Method for activating organic matter degradation of peroxyacetic acid using electrochemically generated atomic hydrogen
By using an electrochemical method to generate atomic hydrogen to activate peracetic acid, and employing an electrochemical reactor with a titanium substrate coated with lead dioxide or tin dioxide and a foamed nickel cathode, the problem of antibiotic pollution being difficult to remove in existing technologies has been solved, achieving efficient and low-cost degradation.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- ZHEJIANG RONGKAI TECH DEV
- Filing Date
- 2023-02-24
- Publication Date
- 2026-06-26
AI Technical Summary
Existing wastewater treatment technologies are unable to completely remove antibiotic contamination, leading to environmental pollution. Furthermore, existing methods are costly and may introduce secondary pollution.
Atomic hydrogen-activated peracetic acid is generated using an electrochemical method. It is then passed through a titanium substrate with a lead dioxide or tin dioxide coating as the anode and a nickel foam cathode in an electrochemical reactor. Metals such as palladium, rhodium, platinum, ruthenium, iridium, and indium are loaded to generate atomic hydrogen-activated peracetic acid, which degrades organic matter.
It achieves highly efficient degradation of antibiotics, with good degradation effect, no need for other catalysts, reduces costs, avoids secondary pollution, has strong anti-interference ability, and is suitable for the treatment of conventional antibiotic wastewater.
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Figure CN116216868B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of compound technology, and in particular to a method for the degradation of organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid. Background Technology
[0002] Antibiotics are secondary metabolites produced by microorganisms (including bacteria, fungi, and actinomycetes) or higher plants and animals during their life processes. They possess antipathogenic or other activities and can interfere with the developmental functions of other living cells. Commonly used antibiotics in clinical practice include extracts from microbial cultures and compounds synthesized or semi-synthesized using chemical methods.
[0003] Currently, widely used antibiotics can be classified according to their chemical structure into lactams, quinolones, tetracyclines, aminoglycosides, macrolides, sulfonamides, etc.
[0004] For a long time, antibiotics have been used extensively in the treatment of diseases in humans and animals, and added to animal feed at sub-therapeutic doses to prevent animal diseases and promote their growth. However, most antibiotics cannot be completely absorbed by the body. About 90% of antibiotics are excreted into the environment in their original form or as metabolites through the feces and urine of patients and livestock, causing pollution to soil and water bodies through various pathways.
[0005] Wastewater containing antibiotics can enter urban wastewater treatment plants through sewers. However, existing wastewater treatment technologies are insufficient to completely remove antibiotics. Some wastewater can also seep into the soil and groundwater, and then be recycled into people's drinking water, posing a threat to personal safety. Summary of the Invention
[0006] This invention aims to solve the problems existing in the prior art by providing a method for the degradation of organic matter by activating peracetic acid with electrochemically generated atomic hydrogen. This method can activate peracetic acid to degrade antibiotics, achieve mineralization, and has a good degradation effect. It does not require the use of other catalysts and is low in cost.
[0007] The technical solution adopted by this invention to solve its technical problem is as follows: This method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid includes the following steps:
[0008] The first step is to prepare the reaction raw materials. Peracetic acid solution and organic pollutant solution are selected as the reaction raw materials. The peracetic acid solution is a peracetic acid solution with a concentration of 35 mg / L to 40 mg / L, and the organic pollutant solution is an organic pollutant solution with a concentration of 7 mg / L to 9 mg / L. The mass ratio of peracetic acid solution to organic pollutant solution is 1:3 to 5.
[0009] The second step involves activating peracetic acid to degrade organic matter. An electrochemical reactor is selected, with the anode being a lead dioxide-plated electrode or a tin dioxide-plated electrode on a titanium substrate, and the cathode being made of nickel foam loaded with metals, including palladium, rhodium, platinum, ruthenium, iridium, and indium. The selected organic pollutant solution is first placed into the electrochemical reactor, and the reactor is started to react for 30 minutes. Then, a peracetic acid solution is added, and the electrochemical reaction continues in the reactor to degrade the organic matter.
[0010] Furthermore, in the above-mentioned method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid, the second step of the electrochemical reactor uses an H-type replaceable ion-exchange membrane electrolytic cell, and the reaction is carried out in the cathode chamber.
[0011] Furthermore, in the above-mentioned method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid, the organic pollutant solution in the first step is any one or any combination of sulfamethoxazole solution, roxithromycin solution, and cephalosporin solution.
[0012] Furthermore, in the above-mentioned method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid, the voltage of the electrochemical reactor in the second step is 1.4V.
