Chemical-physical pretreatment cooperated plasma disinfection method and device

Abstract

The invention discloses a chemical-physical pretreatment cooperated plasma disinfection method and device. According to the method, a water body to be treated passes through a pretreatment chemical reactor, a local enhanced electric field disinfection device and a dielectric barrier discharge plasma reactor; in the pretreatment chemical reactor, a water body is pretreated by adopting a H2O2 / HNO3 mixed solution; the H2O2 / HNO3 mixed solution is used for softening cell walls of resistant bacteria and resistant genes in the water body, then local enhanced electric field treatment is carried out to enable the cell walls to generate electroporation, and then non-thermal plasma treatment is carried out, so that cell inclusions are oxidized by high-reactivity active particles, the cell walls and cell membranes are decomposed under the attack of the high-reactivity active particles, and the resistance of the resistant bacteria and the resistant genes in the water body is improved. The removal of resistance bacteria and resistance genes is realized. According to the invention, common bacteria and viruses can be efficiently killed without residues, and resistant bacteria and resistant genes can be removed.

Description

Technical Field

[0001] The present invention relates to the field of water disinfection, and particularly to a chemical-physical pretreatment collaborative plasma disinfection method and device. Background Art

[0002] For thousands of years, humans have been struggling with waterborne pathogens, which have long threatened human health and ecological safety. At the same time, due to the excessive and improper use of antibiotics, many antibiotic-resistant bacteria (ARB) with antibiotic resistance genes (ARGs) have further increased the difficulty of curing pathogen infections and mortality. Bacterial resistance is caused by ARGs, and ARGs are easily discharged 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 and residue-free water disinfection alternatives.

[0003] Traditional disinfection methods, such as ultraviolet radiation, chlorination, and ozone disinfection, may inactivate ARB but are inefficient in eliminating ARGs. These traditional disinfection technologies require a large amount of energy and chemicals, so they are costly and have a large carbon footprint. In addition, the viable but non-culturable bacterial form can escape traditional disinfection methods, posing a greater difficulty in solving the resistance problem of antibiotic-resistant bacteria.

[0004] Locally enhanced electric field treatment is an emerging physical disinfection method using nanomaterials. It relies on the local strong electric field around vertically grown conductive nanowires to pierce the bacterial cell membrane at a low applied voltage (a few volts). However, there are also some deficiencies to be made up. One is that the bacterial outer wall has strong resistance to electroporation, and the other is that cell inclusions including nucleic acids will leak from the electroporation, which is likely to lead to the spread of antibiotic resistance. Another green disinfection method that has attracted much attention is non-thermal plasma technology, which can generate a variety of highly reactive active species in situ (such as ozone O 3 , superoxide radical anion ·O 2 - , hydroxyl radical ·OH, and singlet oxygen 1 O 2 ), which can effectively damage the bacterial cell structure, cell membrane, lipids, and DNA. However, the non-thermal plasma disinfection speed is relatively slow and usually takes dozens of minutes because the active species need to gradually oxidize and decompose the bacterial cell structure from the outside to the inside. In addition, when the bacterial outer wall is damaged by the active species, cell inclusions (including nucleic acids) leak, which is likely to lead to the spread of ARGs.

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

[0006] To overcome the above-mentioned disadvantages and deficiencies of the prior art, the object of the present invention is to provide a chemical-physical pretreatment collaborative plasma disinfection method, which can efficiently and residue-free disinfect common bacteria and viruses, and remove resistant bacteria and resistance genes, greatly improving the disinfection efficiency and shortening the disinfection time.

[0007] Another object of the present invention is to provide a chemical-physical pretreatment collaborative plasma disinfection device.

[0008] The object of the present invention is achieved by the following technical solutions:

[0009] The present invention provides a chemical-physical pretreatment collaborative plasma disinfection method, which enables the water to be treated to pass through a pretreatment chemical reactor, a local enhanced electric field disinfection device, and a dielectric barrier discharge plasma reactor;

[0010] In the pretreatment chemical reactor, H 2 O 2 / HNO 3 mixed solution is used to pretreat the water body;

[0011] In the H 2 O 2 / HNO 3 mixed solution, the cell walls of resistant bacteria and resistance genes in the water body are softened, and then local enhanced electric field treatment is carried out to cause electroporation of the cell walls. Then, non-thermal plasma treatment is carried out in the dielectric barrier discharge plasma reactor, so that the cell inclusions are oxidized by highly reactive active particles, and the cell walls and cell membranes are decomposed under the attack of highly reactive active particles, realizing the removal of resistant bacteria and resistance genes.

