Chemical-physical pre-treatment synergic with plasma disinfection method and device

Abstract

The application discloses a chemical-physical pretreatment synergic plasma disinfection method and device. The method makes a water body to be treated pass through a pretreatment chemical reactor, a local electric field enhancement disinfection device and a dielectric barrier discharge plasma reactor; in the pretreatment chemical reactor, a H2O2 / HNO3 mixed solution is used to pretreat the water body; the H2O2 / HNO3 mixed solution softens and weakens resistant bacteria and resistant genes in the water body, then the local electric field enhancement treatment is carried out, so that electroporation of cell walls occurs, then non-thermal plasma treatment is carried out, so that intracellular contents are oxidized by high-reactivity active particles, and the cell walls and cell membranes are decomposed under the attack of the high-reactivity active particles, thereby achieving removal of the resistant bacteria and the resistant genes. The application can efficiently and non-residually disinfect and kill common bacteria and viruses, and remove the resistant bacteria and the resistant genes.

Description

Technical Field

[0001] This invention relates to the field of water disinfection, and in particular to a chemical-physical pretreatment synergistic plasma disinfection method and apparatus. Background Technology

[0002] For millennia, humanity has battled waterborne pathogens, a long-standing threat to human health and ecological security. Simultaneously, the overuse and inappropriate use of antibiotics has led to the proliferation of antibiotic-resistant bacteria (ARBs) possessing antibiotic resistance genes (ARGs), further increasing the difficulty of treating pathogen infections and raising mortality rates. Bacterial resistance is caused by ARGs, which are easily released into the aquatic environment through the secretion of living cells or the rupture of dead cells, and spread through horizontal gene transfer. Therefore, there is an urgent need for efficient, residue-free alternatives to water disinfection.

[0003] Traditional disinfection methods, such as ultraviolet radiation, chlorination, and ozone disinfection, may inactivate ARBs but are inefficient at eliminating ARGs. These traditional disinfection technologies require large amounts of energy and chemicals, making them costly and having a large carbon footprint. Furthermore, live but unculturable bacterial forms can evade traditional disinfection methods, posing a greater challenge to addressing antibiotic-resistant bacteria resistance.

[0004] Localized enhanced electric field (LEF) treatment is an emerging physical disinfection method using nanomaterials. It relies on a strong localized electric field around vertically grown conductive nanowires to pierce bacterial cell membranes under low applied voltage (a few volts). However, some drawbacks need to be addressed: firstly, the bacterial outer wall exhibits strong resistance to electroporation; secondly, intracellular contents, including nucleic acids, can leak from the electroporation points, potentially leading to the spread of antibiotic resistance. Another promising green disinfection method is non-thermal plasma technology, which can generate various highly reactive substances in situ (such as ozone (O3) and superoxide radical anions (O2)). - hydroxyl radicals (·OH) and singlet oxygen 1 O2 can effectively damage bacterial cell structure, cell membrane, lipids, and DNA. However, non-thermal plasma sterilization is relatively slow, typically requiring tens of minutes, because the active substance needs to gradually oxidize and decompose the bacterial cell structure from the outside in. Furthermore, when the bacterial outer wall is damaged by the active substance, intracellular contents (including nucleic acids) leak out, easily leading to the spread of ARGs (antibiotics, glycoproteins, and cytokines).

[0005] Therefore, it is necessary to develop a more efficient and residue-free water treatment method to ensure the disinfection effect of water and inhibit the spread of resistance genes. Summary of the Invention

[0006] In order to overcome the above-mentioned shortcomings and deficiencies of the prior art, the present invention aims to provide a chemical-physical pretreatment synergistic plasma disinfection method, which can efficiently and residuelessly disinfect common bacteria and viruses, and remove resistant bacteria and resistance genes, thereby greatly improving disinfection efficiency and shortening disinfection time.

[0007] Another objective of this invention is to provide a chemical-physical pretreatment synergistic plasma sterilization device.

[0008] The objective of this invention is achieved through the following technical solution:

[0009] This invention provides a chemical-physical pretreatment synergistic plasma disinfection method, in which the water to be treated passes through a pretreatment chemical reactor, a locally enhanced electric field disinfection device, and a dielectric barrier discharge plasma reactor.

[0010] In the pretreatment chemical reactor, a mixture of H2O2 and HNO3 is used to pretreat the water.

