An advanced oxidation device and method for degrading emerging contaminants in water

Abstract

The application discloses a kind of advanced oxidation device and method for degrading new pollutants in water, the device includes reaction pool, ozone generator, sulfite storage tank, ozone generator is used to add ozone to reaction pool, sulfite storage tank is used to add sulfite to reaction pool;Reaction pool is equipped with water inlet and water outlet. When using, inject the water sample to be treated into reaction pool, start ozone generator, sulfite storage tank to carry out the addition of ozone and sulfite;The molar ratio of ozone and sulfite addition in reaction pool is 5:1~1:1, the molar ratio of new pollutant concentration in the water sample to be treated and ozone addition amount is: 1:10~1:100.The advanced oxidation system of ozone activated sulfite constructed by the application has high yield of sulfate radical and hydroxyl radical, and can rapidly degrade new pollutants within 5 minutes, and the degradation efficiency of new pollutants such as naproxen, sulfamethoxazole, carbamazepine, atrazine and chloramphenicol in water reaches more than 80%.

Description

Technical Field

[0001] This invention relates to the field of water treatment technology, and in particular to an advanced oxidation device and method for degrading new pollutants in water. Background Technology

[0002] The treatment of new pollutants in water is a new challenge in current water environment management. These new pollutants mainly include persistent organic pollutants, antibiotics, endocrine disruptors, etc. Due to their environmental persistence, wide range of sources and the complexity of treatment, they are frequently detected in water and are difficult to remove effectively, posing a challenge to water quality safety.

[0003] For the removal of new pollutants in water, advanced oxidation (AE) is widely considered one of the most efficient degradation technologies. AE systems primarily degrade new pollutants by generating highly oxidizing free radicals such as sulfate and hydroxyl radicals. Existing AE systems often employ ultraviolet (UV) light to activate peroxides and generate these radicals. However, UV irradiation requires a large external energy input, and UV-based AE systems generally suffer from low free radical yields and long degradation times for new pollutants. Therefore, exploring new AE systems capable of ultra-rapidly degrading new pollutants and constructing suitable integrated devices based on these characteristics is of great significance for the efficient removal of new pollutants from water.

[0004] Sulfite advanced oxidation systems are currently a hot research topic in the removal of new pollutants and represent a promising solution for advanced oxidation technologies in water treatment. Sulfite advanced oxidation primarily utilizes the auto-oxidation process during activation to generate sulfate and hydroxyl radicals, thereby achieving efficient degradation of new pollutants. However, the auto-oxidation process of sulfite is slow, and the yields of sulfate and hydroxyl radicals are low. Constructing an advanced oxidation system that can significantly accelerate sulfite auto-oxidation and efficiently generate sulfate and hydroxyl radicals will further enhance its application prospects. Summary of the Invention

[0005] Purpose of the invention: To address the above-mentioned shortcomings, the present invention provides an advanced oxidation device and method for degrading new pollutants in water, which can accelerate the auto-oxidation of sulfites and generate sulfate free radicals and hydroxyl free radicals more efficiently.

[0006] Technical solution: To solve the above problems, the present invention employs an advanced oxidation device for degrading new pollutants in water, including a reaction tank, an ozone generator, and a sulfite storage tank. The ozone generator is used to add ozone to the reaction tank, and the sulfite storage tank is used to add sulfite to the reaction tank. The reaction tank is provided with an inlet and an outlet.

[0007] Furthermore, it also includes a stirring rod, a stirring motor, and blades. The stirring rod is connected to the blades, the blades extend into the interior of the reaction tank, and the stirring motor is connected to the stirring rod to drive the stirring rod to rotate.

[0008] Furthermore, the stirring rod and blades are both hollow structures, and the stirring rod and blades are connected internally, with nozzles provided on the blades; the ozone generator is connected to the stirring rod, and the ozone generated by the ozone generator enters the reaction tank through the stirring rod and blades.

[0009] Furthermore, it also includes a spray ring pipe installed in the reaction tank, which has multiple outlets. The sulfite storage tank is connected to the spray ring pipe so that the sulfite enters the reaction tank through the spray ring pipe.

[0010] Furthermore, the blades are located below the spray ring pipe.

[0011] Furthermore, the blades are installed at the center of the reaction tank at a distance l1 from the bottom, where l1 = H / 8; the spray ring pipe is installed on the inner wall of the reaction tank at a distance l2 from the bottom, where l2 = H / 4, and H is the height of the reaction tank.

[0012] Furthermore, both the nozzle and the liquid outlet are equipped with titanium plate microporous diffusers.

