Preparation method of a highly active iron-based-sulfide-additive composite material and its product and application

Abstract

The present invention discloses a method for preparing a highly active iron-based sulfide-additive composite material, its products, and applications, and belongs to the field of chemical technology. The method comprises the following steps: adding an iron-based material to a sulfide-additive solution, ultrasonicating, heating for reaction, and cooling to obtain the highly active iron-based sulfide-additive composite material; wherein the additive in the sulfide-additive solution is selected from one of sulfite, sodium borohydride, and manganese oxide. The addition of a strong reducing additive accelerates the reaction process, thereby achieving high efficiency in degrading organic matter in wastewater.

Description

Technical Field

[0001] The present invention belongs to the field of chemical technology, and in particular relates to a preparation method of a high-activity iron-based-sulfide-additive composite material, and a product and application thereof. Background Art

[0002] With the continuous advancement of science and technology, the accelerated pace of industrial development, and the overuse of natural resources, water treatment has become a major issue of global concern. Phenol wastewater, a typical example of a difficult-to-degrade organic wastewater, is discharged into the environment without timely treatment, causing irreparable damage. Therefore, treating phenol wastewater is of vital importance to both the environment and social progress. Fenton technology has played a very effective role in treating wastewater, offering high efficiency, cleanliness, and affordability. However, in industrialization, after entering the neutralization tank, the reaction produces some unnecessary iron-based byproducts, causing secondary pollution to the environment. Previously, hydrothermally synthesized sulfides could be composited with iron-based materials, and while these composites were highly active, they required high economic costs and energy consumption. Therefore, the development of a highly active iron-based-sulfide-additive composite for treating these iron-based byproducts is particularly important. Summary of the Invention

[0003] To address the above technical issues, the present invention proposes a method for preparing a highly active iron-based-sulfide-additive composite material, as well as its product and application, to address the secondary pollution and cost issues associated with Fenton technology wastewater treatment.

[0004] To achieve the above object, the present invention provides the following technical solutions:

[0005] One of the objectives of the present invention is to provide a method for preparing a highly active iron-based-sulfide-additive composite material, comprising the following steps: adding an iron-based material to a sulfide-additive solution, ultrasonically treating, heating for reaction, and cooling to obtain the highly active iron-based-sulfide-additive composite material; wherein the additive in the sulfide-additive solution is selected from one of sulfite, sodium borohydride, and manganese oxide.

[0006] The present invention utilizes the chemical bond between the iron-based material and the sulfide, and then adds a strong reducing agent to prepare a highly active iron-based-sulfide-auxiliary compound material for removing organic pollutants under acidic conditions. The chemical bond between the iron-based material and the sulfide can construct an acidic microenvironment on the surface of the iron-based material, thereby ensuring the stable circulation of iron ions within a local microenvironment. After the strong reducing agent is added, this process can be accelerated, thereby achieving high efficiency in degrading wastewater.

[0007] Because commercial sulfides inevitably experience reduced activity, the present invention adds an additive to the sulfide, compensating for this reduced activity while reducing both economic and energy costs. This heterogeneous Fenton reaction system effectively treats wastewater byproducts, replacing the iron source recycling process in the Fenton reaction. This reduces costs while also avoiding unnecessary secondary pollution, thus possessing significant scientific significance in the environmental field.

[0008] Furthermore, the specific preparation method of the iron-based material includes: adding an iron source and hydrogen peroxide into water, stirring evenly, adjusting the pH to neutral, standing, centrifuging, and drying to obtain the iron-based material.

[0009] Furthermore, the ratio of the iron source, hydrogen peroxide and water is (10-1000) mg: (1-20) mL: (10-1000) mL; and / or

[0010] The iron source is selected from one of ferrous oxide, ferric oxide, ferric oxide, ferric chloride, ferric sulfate and ferrous sulfate; and / or

[0011] The reagent used to adjust the pH is sulfuric acid; and / or

[0012] The standing time is 1-1000 min.