[0011] The H2O2 / HNO3 mixture softens and weakens resistant bacteria and resistance genes in the water. Then, it is subjected to localized enhanced electric field treatment to cause electroporation of the cell wall. Finally, it is subjected to non-thermal plasma treatment in a dielectric barrier discharge plasma reactor, which oxidizes the intracellular contents by highly reactive particles. The cell wall and cell membrane are decomposed under the attack of highly reactive particles, thereby removing resistant bacteria and resistance genes.

[0012] Preferably, in the H2O2 / HNO3 mixture, the concentration of H2O2 is 1-10 mM and the concentration of HNO3 is 0.1-1 mM.

[0013] Preferably, the hydraulic retention time of the pretreatment chemical reactor is 15-20 s, and the flux is 20-30 m³ / s. 3 h -1 m -2 .

[0014] Preferably, the hydraulic residence time of the localized enhanced electric field treatment disinfection device is 10-15 s, and the flux is 30-40 m³ / s. 3 h -1 m -2 .

[0015] Preferably, the hydraulic residence time of the dielectric barrier discharge plasma reactor is 20-25 s, and the flux is 15-25 m³ / s. 3 h -1 m -2 .

[0016] Preferably, the water body to be treated is aquaculture wastewater, medical wastewater, drinking water, high-salinity water body, or farmland drainage.

[0017] The chemical-physical pretreatment synergistic plasma disinfection device for realizing the chemical-physical pretreatment synergistic plasma disinfection method includes a pretreatment chemical reactor, a local enhanced electric field treatment disinfection device, and a dielectric barrier discharge plasma reactor connected in sequence.

[0018] The pretreatment chemical reactor is equipped with a feeding pipe; the feeding pipe is used to feed the H2O2 / HNO3 mixture.

[0019] The localized enhanced electric field treatment disinfection device includes a tank, a cylindrical outer electrode disposed on the inner surface of the tank, and a central electrode fixed in the middle of the tank; the central electrode includes a copper electrode and dopamine-coated copper oxide nanowires, wherein the dopamine-coated copper oxide nanowires are loaded on the copper electrode.

[0020] The dielectric barrier discharge plasma reactor includes a quartz dielectric tube, a grounding electrode, a high-voltage electrode, and a gas supply system. The quartz dielectric tube includes an outer surface layer and an inner surface layer, with a discharge space formed between the outer surface layer and the inner surface layer. Multiple aeration holes are provided on the inner surface layer of the quartz dielectric tube. The space inside the inner surface layer is a water channel, and the grounding electrode is located at the center of the water channel.

[0021] Preferably, in the dielectric barrier discharge plasma reactor, the water channels are filled with a catalyst.

[0022] Preferably, the catalyst is borosilicate glass beads, alumina, zirconium oxide, or cerium oxide.

[0023] Preferably, the energy consumption of the pretreatment chemical reactor, the localized enhanced electric field treatment and disinfection device, and the dielectric barrier discharge plasma reactor are 5-10 Whm, respectively. -3 15-20 Whm -3 and 35-50 Whm -3 .

[0024] Preferably, the chemical-physical pretreatment synergistic plasma disinfection device further includes a water storage tank, which is equipped with a water inlet and an electronic level gauge.

[0025] Preferably, the highly reactive particles include O3 and O2. - ·OH and 1 O2.

[0026] The disinfection method based on the aforementioned chemical-physical pretreatment synergistic plasma disinfection device is as follows:

[0027] S1: Water is introduced into a water storage tank through a water inlet, and the water in the water storage tank is pumped into a pretreatment chemical reactor by a water transfer pump.

[0028] S2: Turn on the feed pipe and electric stirring rod of the pretreatment chemical reactor to load hydrogen peroxide and nitric acid solution into the water body;

[0029] S3: Pass the water obtained in S2 into the local enhanced electric field treatment and disinfection device, turn on the DC power supply, and apply a DC voltage between the two electrodes to perform local enhanced electric field treatment.

[0030] S4: The water obtained in S3 is fed into a dielectric barrier discharge plasma reactor. The plasma power supply is turned on, and a high-voltage AC voltage is applied between the two electrodes to generate non-thermal plasma for treatment. Finally, the treated water is discharged.

