Preparation method of photocatalyst for simultaneously removing ammonia nitrogen, heavy metal ions and bacteria from carbon-based loaded organic photovoltaic material

Abstract

The invention discloses a preparation method of a photocatalyst for simultaneously removing ammonia nitrogen, heavy metal ions and bacteria from a carbon-based loaded organic photovoltaic material. The method comprises the following operation steps: A, cleaning coconut shells, and drying until the coconut shells are completely dried; b, crushing the completely dried coconut shells with a crusher, and sieving with a 200-mesh sieve to obtain coconut shell powder; c, the coconut shell powder is put into a tubular furnace for high-temperature pyrolysis, and modified carbon-based material coconut shell carbon particles are obtained; d, mixing an organic photovoltaic material and chloroform according to the following weight ratio: 0.01-0.02 g of the organic photovoltaic material and 10-20 ml of chloroform to obtain an organic photocatalyst mixed solution; and E, uniformly coating modified carbon-based material coconut shell carbon particles with the organic photocatalyst mixed solution obtained in the step D, and drying at 60 DEG C for 24 hours to obtain the photocatalyst for simultaneously removing ammonia nitrogen, heavy metal ions and bacteria from the carbon-based loaded organic photovoltaic material. The photocatalyst obtained by the method disclosed by the invention can efficiently and quickly remove ammonia nitrogen, heavy metal ions and bacteria in an aquaculture wastewater environment at the same time, and can be repeatedly utilized, so that the problems of a photocatalyst loading process and cyclic utilization are solved, and a real green, environment-friendly and pollution-free treatment method is provided for aquaculture wastewater.

Description

Technical Field

[0001] The present invention relates to the technical field of functional material preparation, in particular to a method for preparing a carbon-based organic photovoltaic material-loaded photocatalyst that simultaneously removes ammonia nitrogen, heavy metal ions and bacteria. Background Art

[0002] There are often large amounts of ammonia nitrogen compounds, heavy metal ions, and bacteria in aquaculture wastewater. When the ammonia nitrogen content in wastewater reaches 20-30 mg / L, the excessive ammonia nitrogen compounds will consume a large amount of oxygen in the water and generate highly toxic byproducts such as NO2. - and NO3 - , causing aquatic organisms to die from lack of oxygen or suffer from a series of diseases. When heavy metal ions (such as Sb(III), As(III), Cd(II), Cr(VI), Pb(II) etc.) in water bodies reach above 6ppb, the probability of people suffering from nephritis, hepatitis, pneumonia and cancer will increase significantly. In addition, intestinal parasitic infections and diarrheal diseases caused by a large number of bacteria have also become the main cause of malnutrition because they can lead to indigestion. Therefore, there is an urgent need to find a suitable method to simultaneously remove large amounts of ammonia nitrogen compounds, heavy metal ions and bacteria in aquaculture wastewater environments.

[0003] Among the many environmental pollution control technologies currently used for aquaculture wastewater treatment, biodegradation is less effective, adsorption simply transfers ammonia nitrogen compounds and bacteria, and poses a risk of secondary pollution. Chemical oxidation is more effective, but may produce a large number of byproducts during the degradation process, which can easily cause secondary pollution. Advanced oxidation is a new and highly efficient aquaculture wastewater treatment technology that primarily relies on the highly oxidizing hydroxyl radicals (·OH) produced under different reaction conditions to reduce ammonia nitrogen compounds to harmless inorganic N2, while simultaneously killing most bacteria in the water and adsorbing harmful heavy metal ions in the aquatic environment, thereby effectively removing ammonia nitrogen compounds, heavy metal ions, and bacteria from the water. The persulfate activation method in the chemical oxidation method has relatively harsh reaction conditions, and the ozone production cost of the ozone method is relatively high.