[0013] Furthermore, the inlet is located below the outlet.

[0014] The present invention also provides a method for using the above-mentioned advanced oxidation device, wherein a water sample to be treated is injected into a reaction tank, and an ozone generator and a sulfite storage tank are started to add ozone and sulfite; the molar ratio of ozone to sulfite added in the reaction tank is 5:1 to 1:1, and the molar ratio of the concentration of new pollutants in the water sample to the amount of ozone added is 1:10 to 1:100.

[0015] Beneficial effects: Compared with the prior art, the significant advantages of this invention are (1) The ozone-activated sulfite advanced oxidation system constructed in this invention has a high yield of sulfate free radicals and hydroxyl free radicals, and can rapidly degrade new pollutants within 5 minutes. The degradation efficiency of new pollutants such as naproxen, sulfamethoxazole, carbamazepine, atrazine, and chloramphenicol in water reaches more than 80%; (2) The final product of ozone reaction is oxygen, and the final product of sulfite is sulfate, which will not cause secondary pollution to the water environment; (3) The advanced oxidation integrated device designed in this invention has a simple structure, is easy to manage, and is suitable for various application scenarios (such as tap water treatment, groundwater remediation, etc.), and can be applied on a large scale. Attached Figure Description

[0016] Figure 1 This is a front view of the advanced oxidation apparatus of the present invention;

[0017] Figure 2This is a left view of the advanced oxidation apparatus of the present invention;

[0018] Figure 3 This is a top view of the advanced oxidation apparatus of the present invention;

[0019] Figure 4 This is a test image of sulfate radicals and hydroxyl radicals generated by ozone-activated sulfite using electron paramagnetic resonance spectroscopy in Example 1;

[0020] Figure 5 This is a comparison chart of the concentrations of the new pollutants before and after treatment in Example 2;

[0021] Figure 6 This is a comparison chart of the concentrations of the new pollutants before and after treatment in Example 3;

[0022] Figure 7 This is a comparison chart of the concentrations of the new pollutants before and after treatment in Example 4;

[0023] Figure 8 This is a comparison chart of the concentrations of the new pollutants before and after treatment in Example 5. Detailed Implementation

[0024] Example 1

[0025] like Figures 1 to 3 As shown, this embodiment of an advanced oxidation device for degrading new pollutants in water includes a reaction tank 1, an ozone generator 4, a sulfite storage tank 5, a stirring paddle 6, a stirring motor 7, a spray ring pipe 8, and blades 10. The reaction tank 1 is equipped with an inlet 2 and an outlet 3, with the inlet 2 located on the lower side of the reaction tank 1 and the outlet 3 located on the upper side, resulting in an upflow of water samples within the reaction tank 1. The ozone generator used is model ZJC-WS1, manufactured by Shanghai Zhongjing Environmental Protection Technology Co., Ltd., and the sodium sulfite (98%) stored in the sulfite storage tank 5 was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0026] Ozone generator 4 is connected to stirring rod 6, which is connected to blades 10. Blades 10 extend into the reaction tank 1. Stirring motor 7 is connected to stirring rod 6 to drive stirring rod 6 to rotate. Stirring rod 6 drives blades 10 to rotate. In this embodiment, the blades are three-bladed, and the blade length is 1 / 3 of the radius of the reaction tank. Both stirring rod 6 and blades 10 have hollow internal structures, and the stirring rod 6 and blades 10 are internally connected. Blades 10 are provided with nozzles, and titanium plate microporous diffusers 9 are provided at the nozzles. Ozone generated by ozone generator 4 enters reaction tank 1 through stirring rod 6 and blades 10.

[0027] A spray ring pipe 8 is installed on the inner wall of the reaction tank 1. Six outlets are evenly spaced on the spray ring pipe 8, and each outlet is equipped with a titanium plate microporous diffuser 9. A sulfite storage tank 5 is connected to the spray ring pipe 8 so that sulfite enters the reaction tank 1 through the spray ring pipe 8. To ensure sufficient contact between ozone and sulfite for reaction, blades 10 are positioned below the spray ring pipe 8, allowing the ozone gas to fully mix and react with the sulfite during its ascent. Specifically, in this embodiment, the blades 10 are installed at the center of the reaction tank 1 at a distance l1 from the bottom, where l1 = H / 8; the spray ring pipe 8 is installed on the inner wall of the reaction tank 1 at a distance l2 from the bottom, where l2 = H / 4, and H is the height of the reaction tank 1.