[0013] Furthermore, in the above-mentioned method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid, the pH of the organic pollutant solution in the first step is 3 to 11.
[0014] Furthermore, in the above-mentioned method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid, the electrochemical reaction time after the peracetic acid solution is placed in the second step is 2h to 3h.
[0015] In this invention, the first step involves preparing the reaction raw materials. Peracetic acid solution and an organic pollutant solution are selected as the reaction raw materials. The peracetic acid solution has a concentration of 35 mg / L to 40 mg / L, and the organic pollutant solution has a concentration of 7 mg / L to 9 mg / L. The mass ratio of the peracetic acid solution to the organic pollutant solution is 1:3 to 5. The organic pollutant solution is any one or any combination of sulfamethoxazole solution, roxithromycin solution, and cephalosporin solution. The second step involves activating the peracetic acid to degrade the organic matter. An electrochemical reactor is selected. The anode in the electrochemical reactor is a lead dioxide-plated electrode or a tin dioxide-plated electrode on a titanium substrate, and the cathode electrode is made of nickel foam and loaded with metals, including palladium, rhodium, platinum, ruthenium, iridium, and indium. The selected organic pollutant solution is first placed into the electrochemical reactor, and the reactor is started and reacted for 30 minutes. Then, the peracetic acid solution is added, and the electrochemical reaction continues in the electrochemical reactor to degrade the organic matter. After the electrochemical reactor is started, the cathode electrode, made of foamed nickel and loaded with metals including palladium, rhodium, platinum, ruthenium, iridium, and indium, generates adsorbed atomic hydrogen at the cathode electrode. This atomic hydrogen undergoes electron transfer, activating the hydroxyl-oxygen bonds and peroxy bonds of peracetic acid, producing hydroxyl radicals, acetyloxy radicals, acetylperoxy radicals, and methyl radicals. These radicals react with organic matter, achieving a mineralization process and thus degrading the organic matter. This process, using electrochemically generated atomic hydrogen to activate peracetic acid for organic matter degradation, ensures thorough degradation of antibiotic organic matter, improving degradation efficiency and effectiveness. No other catalysts are needed, eliminating the activation process and reducing costs while avoiding secondary pollution. It can be applied to conventional antibiotic wastewater. Furthermore, because the principle involves electrochemically generating atomic hydrogen to activate peracetic acid for degradation, it reduces interference from chloride ions and other substances in the wastewater, achieving targeted degradation with strong anti-interference capabilities and excellent degradation effect.
[0016] In this invention, the cathode electrode of the electrochemical reactor is made of nickel foam and loaded with metals, including palladium, rhodium, platinum, ruthenium, iridium and indium. Its function is to enable the anode electrode to generate atomic hydrogen after the electrochemical reactor starts working, so as to realize its operation. Since the cathode is made of nickel foam, the metal can be uniformly dispersed on the porous three-dimensional nickel foam, which can confine peracetic acid and organic matter in the porous three-dimensional space, forming a high-concentration reaction zone, forming a confinement effect, and improving the degradation effect.
[0017] In this invention, the electrochemical reactor is first started for 30 minutes to generate more atomic hydrogen, thereby increasing the atomic hydrogen concentration in the electrochemical reactor. After adding peracetic acid, the reaction proceeds rapidly, improving the degradation efficiency.
[0018] The electrochemical reactor uses an H-type replaceable ion-exchange membrane electrolytic cell. The anode only serves to conduct electricity, and the reaction takes place in the cathode chamber. This can effectively avoid the phenomenon of producing a large number of toxic byproducts due to incomplete mineralization in traditional anodizing.
[0019] The beneficial effects of this invention are: the organic matter degradation method of this invention, which utilizes electrochemically generated atomic hydrogen to activate peracetic acid, degrades organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid, achieving mineralization and improving degradation efficiency. It eliminates the need for other catalysts and energy inputs, reducing costs and avoiding secondary pollution. It also achieves targeted degradation, exhibits strong anti-interference ability, and demonstrates good performance, making it easy to promote. Attached Figure Description
[0020] Figure 1 This is a schematic diagram illustrating the degradation effect of Embodiment 2 of the present invention;
[0021] Figure 2 This is a schematic diagram of the degradation curves of Embodiment 2 of the present invention under different voltages, including comparative curves at voltages of 0.8V, 1.0V, and 1.2V;
[0022] Figure 3 This is a schematic diagram of the degradation curves of Embodiment 2 of the present invention at different pH values, including comparative curves for pH=3, pH=5, pH=9, and pH=11.
