Photocatalytic in-situ repairing agent for black and odorous river sediment water body and application method of photocatalytic in-situ repairing agent

Abstract

The invention belongs to the technical field of black and odorous riverway water treatment, and particularly relates to a black and odorous riverway bottom mud water body photocatalysis in-situ repairing agent and an application method thereof, the black and odorous riverway bottom mud water body photocatalysis in-situ repairing agent comprises the following raw materials by mass: ferrous sulfate, polyacrylic acid, sodium sulfide and sulfur powder; wherein the molar mass of the ferrous sulfate is 2-6 mmol, the mass of the polyacrylic acid is 0.4-0.8 g, the molar mass of the sodium sulfide is 2-6 mmol, and the mass of the sulfur powder is 0.4-0.8 g. Sunlight is adopted as driving force, efficient degradation of algal toxin in black and odorous river water is achieved, and the method has the following advantages that the material preparation cost is low, and the method is suitable for large-scale application; the preparation process is simple and easy to operate; sunlight is adopted as driving energy, additional electric power is not needed, and the environment-friendly requirement is met. Under the irradiation of sunlight, algal toxin in a black and odorous river water body can be efficiently degraded, and the remediation effect is remarkable; the method is suitable for water bodies with different pH ranges, and can effectively deal with the pollution problem of various black and odorous river water bodies.

Description

Technical Field

[0001] The invention relates to the technical field of black and smelly river water treatment, and specifically to a black and smelly river bottom mud water body photocatalytic in-situ repair agent and an application method thereof. Background Art

[0002] Traditional algal toxin treatment methods mainly include chemical precipitation, adsorption and physical filtration. Although these methods can remove algal toxins to a certain extent, they often fail to meet the requirements of low cost, environmental friendliness and high efficiency due to the use of more chemical agents, high cost, serious secondary pollution and the need for a lot of manual operations.

[0003] As an emerging water treatment technology, photocatalysis has the advantage of rapidly degrading pollutants under light without causing secondary pollution. In recent years, photocatalysts based on semiconductor materials have been widely used in the field of water treatment, especially in the degradation of organic pollutants, showing significant effects.

[0004] The prior art has the following defects or problems:

[0005] The existing photocatalytic materials still face problems such as low degradation efficiency, short service life, and high catalyst cost in the application of black and smelly river water. Therefore, it is urgent to develop a low-cost, high-efficiency, and environmentally friendly photocatalytic remediation agent that can achieve efficient degradation of algal toxins in water under natural light.

[0006] It should be noted that the above contents belong to the technical knowledge of the inventor and do not necessarily constitute prior art. Summary of the invention

[0007] In view of the deficiencies in the prior art, the present invention provides a photocatalytic in-situ repair agent for black and smelly riverbed mud water and an application method thereof, which solves the current problems.

[0008] To achieve the above-mentioned purpose, the present invention provides the following technical solutions: a photocatalytic in-situ repair agent for black and smelly riverbed mud water, comprising the following quality raw materials: ferrous sulfate, polyacrylic acid, sodium sulfide and sulfur powder;

[0009] The molar mass of ferrous sulfate is 2-6 mmol, the mass of the polyacrylic acid is 0.4-0.8 g, the molar mass of the sodium sulfide is 2-6 mmol, and the mass of the sulfur powder is 0.4-0.8 g.

[0010] Another technical problem to be solved by the present invention is to provide an application method of a photocatalytic in-situ repair agent for black and smelly riverbed mud water, comprising the following steps:

[0011] Step 1: Place the raw materials in a container containing deionized water, and mix them evenly through an external mixing device to ensure that the raw materials are fully dissolved in the deionized water, thereby obtaining a uniform mixed solution;

[0012] Step 2: transferring the mixed solution into a high-pressure reactor and heating it in a constant temperature oven, and cooling it to room temperature after the reaction is completed to obtain a ferrous disulfide heterocomplex;

[0013] Step 3: The iron disulfide compound is washed in deionized water and ethanol, and then dried in a vacuum oven to obtain ferrous disulfide after removing impurities;

[0014] Step 4: annealing the ferrous disulfide under vacuum conditions to obtain oxidized ferrous disulfide, which can be used as a photocatalytic material;

[0015] Step 5: Use irradiation light source to catalytically degrade algae toxins in water;

[0016] Step 6: Add the above-mentioned photocatalytic material into the water body and perform trace aeration at the same time to complete the in-situ restoration operation of the black and smelly river water body.