[0028] In operation, the water sample to be treated is first injected into reaction tank 1. Then, the ozone generator 4 and sulfite storage tank 5 are started to add ozone and sulfite. The stirring paddle 6 and blades 10 ensure sufficient ozone aeration, improve ozone mass transfer efficiency, and thoroughly mix the water sample in the reaction tank. The spray ring pipe 8 ensures that sulfite is added evenly to the reaction tank.

[0029] Example 2

[0030] To verify the effectiveness of the ozone-activated sulfite advanced oxidation system, pure water was injected into the aforementioned advanced oxidation device. The residence time of the pure water in the reaction tank was 5 minutes. The ozone dosage was 40 μmol / L, the sulfite dosage was 40 μmol / L, the stirring speed was 600 rpm, and 100 mmol / L of 5,5-dimethyl-1-pyrrolline-N-oxide (free radical scavenger) was added to the reaction solution. The reaction process in the reaction tank is as follows:

[0031] O3+SO3 2- →OOOOSO3 2- →SO3 ·- +O3 ·-

[0032] SO3 ·- +O2→SO5 ·-

[0033] SO5 ·- +H₂O→SO₄ ·- +2·OH

[0034] The free radicals generated in the system were determined using electron paramagnetic resonance spectroscopy, and the results are shown in the appendix. Figure 4 As can be seen from the figure, a large number of sulfate radicals and hydroxyl radicals were detected, indicating that the addition of ozone accelerates the auto-oxidation of sulfite and generates sulfate radicals and hydroxyl radicals more efficiently.

[0035] Example 3

[0036] This embodiment provides a method for using the advanced oxidation apparatus of Embodiment 1. First, a water sample containing new contaminants is injected into reaction tank 1. The water sample is prepared using pure water to obtain a solution of the new contaminants, which includes naproxen, sulfamethoxazole, carbamazepine, atrazine, and chloramphenicol. In this embodiment, the concentration of each new contaminant is 1 μmol / L. The residence time of the water sample in the reaction tank is 5 minutes. The ozone dosage is 100 μmol / L, the sulfite dosage is 25 μmol / L, and the stirring speed is 600 rpm.

[0037] After treatment, the concentration changes of new pollutants in the water were measured, and the results are as follows: Naproxen: 0.012 μmol / L; Sulfamethoxazole: 0.033 μmol / L; Carbamazepine: 0.019 μmol / L; Atrazine: 0.127 μmol / L; Chloramphenicol: 0.148 μmol / L. The corresponding removal rates of new pollutants were: Naproxen: 98.8%; Sulfamethoxazole: 96.7%; Carbamazepine: 98.1%; Atrazine: 87.3%; Chloramphenicol: 85.2%. Detailed results are attached. Figure 5 .

[0038] Example 4

[0039] This embodiment provides a method for using the advanced oxidation apparatus of Embodiment 1. First, a water sample containing new contaminants is injected into reaction tank 1. The water sample is prepared using pure water to create a solution of the new contaminants, which includes naproxen, sulfamethoxazole, carbamazepine, atrazine, and chloramphenicol. In this embodiment, the concentration of each new contaminant is 10 μmol / L. The residence time of the water sample in the reaction tank is 3 minutes. The ozone dosage is 100 μmol / L, the sulfite dosage is 100 μmol / L, and the stirring speed is 600 rpm.

[0040] After treatment, the concentration changes of new pollutants in the water were measured, and the results are as follows: Naproxen: 0.87 μmol / L; Sulfamethoxazole: 1.28 μmol / L; Carbamazepine: 1.02 μmol / L; Atrazine: 1.55 μmol / L; Chloramphenicol: 1.66 μmol / L. The corresponding removal rates of new pollutants were: Naproxen: 91.3%; Sulfamethoxazole: 87.2%; Carbamazepine: 89.8%; Atrazine: 84.5%; Chloramphenicol: 83.4%. Detailed results are attached. Figure 6 .

[0041] Example 5

[0042] This embodiment provides a method for using the advanced oxidation apparatus of Embodiment 1. First, a water sample containing new pollutants is injected into reaction tank 1. The water sample is prepared using pure water to create a solution of the new pollutants, which includes naproxen, sulfamethoxazole, carbamazepine, atrazine, and chloramphenicol. In this embodiment, the concentration of each new pollutant is 5 μmol / L. The residence time of the water sample in the reaction tank is 3 minutes. The ozone dosage is 50 μmol / L, the sulfite dosage is 25 μmol / L, and the stirring speed is 600 rpm.

