose the hydrogen peroxide to generate hydroxyl radicals. By degrading pollutants and using transition metal sulfides as co-catalysts, its own performance will not be destroyed, and it can play a sustainable and stable role as co-catalyst. Therefore, transition metal sulfides can improve the generation of ferrous ions on the surface of ferrous disulfide. Efficiency and stability enable the heterogeneous Fenton reagent provided by the present invention to continuously generate hydroxyl radicals to degrade pollutants in wastewater, improve the catalytic effect, and also overcome the ferric iron ions contained in the homogeneous Fenton system solution. secondary pollution problems.

The results of the examples show that when the multiphase Fenton reagent provided by the present invention is used for the treatment of the waste water body of the polluted system containing rhodamine B, for the degradation of the organic pollutant rhodamine B in the waste water, the degradation rate reaches 5 min after 5 minutes. When the pH range of the wastewater is 1-12, the multiphase Fenton reagent provided by the invention has excellent catalytic performance and is suitable for a wide range of wastewater pH values.

Further, the ferrous disulfide in the multiphase Fenton reagent provided by the present invention can be recovered, and when it is recovered and used for water treatment again, the treatment effect remains basically unchanged, indicating that the multiphase Fenton reagent provided by the present invention has good circulation stability. sex;

Detailed ways

The invention provides a heterogeneous Fenton reagent, which is characterized in that it comprises ferrous disulfide, hydrogen peroxide and transition metal sulfide;

The transition metal sulfide includes one or more of molybdenum disulfide, zinc sulfide and tungsten disulfide;

The hydrogen peroxide is separately packaged.

In the present invention, unless otherwise specified, the components are all commercially available products well known to those skilled in the art.

In the present invention, the heterogeneous Fenton reagent includes ferrous disulfide. The present invention has no special requirements on the source of the ferrous disulfide, which is obtained by using commercially available commodities or ore pulverization or other methods known in the art well-known to those skilled in the art. In the present invention, the ore in the ore pulverization is an ore containing ferrous disulfide, preferably pyrite; the mass content of FeS ₂ in the pyrite is preferably ≥30%. In the present invention, the pulverization is preferably crushing and/or ball milling; after the pulverization, the present invention can directly use the obtained pulverized material without extracting ferrous disulfide.

In the present invention, the particle size of the ferrous disulfide is preferably ≤300 μm, more preferably ≤50 μm, and even more preferably 0.1 to 10 μm. In the present invention, the particle size of ferrous disulfide is controlled within the above range, which is beneficial to further promote the contact effect between organic pollutants and ferrous disulfide in the water body, and the surface of ferrous disulfide provides more active sites, which helps to improve the catalytic performance.

The ferrous disulfide of the present invention has a large amount of ferrous ions (Fe ²⁺ ) on the surface in the water system, and as an active site for decomposing H ₂ O ₂ , hydrogen peroxide can be decomposed to generate hydroxyl radicals with degrading properties. Degrade organic pollutants. In addition, the ferrous disulfide used in the present invention is solid, and the surface of FeS ₂ contains iron ions with +2 valence, as the active site of the reaction, in the process of degrading the organic pollutants in the water body, it will not dissolve in the water body, avoid cause secondary pollution of water bodies.

In the present invention, the heterogeneous Fenton reagent includes a transition metal sulfide, and the transition metal sulfide includes one or more of molybdenum disulfide, zinc sulfide and tungsten disulfide. When there are multiple types of transition metal sulfides, the present invention does not specifically limit the proportions of multiple transition metal sulfides in the transition metal sulfides, and any proportion can be used.

The source of the transition metal sulfide is not particularly limited in the present invention, and is obtained by using commercially available commodities or ore pulverization well-known to those skilled in the art or other methods known in the art. In the present invention, the minerals contained in the ore in the ore pulverization preferably contain one or more of molybdenum disulfide, zinc sulfide and tungsten disulfide. In the present invention, the pulverization is preferably crushing and/or ball milling.

In the present invention, the mass ratio of the transition metal sulfide to ferrous disulfide is preferably (1-30):100, more preferably (5-25):30, still more preferably (10-20):30 .

In the present invention, the heterogeneous Fenton reagent includes hydrogen peroxide. In the present invention, the hydrogen peroxide is separately packaged.