[0017] In some embodiments, the external mixing device is an ion mixer, the rotation speed of which is controlled at 100-150 rpm, and the mixing time is determined according to the mixing conditions.

[0018] In some of the embodiments, the mixed solution needs to undergo a pH adjustment operation before entering the reactor, which is performed by hydrochloric acid and hydrogen oxidation, and the pH value needs to be maintained at 6-8. The reactor is a stainless steel high-pressure reactor lined with polytetrafluoroethylene.

[0019] In some of the embodiments, the internal temperature of the constant temperature oven needs to be controlled between 200-300 degrees Celsius, and the heating time is 24 hours.

[0020] In some embodiments, the internal temperature of the vacuum oven is controlled at 40-60 degrees Celsius.

[0021] In some of the embodiments, the heating rate during the annealing process is 3-5 degrees Celsius per minute, from room temperature to 300-400 degrees Celsius, and the annealing operation time is controlled to be 2-3 hours.

[0022] In some embodiments, the irradiation light source includes one of natural, artificial simulated sunlight and visible light, and the irradiation intensity is 50-500W / m 2 , and the light source irradiation time is 6-12 hours. The degradation efficiency of algae toxins in the water body can be determined by regularly measuring the algae toxin concentration in the water body, which is detected by high performance liquid chromatography.

[0023] In some of the embodiments, the photocatalytic material is added to the water body in the form of powder, loaded on a film, and wrapped on a carrier, wherein the carrier includes zeolite and gravel, the photocatalytic material is added in an amount of 0.2-10 g / L, and the aeration volume is 50-100 mL / min.

[0024] Compared with the prior art, the present invention provides a photocatalytic in-situ repair agent for black and smelly riverbed mud and its application method, which has the following beneficial effects:

[0025] The photocatalytic in-situ repair agent for black and smelly riverbed mud water and its application method adopt sunlight as a driving force to achieve efficient degradation of algae toxins in black and smelly riverbed water, and have the following advantages: low material preparation cost, suitable for large-scale application; simple preparation process, easy operation; adopts sunlight as driving energy, no external electricity is required, and meets green environmental protection requirements; under the irradiation of sunlight, it can efficiently degrade algae toxins in black and smelly riverbed water, and the repair effect is significant; it is suitable for water bodies with different pH ranges, and can effectively deal with the pollution problems of various black and smelly riverbed water bodies. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 A schematic diagram showing the comparison of the effect of the photocatalytic material of the present invention on the degradation of algae toxins by sunlight;

[0027] Figure 2 A comparison diagram of the effect of solar photocatalytic degradation of algae toxins with and without aeration in the present invention;

[0028] Figure 3 Schematic diagram of the applicable range of pH value of the catalytic material of the present invention. DETAILED DESCRIPTION

[0029] The following will be combined with the embodiments of the present invention and the accompanying drawings to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments 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 creative work are within the scope of protection of the present invention.

[0030] It should be understood that the step numbers used in this article are only for the convenience of description and are not intended to limit the order in which the steps are executed.

[0031] It should be understood that the terms used in the present specification are only for the purpose of describing specific embodiments and are not intended to limit the present invention. As used in the present specification and the appended claims, unless the context clearly indicates otherwise, the singular forms "a", "an" and "the" are intended to include plural forms.

[0032] The terms “include” and “comprising” indicate the presence of described features, integers, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components and / or combinations thereof.

[0033] The term "and / or" means and includes any and all possible combinations of one or more of the associated listed items.

[0034] Embodiment 1, a photocatalytic in-situ repair agent for black and smelly riverbed mud water body, comprising the following quality raw materials: ferrous sulfate, polyacrylic acid, sodium sulfide and sulfur powder;

[0035] The molar mass of ferrous sulfate is 2-6 mmol, the mass of polyacrylic acid is 0.4-0.8 g, the molar mass of sodium sulfide is 2-6 mmol, and the mass of sulfur powder is 0.4-0.8 g.