[0004] Therefore, there is an urgent need to develop a green and environmentally friendly photocatalyst preparation method with simple use conditions that can simultaneously remove ammonia nitrogen compounds, heavy metal ions and bacteria from aquaculture wastewater. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a method for preparing a carbon-based photocatalyst loaded with organic photovoltaic materials for simultaneously removing ammonia nitrogen, heavy metal ions and bacteria. The photocatalyst obtained by this method can achieve efficient removal of ammonia nitrogen compounds, heavy metal ions and bacteria in aquaculture wastewater at the same time and is reusable, providing a truly green, environmentally friendly and pollution-free treatment method for aquaculture wastewater.

[0006] The present invention solves the above technical problems with the following technical solutions:

[0007] The method for preparing a photocatalyst for simultaneously removing ammonia nitrogen, heavy metal ions and bacteria from a carbon-based organic photovoltaic material according to the present invention comprises the following steps:

[0008] A. Clean the coconut shell and dry it until it is completely dry;

[0009] B. After thorough drying, coconut shell is pulverized with a pulverizer and sieved through 200 meshes to obtain coconut shell powder;

[0010] C. Dry the coconut shell powder at 100° C. for 30 min and then place it in a tube furnace for high-temperature pyrolysis treatment to obtain modified carbon-based material coconut shell carbon particles;

[0011] D. Mixing an organic photovoltaic material and chloroform in the following weight ratio: 0.01-0.02 g of organic photovoltaic material: 10-20 ml of chloroform to obtain an organic photocatalyst mixed solution; the organic photovoltaic material is PCE10:IT-M, P3BH:IT-M, or PCE10:P3BH:IT-M;

[0012] A. The organic photocatalyst mixed solution obtained in step D is evenly coated on the modified carbon-based coconut shell carbon particles, and then dried at 60° C. for 24 hours to obtain a carbon-based organic photovoltaic material-loaded photocatalyst that simultaneously removes ammonia nitrogen, heavy metal ions and bacteria.

[0013] In step A of the present invention, the drying treatment refers to placing the coconut shell in a forced air drying oven at a temperature of 70° C. and drying it for 48 hours.

[0014] In step B of the present invention, the coconut shell is crushed for 3 to 5 minutes.

[0015] In step C of the present invention, the operation of performing high-temperature pyrolysis in the tubular furnace is as follows: placing the coconut shell powder in the tubular furnace, closing the furnace plug, evacuating for 15 minutes, passing nitrogen for 20 minutes, heating to 200° C. at a heating rate of 5° C. / min under nitrogen protection, then heating to 700° C. at a heating rate of 10° C. / min, maintaining for 3 hours, cooling to room temperature, and bagging for later use.

[0016] In step E of the present invention, the weight ratio of the organic photocatalyst mixed solution to the modified carbon-based coconut shell carbon particles is 1:5000-10000.

[0017] In step D of the present invention, the PCE10:IT-M and P3BH:IT-M are mixed in a weight ratio of 1:1, and the PCE10:P3BH:IT-M is mixed in a weight ratio of 1:1:1.

[0018] In step D of the present invention, during preparation, the organic photovoltaic material is mixed with chloroform and then stirred and dissolved at 80° C. for 1 hour.

[0019] The method of the present invention has the following beneficial effects:

[0020] (1) The photocatalyst obtained by the method of the present invention can realize the removal of ammonia nitrogen compounds, heavy metal ions and bacteria in aquaculture wastewater by modified carbon-based materials. The removal effect is very good, with a removal rate of about 99%, and it can be reused.

[0021] (2) Compared with inorganic catalysts, the photocatalyst obtained by the method of the present invention has unique advantages in wastewater purification. It has the advantages of rapid and effective exciton dissociation, adjustable energy level, wide absorption spectrum and excellent chemical stability. It can generate a large number of hydroxyl radicals and holes with strong oxidizing properties in water, which can completely and quickly adsorb heavy metal ions in aquaculture wastewater, quickly oxidize ammonia nitrogen compounds and kill a large number of bacteria.