In the present invention, the hydrogen peroxide is preferably provided in the form of an aqueous hydrogen peroxide solution, that is, in the form of hydrogen peroxide. The present invention does not specifically limit the concentration of the hydrogen peroxide, and the concentration of hydrogen peroxide well known to those skilled in the art can be used.

In the present invention, the concentration of the hydrogen peroxide is preferably 0.01-1 mol/L, more preferably 0.1-0.8 mol/L, still more preferably 0.2-0.7 mol/L.

In the present invention, the ferrous disulfide and the transition metal sulfide in the heterogeneous Fenton reagent are preferably an independent package system or a composite system.

When the ferrous disulfide and the transition metal sulfide in the heterogeneous Fenton reagent are a composite system, the preparation method of the composite system is: mixing ferrous disulfide and the transition metal sulfide in hydrogen peroxide, and the Ferrous disulfide and transition metal sulfide undergo a self-assembly reaction to obtain a composite system; the present invention does not specifically limit the concentration of the hydrogen peroxide, and any concentration of hydrogen peroxide can be used.

The heterogeneous Fenton catalyst ferrous disulfide of the present invention provides active sites, and in the aqueous solution, the surface has a large number of divalent iron ions as active sites, which is conducive to promoting the dissociation of hydrogen peroxide to generate hydroxyl radicals, which are used for degradation Organic pollutants in the water system; ferrous ions are oxidized to ferric ions after reacting with hydrogen peroxide, and the transition metal sulfides with the role of co-catalysts can reduce ferric ions to ferrous ions in time , to improve the generation efficiency and stability of ferrous ions on the surface of ferrous disulfide, so that the heterogeneous Fenton reagent can continuously generate hydroxyl radicals to degrade organic pollutants.

When the multiphase Fenton reagent provided by the invention is used to degrade pollutants in water, it has excellent mineralization ability, stable catalytic performance, ferrous disulfide and cocatalyst can be reused repeatedly, low product price, and universal pollutant types. It has the advantages of wide performance and industrial application value.

The present invention also provides the application of the heterogeneous Fenton reagent described in the above technical solution in the field of wastewater treatment.

In the present invention, the waste water preferably includes one or more of garbage permeate, pesticide waste water, pharmaceutical waste water, papermaking waste water, dye waste liquid, electroplating industry waste water and laboratory waste water. In the present invention, the pH value of the wastewater is preferably 1-12.

In the present invention, the pollutants in the wastewater preferably include one or more of Rhodamine B, methyl orange, methylene blue and p-nitrophenol. The present invention has no special requirements on the concentration of pollutants in the wastewater, and any concentration can be used; in the embodiment of the present invention, the concentration of organic pollutants in the wastewater is 20 mg/L.

In the present invention, the application preferably comprises the following steps:

When the ferrous disulfide and the transition metal sulfide are separately packaged, the ferrous disulfide is mixed with the waste water and adsorbed to obtain the primary treatment waste water;

After the primary treatment wastewater is obtained, the primary treatment wastewater, hydrogen peroxide and transition metal sulfide are mixed to carry out a degradation reaction to obtain treated water;

Or, when ferrous disulfide and transition metal sulfide are composite systems, the composite system of ferrous disulfide and transition metal sulfides is mixed with wastewater, and adsorbed to obtain primary treatment wastewater;

After the primary treatment wastewater is obtained, the primary treatment wastewater is mixed with hydrogen peroxide to carry out a degradation reaction to obtain treated water.

When the ferrous disulfide and the transition metal sulfide are separately packaged, the present invention mixes the ferrous disulfide with the waste water and carries out adsorption to obtain the primary treatment waste water. In the present invention, the concentration of the ferrous disulfide in the wastewater is preferably 0.01-5 g/L, more preferably 0.1-4.5 g/L, still more preferably 0.5-4 g/L. The present invention does not specifically limit the mixing, and the mixing well known to those skilled in the art can be used. In the present invention, the temperature of the adsorption is preferably room temperature, specifically, such as 18-25°C; the time is preferably ≥2h. In the present invention, the adsorption is preferably carried out under stirring conditions. In the present invention, the stirring speed is preferably 200-600 rpm, more preferably 250-550 rpm, and still more preferably 300-500 rpm.