[0013] Furthermore, the specific preparation method of the sulfide-additive solution includes: adding a molybdenum source and a sulfur source into water, adding the additive after ultrasonication, and continuing ultrasonication to obtain the sulfide-additive solution.

[0014] Furthermore, the molybdenum source is selected from one or more of ammonium molybdate, sodium molybdate, molybdenum trioxide, molybdenum dioxide and molybdenum powder; and / or

[0015] The sulfur source is selected from one or more of thioacetamide, thiourea, sulfur powder and sodium sulfide; and / or

[0016] The molybdenum source, sulfur source, water and auxiliary agent are used in a ratio of (1-1000) mg: (1-2000) mg: (10-100) mL: (1-1000) mg; and / or

[0017] The ultrasonic time is 1-60 min.

[0018] Furthermore, the ultrasonic treatment time is 1-100 min.

[0019] Furthermore, the heating reaction conditions are: reaction at 60-100° C. for 1-5 hours.

[0020] The second object of the present invention is to provide a high-activity iron-based-sulfide-additive composite material prepared by the above-mentioned preparation method.

[0021] A third object of the present invention is to provide a highly active iron-based-sulfide-additive composite material for use in removing organic pollutants from wastewater.

[0022] The fourth object of the present invention is to provide a method for removing organic pollutants, comprising the following steps: adding the highly active iron-based-sulfide-additive composite material into wastewater containing organic pollutants, adding an initiator, and stirring to achieve the removal of organic matter; wherein,

[0023] The organic pollutant is phenol, and the concentration of phenol in the wastewater is 1-2000 mg / L;

[0024] The initiator is 30wt% hydrogen peroxide;

[0025] The input amount of the highly active iron-based-sulfide-auxiliary composite material is 300 mg / L;

[0026] The wastewater containing organic pollutants is acidic.

[0027] Compared with the prior art, the present invention has the following advantages and technical effects:

[0028] 1. Compared with the traditional wastewater treatment system, the present invention solves the secondary pollution problem of by-products. After resource utilization, it can achieve excellent results in removing pollutants in wastewater;

[0029] 2. The amount of catalyst added in the present invention is relatively small, and the catalyst is magnetic, so the recovery is convenient and simple, and secondary pollution to the environment can be avoided.

[0030] 3. The present invention synthesizes a highly active iron-based-sulfide-auxiliary agent composite material, which has a pollutant removal efficiency of 90-100% for phenol removal within 10 minutes. It can also replace the iron source used in the Fenton technology to a certain extent when removing COD (chemical oxygen demand) from wastewater, providing the possibility of using heterogeneous Fenton reaction to treat wastewater at low cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The accompanying drawings, which constitute part of the present invention, are provided to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are provided to explain the present invention and do not constitute an undue limitation of the present invention. In the accompanying drawings:

[0032] Figure 1 This is a comparison chart of the degradation effects of the products prepared in Example 1, Comparative Example 1, and Comparative Example 2 on phenol;

[0033] Figure 2 This is a comparison chart of the degradation effects of the products prepared in Examples 1-3 and Comparative Examples 3-4 on phenol;

[0034] Figure 3 This is a comparison chart of the COD degradation effects of the product prepared in Example 3 and ferrous oxide mixed in different proportions as catalysts. DETAILED DESCRIPTION

[0035] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0036] It should be understood that the terms described herein are intended only to describe particular embodiments and are not intended to limit the present invention. In addition, for numerical ranges herein, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each smaller range between any intermediate value within a stated value or stated range and any other stated value or intermediate value within the stated range is also encompassed by the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded within the scope.

[0037] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of any conflict with any incorporated document, the contents of this specification shall prevail.

[0038] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the invention. The description and examples are intended to be illustrative only.