[0022] (3) The matrix material used in the present invention is a natural product carbon-based material with many excellent properties such as hydrophilicity, greenness, high porosity, and large specific surface area. In addition, the organic photovoltaic material can be loaded on the matrix material for repeated use and is degradable, thus achieving true green friendliness and environmental pollution-free. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a stability test chart of the photocatalyst obtained in Example 1 of the present invention for removing three pollutants: ammonia nitrogen compounds, heavy metal ions, and bacteria. DETAILED DESCRIPTION

[0024] The technical solution of the present invention is further described below with reference to specific embodiments, but the present invention is not limited thereto.

[0025] Example 1

[0026] The method for preparing a photocatalyst for simultaneously removing ammonia nitrogen, heavy metal ions and bacteria by using a carbon-based organic photovoltaic material is as follows:

[0027] A. Clean the coconut shell with ultrapure water and place it in a blast drying oven at 70°C for 48 hours to dry it completely.

[0028] B. Grind the completely dried coconut shell with a grinder for 3-5 minutes and then pass it through a 200 mesh sieve to obtain coconut shell powder;

[0029] C. After the coconut shell powder is dried at 100°C for 30min, it is placed in a tubular furnace for high-temperature pyrolysis treatment to obtain modified carbon-based material coconut shell carbon particles; during operation, the coconut shell powder is placed in a tubular furnace, the furnace plug is closed, vacuumed for 15min, nitrogen is passed through for 20min, and then heated to 200°C at a heating rate of 5°C / min under nitrogen protection, and then heated to 700°C at a heating rate of 10°C / min, kept for 3h, and then cooled to room temperature and bagged for standby use;

[0030] D. Mixing 0.015 g of an organic photovoltaic material PCE10:IT-M with 15 ml of chloroform to obtain an organic photocatalyst mixed solution, wherein PCE10:IT-M is obtained by mixing PCE10 and IT-M in a weight ratio of 1:1. During the preparation, the organic photovoltaic material and chloroform are mixed and then stirred and dissolved at 80° C. for 1 hour;

[0031] E. The organic photocatalyst mixed solution obtained in step D is evenly coated on the modified carbon-based material coconut shell carbon particles, and then dried at 60° C. for 24 hours to obtain the carbon-based organic photovoltaic material-loaded photocatalyst of the present invention for simultaneously removing ammonia nitrogen, heavy metal ions and bacteria, wherein the weight ratio of the organic photocatalyst mixed solution to the modified carbon-based material coconut shell carbon particles is 1:7500.

[0032] Under light conditions, 200 mg of the photocatalyst prepared in this example was added to 70 ml of aquaculture wastewater containing 50 mg / l of ammonia nitrogen compounds, heavy metal ions, and bacteria. The removal rate of ammonia nitrogen compounds was 99.5% in 120 minutes, the removal rate of heavy metal ions was 98.9% in 9 minutes, and the antibacterial effect reached 99.5% in 15 minutes. The removal effect and stability are shown in Figure 2. Figure 1 shown.

[0033] Example 2

[0034] The method for preparing a photocatalyst for simultaneously removing ammonia nitrogen, heavy metal ions and bacteria by using a carbon-based organic photovoltaic material is as follows:

[0035] A. Clean the coconut shell with ultrapure water and place it in a blast drying oven at 70°C for 48 hours to completely dry the coconut shell.

[0036] B. Grind the completely dried coconut shell with a grinder for 3-5 minutes and then pass it through a 200 mesh sieve to obtain coconut shell powder;

[0037] C. After the coconut shell powder is dried at 100°C for 30min, it is placed in a tubular furnace for high-temperature pyrolysis treatment to obtain modified carbon-based material coconut shell carbon particles; during operation, the coconut shell powder is placed in a tubular furnace, the furnace plug is closed, vacuumed for 15min, nitrogen is passed through for 20min, and then heated to 200°C at a heating rate of 5°C / min under nitrogen protection, and then heated to 700°C at a heating rate of 10°C / min, kept for 3h, and then cooled to room temperature and bagged for standby use;