After the primary treatment wastewater is obtained, the present invention mixes the primary treatment wastewater, hydrogen peroxide and transition metal sulfide to carry out a degradation reaction to obtain treated water. In the present invention, the concentration of the hydrogen peroxide in the wastewater is preferably 0.01 mmol/L to 1 mol/L, more preferably 0.01 to 200 mmol/L, and still more preferably 0.05 to 100 mmol/L. In the present invention, the mass ratio of the transition metal sulfide to ferrous disulfide is preferably (1-30):100, more preferably (5-25):100, still more preferably (10-20):100 . The present invention does not specifically limit the mixing, and the mixing well known to those skilled in the art can be used. In the present invention, the temperature of the degradation reaction is preferably room temperature, specifically, such as 18-25° C.; the time is preferably ≤ 1 h.

When ferrous disulfide and transition metal sulfide are composite systems, the present invention mixes the composite system of ferrous disulfide and transition metal sulfides with waste water, and carries out adsorption to obtain primary treatment waste water. In the present invention, in the composite system formed by the ferrous disulfide and the transition metal sulfide, the mass ratio of the transition metal sulfide to the ferrous disulfide is preferably (1-30):100, more preferably (5- 25): 100, more preferably (10-20): 100. In the present invention, the concentration of the ferrous disulfide and the ferrous disulfide in the transition metal sulfide in the wastewater is preferably 0.01-5 g/L, more preferably 0.1-4.5 g/L, still more preferably 0.5- 4g/L. The present invention does not specifically limit the mixing, and the mixing well known to those skilled in the art can be used. In the present invention, the temperature of the adsorption is preferably room temperature, specifically, such as 18-25°C; the time is preferably ≥2h. In the present invention, the adsorption is preferably carried out under stirring conditions. In the present invention, the stirring speed is preferably 200-600 rpm, more preferably 250-550 rpm, and still more preferably 300-500 rpm.

After the primary treatment wastewater is obtained, the present invention mixes the primary treatment wastewater with hydrogen peroxide to carry out a degradation reaction to obtain treated water. In the present invention, the concentration of the hydrogen peroxide in the wastewater is preferably 0.01 mmol/L to 1 mol/L, more preferably 0.01 to 200 mmol/L, and still more preferably 0.05 to 100 mmol/L. The present invention does not specifically limit the mixing, and the mixing well known to those skilled in the art can be used. In the present invention, the temperature of the degradation reaction is preferably room temperature, specifically, such as 18-25° C.; the time is preferably ≤ 1 h.

In the system formed by the heterogeneous Fenton reagent provided by the present invention, the transition metal sulfide easily forms sulfur defects in H2O2, exposes low-valent metal ions, undergoes redox reaction with Fe3+, and re-reduces Fe3+ to form Fe2+, thereby ensuring the stability of Fe2+ ion content in the heterogeneous Fenton reagent.

In order to further illustrate the present invention, the heterogeneous Fenton reagent provided by the present invention and its application are described in detail below with reference to the examples, but they should not be construed as limiting the protection scope of the present invention. Obviously, the described embodiments are only some, but not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Example 1

A multiphase Fenton reagent is provided, the heterogeneous Fenton reagent includes ferrous disulfide, molybdenum disulfide and hydrogen peroxide, wherein the ferrous disulfide and molybdenum disulfide are dispersed systems, and the hydrogen peroxide is separately packaged.

Example 2

A multiphase Fenton reagent is provided, the multiphase Fenton reagent includes ferrous disulfide, zinc sulfide and hydrogen peroxide, wherein the ferrous disulfide and zinc sulfide are dispersed systems, and the hydrogen peroxide is separately packaged.

Example 3

A multiphase Fenton reagent is provided, the multiphase Fenton reagent includes ferrous disulfide, tungsten disulfide and hydrogen peroxide, wherein the ferrous disulfide and tungsten disulfide are dispersed systems, and the hydrogen peroxide is separately packaged.

Comparative Example 1

Homogeneous Fenton's reagents are supplied, which contain only ferrous disulfide and hydrogen peroxide in separate aliquots.

Comparative Example 2

Homogeneous Fenton's reagents are available which contain only ferrous chloride and hydrogen peroxide in separate aliquots.

