Preparation method of diamond-based high-activity three-dimensional particle electrode material, three-dimensional electrode reactor and application

Abstract

The present invention discloses a method for preparing a diamond-based high-activity three-dimensional particle electrode material, a three-dimensional electrode reactor and its application. The method for preparing the electrode material comprises the following steps: purifying the diamond; uniformly mixing the purified diamond with titanium dioxide, silicon carbide and a catalyst, and then pressing and forming; calcining the pressed sample at high temperature to obtain the diamond-based high-activity three-dimensional particle electrode material. The present invention uses a mixture of diamond micropowder, silicon carbide and titanium dioxide as the main raw materials. By adding a suitable catalyst, the silicon carbide and titanium dioxide components melt under high temperature conditions, which not only improves the activity of the electrode material, but also increases the mechanical strength of the electrode material. The process flow of the present invention is simple and easy to operate. The obtained electrode material has good conductivity and strong stability. Filling the material into a three-dimensional electrode reactor can effectively reduce the COD value in organic wastewater.

Description

Technical Field

[0001] The present invention belongs to the technical field of wastewater treatment materials, and in particular relates to a preparation method of a diamond-based high-activity three-dimensional particle electrode material, a three-dimensional electrode reactor and applications. Background Art

[0002] With the rapid development of my country's manufacturing industry, water pollution has become an unavoidable reality. The large amount of wastewater discharged during industrial production is complex in composition, posing an increasingly serious threat to the human environment, and its treatment continues to become increasingly difficult. Among these, high-concentration organic wastewater from numerous industrial sectors, such as chemical production, printing and dyeing, textiles, and rubber manufacturing, has long been a key concern for scholars in this field.

[0003] Organic wastewater is typically complex, highly concentrated, toxic, and difficult to degrade, making it challenging to treat. Even after treatment, the compliance rate for wastewater discharge remains low, and the discharge of substandard wastewater can easily cause varying degrees of pollution in rivers and lakes. Wastewater treatment solutions based on traditional materials are often costly and challenging, making the search for economical, practical, and environmentally friendly water treatment materials crucial.

[0004] In recent years, numerous researchers at home and abroad have conducted extensive research on the efficient treatment of high-concentration organic wastewater. Among these, electrolytic treatment technology has been widely used due to its simple operation, significant results, and environmental friendliness. Three-dimensional electrolysis is a new process developed based on two-dimensional electrolysis. It boasts advantages over two-dimensional electrolysis, such as large electrode contact area, rapid electrolytic reaction, and high pollutant degradation efficiency. However, this process also has some shortcomings, primarily the insufficient activity of the three-dimensional particle electrode material used, and the electrode material is easily broken or hardened when immersed in high-concentration organic wastewater. Summary of the Invention

[0005] To address the aforementioned technical issues, the present invention provides a method for preparing a diamond-based, highly active three-dimensional particle electrode material, a three-dimensional electrode reactor, and its application. The electrode material produced using this method exhibits excellent conductivity and stability. When filled into a three-dimensional electrode reactor, this material can effectively reduce the COD content in organic wastewater, demonstrating strong industrial feasibility.

[0006] To achieve the above object, the present invention is implemented through the following technical solutions:

[0007] A method for preparing a diamond-based highly active three-dimensional particle electrode material comprises the following steps:

[0008] (1) Purify the diamond;

[0009] (2) mixing the diamond purified in step (1) with titanium dioxide, silicon carbide, and a catalyst, and then pressing and molding;

[0010] (3) The sample pressed and formed in step (2) is subjected to high-temperature calcination to obtain the diamond-based high-activity three-dimensional particle electrode material.

[0011] Preferably, the method for purifying the diamond in step (1) is: boiling the diamond in sodium hydroxide solution and hydrochloric acid solution respectively, and then filtering, washing and drying to obtain surface-purified diamond.

[0012] Preferably, the concentrations of sodium hydroxide and hydrochloric acid are both 10%, and the boiling time is 15 to 30 minutes.