[0036] Based on the above-mentioned black and smelly riverbed mud water body photocatalytic in-situ repair agent, a method for applying the black and smelly riverbed mud water body photocatalytic in-situ repair agent is proposed, comprising the following steps:

[0037] Step 1: Dissolve 5 mmol of ferrous sulfate, 0.5 g of polyacrylic acid, 5 mmol of sodium sulfide and 0.5 g of sulfur powder in 100 mL of deionized water under continuous stirring, and mix them evenly through an external mixing device to ensure that the raw materials are fully dissolved in the deionized water, thereby preparing a uniform mixed solution;

[0038] The external mixing equipment uses an ion mixer, the speed of which is controlled at 100 rpm, and the mixing time is determined according to the mixing conditions;

[0039] Step 2: transferring the mixed solution into a high-pressure reactor and heating it in a constant temperature oven, and cooling it to room temperature after the reaction is completed to obtain a ferrous disulfide heterocomplex;

[0040] The mixed solution needs to be PH-adjusted before entering the reactor, which is done by hydrochloric acid and hydrogen peroxide, and the pH value is 7. The reactor is a stainless steel high-pressure reactor lined with polytetrafluoroethylene;

[0041] The internal temperature of the constant temperature oven needs to be controlled at 220 degrees Celsius, and the heating time is 24 hours;

[0042] Step 3: The iron disulfide compound is washed in deionized water and ethanol, and then dried in a vacuum oven to obtain ferrous disulfide after removing impurities;

[0043] The internal temperature of the vacuum oven was controlled at 50 degrees Celsius, and the drying time was 8 hours;

[0044] Step 4: annealing the ferrous disulfide under vacuum conditions to obtain oxidized ferrous disulfide, which can be used as a photocatalytic material;

[0045] During the annealing process, the heating rate is 3-5 degrees Celsius per minute, from room temperature to 300 degrees Celsius, and the annealing operation time is controlled to be 2 hours.

[0046] See also Figure 1

[0047] Example 2: Comparison of the effect of photocatalytic materials on the degradation of algae toxins by sunlight:

[0048] Weigh 20 mg of the photocatalytic material prepared in Example 1 and 20 mg of ferrous disulfide powder as a control, add 50 ml of deionized water to prepare a 0.5 g / L solid solution, and add algae toxins to adjust the initial concentration to 10 mg / L. After adsorption equilibrium, aeration (50 mL / min) was performed, and the reaction was carried out under sunlight for 120 minutes. At the same dosage, the algae toxin degradation rate of FeS2-O photocatalytic material was 92%, while the degradation rate of FeS2 was only 50%;

[0049] See also Figure 2

[0050] Example 3: Comparison of the effect of solar photocatalytic degradation of algae toxins with and without aeration:

[0051] 20 mg of the photocatalytic material prepared in Example 1 was weighed and added to 50 ml of deionized water to prepare a 0.5 g / L solid solution, and algae toxin was added to make its initial concentration 10 mg / L. After adsorption equilibrium, trace air aeration (50 mL / min) and nitrogen aeration (100 mL / min) were performed respectively, and the reaction was carried out under sunlight catalysis for 120 minutes. Under air aeration, the algae toxin degradation rate of the FeS2-O photocatalytic material reached 92%, while under nitrogen aeration conditions, the degradation rate was only 50%;

[0052] See also Figure 3

[0053] Example 4, pH value applicable range of the catalytic material:

[0054] Weigh 20 mg of the photocatalytic material prepared in Example 1, add 50 ml of deionized water, adjust the initial pH value to 4, 6, 8 and 10 respectively, and then add algae toxin to make its initial concentration 10 mg / L. After adsorption equilibrium, carry out solar light catalytic degradation reaction for 120 minutes. The results are as follows: Figure 3 As shown in Figure 2, under different pH conditions, the catalytic degradation rate of FeS2-O photocatalytic material remained above 80%.