[0039] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0040] The present invention provides a method for preparing a highly active iron-based-sulfide-additive composite material, comprising the following steps:

[0041] 1) Preparation of iron-based materials;

[0042] 2) preparing a sulfide-builder solution;

[0043] 3) adding the iron-based material to the sulfide-additive solution, performing ultrasonic treatment, heating for reaction, cooling after the reaction is completed, and drying to obtain a highly active iron-based-sulfide-additive composite material.

[0044] In some embodiments, in step 1), the specific preparation method of the iron-based material includes: adding an iron source and hydrogen peroxide to a beaker filled with water, stirring with a magnetic bar to obtain a uniform solution; adjusting the pH of the uniform solution to neutral, stopping stirring, standing, centrifuging, and drying to obtain the iron-based material.

[0045] The ratio of the iron source, hydrogen peroxide and water is (10-1000) mg: (1-20) mL: (10-1000) mL. For example, in the following preferred embodiments of the present invention, the ratio of the iron source, hydrogen peroxide and water can be selected as 300 mg: 20 mL: 100 mL.

[0046] The iron source is selected from one of ferrous oxide, ferric oxide, ferric oxide, ferric chloride, ferric sulfate and ferrous sulfate. For example, in the following preferred embodiments of the present invention, the iron source can be selected from ferrous oxide.

[0047] The stirring time is 1-100 hours. For example, in the following preferred embodiments of the present invention, the stirring time can be selected as 24 hours.

[0048] The reagent used for adjusting pH is sulfuric acid.

[0049] The standing time is 1-1000 min. For example, in the following preferred embodiments of the present invention, the standing time can be selected as 180 min.

[0050] In some embodiments, in step 2), the specific preparation method of the sulfide-additive solution includes: adding a molybdenum source and a sulfur source into a beaker containing water, adding the additive after ultrasonication, and continuing ultrasonication to obtain the sulfide-additive solution.

[0051] The molybdenum source is selected from one or more of ammonium molybdate, sodium molybdate, molybdenum trioxide, molybdenum dioxide and molybdenum powder. For example, in the following preferred embodiments of the present invention, the molybdenum source can be sodium molybdate.

[0052] The sulfur source is selected from one or more of thioacetamide, thiourea, sulfur powder and sodium sulfide. For example, in the following preferred embodiments of the present invention, the sulfur source can be selected from thioacetamide.

[0053] The auxiliary agent in the sulfide-auxiliary agent solution is selected from one of sulfite, sodium borohydride and manganese oxide. For example, in the following preferred embodiments of the present invention, the auxiliary agent can be selected from sulfite, sodium borohydride or manganese oxide.

[0054] The molybdenum source, sulfur source, water, and auxiliary agent are used in a ratio of (1-1000) mg: (1-2000) mg: (10-100) mL: (1-1000) mg. For example, in the following preferred embodiments of the present invention, the molybdenum source, sulfur source, water, and auxiliary agent can be used in a ratio of (400-800) mg: (200-500) mg: (100) mL: (100-300) mg.

[0055] The ultrasonic time is 1-60 minutes. For example, in the following preferred embodiments of the present invention, the ultrasonic time is 60 minutes.

[0056] In some embodiments, in step 3), the ultrasonic treatment time is 1-100 min. For example, in the following preferred embodiments of the present invention, the ultrasonic treatment time can be selected to be 30 min.

[0057] In some embodiments, in step 3), the heating reaction is carried out at 60-100° C. for 1-5 hours. For example, in the following preferred embodiments of the present invention, the heating reaction can be carried out at 80° C. for 4 hours.

[0058] The above preparation method can be used to prepare highly active iron-based-sulfide-additive composite materials. For example, a highly active ferroferric oxide-ammonium thiomolybdate-sulfite composite material can be constructed by chemically combining the byproduct ferroferric oxide with ammonium thiomolybdate through the addition of sulfite. This creates an acidic microenvironment on the surface of the ferroferric oxide, thereby ensuring the stable circulation of iron ions within a local microenvironment. The addition of sulfite accelerates this process, thereby achieving efficient wastewater degradation.