[0038] D. Mixing 0.015 g of an organic photovoltaic material P3BH:IT-M with 15 ml of chloroform to prepare an organic photocatalyst mixed solution, wherein P3BH:IT-M is prepared by mixing P3BH and IT-M in a weight ratio of 1:1. During the preparation, the organic photovoltaic material and chloroform are mixed and then stirred and dissolved at 80° C. for 1 hour;

[0039] E. The organic photocatalyst mixed solution obtained in step D is evenly coated on the modified carbon-based material coconut shell carbon particles, and then dried at 60° C. for 24 hours to obtain the carbon-based organic photovoltaic material-loaded photocatalyst of the present invention for simultaneously removing ammonia nitrogen, heavy metal ions and bacteria, wherein the weight ratio of the organic photocatalyst mixed solution to the modified carbon-based material coconut shell carbon particles is 1:7500.

[0040] Under light conditions, 200 mg of the photocatalyst prepared in this example was added to 70 ml of aquaculture wastewater with an ammonia nitrogen compound, heavy metal ion and bacterial content of 50 mg / l. The removal rate of ammonia nitrogen compounds was 99.3% in 120 minutes, the removal rate of heavy metal ions was 98.5% in 9 minutes, and the antibacterial amount reached 99.1% in 15 minutes.

[0041] Example 3

[0042] The method for preparing a photocatalyst for simultaneously removing ammonia nitrogen, heavy metal ions and bacteria by using a carbon-based organic photovoltaic material is as follows:

[0043] A. Clean the coconut shell with ultrapure water and place it in a blast drying oven at 70°C for 48 hours to dry it completely.

[0044] B. Grind the completely dried coconut shell with a grinder for 3-5 minutes and then pass it through a 200 mesh sieve to obtain coconut shell powder;

[0045] C. After the coconut shell powder is dried at 100°C for 30min, it is placed in a tubular furnace for high-temperature pyrolysis to obtain modified carbon-based material coconut shell carbon particles; during operation, the coconut shell powder is placed in a tubular furnace, the furnace plug is closed, vacuumed for 15min, nitrogen is passed through for 20min, and then heated to 200°C at a heating rate of 5°C / min under nitrogen protection, and then heated to 700°C at a heating rate of 10°C / min, kept for 3h, and then cooled to room temperature and bagged for standby use;

[0046] D. Mixing 0.015 g of an organic photovoltaic material PCE10:P3BH:IT-M with 15 ml of chloroform to prepare an organic photocatalyst mixed solution, wherein PCE10:P3BH:IT-M is prepared by mixing PCE10, P3BH, and IT-M in a weight ratio of 1:1:1. During the preparation, the organic photovoltaic material and chloroform are mixed and dissolved with stirring at 80° C. for 1 hour.

[0047] E. The organic photocatalyst mixed solution obtained in step D is evenly coated on the modified carbon-based material coconut shell carbon particles, and then dried at 60° C. for 24 hours to obtain the carbon-based organic photovoltaic material-loaded photocatalyst of the present invention for simultaneously removing ammonia nitrogen, heavy metal ions and bacteria, wherein the weight ratio of the organic photocatalyst mixed solution to the modified carbon-based material coconut shell carbon particles is 1:7500.

[0048] Under light conditions, 200 mg of the photocatalyst prepared in this example was added to 70 ml of aquaculture wastewater with an ammonia nitrogen compound, heavy metal ion and bacterial content of 50 mg / l. The removal rate of ammonia nitrogen compounds was 99.9% in 120 minutes, the removal rate of heavy metal ions was 98.7% in 9 minutes, and the antibacterial amount reached 99.4% in 15 minutes.

[0049] Example 4

[0050] The method for preparing a photocatalyst for simultaneously removing ammonia nitrogen, heavy metal ions and bacteria by using a carbon-based organic photovoltaic material is as follows:

[0051] A. Clean the coconut shell with ultrapure water and place it in a blast drying oven at 70°C for 48 hours to dry it completely.