Application examples 1 to 4

Using the heterogeneous Fenton reagents of Examples 1 to 3 and the homogeneous Fenton reagent of Comparative Example 1 to treat the polluted water body containing Rhodamine B, the wastewater treatment method is as follows:

Provide 100 mL of Rhodamine B solution with a concentration of 20 mg/L, wherein the pH of Rhodamine B solution is 7;

Add 10 mg of ferrous disulfide and 2 mg of transition metal sulfide to the Rhodamine B solution (the process of adding transition metal sulfide is not required in Application Example 4) to satisfy the concentration of ferrous disulfide in the wastewater system of 0.1 g/L , Adsorption was carried out under the stirring conditions of room temperature and rotating speed of 400 rpm, and the adsorption reached the adsorption equilibrium for 2 h, and the primary treatment wastewater was obtained;

Hydrogen peroxide was added to the obtained primary treated wastewater so that the concentration of hydrogen peroxide in the system was 0.5 mmol/L, the degradation reaction was carried out at room temperature, and the treated water was obtained after degrading for 10 min.

Take 1.5 mL of treated water, centrifuge to precipitate ferrous disulfide and transition metal sulfides, and take the supernatant to measure the absorbance of the supernatant using a UV-Vis spectrophotometer. Calculate the degradation amount of organic pollutants at different times, expressed as C, and the calculation formula is C=C ₀ -C _{test value} , where C ₀ represents the initial concentration of organic pollutants in the organically polluted water after the adsorption equilibrium, C _{test value} Indicates the concentration of organic pollutants in the water at the corresponding degradation time. The degradation rate is calculated as the ratio of the degradation amount of organic pollutants to the initial concentration of organic pollutants, and the calculation method is C/C ₀ (%).

Table 1 Application Examples 1-4 Reagent dosage and test results

As can be seen from Table 1, by adding a very small amount of transition metal sulfide to the water body as a cocatalyst, the degradation rate of Rhodamine B in the organically polluted water body is increased from 32% to 90% in a very short time (10min). % or more, indicating that the heterogeneous Fenton reagent provided by the present invention can significantly improve the catalytic performance of the homogeneous Fenton reagent composed of ferrous disulfide and hydrogen peroxide for the degradation of Rhodamine B.

Application examples 5 to 12

Using the heterogeneous Fenton reagent of Example 1 and the homogeneous Fenton reagent of Comparative Example 2 to treat the polluted water body containing Rhodamine B, the treatment method is:

Provide 100mL of Rhodamine B solution with a concentration of 20mg/L, wherein the pH value of Rhodamine B solution is 8-10;

Add 10 mg of ferrous disulfide and 2 mg of transition metal sulfide to the Rhodamine B solution (the process of adding transition metal sulfide is not required in Application Example 4) to satisfy the concentration of ferrous disulfide in the wastewater system of 0.1 g/L , Adsorption was carried out under the stirring conditions of room temperature and rotating speed of 400 rpm, and the adsorption reached the adsorption equilibrium for 2 h, and the primary treatment wastewater was obtained;

Hydrogen peroxide was added to the obtained primary treated wastewater so that the concentration of hydrogen peroxide in the system was 0.5 mmol/L, the degradation reaction was carried out at room temperature, and the treated water was obtained after degrading for 10 min.

Take 1.5 mL of treated water, centrifuge to precipitate ferrous disulfide and transition metal sulfides, and take the supernatant to measure the absorbance of the supernatant using a UV-Vis spectrophotometer. Calculate the degradation amount of organic pollutants at different times, expressed as C, and the calculation formula is C=C ₀ -C _{test value} , where C ₀ represents the initial concentration of organic pollutants in the organically polluted water after the adsorption equilibrium, C _{test value} Indicates the concentration of organic pollutants in the water at the corresponding degradation time. The degradation rate is calculated as the ratio of the degradation amount of organic pollutants to the initial concentration of organic pollutants, and the calculation method is C/C ₀ (%).

Table 2 Application Examples 5-8 Reagent dosage and test results

Table 3 Application Examples 9-12 Reagent dosage and test results

As can be seen from Table 2 and Table 3, when pH>9, the homogeneous Fenton reagent composed of ferrous chloride containing divalent ferrous ion and hydrogen peroxide has extremely low degradation activity to Rhodamine B; and the present invention provides The degradation rate of Rhodamine B by the heterogeneous Fenton reagents was higher.