[0059] The highly active iron-based-sulfide-auxiliary compound material can be used to remove organic pollutants from wastewater. The organic pollutant can be phenol. The highly active iron-based-sulfide-auxiliary compound material prepared by the present invention can also reduce the COD in wastewater.

[0060] The method for removing organic pollutants comprises the following steps: adding a high-activity iron-based-sulfide-auxiliary agent composite material into wastewater containing organic pollutants, adding an initiator, and stirring to achieve removal of the organic matter.

[0061] In some embodiments, the organic pollutant is phenol, and the concentration of the phenol in the wastewater is 1-2000 mg / L; illustratively, in the following preferred embodiments of the present invention, the concentration of the phenol can be selected to be 20 mg / L.

[0062] In some embodiments, the initiator is 30 wt% hydrogen peroxide; the amount of hydrogen peroxide added to 100 mL of wastewater is 250 μL;

[0063] In some embodiments, the input amount of the high-activity iron-based-sulfide-additive composite material is 300 mg / L.

[0064] In some embodiments, the wastewater is acidic wastewater. For example, in the following preferred embodiments of the present invention, the pH of the wastewater can be set to 4.

[0065] The raw materials used in the present invention are all purchased from the market.

[0066] The technical solution of the present invention is further illustrated by the following examples.

[0067] Example 1

[0068] A method for preparing a highly active iron-based-sulfide-additive composite material comprises the following steps:

[0069] 1) Preparation of iron-based materials:

[0070] 300 mg of ferrous oxide and 20 mL of hydrogen peroxide were added to a beaker containing 100 mL of water and stirred with a magnetic stirrer for 24 h to obtain a homogeneous solution. The pH of the homogeneous solution was adjusted to neutral with sulfuric acid, and then stirring was stopped. The solution was allowed to stand for 180 min, centrifuged, and dried to obtain ferrosoferric oxide.

[0071] 2) Preparation of sulfide-builder solution: 400 mg of sodium molybdate and 200 mg of thioacetamide were added to a beaker containing 100 mL of water. After sonication for 60 min, 100 mg of sulfite was added to the beaker and sonication was continued for 60 min to obtain an ammonium thiomolybdate-sulfite solution.

[0072] 3) The ferroferric oxide and ammonium thiomolybdate-sulfite solution was ultrasonically treated for 30 minutes, placed in a water bath, and mechanically stirred at 80° C. for 4 hours. After the reaction was completed, it was cooled and dried to obtain a highly active ferroferric oxide-ammonium thiomolybdate-sulfite composite material.

[0073] Example 2

[0074] A method for preparing a highly active iron-based-sulfide-additive composite material comprises the following steps:

[0075] 1) Preparation of iron-based materials:

[0076] 300 mg of ferrous oxide and 20 mL of hydrogen peroxide were added to a beaker containing 100 mL of water and stirred with a magnetic stirrer for 24 h to obtain a homogeneous solution. The pH of the homogeneous solution was adjusted to neutral with sulfuric acid, and then stirring was stopped. The solution was allowed to stand for 180 min, centrifuged, and dried to obtain ferrosoferric oxide.

[0077] 2) Preparation of sulfide-promoter solution: 800 mg of ammonium molybdate and 500 mg of thiourea were added to a beaker containing 100 mL of water. After sonication for 60 minutes, 300 mg of sodium borohydride was added to the beaker and sonication was continued for 60 minutes to obtain an ammonium thiomolybdate-sodium borohydride solution.

[0078] 3) The ferroferric oxide and ammonium thiomolybdate-sodium borohydride solution were ultrasonically treated for 30 minutes, placed in a water bath, and mechanically stirred for reaction at 80° C. for 4 hours. After the reaction was completed, the solution was cooled and dried to obtain a highly active ferroferric oxide-ammonium thiomolybdate-sodium borohydride composite material.