[0023] Figure 4 This is a schematic diagram of the degradation curves of the present invention under different oxidants in Example 2, including comparative curves of hydrogen peroxide, persulfate, and persulfate. Detailed Implementation
[0024] The present invention will be further described below:
[0025] Example 1:
[0026] This method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid includes the following steps:
[0027] The first step is to prepare the reaction raw materials. Peracetic acid solution and organic pollutant solution are selected as the reaction raw materials. The peracetic acid solution is a peracetic acid solution with a concentration of 35 mg / L, and the organic pollutant solution is an organic pollutant solution with a concentration of 7 mg / L. The mass ratio of peracetic acid solution to organic pollutant solution is 1:3.
[0028] The second step involves activating peracetic acid to degrade organic matter. An electrochemical reactor is selected, with the anode being a lead dioxide-plated electrode or a tin dioxide-plated electrode on a titanium substrate, and the cathode being made of nickel foam loaded with metals, including palladium, rhodium, platinum, ruthenium, iridium, and indium. The selected organic pollutant solution is first placed into the electrochemical reactor, and the reactor is started to react for 30 minutes. Then, a peracetic acid solution is added, and the electrochemical reaction continues in the reactor to degrade the organic matter.
[0029] Furthermore, in the above-mentioned method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid, the second step of the electrochemical reactor uses an H-type replaceable ion-exchange membrane electrolytic cell, and the reaction is carried out in the cathode chamber.
[0030] Furthermore, in the above-mentioned method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid, the organic pollutant solution in the first step is a cephalosporin solution.
[0031] Furthermore, in the above-mentioned method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid, the voltage of the electrochemical reactor in the second step is 1.4V.
[0032] Furthermore, in the above-mentioned method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid, the pH of the organic pollutant solution in the first step is 6.
[0033] Furthermore, in the above-mentioned method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid, the electrochemical reaction time after the peracetic acid solution is placed in the second step is 3 hours.
[0034] Example 2:
[0035] This method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid includes the following steps:
[0036] The first step is to prepare the reaction raw materials. Peracetic acid solution and organic pollutant solution are selected as the reaction raw materials. The peracetic acid solution is a peracetic acid solution with a concentration of 38 mg / L, and the organic pollutant solution is an organic pollutant solution with a concentration of 9 mg / L. The mass ratio of peracetic acid solution to organic pollutant solution is 1:4.
[0037] The second step involves activating peracetic acid to degrade organic matter. An electrochemical reactor is selected, with the anode being a lead dioxide-plated electrode or a tin dioxide-plated electrode on a titanium substrate, and the cathode being made of nickel foam loaded with metals, including palladium, rhodium, platinum, ruthenium, iridium, and indium. The selected organic pollutant solution is first placed into the electrochemical reactor, and the reactor is started to react for 30 minutes. Then, a peracetic acid solution is added, and the electrochemical reaction continues in the reactor to degrade the organic matter.
[0038] Furthermore, in the above-mentioned method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid, the second step of the electrochemical reactor uses an H-type replaceable ion-exchange membrane electrolytic cell, and the reaction is carried out in the cathode chamber.
[0039] Furthermore, in the above-mentioned method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid, the organic pollutant solution in the first step is a sulfamethoxazole solution.
[0040] Furthermore, in the above-mentioned method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid, the voltage of the electrochemical reactor in the second step is 1.4V.
[0041] Furthermore, in the above-mentioned method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid, the pH of the organic pollutant solution in the first step is 7.
[0042] Furthermore, in the above-mentioned method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid, the electrochemical reaction time after the peracetic acid solution is placed in the second step is 3 hours.
[0043] In this embodiment, as Figure 1 As shown, E+PdNPs+PAA is a schematic diagram of the degradation effect curve in this embodiment. Complete degradation was achieved after 3 hours of reaction. PAA is peracetic acid. Figure 1 The separate PAA curves in the figure represent the degradation effect of adding only peracetic acid. The comparison shows that the degradation effect of directly adding peracetic acid is poor, while the method described in this embodiment achieves complete degradation. Figure 2 As shown, the comparison curves for voltages of 0.8V, 1.0V, and 1.2V demonstrate that the solution effect of this invention is best at 1.4V. Figure 3 As shown, the degradation curves at different pH values show only minor differences. Figure 4 As shown, the comparison curves of degradation using different oxidants show that the peracetic acid used in the embodiment of the present invention has the best degradation effect.