Example 4

Provided is a heterogeneous Fenton reagent, the heterogeneous Fenton reagent includes ferrous disulfide, molybdenum disulfide and hydrogen peroxide, wherein the ferrous disulfide and molybdenum disulfide are a composite system, and the hydrogen peroxide is separately packaged.

Example 5

Provided is a heterogeneous Fenton reagent, the heterogeneous Fenton reagent includes ferrous disulfide, zinc sulfide and hydrogen peroxide, wherein the ferrous disulfide and zinc sulfide are a composite system, and the hydrogen peroxide is separately packaged.

Example 6

Provided is a heterogeneous Fenton reagent, the heterogeneous Fenton reagent includes ferrous disulfide, tungsten disulfide and hydrogen peroxide, wherein the ferrous disulfide and tungsten disulfide are a composite system, and the hydrogen peroxide is separately packaged.

Comparative Example 3

A multiphase Fenton reagent is provided, the multiphase Fenton reagent includes ferric tetroxide, molybdenum disulfide and hydrogen peroxide, wherein the ferric tetroxide and molybdenum disulfide are a composite system, and the hydrogen peroxide is separately packaged.

Comparative Example 4

Provided is a heterogeneous Fenton reagent, the heterogeneous Fenton reagent includes ferrous oxide, molybdenum disulfide and hydrogen peroxide, wherein the ferrous oxide and molybdenum disulfide are a composite system, and the hydrogen peroxide is separately packaged.

Application examples 13 to 15

The polluted water bodies containing Rhodamine B were treated with the multiphase Fenton reagents of Examples 4 to 6, respectively, and the treatment method was as follows:

Provide 100 mL of Rhodamine B solution with a concentration of 20 mg/L, wherein the pH of Rhodamine B solution is 7;

To the Rhodamine B solution, add 10 mg of the composite system of ferrous disulfide and transition metal sulfide to satisfy the concentration of ferrous disulfide in the wastewater system of 0.1 g/L. Adsorption, adsorption reached adsorption equilibrium for 2h, and primary treatment wastewater was obtained;

Hydrogen peroxide was added to the obtained primary treated wastewater so that the concentration of hydrogen peroxide in the system was 0.5 mmol/L, the degradation reaction was carried out at room temperature, and the treated water was obtained after degrading for 10 min.

Take 1.5mL of treated water, centrifuge to precipitate ferrous disulfide and transition metal sulfides, take the supernatant to measure the absorbance of the supernatant using a UV-Vis spectrophotometer, the calculation method of the degradation rate is the same as that of application example 1, and application examples 13～ 15 Reagent dosage and test results are shown in Table 4.

Table 4 Reagent dosage and test results of application examples 13-15

It can be seen from Table 4 that when ferrous disulfide and transition metal sulfide are composite systems, the heterogeneous Fenton reagent provided by the present invention has an extremely significant catalytic degradation effect on Rhodamine B.

Application examples 16 to 21

The polluted water body containing Rhodamine B was treated with the multiphase Fenton reagent of Example 1, and the treatment method was as follows:

Provide 100 mL of Rhodamine B solution with a concentration of 20 mg/L, wherein the pH of Rhodamine B solution is 7;

Add 10 mg of ferrous disulfide and 2 mg of molybdenum disulfide to the Rhodamine B solution to satisfy the concentration of ferrous disulfide in the wastewater system of 0.1 g/L, and carry out adsorption at room temperature and under stirring conditions of 400 rpm. The adsorption equilibrium was reached in 2h, and the primary treatment wastewater was obtained;

Hydrogen peroxide was added to the obtained primary treatment wastewater, and the degradation reaction was carried out at room temperature, and the treated water was obtained after degrading for 10 min.

Take 1.5mL of treated water, centrifuge to precipitate ferrous disulfide and molybdenum disulfide, take the supernatant to measure the absorbance of the supernatant using a UV-Vis spectrophotometer, the calculation method of the degradation rate is the same as that of application example 1, application examples 16-21 The amount of reagents and test results are shown in Table 5.

Table 5 Reagent dosage and test results of application examples 16-21

As can be seen from Table 5, when ferrous disulfide and transition metal sulfide are dispersed systems, within the scope of the heterogeneous Fenton reagent hydrogen peroxide provided by the present invention, the present invention has fast and excellent catalytic degradation to the organic pollutant Rhodamine B. Effect.