[0052] B. Grind the completely dried coconut shell with a grinder for 3-5 minutes and then pass it through a 200 mesh sieve to obtain coconut shell powder;

[0053] C. After the coconut shell powder is dried at 100°C for 30min, it is placed in a tubular furnace for high-temperature pyrolysis to obtain modified carbon-based material coconut shell carbon particles; during operation, the coconut shell powder is placed in a tubular furnace, the furnace plug is closed, vacuumed for 15min, nitrogen is passed through for 20min, and then heated to 200°C at a heating rate of 5°C / min under nitrogen protection, and then heated to 700°C at a heating rate of 10°C / min, kept for 3h, and then cooled to room temperature and bagged for standby use;

[0054] D. Mixing 0.01 g of an organic photovoltaic material PCE10:P3BH:IT-M with 10 ml of chloroform to prepare an organic photocatalyst mixed solution, wherein PCE10:P3BH:IT-M is prepared by mixing PCE10, P3BH, and IT-M in a weight ratio of 1:1:1. During the preparation, the organic photovoltaic material and chloroform are mixed and then stirred and dissolved at 80° C. for 1 hour.

[0055] E. The organic photocatalyst mixed solution obtained in step D is evenly coated on the modified carbon-based material coconut shell carbon particles, and then dried at 60° C. for 24 hours to obtain the carbon-based organic photovoltaic material-loaded photocatalyst of the present invention for simultaneously removing ammonia nitrogen, heavy metal ions and bacteria, wherein the weight ratio of the organic photocatalyst mixed solution to the modified carbon-based material coconut shell carbon particles is 1:5000.

[0056] Under light conditions, 200 mg of the photocatalyst prepared in this example was added to 70 ml of aquaculture wastewater with an ammonia nitrogen compound, heavy metal ion and bacterial content of 50 mg / l. The removal rate of ammonia nitrogen compounds was 98.1% in 120 minutes, the removal rate of heavy metal ions was 99.2% in 9 minutes, and the antibacterial amount reached 98.6% in 15 minutes.

[0057] Example 5

[0058] The method for preparing a photocatalyst for simultaneously removing ammonia nitrogen, heavy metal ions and bacteria by using a carbon-based organic photovoltaic material is as follows:

[0059] A. Clean the coconut shell with ultrapure water and place it in a blast drying oven at 70°C for 48 hours to dry it completely.

[0060] B. Grind the completely dried coconut shell with a grinder for 3-5 minutes and then pass it through a 200 mesh sieve to obtain coconut shell powder;

[0061] C. After the coconut shell powder is dried at 100°C for 30min, it is placed in a tubular furnace for high-temperature pyrolysis to obtain modified carbon-based material coconut shell carbon particles; during operation, the coconut shell powder is placed in a tubular furnace, the furnace plug is closed, vacuumed for 15min, nitrogen is passed through for 20min, and then heated to 200°C at a heating rate of 5°C / min under nitrogen protection, and then heated to 700°C at a heating rate of 10°C / min, kept for 3h, and then cooled to room temperature and bagged for standby use;

[0062] D. Mixing 0.02 g of an organic photovoltaic material PCE10:P3BH:IT-M with 20 ml of chloroform to prepare an organic photocatalyst mixed solution, wherein PCE10:P3BH:IT-M is prepared by mixing PCE10, P3BH, and IT-M in a weight ratio of 1:1:1. During the preparation, the organic photovoltaic material and chloroform are mixed and dissolved with stirring at 80° C. for 1 hour.

[0063] E. The organic photocatalyst mixed solution obtained in step D is evenly coated on the modified carbon-based material coconut shell carbon particles, and then dried at 60° C. for 24 hours to obtain the carbon-based organic photovoltaic material-loaded photocatalyst of the present invention for simultaneously removing ammonia nitrogen, heavy metal ions and bacteria, wherein the weight ratio of the organic photocatalyst mixed solution to the modified carbon-based material coconut shell carbon particles is 1:10000.