[0013] Preferably, the catalyst in step (2) is at least one of cobalt powder, iron powder and nickel powder, and the amount of the catalyst accounts for 5% to 12% of the total mass of diamond, titanium dioxide and silicon carbide.

[0014] Preferably, in step (2), the mass ratio of diamond, titanium dioxide and silicon carbide is (0.1-0.8): (0.1-0.8): (0.1-0.8).

[0015] Preferably, the molding pressure in step (2) is 10 to 20 MPa, and the molding time is 30 to 40 seconds.

[0016] Preferably, the high temperature calcination in step (3) is performed at a temperature of 1000-1300° C. and for a time of 3-5 hours.

[0017] A diamond-based high-activity three-dimensional particle electrode material prepared according to the above preparation method.

[0018] A three-dimensional electrode reactor comprises a diamond-based high-activity three-dimensional particle electrode material prepared by the above preparation method.

[0019] The present invention also provides an application of the three-dimensional electrode reactor in reducing COD in organic wastewater.

[0020] The beneficial effects of the present invention are:

[0021] To address the shortcomings of existing conventional particle electrode materials, such as activated carbon and iron-carbon, such as poor activity and fragility, the present invention provides a method for preparing a highly active three-dimensional particle electrode material based on diamond micropowder. This method uses a mixture of diamond micropowder, silicon carbide, and titanium dioxide as the primary raw materials. By adding a suitable catalyst, the silicon carbide and titanium dioxide components fuse under high-temperature conditions, enhancing both the electrode material's activity and its mechanical strength. The process is simple and easy to operate, resulting in an electrode material with excellent conductivity and stability. When this material is applied to a three-dimensional electrode reactor, it can effectively reduce the COD value in organic wastewater. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings of the embodiments are briefly introduced below.

[0023] Figure 1 This is a flow chart of the preparation method of a diamond-based highly active three-dimensional particle electrode material of the present invention. DETAILED DESCRIPTION

[0024] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0025] Unless otherwise specified, the test methods described in the examples of the present invention are all conventional methods; the reagents and materials described are all commercially available unless otherwise specified.

[0026] The present invention provides a method for preparing a diamond-based highly active three-dimensional particle electrode material. Figure 1 As shown, the following steps are included:

[0027] (1) Purification treatment: Diamond powder was boiled in 10% NaOH and 10% HCl solutions for 15 to 30 minutes, and then filtered, washed, and dried to obtain surface-purified diamonds;

[0028] (2) mixing the diamond powder purified in step (1) with titanium dioxide and silicon carbide in a mass ratio of (0.1-0.8): (0.1-0.8): (0.1-0.8), adding a catalyst accounting for 5%-12% of the total mass of the diamond powder, titanium dioxide and silicon carbide, mixing well, and pressing and molding at a pressure of 10-20 MPa for 30-40 seconds; the catalyst is at least one of cobalt powder, iron powder and nickel powder;

[0029] (3) The sample formed by pressing in step (2) is calcined at a temperature of 1000-1300° C. for 3-5 hours to obtain a diamond-based high-activity three-dimensional particle electrode material.

[0030] In order to enable those skilled in the art to fully understand the preparation method and beneficial effects of the three-dimensional electrode in the present invention, the present invention is further described below with reference to specific examples.

[0031] Example 1

[0032] A method for preparing a diamond-based highly active three-dimensional particle electrode material comprises the following steps:

[0033] (1) Purification: Boil the diamond powder in 10% NaOH and 10% HCl solutions for 15 min, filter and rinse with deionized water. Ensure that the final solution is neutral and then dry it in an oven to remove surface impurities and ensure the purity of the raw materials.

[0034] (2) Compression molding: The diamond micropowder purified in step (1) was mixed with titanium dioxide and silicon carbide in a mass ratio of 0.5:0.3:0.2, with a total mass of 50 g, and 3 g of cobalt powder was added. The mixture was mixed evenly and pressed into shape using a tablet press at a pressure of 10 MPa for 30 seconds.