Application examples 22 to 27

The polluted water body containing Rhodamine B was treated with the multiphase Fenton reagent of Example 4, and the treatment method was as follows:

Provide 100 mL of Rhodamine B solution with a concentration of 20 mg/L, wherein the pH of Rhodamine B solution is 7;

Add 10 mg of the composite system of ferrous disulfide and molybdenum disulfide to the Rhodamine B solution to satisfy the concentration of ferrous disulfide in the wastewater system of 0.1 g/L, and carry out the adsorption at room temperature and under the stirring conditions of 400 rpm. , the adsorption reached the adsorption equilibrium for 2h, and the primary treatment wastewater was obtained;

Hydrogen peroxide was added to the obtained primary treatment wastewater, and the degradation reaction was carried out at room temperature, and the treated water was obtained after degrading for 10 min.

Take 1.5mL of treated water, centrifuge to precipitate a composite system of ferrous disulfide and molybdenum disulfide, take the supernatant and use a UV-Vis spectrophotometer to measure the absorbance of the supernatant. The calculation method of the degradation rate is the same as that of Application Example 1. Application Example The dosage of 22-27 reagents and the test results are shown in Table 6.

Table 6 Reagent dosage and test results of application examples 22-27

As can be seen from Table 6, when ferrous disulfide and transition metal sulfide are composite systems, within the scope of the heterogeneous Fenton reagent hydrogen peroxide provided by the present invention, the present invention has fast and excellent catalytic degradation to the organic pollutant Rhodamine B. Effect.

Application examples 28 to 30

The polluted water body containing Rhodamine B was treated with the multiphase Fenton reagent of Example 1, and the treatment method was:

Provide 100 mL of Rhodamine B solution with a concentration of 20 mg/L, wherein the pH of Rhodamine B solution is 7;

Add 10 mg of ferrous disulfide and transition metal sulfides to the Rhodamine B solution to satisfy the concentration of ferrous disulfide in the wastewater system of 0.1 g/L, and carry out adsorption at room temperature and under stirring conditions of 400 rpm. The adsorption equilibrium was reached in 2h, and the primary treatment wastewater was obtained;

Hydrogen peroxide was added to the obtained primary treated wastewater so that the concentration of hydrogen peroxide in the system was 0.5 mmol/L, the degradation reaction was carried out at room temperature, and the treated water was obtained after degrading for 10 min.

Take 1.5 mL of treated water, centrifuge to precipitate ferrous disulfide and transition metal sulfide, take the supernatant to measure the absorbance of the supernatant using a UV-Vis spectrophotometer, the calculation method of the degradation rate is the same as that of application example 1, and application examples 28～ 30 Reagent dosage and test results are shown in Table 7.

Table 7 Application example 28～30 Reagent dosage and test results

As can be seen from Table 7, when ferrous disulfide and transition metal sulfide are dispersed systems, within the content range of transition metal sulfide defined in the present invention, the present invention has fast and excellent catalytic degradation effect on the organic pollutant Rhodamine B. .

Application examples 31 to 34

With the heterogeneous Fenton reagent of embodiment 4, the polluted water body containing different organic pollutants is respectively carried out waste water treatment, and the treatment method is:

Provide 100mL of organic pollutant solution with a concentration of 20mg/L, wherein the pH value of the organic pollutant solution is 7;

Add 10mg of the composite system of ferrous disulfide and molybdenum disulfide to the organic pollutant solution to satisfy the concentration of ferrous disulfide in the wastewater system is 0.1g/L, and the adsorption is carried out under the stirring conditions of room temperature and rotation speed of 400rpm , the adsorption reached the adsorption equilibrium for 2h, and the primary treatment wastewater was obtained;

Hydrogen peroxide was added to the obtained primary treatment wastewater, and the degradation reaction was carried out at room temperature, and the treated water was obtained after degrading for 10 min.

Take 1.5mL of treated water, centrifuge to precipitate a composite system of ferrous disulfide and molybdenum disulfide, take the supernatant and use a UV-Vis spectrophotometer to measure the absorbance of the supernatant. The calculation method of the degradation rate is the same as that of Application Example 1. Application Example The dosage of reagents 31-34 and the test results are shown in Table 8.