[0044] Example 3:
[0045] This method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid includes the following steps:
[0046] The first step is to prepare the reaction raw materials. Peracetic acid solution and organic pollutant solution are selected as the reaction raw materials. The peracetic acid solution is a 40 mg / L peracetic acid solution, and the organic pollutant solution is a 9 mg / L organic pollutant solution. The mass ratio of peracetic acid solution to organic pollutant solution is 1:5.
[0047] The second step involves activating peracetic acid to degrade organic matter. An electrochemical reactor is selected, with the anode being a lead dioxide-plated electrode or a tin dioxide-plated electrode on a titanium substrate, and the cathode being made of nickel foam loaded with metals, including palladium, rhodium, platinum, ruthenium, iridium, and indium. The selected organic pollutant solution is first placed into the electrochemical reactor, and the reactor is started to react for 30 minutes. Then, a peracetic acid solution is added, and the electrochemical reaction continues in the reactor to degrade the organic matter.
[0048] Furthermore, in the above-mentioned method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid, the second step of the electrochemical reactor uses an H-type replaceable ion-exchange membrane electrolytic cell, and the reaction is carried out in the cathode chamber.
[0049] Furthermore, in the above-mentioned method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid, the organic pollutant solution in the first step is an erythromycin solution.
[0050] Furthermore, in the above-mentioned method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid, the voltage of the electrochemical reactor in the second step is 1.4V.
[0051] Furthermore, in the above-mentioned method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid, the pH of the organic pollutant solution in the first step is 8.
[0052] Furthermore, in the above-mentioned method for degrading organic matter by using electrochemically generated atomic hydrogen to activate peracetic acid, the electrochemical reaction time after the peracetic acid solution is placed in the second step is 3 hours.
[0053] In the embodiments of the present invention, Embodiment 1 and Embodiment 3 can also achieve the effect of complete degradation. Therefore, the accompanying drawings are illustrated with Embodiment 2 as an example, and Embodiments 1 and 3 are not illustrated in the accompanying drawings.
[0054] The features of this invention are: the organic degradation method of this invention, which utilizes electrochemically generated atomic hydrogen to activate peracetic acid, degrades antibiotics by using electrochemically generated atomic hydrogen to activate peracetic acid, achieving mineralization and improving degradation efficiency. It eliminates the need for other catalysts and energy inputs, reducing costs, avoiding secondary pollution, and has good performance, making it easy to promote.
[0055] Although the invention has been described with reference to preferred embodiments, those skilled in the art will understand that various changes in form and detail are possible within the scope of the claims.
Claims
1. A method for degrading organic pollutants by using electrochemically generated atomic hydrogen to activate peracetic acid, characterized in that, Includes the following steps: (1) Prepare reaction raw materials. Select peracetic acid solution and organic pollutant solution as reaction raw materials. The peracetic acid solution is a peracetic acid solution with a concentration of 35 mg / L to 40 mg / L, and the organic pollutant solution is an organic pollutant solution with a concentration of 7 mg / L to 9 mg / L. The mass ratio of peracetic acid solution to organic pollutant solution is 1:3 to 5. (2) Activate peracetic acid to degrade organic matter. Select an electrochemical reactor. The anode in the electrochemical reactor is a lead dioxide-plated electrode or a tin dioxide-plated electrode on a titanium substrate. The cathode electrode is made of nickel foam and loaded with metal. The metal is selected from one or more of palladium, rhodium, platinum, ruthenium, iridium and indium. The selected organic pollutant solution is first placed into the electrochemical reactor and the electrochemical reactor is started to react for 30 minutes. Then, the peracetic acid solution is placed in the electrochemical reactor and the electrochemical reaction continues to degrade the organic matter. In step (2), the electrochemical reactor is an H-type electrolytic cell with a replaceable ion exchange membrane; the reaction is carried out in the cathode chamber.
2. The method for degrading organic pollutants by using electrochemically generated atomic hydrogen to activate peracetic acid according to claim 1, characterized in that: In step (1), the organic pollutant solution is any one or any combination of sulfamethoxazole solution, roxithromycin solution, and cephalosporin solution.
3. The method for degrading organic pollutants by using electrochemically generated atomic hydrogen to activate peracetic acid according to claim 1, characterized in that: The voltage of the electrochemical reactor in step (2) is 1.4V.
4. The method for degrading organic pollutants by utilizing electrochemically generated atomic hydrogen to activate peracetic acid according to claim 1, characterized in that: The pH of the organic pollutant solution in step (1) is 3 to 11.
5. The method for degrading organic pollutants by utilizing electrochemically generated atomic hydrogen to activate peracetic acid according to claim 1, characterized in that: The electrochemical reaction time after the peracetic acid solution is placed in step (2) is 2h to 3h.