[0035] (3) High-temperature calcination: The sample formed by pressing in step (2) is placed in a box furnace and calcined at 1230°C for 4.5 hours, and then naturally cooled to room temperature to obtain a highly active three-dimensional particle electrode material based on diamond micropowder.

[0036] The three-dimensional particle electrode material obtained above was used as filler in a three-dimensional electrode reactor. High-concentration industrial organic wastewater (2800 mg / L) was introduced and electrolyzed for 2 hours at a voltage of 3V and a current of 3A. No breakage or compaction of the electrode material was observed. The COD values ​​of the organic wastewater before and after electrolysis were measured using microwave digestion, resulting in a calculated COD removal rate of 85%.

[0037] Example 2

[0038] A method for preparing a diamond-based highly active three-dimensional particle electrode material comprises the following steps:

[0039] (1) Purification: Boil the diamond powder in 10% NaOH and 10% HCl solutions for 15 min, filter and rinse with deionized water. Ensure that the final solution is neutral and then dry it in an oven to remove surface impurities and ensure the purity of the raw materials.

[0040] (2) Compression molding: The diamond powder treated in step (1) was mixed with titanium dioxide and silicon carbide in a mass ratio of 0.4:0.4:0.2, with a total mass of 50 g, and 3 g of cobalt powder was added. The mixture was mixed evenly and pressed into shape using a tablet press at a pressure of 10 MPa for 30 seconds.

[0041] (3) High-temperature calcination: The sample formed by pressing in step (2) is placed in a box furnace and calcined at 1250°C for 4.5 hours, and then naturally cooled to room temperature to obtain a highly active three-dimensional particle electrode material based on diamond micropowder.

[0042] The three-dimensional particle electrode material obtained above was used as filler in a three-dimensional electrode reactor. High-concentration industrial organic wastewater (2800 mg / L) was introduced and electrolyzed for 2 hours at a voltage of 3V and a current of 3A. No breakage or compaction of the electrode material was observed. The COD values ​​of the organic wastewater before and after electrolysis were measured using microwave digestion, resulting in a calculated COD removal rate of 82%.

[0043] Example 3

[0044] A method for preparing a diamond-based highly active three-dimensional particle electrode material comprises the following steps:

[0045] (1) Purification: Boil the diamond powder in 10% NaOH and 10% HCl solutions for 15 min, filter and rinse with deionized water. Ensure that the final solution is neutral and then dry it in an oven to remove surface impurities and ensure the purity of the raw materials.

[0046] (2) Compression molding: The diamond powder treated in step (1) was mixed with titanium dioxide and silicon carbide in a mass ratio of 0.3:0.4:0.3, with a total mass of 50 g, and 3 g of cobalt powder was added. The mixture was mixed evenly and pressed into shape using a tablet press at a pressure of 10 MPa for 30 seconds.

[0047] (3) High-temperature calcination: The sample formed by pressing in step (2) is placed in a box furnace and calcined at 1250°C for 4.5 hours, and then naturally cooled to room temperature to obtain a highly active three-dimensional particle electrode material based on diamond micropowder.

[0048] The three-dimensional particle electrode material obtained above was used as filler in a three-dimensional electrode reactor. High-concentration industrial organic wastewater (2800 mg / L) was introduced and electrolyzed for 2 hours at a voltage of 3V and a current of 3A. No breakage or compaction of the electrode material was observed. The COD values ​​of the organic wastewater before and after electrolysis were measured using microwave digestion, resulting in a calculated COD removal rate of 61%.

[0049] Example 4

[0050] A method for preparing a diamond-based highly active three-dimensional particle electrode material comprises the following steps:

[0051] (1) Purification: Boil the diamond powder in 10% NaOH and 10% HCl solutions for 15 min, filter and rinse with deionized water. Ensure that the final solution is neutral and then dry it in an oven to remove surface impurities and ensure the purity of the raw materials.

[0052] (2) Compression molding: The diamond micropowder treated in step (1) was mixed with titanium dioxide and silicon carbide in a mass ratio of 0.5:0.3:0.2, with a total mass of 50 g. 3 g of cobalt powder and 3 g of iron powder were added and mixed evenly. The mixture was pressed into shape using a tablet press at a pressure of 10 MPa for 30 s.