[0031] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0032] First, pre-loaded H2O2 / HNO3 is used to soften and weaken the bacterial outer wall, reducing its defense against electroporation. Then, electroporation is combined with non-thermal plasma to remove ARBs and ARGs. Next, the pre-treated bacteria are easily penetrated by electroporation, and finally, highly reactive particles are generated through discharge to treat the bacteria. Under the sequential water disinfection process of "chemical (H2O2 / HNO3 pretreatment) - physical (locally enhanced electric field) - chemical (non-thermal plasma)," intracellular contents (especially nucleic acids) are reacted with highly reactive particles (such as O3 and O2). - ·OH and 1 O2 effectively oxidizes the cells, and the cell walls and membranes decompose under the attack of highly reactive particles, resulting in damage to the entire cell structure from the inside out. Simultaneously, preloading HNO3 and H2O2 into the water induces the generation of more highly reactive substances in subsequent non-thermal plasma treatment, increasing productivity by more than 100 times and significantly shortening disinfection time. This sequential water disinfection process can achieve high throughput (approximately 10-50 m³ / s) with short residence times (10-20 s). 3 h -1 m -2 ) and low energy consumption (50-80 Whm) -3Under ideal conditions, this system inactivates resistant bacteria in water (>99.9999%) and removes resistance genes (>99%) after 50 days of continuous operation. It shows great potential for microbial disinfection in drinking water, reclaimed water, and wastewater systems to protect public health and ensure water safety. Furthermore, this water disinfection equipment is expected to be deployed in communities lacking adequate water sanitation facilities. Firstly, the equipment has a simple design and is not limited by geographical location or weather conditions. Secondly, it is suitable for various water qualities and quantities. Finally, the equipment has low power input requirements and can be powered by distributed energy sources (including solar cells and nanogenerators). The use of solar cells for power distribution reduces the requirements for plasma power. Therefore, it can be applied in communities where traditional water disinfection methods are not feasible. Attached Figure Description

[0033] Figure 1 This is a schematic diagram of the structure of the chemical-physical pretreatment synergistic plasma disinfection device according to an embodiment of the present invention.

[0034] In the diagram: 1. Water inlet, 2. Water storage tank, 3. Electronic level gauge, 4. Electromagnetic switch valve, 5. Water transfer pump, 6. Pretreatment chemical reactor, 7. Electric stirring rod, 8. Feeding pipe, 9. Localized enhanced electric field treatment and disinfection device, 10. DC power supply, 11. Central electrode, 12. Coaxial cylindrical external electrode, 13. Acrylic glass support, 14. Dielectric barrier discharge plasma reactor, 15. Plasma power supply, 16. Quartz dielectric tube, 17. Grounding electrode, 18. High voltage electrode, 19. Gas supply system, 20. Water outlet.

[0035] Figure 2 The calculation results of the chemical-physical pretreatment synergistic plasma disinfection device according to an embodiment of the present invention for the inactivation rate of typical bacteria and viruses;

[0036] Figure 3 The chemical-physical pretreatment synergistic plasma disinfection device of the present invention shows the conversion rate and mineralization rate of antibiotics (tetracycline and methicillin) that induce bacterial resistance.

[0037] Figure 4 The stability of the chemical-physical pretreatment synergistic plasma disinfection device according to an embodiment of the present invention during long-term (50 days) continuous operation disinfection process;

[0038] Figure 5 The chemical-physical pretreatment synergistic plasma disinfection device in the embodiments of the present invention demonstrates the inactivation efficiency and reactivation rate of Escherichia coli and Staphylococcus aureus compared with other disinfection processes. Detailed Implementation

[0039] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for illustrative purposes only and are not intended to limit the invention.

[0040] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be readily apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0041] The terms "including," "have," etc., used in this article are all open-ended, meaning they include but are not limited to.

[0042] Example 1

[0043] Please refer to Figure 1 , Figure 1 This is a schematic diagram of the chemical-physical pretreatment synergistic plasma disinfection device in this embodiment.

[0044] This embodiment provides a chemical-physical pretreatment synergistic plasma disinfection device. The treatment equipment includes a water storage tank 2, a pretreatment chemical reactor 6, a local enhanced electric field treatment disinfection device 9, and a dielectric barrier discharge plasma reactor 14. The water storage tank 2 is connected to the pretreatment chemical reactor 6 via a water transfer pump 5, and has a water inlet 1 and an ultrasonic level gauge 3 inside. The pretreatment chemical reactor 6 is connected to the local enhanced electric field treatment disinfection device 9 via a water connection pipeline, and the pretreatment chemical reactor 6 is equipped with an electric stirring rod 7 and multiple feeding pipes 8. The local enhanced electric field treatment disinfection device 9 is connected to the dielectric barrier discharge plasma reactor 14 via a water connection pipeline. The dielectric barrier discharge plasma reactor 14 is equipped with a water outlet 20.