[0079] Example 3

[0080] A method for preparing a highly active iron-based-sulfide-additive composite material comprises the following steps:

[0081] 1) Preparation of iron-based materials:

[0082] 300 mg of ferrous oxide and 20 mL of hydrogen peroxide were added to a beaker containing 100 mL of water and stirred with a magnetic stirrer for 24 h to obtain a homogeneous solution. The pH of the homogeneous solution was adjusted to neutral with sulfuric acid, and then stirring was stopped. The solution was allowed to stand for 180 min, centrifuged, and dried to obtain ferrosoferric oxide.

[0083] 2) Preparation of sulfide-builder solution: 600 mg of ammonium molybdate and 300 mg of sulfur powder were added to a beaker containing 100 mL of water. After sonication for 60 minutes, 200 mg of manganese oxide was added to the beaker and sonication was continued for 60 minutes to obtain an ammonium thiomolybdate-manganese oxide solution.

[0084] 3) The ferroferric oxide and ammonium thiomolybdate-manganese oxide solution was ultrasonically treated for 30 minutes, placed in a water bath, and mechanically stirred at 80° C. for 4 hours. After the reaction was completed, it was cooled and dried to obtain a highly active ferroferric oxide-ammonium thiomolybdate-manganese oxide composite material.

[0085] Comparative Example 1

[0086] A method for preparing a highly active iron-based-sulfide composite material comprises the following steps:

[0087] 1) Preparation of iron-based materials:

[0088] 300 mg of ferrous oxide and 20 mL of hydrogen peroxide were added to a beaker containing 100 mL of water and stirred with a magnetic stirrer for 24 h to obtain a homogeneous solution. The pH of the homogeneous solution was adjusted to neutral with sulfuric acid, and then stirring was stopped. The solution was allowed to stand for 180 min, centrifuged, and dried to obtain ferrosoferric oxide.

[0089] 2) Preparation of sulfide-promoter solution: 400 mg of sodium molybdate and 200 mg of thioacetamide were added to a beaker containing 100 mL of water and ultrasonicated for 60 min to obtain ammonium thiomolybdate solution;

[0090] 3) The ferrosoferric oxide and ammonium thiomolybdate solution was ultrasonically treated for 30 minutes, placed in a water bath, and mechanically stirred at 80° C. for 4 hours. After the reaction was completed, it was cooled and dried to obtain a highly active ferrosoferric oxide-ammonium thiomolybdate composite material.

[0091] Comparative Example 2

[0092] A method for preparing an iron-based material comprises the following steps:

[0093] Add 300 mg of ferrous oxide and 20 mL of hydrogen peroxide to a beaker containing 100 mL of water, stir with a magnetic stirrer for 24 hours, and then obtain a uniform solution. Adjust the pH of the uniform solution to neutral with sulfuric acid, then stop stirring, let it stand for 180 minutes, centrifuge, and dry to obtain ferrosoferric oxide.

[0094] Comparative Example 3

[0095] A method for preparing a highly active iron-based-sulfide-additive composite material comprises the following steps:

[0096] 1) Preparation of iron-based materials:

[0097] 300 mg of ferrous oxide and 20 mL of hydrogen peroxide were added to a beaker containing 100 mL of water and stirred with a magnetic stirrer for 24 h to obtain a homogeneous solution. The pH of the homogeneous solution was adjusted to neutral with sulfuric acid, and then stirring was stopped. The solution was allowed to stand for 180 min, centrifuged, and dried to obtain ferrosoferric oxide.

[0098] 2) Preparation of sulfide-promoter solution: 400 mg of sodium molybdate and 200 mg of thioacetamide were added to a beaker containing 100 mL of water. After sonication for 60 min, 100 mg of methanol was added to the beaker and sonication was continued for 60 min to obtain ammonium thiomolybdate-methanol solution.

[0099] 3) The ferrosoferric oxide and ammonium thiomolybdate-methanol solution were ultrasonically treated for 30 minutes, placed in a water bath, and mechanically stirred for reaction at 80° C. for 4 hours. After the reaction was completed, the solution was cooled and dried to obtain a highly active ferrosoferric oxide-ammonium thiomolybdate-methanol composite material.