[0053] (3) High-temperature calcination: The sample formed by pressing in step (2) is placed in a box furnace and calcined at 1230°C for 4.5 hours, and then naturally cooled to room temperature to obtain a highly active three-dimensional particle electrode material based on diamond micropowder.

[0054] The three-dimensional particle electrodes obtained above were used as fillers in a three-dimensional electrode reactor. High-concentration industrial organic wastewater (2800 mg / L) was introduced and electrolyzed for 2 hours at a voltage of 3V and a current of 3A. No breakage or compaction of the electrode material was observed. The COD values ​​of the organic wastewater before and after electrolysis were measured using microwave digestion, resulting in a calculated COD removal rate of 89%.

[0055] Example 5

[0056] A method for preparing a diamond-based highly active three-dimensional particle electrode material comprises the following steps:

[0057] (1) Purification: Boil the diamond powder in 10% NaOH and 10% HCl solutions for 15 min, filter and rinse with deionized water. Ensure that the final solution is neutral and then dry it in an oven to remove surface impurities and ensure the purity of the raw materials.

[0058] (2) Compression molding: The diamond micropowder treated in step (1) was mixed with titanium dioxide and silicon carbide in a mass ratio of 0.4:0.3:0.3, with a total mass of 50 g. 3 g of cobalt powder and 3 g of iron powder were added and mixed evenly. The mixture was pressed into shape using a tablet press at a pressure of 10 MPa for 30 s.

[0059] (3) High-temperature calcination: The sample formed by pressing in step (2) is placed in a box furnace and calcined at 1230°C for 4.5 hours, and then naturally cooled to room temperature to obtain a highly active three-dimensional particle electrode material based on diamond micropowder.

[0060] The three-dimensional particle electrodes obtained above were used as fillers in a three-dimensional electrode reactor. High-concentration industrial organic wastewater (2800 mg / L) was introduced and electrolyzed for 2 hours at a voltage of 3V and a current of 3A. No breakage or compaction of the electrode material was observed. The COD values ​​of the organic wastewater before and after electrolysis were measured using microwave digestion, resulting in a calculated COD removal rate of 77%.

[0061] Example 6

[0062] A method for preparing a diamond-based highly active three-dimensional particle electrode material comprises the following steps:

[0063] (1) Purification: Boil the diamond powder in 10% NaOH and 10% HCl solutions for 15 min, filter and rinse with deionized water. Ensure that the final solution is neutral and then dry it in an oven to remove surface impurities and ensure the purity of the raw materials.

[0064] (2) Compression molding: The diamond powder treated in step (1) was mixed with titanium dioxide and silicon carbide in a mass ratio of 0.4:0.2:0.4, with a total mass of 50 g, and 3 g of nickel powder was added. The mixture was mixed evenly and pressed into shape using a tablet press at a pressure of 10 MPa for 30 seconds.

[0065] (3) High-temperature calcination: The sample formed by pressing in step (2) is placed in a box furnace and calcined at 1230°C for 4.5 hours, and then naturally cooled to room temperature to obtain a highly active three-dimensional particle electrode material based on diamond micropowder.

[0066] The three-dimensional particle electrodes obtained above were used as fillers in a three-dimensional electrode reactor. High-concentration industrial organic wastewater (2800 mg / L) was introduced and electrolyzed for 2 hours at a voltage of 3V and a current of 3A. No breakage or compaction of the electrode material was observed. The COD values ​​of the organic wastewater before and after electrolysis were measured using microwave digestion, resulting in a calculated COD removal rate of 70%.

[0067] Comparative Example 1

[0068] Purified diamond micropowder and silicon carbide were mixed in a mass ratio of 0.5:0.5, totaling 50 g. 3 g of cobalt powder was added and mixed thoroughly. Other steps were the same as in Example 1. The resulting three-dimensional particle electrode was used as filler in a three-dimensional electrode reactor. High-concentration industrial organic wastewater (2800 mg / L) was introduced and electrolyzed at a voltage of 3 V and a current of 3 A for 2 hours. The COD values ​​of the organic wastewater before and after electrolysis were measured using microwave digestion, and a COD removal rate of 46% was calculated.