Table 8 Reagent dosage and test results of application examples 31 to 34

As can be seen from Table 8, when ferrous disulfide and transition metal sulfide are composite systems, in the scope of heterogeneous Fenton reagent hydrogen peroxide provided by the invention, the present invention has no effect on the organic pollutants p-nitrophenol, saffron, methyl methacrylate. Both amidophos and Sudan red have fast and excellent catalytic degradation effects.

Application examples 35 to 36

The ferrous disulfide in the heterogeneous Fenton reagent of Example 4 is replaced with ferric oxide and ferrous oxide, respectively, and the polluted water body containing Rhodamine B is treated as waste water, and the treatment method is:

Provide 100 mL of Rhodamine B solution with a concentration of 20 mg/L, wherein the pH of Rhodamine B solution is 7;

Add 10mg of the composite system of ferric oxide and molybdenum disulfide or the composite system of ferrous oxide and molybdenum disulfide to the rhodamine B solution, so that the concentration of ferrous ions in the wastewater system is 0.1g/L, at room temperature The adsorption is carried out under the stirring condition of the rotating speed of 400rpm, and the adsorption reaches the adsorption equilibrium for 2h, and the primary treatment wastewater is obtained;

Hydrogen peroxide was added to the obtained primary treatment wastewater, and the degradation reaction was carried out at room temperature, and the treated water was obtained after degrading for 10 min.

Take 1.5mL of treated water, centrifuge to precipitate a composite system of iron compounds and molybdenum disulfide, take the supernatant to measure the absorbance of the supernatant using a UV-Vis spectrophotometer, the calculation method of the degradation rate is the same as that of Application Example 1, and Application Example 23 and Application examples 35-36 reagent dosage and test results are shown in Table 9.

Table 9 Reagent dosage and test results of application example 23 and application example 35-36

As can be seen from Table 9, when ferric oxide and ferrous oxide are composite systems with transition metal sulfides respectively, the obtained compounds show lower catalytic degradation performance to organic pollutants, and the heterogeneous Fenton reagent provided by the invention It has fast and excellent catalytic degradation effect on the organic pollutant rhodamine B.

The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made. It should be regarded as the protection scope of the present invention.

Claims (10)

1. a heterogeneous Fenton reagent, is characterized in that, comprises ferrous disulfide, hydrogen peroxide and transition metal sulfide; The transition metal sulfide includes one or more of molybdenum disulfide, zinc sulfide and tungsten disulfide; The hydrogen peroxide is separately packaged. 2. The multiphase Fenton reagent according to claim 1, wherein the mass ratio of the transition metal sulfide to ferrous disulfide is (1～30): 100; Provided in the form of hydrogen peroxide in a concentration of 0.01 to 1 mol/L. 3 . The multiphase Fenton reagent according to claim 1 , wherein the ferrous disulfide and the transition metal sulfide in the multiphase Fenton reagent are independent packaging systems or composite systems. 4 . 4. The application of the heterogeneous Fenton reagent according to any one of claims 1 to 3 in wastewater treatment. 5. The application according to claim 4, wherein the waste water comprises one or more of garbage permeate, pesticide waste water, pharmaceutical waste water, papermaking waste water, dye waste liquid, electroplating industry waste water and laboratory waste water. kind. 6 . The application according to claim 5 , wherein the pH value of the wastewater is 1-12. 7 . 7. The application according to claim 4, wherein the pollutants in the waste water comprise one or more of Rhodamine B, methyl orange, methylene blue and p-nitrophenol. 8. The application according to any one of claims 4 to 7, wherein the application comprises the following steps: When the ferrous disulfide and the transition metal sulfide are separately packaged, the ferrous disulfide is mixed with the waste water and adsorbed to obtain the primary treatment waste water; Mixing the primary treatment wastewater, hydrogen peroxide and transition metal sulfide to carry out a degradation reaction; Or, when ferrous disulfide and transition metal sulfide are composite systems, the composite system of ferrous disulfide and transition metal sulfides is mixed with wastewater, and adsorbed to obtain primary treatment wastewater; The primary treatment wastewater is mixed with hydrogen peroxide to carry out a degradation reaction. 9 . The application according to claim 8 , wherein the concentration of the ferrous disulfide in the wastewater is 0.01-5 g/L. 10 . 10 . The application according to claim 8 , wherein the concentration of the hydrogen peroxide in the wastewater is 0.01 mmol/L to 1 mol/L. 11 .