[0045] In this embodiment, the water inlet 1 is connected to the water to be treated, which is stored in the water storage tank 2. The water level in the water storage tank 2 can be monitored in real time by the ultrasonic level gauge 3. The water transfer pump 5 is started to send the water from the water storage tank 2 to the pretreatment chemical reactor 6 for pretreatment. The pretreated effluent then enters the local enhanced electric field treatment and disinfection device 9. After the local enhanced electric field treatment is completed, the water is transported to the dielectric barrier discharge plasma reactor 14 for further disinfection, and finally discharged from the drain pipe.

[0046] In this embodiment, the pretreatment chemical reactor is provided with two feed pipes 8, which are used for feeding the H2O2 / HNO3 mixture, wherein the concentration of H2O2 is 5 mM and the concentration of HNO3 is 0.5 mM.

[0047] In this embodiment, the aforementioned localized enhanced electric field treatment disinfection device 9 is a tubular coaxial electrode device, consisting of a tubular tank, a DC power supply 10, a central electrode 11, a coaxial cylindrical copper electrode 12, and an plexiglass support 13. The DC power supply provides a 2V operating voltage. The coaxial cylindrical copper electrode 12 is in close contact with the inner surface of the tubular tank. The central electrode 11 is coaxially arranged with the coaxial cylindrical copper electrode 12. The central electrode 11 includes a copper electrode and dopamine-coated copper oxide nanowires, with the dopamine-coated copper oxide nanowires loaded on the copper electrode.

[0048] In this embodiment, the dielectric barrier discharge plasma reactor 14 is a tubular coaxial electrode device, including a plasma power supply 15, a quartz dielectric tube 16, a grounding electrode 17, a stainless steel mesh high-voltage electrode 18, and a gas supply system 19. The plasma power supply 15 can provide up to 50 kV (V p-p The plasma discharge system generates a high-voltage pulse with a repetitive pulse frequency of 1000 Hz. The quartz dielectric tube 16 includes an outer layer and an inner layer, forming a discharge space between them. The space inside the inner layer is a water channel, and a grounding electrode 17 is located at the center of the water channel. A stainless steel mesh high-voltage electrode 18 is wound around the outer layer of the quartz dielectric tube 16. The stainless steel mesh high-voltage electrode 18 and the grounding electrode 17 are connected to the positive and negative terminals of an external plasma power supply 15 via metal wires, respectively. The inner layer of the quartz dielectric tube has several aeration holes. The water channel of the quartz dielectric tube 16 is filled with cerium oxide catalyst. The gas supply system provides the working gas for plasma discharge, which is air or a nitrogen-oxygen mixture.

[0049] The chemical-physical pretreatment synergistic plasma disinfection device of this embodiment is used to disinfect typical bacteria, viruses, and antibiotics that cause bacterial resistance. The specific process is as follows:

[0050] All bacterial cultures (tetracycline-resistant Escherichia coli, methicillin-resistant Staphylococcus aureus, Bacillus subtilis, non-toxic Listeria, Candida albicans, and bacteriophage MS2) were cultured in Luria-Bertani broth at 37 °C until they reached the logarithmic growth phase. The target microorganisms (bacteria at ~10⁻⁶) were then cultured. 6 CFU mL -1 Or the virus is ~10 6 PFU mL -1It was diluted in a solution consisting of 5 mM phosphate buffered saline and 10 mM NaHCO3 to adjust the salinity and maintain pH buffering capacity.

[0051] The prepared bacterial suspension was selected as the test water body, and the water disinfection method proposed in this invention was used for treatment:

[0052] A chemical-physical pretreatment synergistic plasma disinfection method involves passing the water to be treated through a pretreatment chemical reactor, a locally enhanced electric field disinfection device, and a dielectric barrier discharge plasma reactor. The water is softened and weakened by an H2O2 / HNO3 mixture to remove resistant bacteria and resistance genes. Following this, a locally enhanced electric field treatment causes electroporation of the cell walls. Non-thermal plasma treatment then oxidizes intracellular contents with highly reactive particles, and the cell walls and membranes decompose under the attack of these particles, thus removing resistant bacteria and resistance genes. The specific operation steps are as follows:

[0053] S1: The prepared bacterial suspension is introduced into the water storage tank 2 through the water inlet, and the water in the water storage tank 2 is pumped into the pretreatment chemical reactor 6 by the water transfer pump 5.