[0055] Each embodiment in this specification is described in a progressive manner, and the same or similar parts between the embodiments can be referred to each other, and each embodiment focuses on the differences from other embodiments. In particular, for the system embodiment, since it is basically similar to the method embodiment, the description is relatively simple, and the relevant parts can be referred to the partial description of the method embodiment.

[0056] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A photocatalytic in-situ repair agent for black and smelly riverbed mud water, characterized in that: The raw materials include the following quality materials: ferrous sulfate, polyacrylic acid, sodium sulfide and sulfur powder; The molar mass of ferrous sulfate is 2-6 mmol, the mass of the polyacrylic acid is 0.4-0.8 g, the molar mass of the sodium sulfide is 2-6 mmol, and the mass of the sulfur powder is 0.4-0.8 g.

2. An application method of a photocatalytic in-situ repair agent for black and smelly riverbed mud water, characterized in that: The steps include: Step 1: Place the raw materials in a container containing deionized water, and mix them evenly through an external mixing device to ensure that the raw materials are fully dissolved in the deionized water, thereby obtaining a uniform mixed solution; Step 2: transferring the mixed solution into a high-pressure reactor and heating it in a constant temperature oven, and cooling it to room temperature after the reaction is completed to obtain a ferrous disulfide heterocomplex; Step 3: The iron disulfide compound is washed in deionized water and ethanol, and then dried in a vacuum oven to obtain ferrous disulfide after removing impurities; Step 4: annealing the ferrous disulfide under vacuum conditions to obtain oxidized ferrous disulfide, which can be used as a photocatalytic material; Step 5: Use irradiation light source to catalytically degrade algae toxins in water; Step 6: Add the above-mentioned photocatalytic material into the water body and perform trace aeration at the same time to complete the in-situ restoration operation of the black and smelly river water body.

3. The application method of a photocatalytic in-situ repair agent for black and smelly riverbed mud water body according to claim 2 is characterized by: The external mixing device in step 1 is an ion mixer, the rotation speed of which is controlled at 100-150 rpm, and the mixing time is determined according to the mixing conditions.

4. The application method of a photocatalytic in-situ repair agent for black and smelly riverbed mud water body according to claim 2 is characterized by: The mixed solution in step 2 needs to undergo a pH adjustment operation before entering the reactor, which is performed by hydrochloric acid and hydrogen peroxide, and the pH value needs to be maintained at 6-8. The reactor is a stainless steel high-pressure reactor lined with polytetrafluoroethylene.

5. The application method of a photocatalytic in-situ repair agent for black and smelly riverbed mud water body according to claim 2 is characterized by: The internal temperature of the constant temperature oven in step 2 needs to be controlled between 200-300 degrees Celsius, and the heating time is 24 hours.

6. The application method of a photocatalytic in-situ repair agent for black and smelly riverbed mud water body according to claim 2 is characterized by: The internal temperature of the vacuum oven described in step 3 is controlled at 40-60 degrees Celsius.

7. The application method of a photocatalytic in-situ repair agent for black and smelly riverbed mud water body according to claim 2 is characterized by: The heating rate during the annealing process in step 4 is 3-5 degrees Celsius per minute, from room temperature to 300-400 degrees Celsius, and the annealing operation time is controlled at 2-3 hours.

8. The application method of a photocatalytic in-situ repair agent for black and smelly riverbed mud water body according to claim 2 is characterized by: The irradiation light source in step 5 includes one of natural, artificial simulated sunlight and visible light, and the irradiation intensity is 50-500W / m 2 , and the light source irradiation time is 6-12 hours. The degradation efficiency of algae toxins in the water body can be determined by regularly measuring the algae toxin concentration in the water body, which is detected by high performance liquid chromatography.

9. The application method of a photocatalytic in-situ repair agent for black and smelly riverbed mud water body according to claim 2 is characterized by: In step six, the photocatalytic material is added to the water body in the form of powder, loaded on a film or wrapped on a carrier, wherein the carrier includes zeolite and gravel, the amount of the photocatalytic material added is 0.2-10 g / L, and the aeration volume is 50-100 mL / min.

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