[0069] Comparative Example 2

[0070] Purified diamond micropowder and titanium dioxide were mixed in a mass ratio of 0.5:0.5, totaling 50 g. 3 g of cobalt powder was added and mixed thoroughly. Other steps were the same as in Example 1. The resulting three-dimensional particle electrode was used as filler in a three-dimensional electrode reactor. High-concentration industrial organic wastewater (2800 mg / L) was introduced and electrolyzed for 2 hours at a voltage of 3 V and a current of 3 A. The COD values ​​of the organic wastewater before and after electrolysis were measured using microwave digestion, and a calculated COD removal rate of 57% was obtained.

[0071] This invention uses diamond, silicon carbide, and titanium dioxide as the primary materials, and enhances their performance through the addition of a certain amount of catalyst. Through several steps, including surface purification of diamond micropowder, catalyst preparation, material compression molding, and calcination, a highly active three-dimensional particle electrode material with a cylindrical honeycomb microporous structure is prepared. The preparation process is simple and easy to operate. The resulting electrode material exhibits excellent conductivity and stability, overcoming the problem of traditional materials breaking and agglomerating. When used as filler in a three-dimensional electrode reactor, this electrode material effectively degrades COD in organic wastewater at relatively low current and voltage conditions.

[0072] It should be noted that the above embodiments all belong to the same inventive concept, and the description of each embodiment has its own focus. For any details not described in individual embodiments, reference may be made to the description in other embodiments.

[0073] The above-described embodiments merely illustrate the implementation methods of the present invention. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make various modifications and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. A method for preparing a diamond-based highly active three-dimensional particle electrode material, characterized in that: The following steps are involved: (1) Purify the diamond; (2) Evenly mixing the diamond purified in step (1) with titanium dioxide, silicon carbide, and a catalyst, and then pressing and molding the mixture; wherein the mass ratio of the diamond, titanium dioxide, and silicon carbide is (0.1-0.8): (0.1-0.8): (0.1-0.8); (3) The sample pressed and formed in step (2) is subjected to high-temperature calcination to obtain the diamond-based high-activity three-dimensional particle electrode material.

2. The method for preparing a diamond-based highly active three-dimensional particle electrode material according to claim 1, characterized in that: The method for purifying the diamond in step (1) is as follows: the diamond is placed in sodium hydroxide solution and hydrochloric acid solution and boiled, and then filtered, washed and dried to obtain surface-purified diamond.

3. The method for preparing a diamond-based high-activity three-dimensional particle electrode material according to claim 2, characterized in that: The concentrations of the sodium hydroxide and hydrochloric acid are both 10%, and the boiling time is 15 to 30 minutes.

4. The method for preparing a diamond-based high-activity three-dimensional particle electrode material according to claim 1, characterized in that: The catalyst in step (2) is at least one of cobalt powder, iron powder, and nickel powder, and the amount of the catalyst used accounts for 5% to 12% of the total mass of the diamond, titanium dioxide, and silicon carbide.

5. The method for preparing a diamond-based high-activity three-dimensional particle electrode material according to claim 1, wherein: The molding pressure of the pressing molding in step (2) is 10~20 MPa, and the pressing molding time is 30~40s.

6. The method for preparing a diamond-based high-activity three-dimensional particle electrode material according to claim 1, characterized in that: The high temperature calcination in step (3) is performed at a temperature of 1000-1300° C. and for a time of 3-5 hours.

7. A diamond-based high-activity three-dimensional particle electrode material prepared according to the preparation method according to any one of claims 1 to 6.

8. A three-dimensional electrode reactor, characterized in that The invention comprises a diamond-based high-activity three-dimensional particle electrode material prepared by the preparation method according to any one of claims 1 to 6.

9. Use of the three-dimensional electrode reactor according to claim 8 in reducing COD in organic wastewater.

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