[0043] After treatment, the concentration changes of new pollutants in the water were measured, and the results are as follows: Naproxen: 0.525 μmol / L; Sulfamethoxazole: 0.825 μmol / L; Carbamazepine: 0.670 μmol / L; Atrazine: 0.920 μmol / L; Chloramphenicol: 0.965 μmol / L. The corresponding removal rates of new pollutants were: Naproxen: 89.5%; Sulfamethoxazole: 83.5%; Carbamazepine: 86.6%; Atrazine: 81.6%; Chloramphenicol: 80.7%. Detailed results are attached. Figure 7 .

[0044] Example 6

[0045] This embodiment provides a method for using the advanced oxidation apparatus of Embodiment 1. First, a water sample containing new contaminants is injected into reaction tank 1. The water sample is prepared using pure water to create a solution of the new contaminants, which includes naproxen, sulfamethoxazole, carbamazepine, atrazine, and chloramphenicol. In this embodiment, the concentration of each new contaminant is 10 μmol / L. The residence time of the water sample in the reaction tank is 4 minutes. The ozone dosage is 25 μmol / L, the sulfite dosage is 5 μmol / L, and the stirring speed is 600 rpm.

[0046] After treatment, the concentration changes of new pollutants in the water were measured, and the results are as follows: Naproxen: 0.066 μmol / L; Sulfamethoxazole: 0.123 μmol / L; Carbamazepine: 0.089 μmol / L; Atrazine: 0.155 μmol / L; Chloramphenicol: 0.174 μmol / L. The corresponding removal rates of new pollutants were: Naproxen: 93.4%; Sulfamethoxazole: 87.7%; Carbamazepine: 91.1%; Atrazine: 84.5%; Chloramphenicol: 82.6%. Detailed results are attached. Figure 8 .

Claims

1. An advanced oxidation device for degrading new pollutants in water, characterized in that, It includes a reaction tank (1), an ozone generator (4), and a sulfite storage tank (5). The ozone generator (4) is used to add ozone to the reaction tank (1), and the sulfite storage tank (5) is used to add sulfite to the reaction tank (1). The reaction tank (1) is provided with an inlet (2) and an outlet (3).

2. The advanced oxidation device for degrading new pollutants in water as described in claim 1, characterized in that, It also includes a stirring rod (6), a stirring motor (7), and blades (10). The stirring rod (6) is connected to the blades (10), and the blades (10) extend into the reaction tank (1). The stirring motor (7) is connected to the stirring rod (6) to drive the stirring rod (6) to rotate.

3. The advanced oxidation device for degrading new pollutants in water as described in claim 2, characterized in that, The stirring rod (6) and blade (10) are both hollow structures, and the stirring rod (6) and blade (10) are connected internally. The blade (10) is provided with a nozzle. The ozone generator (4) is connected to the stirring rod (6), and the ozone generated by the ozone generator (4) enters the reaction tank (1) through the stirring rod (6) and blade (10).

4. The advanced oxidation device for degrading new pollutants in water as described in claim 3, characterized in that, It also includes a spray ring pipe (8) installed in the reaction tank (1), the spray ring pipe (8) is provided with multiple liquid outlets, and the sulfite storage tank (5) is connected to the spray ring pipe (8) so that the sulfite enters the reaction tank (1) through the spray ring pipe (8).

5. The advanced oxidation device for degrading new pollutants in water as described in claim 4, characterized in that, The blade (10) is located below the spray ring pipe (8).

6. The advanced oxidation device for degrading new pollutants in water as described in claim 5, characterized in that, The blade (10) is installed at the center of the reaction tank (1) at a distance l1 from the bottom, where l1 = H / 8; the spray ring pipe (8) is installed on the inner wall of the reaction tank (1) at a distance l2 from the bottom, where l2 = H / 4, and H is the height of the reaction tank (1).

7. The advanced oxidation device for degrading new pollutants in water as described in claim 4, characterized in that, Both the nozzle and the liquid outlet are equipped with titanium plate microporous diffusers (9).

8. The advanced oxidation device for degrading new pollutants in water as described in claim 1, characterized in that, The inlet (2) is located below the outlet (3).

9. A method using the advanced oxidation apparatus as described in any one of claims 1-8, characterized in that, Inject the water sample to be treated into the reaction tank (1), and start the ozone generator (4) and sulfite storage tank (5) to add ozone and sulfite; the molar ratio of ozone to sulfite in the reaction tank (1) is 5:1 to 1:1, and the molar ratio of the concentration of new pollutants in the water sample to the amount of ozone added is 1:10 to 1:100.

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