[0054] S2: Turn on the feed pipe 8 and electric stirring rod 7 of the pretreatment chemical reactor so that the mixed solution of 5 mM H2O2 and 0.5 mM HNO3 is loaded into the prepared bacterial suspension;

[0055] S3: Pass the prepared bacterial suspension obtained in S2 into the local enhanced electric field treatment disinfection device 9, turn on the DC power supply 10, and apply a 5 V DC voltage between the two electrodes to perform local enhanced electric field treatment.

[0056] S4: The prepared bacterial suspension obtained in S3 is passed into the dielectric barrier discharge plasma reactor 14, the plasma power supply 15 is turned on, a high voltage AC voltage is applied between the two electrodes to generate non-thermal plasma for treatment, and finally the treated water is discharged.

[0057] During operation, the hydraulic residence times in the pretreatment chemical reactor, the localized enhanced electric field treatment and disinfection device, and the dielectric barrier discharge plasma reactor were 15-20 s, 10-15 s, and 20-25 s, respectively, with fluxes of 20-30 m³ / s. 3 h -1 m -2 30-40 m 3 h -1 m -2 and 15-25 m 3 h -1 m- 2 The energy consumption of the water disinfection equipment is 5-10 Whm. -315-20 Whm -3 and 35-50 Whm -3 Based on the above parameters, the chemical pretreatment reactor can complete 60% oxidation of organic matter in 10 seconds and achieve over 90% cell wall softening in 15-20 seconds; the locally enhanced electric field reactor can complete 3-5 pulse treatments within 10 seconds; and the plasma reactor can complete DNA strand breaks in 25 seconds.

[0058] The concentrations of bacteria and viruses were determined using the standard plate method and the double agar layer method. Figure 2 Two types of ARBs, namely tetracycline-resistant Escherichia coli (Gram-negative) and methicillin-resistant Staphylococcus aureus (Gram-positive), were completely inactivated. Other typical bacteria and even viruses, such as Bacillus subtilis, non-toxic Listeria, Candida albicans, and bacteriophage MS2, can also be effectively inactivated by this water disinfection equipment (>99.999%).

[0059] In addition to bacteria, antibiotics that cause bacterial resistance, including tetracycline and methicillin, can also be effectively degraded in this water disinfection equipment. Figure 3 The removal rate and mineralization rate of antibiotics are as high as ~99.9% and ~66%, respectively. Highly reactive particles react with antibiotic molecules, rapidly converting them into various intermediate products within a short time. These intermediate products can be further oxidized, ultimately decomposing into CO2, H2O, etc. Furthermore, this water disinfection equipment can effectively disinfect actual water bodies such as lakes, rivers, and groundwater (>99.99%), and exhibits excellent stability during long-term (>50 days) continuous operation. Figure 4 ).

[0060] Comparative Example 1

[0061] The prepared bacterial suspension was selected as the test water body. The hydraulic residence time of the disinfection device of the present invention was compared under the condition that other conditions remained unchanged. The hydraulic residence times of the prepared bacterial suspension in the pretreatment chemical reactor, the local enhanced electric field treatment disinfection device, and the dielectric barrier discharge plasma reactor were 30s, 15s, and 25s, respectively.

[0062] Comparative Example 2

[0063] The prepared bacterial suspension was selected as the test water. The hydraulic residence time of the disinfection device of the present invention was compared under the condition that other conditions remained unchanged. The hydraulic residence times of the prepared bacterial suspension in the pretreatment chemical reactor, the local enhanced electric field treatment disinfection device, and the dielectric barrier discharge plasma reactor were 20s, 25s, and 25s, respectively.

[0064] Comparative Example 3

[0065] The prepared bacterial suspension was selected as the test water. The hydraulic residence time of the disinfection device of the present invention was compared under the condition that other conditions remained unchanged. The hydraulic residence times of the prepared bacterial suspension in the pretreatment chemical reactor, the local enhanced electric field treatment disinfection device, and the dielectric barrier discharge plasma reactor were 30s, 25s, and 25s, respectively.