[0100] Comparative Example 4

[0101] A method for preparing a highly active iron-based-sulfide-additive composite material comprises the following steps:

[0102] 1) Preparation of iron-based materials:

[0103] 300 mg of ferrous oxide and 20 mL of hydrogen peroxide were added to a beaker containing 100 mL of water and stirred with a magnetic stirrer for 24 h to obtain a homogeneous solution. The pH of the homogeneous solution was adjusted to neutral with sulfuric acid, and then stirring was stopped. The solution was allowed to stand for 180 min, centrifuged, and dried to obtain ferrosoferric oxide.

[0104] 2) Preparation of sulfide-promoter solution: 400 mg of sodium molybdate and 200 mg of thioacetamide were added to a beaker containing 100 mL of water. After sonication for 60 min, 100 mg of ethanol was added to the beaker and sonication was continued for 60 min to obtain an ammonium thiomolybdate-ethanol solution.

[0105] 3) The ferrosoferric oxide and ammonium thiomolybdate-methanol solution were ultrasonically treated for 30 minutes, placed in a water bath, and mechanically stirred for reaction at 80° C. for 4 hours. After the reaction was completed, the solution was cooled and dried to obtain a highly active ferrosoferric oxide-ammonium thiomolybdate-ethanol composite material.

[0106] Application Example 1

[0107] The products prepared in Example 1, Comparative Example 1, and Comparative Example 2 were used as catalysts for a degradation experiment, specifically comprising the following steps: 100 mL of wastewater to be treated with a pH of 4, wherein the concentration of phenol was 20 mg / L, the amount of catalyst added was 30 mg, 250 μL of 30 wt% hydrogen peroxide was added to initiate the reaction, and the mixture was stirred.

[0108] Figure 1 The following is a comparison of the degradation effects of the products prepared in Example 1, Comparative Example 1, and Comparative Example 2 on phenol. The experimental results show that the compounding of ammonium thiomolybdate and sulfite on the ferroferric oxide byproduct produced by the Fenton reaction can efficiently degrade phenol within 10 minutes, with a degradation rate of 99%. However, the degradation rate of the material with only ammonium thiomolybdate compounded with ferroferric oxide is less than 20%, and the uncompounded ferroferric oxide is almost incapable of degrading phenol. This indicates that the presence of sulfite can make the compound modification of ammonium thiomolybdate on ferroferric oxide more active, further demonstrating the importance of sulfite.

[0109] Application Example 2

[0110] The products prepared in Examples 1-3 and Comparative Examples 3-4 were used as catalysts for a degradation experiment, specifically comprising the following steps: 100 mL of wastewater to be treated with a pH of 4, wherein the concentration of phenol was 20 mg / L, the amount of catalyst added was 30 mg, 250 μL of 30 wt% hydrogen peroxide was added to initiate the reaction, and the mixture was stirred.

[0111] Figure 2The following chart compares the phenol degradation effects of the products prepared in Examples 1-3 and Comparative Examples 3-4. The experimental results demonstrate that the compounding of ammonium thiomolybdate with sulfite, sodium borohydride, and manganese oxide on ferroferric oxide produced by the Fenton reaction can efficiently degrade phenol within 10 minutes, with a degradation rate exceeding 90%. However, the compounding of ferroferric oxide with methanol and ethanol is almost ineffective in degrading phenol. This demonstrates that the compounding of ammonium thiomolybdate with ferroferric oxide exhibits higher activity only in the presence of sulfite, sodium borohydride, and manganese oxide, further demonstrating the importance of sulfite, sodium borohydride, and manganese oxide as additives.

[0112] Application Example 3

[0113] The product prepared in Example 3 and ferrous oxide were used as catalysts for a degradation experiment, specifically comprising the following steps: 100 mL of wastewater to be treated with a pH of 4, wherein the COD concentration was 1000 mg / L, the total amount of catalyst added was 30 mg, 250 μL of 30 wt% hydrogen peroxide was added to initiate the reaction, and the mixture was stirred.