[0064] Under light conditions, 200 mg of the photocatalyst prepared in this example was added to 70 ml of aquaculture wastewater with an ammonia nitrogen compound, heavy metal ion and bacterial content of 50 mg / l. The removal rate of ammonia nitrogen compounds was 99.7% in 120 minutes, the removal rate of heavy metal ions was 98.9% in 9 minutes, and the antibacterial amount reached 98.1% in 15 minutes.

Claims

1. A method for preparing a photocatalyst for simultaneously removing ammonia nitrogen, heavy metal ions and bacteria by carbon-based organic photovoltaic materials, characterized in that: The method comprises the following steps: A. Clean the coconut shell and dry it until it is completely dry; B. Crushing the completely dried coconut shell with a pulverizer and passing it through a 200 mesh sieve to obtain coconut shell powder; C. Drying the coconut shell powder at 100° C. for 30 min and then placing it in a tubular furnace for high-temperature pyrolysis treatment to obtain modified carbon-based material coconut shell carbon particles; D. Mixing an organic photovoltaic material and chloroform in the following weight ratio: 0.01-0.02 g of organic photovoltaic material: 10-20 ml of chloroform to obtain an organic photocatalyst mixed solution; the organic photovoltaic material is PCE10:IT-M, P3BH:IT-M or PCE10:P3BH:IT-M; E. The organic photocatalyst mixed solution obtained in step D is evenly coated on the modified carbon-based coconut shell carbon particles, and then dried at 60° C. for 24 hours to obtain a carbon-based organic photovoltaic material-loaded photocatalyst that simultaneously removes ammonia nitrogen, heavy metal ions and bacteria.

2. The method for preparing a photocatalyst for simultaneously removing ammonia nitrogen, heavy metal ions and bacteria by carbon-based organic photovoltaic materials according to claim 1, characterized in that: In step A, the drying process refers to placing the coconut shell in a forced air drying oven at a temperature of 70° C. and drying it for 48 hours.

3. The method for preparing a photocatalyst for simultaneously removing ammonia nitrogen, heavy metal ions and bacteria by carbon-based organic photovoltaic materials according to claim 1 or 2, characterized in that: In step B, the coconut shell is crushed for 3 to 5 minutes.

4. The method for preparing a photocatalyst for simultaneously removing ammonia nitrogen, heavy metal ions and bacteria by carbon-based organic photovoltaic materials according to claim 1 or 2, characterized in that: In step C, the operation of the tubular furnace for high-temperature pyrolysis treatment is: putting the coconut shell powder into the tubular furnace, closing the furnace plug, evacuating for 15 minutes, passing nitrogen for 20 minutes, heating to 200°C at a heating rate of 5°C / min under nitrogen protection, and then heating to 700°C at a heating rate of 10°C / min, keeping for 3 hours, cooling to room temperature, and bagging for later use.

5. The method for preparing a photocatalyst for simultaneously removing ammonia nitrogen, heavy metal ions and bacteria by carbon-based organic photovoltaic materials according to claim 1 or 2, characterized in that: In step E, the weight ratio of the organic photocatalyst mixed solution to the modified carbon-based material coconut shell carbon particles is 1:5000-10000.

6. The method for preparing a photocatalyst for simultaneously removing ammonia nitrogen, heavy metal ions and bacteria by carbon-based organic photovoltaic materials according to claim 1 or 2, characterized in that: In the step D, the PCE10:IT-M and P3BH:IT-M are mixed in a weight ratio of 1:1, and the PCE10:P3BH:IT-M is mixed in a weight ratio of 1:1:

1.

7. The method for preparing a photocatalyst for simultaneously removing ammonia nitrogen, heavy metal ions and bacteria by carbon-based organic photovoltaic materials according to claim 1 or 2, characterized in that: In the step D, during preparation, the organic photovoltaic material is mixed with chloroform and then stirred and dissolved at 80° C. for 1 hour.

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