[0066] Table 1 compares the results of the pretreatment chemical reactor, the local enhanced electric field treatment disinfection device, and the dielectric barrier discharge plasma reactor in the disinfection apparatus of this invention under conditions of excessively long hydraulic residence time. It can be seen that in the chemical pretreatment stage, the H2O2 / HNO3 mixture, due to excessive residence time within 30 s, undergoes partial decomposition of H2O2 (especially under acidic conditions), leading to a decrease in oxidation capacity. Furthermore, some microorganisms initiate stress repair mechanisms, resulting in a reduction in subsequent electroporation efficiency. When the local enhanced electric field treatment stage is extended to 25 s, the cell wall pores formed by electroporation are exposed for too long, and some microorganisms undergo self-repair through membrane fluidity (such as lipid layer remodeling), weakening the oxidation efficiency of intracellular substances by subsequent plasma active particles (such as ·OH, O3). Any deviation in the hydraulic residence time of any single step (especially in the chemical and electric field stages) will disrupt the synergistic chain of "oxidation-perforation-oxidation," leading to decreased disinfection efficiency and increased energy consumption.

[0067] Table 1

[0068]

[0069] Comparative Example 4

[0070] The prepared bacterial suspension was selected as the test water body. Ultraviolet (UV) disinfection was used alone to treat the bacterial suspension, which was then exposed to UV light at an intensity of 300 μW / cm². 2 The ultraviolet radiation dose was 180 mJ / cm. 2 The illumination time under these conditions is 5 minutes.

[0071] Comparative Example 5

[0072] The same bacterial suspension as in the example was selected as the test water. Sodium hypochlorite was used alone to treat the bacterial suspension. The sodium hypochlorite solution was transported into the bacterial suspension for mixing and disinfection for 30 minutes at a dosage of 2 mg / L.

[0073] Comparative Example 6

[0074] The same bacterial suspension as in the example was selected as the test water. The bacterial suspension was treated with Fenton oxidation alone. Fenton reagent was delivered to the bacterial suspension and mixed for 20 min for disinfection.

[0075] Comparative Example 7

[0076] The same bacterial suspension as in the previous example was selected as the test water. The bacterial suspension was treated solely using photocatalysis, and then passed into a P25 titanium dioxide photoelectrocatalytic oxidation water purification device. The bacterial suspension was disinfected for 15 minutes using a P25 nano-TiO2 catalyst under ultraviolet light.

[0077] Comparative Example 8

[0078] The same bacterial suspension as in the previous example was selected as the test water. Ozone disinfection was used alone to treat the bacterial suspension, which was then passed into an ozone generator. The generated ozone gas was added to the bacterial suspension and thoroughly mixed for 10 minutes for disinfection.

[0079] Figure 5 The inactivation efficiency and reactivation rate of the device in the embodiments of the present invention against *Escherichia coli* and *Staphylococcus aureus* are compared with those of other disinfection processes. It can be seen that the high disinfection rate of the chemical-physical pretreatment synergistic plasma is hundreds of times higher than that of several common sterilization technologies. In contrast, traditional disinfection methods, including ultraviolet light, sodium hypochlorite, Fenton, photocatalysis, and ozone, often require longer reaction times (5-30 min) and higher energy consumption (300 Wh / m³). -3 -1 kWh m -3 Only then can the same level of processing be achieved.

[0080] Comparative Example 9

[0081] Comparative experiments were conducted on the pretreatment chemical reactor, the local enhanced electric field treatment disinfection device, and the dielectric barrier discharge plasma reactor of the disinfection device of the present invention under the condition that other conditions remain unchanged. Reference Examples 1 to 11 were set up, and the comparison results are shown in Table 1 (where I represents the device connected in the first step, II represents the device connected in the second step, III represents the device connected in the third step, and ~ represent the unconnected device).

[0082] Table 2

[0083]

[0084] As shown in Table 2, the optimal operating steps in the technical solution of this invention are: pretreatment chemical reactor → local enhanced electric field treatment and disinfection device → dielectric barrier discharge plasma reactor.