[0114] Among them, in 30 mg of the catalyst, the mass ratios of the high-activity ferrosoferric oxide-ammonium thiomolybdate-manganese oxide composite material prepared in Example 3 and ferrous oxide were set to 1:0, 1:1, and 0:1, respectively.

[0115] Figure 3 The following is a comparison chart of the COD degradation effects of the product prepared in Example 3 and ferrous oxide mixed in different proportions as catalysts. The experimental results show that the COD removed by the prepared high-activity ferrous oxide-ammonium thiomolybdate-manganese oxide composite material is almost equal to that of the ferrous oxide used in traditional Fenton at a dosage ratio of 1:1 and 0:1, indicating that the high-activity ferrous oxide-ammonium thiomolybdate-manganese oxide composite material can replace the ferrous oxide used in traditional Fenton to a certain extent. Since the high-activity ferrous oxide-ammonium thiomolybdate-manganese oxide composite material is reusable, it provides feasibility for achieving low-cost use of heterogeneous Fenton technology.

[0116] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims.

Claims

1. A method for preparing a highly active iron-based-sulfide-additive composite material, characterized in that: The following steps are involved: The iron-based material is added to the sulfide-additive solution, subjected to ultrasonic treatment, heated for reaction, and cooled to obtain a highly active iron-based-sulfide-additive composite material; Wherein, the auxiliary agent in the sulfide-auxiliary agent solution is selected from one of sulfite, sodium borohydride and manganese oxide; The specific preparation method of the iron-based material comprises: adding an iron source and hydrogen peroxide to water, stirring, adjusting the pH to neutral, standing, centrifuging, and drying to obtain the iron-based material; wherein the iron source is ferrous oxide; The specific preparation method of the sulfide-additive solution includes: adding a molybdenum source and a sulfur source into water, adding the additive after ultrasonication, and continuing ultrasonication to obtain the sulfide-additive solution; wherein the molybdenum source is ammonium molybdate; and the sulfur source is thioacetamide.

2. The method for preparing the high-activity iron-based-sulfide-additive composite material according to claim 1, characterized in that: During the preparation of the iron-based material: The ratio of the iron source, hydrogen peroxide and water is (10-1000) mg: (1-20) mL: (10-1000) mL; and / or The reagent used to adjust the pH is sulfuric acid; and / or The standing time is 1-1000 min.

3. The method for preparing the high-activity iron-based-sulfide-additive composite material according to claim 1, characterized in that: During the preparation of the sulfide-builder solution: The molybdenum source, sulfur source, water and auxiliary agent are used in a ratio of (1-1000) mg: (1-2000) mg: (10-100) mL: (1-1000) mg; and / or The ultrasonic time is 1-60 min.

4. The method for preparing the high-activity iron-based-sulfide-additive composite material according to claim 1, characterized in that: The ultrasonic treatment time is 1-100 min.

5. The method for preparing the high-activity iron-based-sulfide-additive composite material according to claim 1, characterized in that: The heating reaction conditions are: reaction at 60-100° C. for 1-5 hours.

6. A high-activity iron-based-sulfide-additive composite material prepared by the preparation method according to any one of claims 1 to 5.

7. Use of the highly active iron-based-sulfide-additive composite material according to claim 6 in removing organic pollutants from wastewater.

8. A method for removing organic pollutants, characterized in that: The method comprises the following steps: adding the high-activity iron-based-sulfide-additive composite material according to claim 6 into wastewater containing organic pollutants, adding an initiator, and stirring to remove the organic matter; wherein, The organic pollutant is phenol, and the concentration of phenol in the wastewater is 1-2000 mg / L; The initiator is 30wt% hydrogen peroxide; The input amount of the highly active iron-based-sulfide-auxiliary composite material is 300 mg / L; The wastewater containing organic pollutants is acidic.

Images