[0085] Theoretically, this phenomenon is caused by the following: the pretreatment chemical reactor in this invention uses H2O2 / HNO3 pretreatment to soften and weaken ARB, effectively reducing the bacterial outer wall's defense against electroporation. Simultaneously, preloading HNO3 and H2O2 into the water induces the generation of more highly reactive substances in subsequent non-thermal plasma treatment, increasing productivity by more than 100 times. The localized enhanced electric field disinfection device utilizes the combined effects of electroporation and physical puncture and tearing caused by nano-tip to act on ARB, making it easily punctured by electroporation. The dielectric barrier discharge plasma reactor then generates a large number of highly reactive particles (such as O3 and O2) in situ. - ·OH and 1 O2 floods into the cell. Bacterial contents (including the nucleus and cytoplasm) are effectively oxidized and decomposed by the active particles. At the same time, the cell wall and cell membrane are also gradually decomposed under the attack of the active particles, resulting in the destruction of the entire cell structure from the inside out.

[0086] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the embodiments described above. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A chemical-physical pretreatment synergistic plasma disinfection method, characterized in that, The water to be treated is passed through a pretreatment chemical reactor, a localized enhanced electric field disinfection device, and a dielectric barrier discharge plasma reactor. In the pretreatment chemical reactor, a mixture of H2O2 and HNO3 is used to pretreat the water. The H2O2 / HNO3 mixture softens and weakens resistant bacteria and resistance genes in the water. Then, it is subjected to local enhanced electric field treatment to cause electroporation of the cell wall. Then, it is subjected to non-thermal plasma treatment in a dielectric barrier discharge plasma reactor, so that the intracellular contents are oxidized by highly reactive particles, and the cell wall and cell membrane are decomposed under the attack of highly reactive particles, thereby removing resistant bacteria and resistance genes. The hydraulic retention time of the pretreatment chemical reactor is 15-20 s, and the flux is 20-30 m³ / s. 3 h -1 m -2 ; The hydraulic residence time of the localized enhanced electric field disinfection device is 10-15 s, and the flux is 30-40 m³ / s. 3 h -1 m -2 ; The hydraulic residence time of the dielectric barrier discharge plasma reactor is 20-25 s, and the flux is 15-25 m³ / s. 3 h -1 m -2 .

2. The chemical-physical pretreatment synergistic plasma disinfection method according to claim 1, characterized in that, In the H2O2 / HNO3 mixture, the concentration of H2O2 is 1-10 mM; the concentration of HNO3 is 0.1-1 mM.

3. The chemical-physical pretreatment synergistic plasma disinfection method according to claim 1, characterized in that, The water bodies to be treated are aquaculture wastewater, medical wastewater, drinking water, high-salinity water bodies, or farmland drainage.

4. A chemical-physical pretreatment synergistic plasma disinfection apparatus for implementing the chemical-physical pretreatment synergistic plasma disinfection method according to any one of claims 1 to 3, characterized in that, It includes a pretreatment chemical reactor, a locally enhanced electric field treatment and disinfection device, and a dielectric barrier discharge plasma reactor connected in sequence; The pretreatment chemical reactor is equipped with a feeding pipe; the feeding pipe is used to feed the H2O2 / HNO3 mixture. The localized enhanced electric field treatment disinfection device includes a tank, a cylindrical outer electrode disposed on the inner surface of the tank, and a central electrode fixed in the middle of the tank; the central electrode includes a copper electrode and dopamine-coated copper oxide nanowires, wherein the dopamine-coated copper oxide nanowires are loaded on the copper electrode. The dielectric barrier discharge plasma reactor includes a quartz dielectric tube, a grounding electrode, a high-voltage electrode, and a gas supply system. The quartz dielectric tube includes an outer surface layer and an inner surface layer, with a discharge space formed between the outer surface layer and the inner surface layer. Multiple aeration holes are provided on the inner surface layer of the quartz dielectric tube. The space inside the inner surface layer is a water channel, and the grounding electrode is located at the center of the water channel.

5. The chemical-physical pretreatment synergistic plasma sterilization device according to claim 4, characterized in that, In the dielectric barrier discharge plasma reactor, the water channels are filled with a catalyst.

6. The chemical-physical pretreatment synergistic plasma sterilization device according to claim 5, characterized in that, The catalyst is borosilicate glass beads, alumina, zirconium oxide, or cerium oxide.

7. The chemical-physical pretreatment synergistic plasma sterilization device according to claim 4, characterized in that, The energy consumption of the pretreatment chemical reactor, the localized enhanced electric field treatment and disinfection device, and the dielectric barrier discharge plasma reactor are 5-10 Whm, respectively. -3 15-20 Whm -3 and 35-50 Whm -3 .

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