[0012] Preferably, in the H 2 O 2 / HNO 3 mixed solution, the concentration of H 2 O 2 is 1-10 mM; the concentration of HNO 3 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 m 3 h -1 m -2 .

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

[0015] Preferably, the hydraulic retention time of the dielectric barrier discharge plasma reactor is 20 - 25 s, and the flux is 15 - 25 m 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 water.

[0017] The chemical - physical pretreatment collaborative plasma disinfection device for implementing the chemical - physical pretreatment collaborative plasma disinfection method includes a pretreatment chemical reactor, a locally enhanced electric field treatment disinfection device and a dielectric barrier discharge plasma reactor connected in sequence;

[0018] A feeding pipe is provided in the pretreatment chemical reactor; the feeding pipe is used to feed the H 2 O 2 / HNO 3 mixed liquid;

[0019] The locally enhanced electric field treatment disinfection device includes a tank body, a cylindrical outer electrode arranged on the inner surface of the tank body, and a central electrode fixed in the middle of the tank body; the central electrode includes a copper electrode and dopamine - coated cupric oxide nanowires, and the dopamine - coated cupric 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, and a discharge space is formed between the outer surface layer and the inner surface layer. A plurality of air holes are arranged 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 arranged at the central position of the water channel.

[0021] Preferably, in the dielectric barrier discharge plasma reactor, a catalyst is filled in the water channel.

[0022] Preferably, the catalyst is borosilicate glass beads, alumina, zirconia or ceria.

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

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

[0025] Preferably, the highly reactive active particles include O 3 , ·O 2 - , ·OH and 1 O 2 .

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

[0027] S1: Introduce the water body into the water body storage tank through the water body inlet, and pump the water body in the water body storage tank into the pretreatment chemical reactor through the water body delivery pump path;

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

[0029] S3: Introduce the water body obtained in S2 into the locally enhanced electric field treatment disinfection device, turn on the DC power supply, and apply a DC voltage between the two electrodes for locally enhanced electric field treatment;

[0030] S4: Introduce the water body obtained in S3 into the dielectric barrier discharge plasma reactor, turn on the plasma power supply, apply a high-voltage AC voltage between the two electrodes to generate non-thermal plasma for treatment, and finally discharge the treated water body.

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

[0032] Firstly, the pre-loaded H 2 O 2 / HNO 3 is used to soften and weaken the outer wall of bacteria, reduce the defense ability against electroporation, and then combine electroporation with non-thermal plasma to remove ARB and ARGs. Then, the pre-treated bacteria are easily penetrated by electroporation, and finally, highly reactive active particles are generated by discharging to treat the bacteria. Under the sequential water body disinfection process of "chemical (H 2 O 2 / HNO 3 pretreatment)-physical (locally enhanced electric field)-chemical (non-thermal plasma)", the cell inclusions (especially nucleic acids) will be effectively oxidized by highly reactive active particles (such as O 3 , ·O 2 - , ·OH and 1 O 2 ), and the cell wall and cell membrane will also be decomposed under the attack of highly reactive active particles, resulting in the destruction of the entire cell structure from the inside out. At the same time, the pre-loaded HNO 3 and H 2 O 2When introduced into the water body, it will induce the generation of more highly reactive reactive substances during subsequent non-thermal plasma treatment, with the productivity increased by more than 100 times and the disinfection time significantly shortened. This sequential water body disinfection process can inactivate resistant bacteria (>99.9999%) in the water body under the conditions of short residence time (10 - 20 s), high throughput (about 10 - 50 m 3 h -1 m -2 ) and low energy consumption (50 - 80 Whm -3 ), and remove resistant genes (>99%) after 50 days of continuous operation, showing great potential applications in the microbial disinfection of drinking water, reclaimed water and wastewater systems to protect public health and ensure water environment safety. At the same time, this set of water body disinfection equipment is expected to be dispersed and applied in communities lacking water sanitation facilities. First, the water body disinfection equipment has a simple device scheme and is not restricted by geographical location or weather conditions. Second, the water body disinfection equipment is applicable to various water quality and water volume conditions. Finally, the water body disinfection equipment has low requirements for power input and can be provided by distributed energy sources (including solar cells and nanogenerators). Since the distributed energy source of solar cells is used for its power distribution, the requirements for the plasma power supply will be reduced. Therefore, it can be applied to communities where traditional water body disinfection methods cannot be used. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 It is a schematic structural diagram of the chemical-physical pretreatment collaborative plasma disinfection device according to the embodiment of the present invention.

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

[0035] Figure 2 It is the calculation result of the inactivation rate of typical bacteria and viruses by the chemical-physical pretreatment collaborative plasma disinfection device according to the embodiment of the present invention;

[0036] Figure 3 It is the conversion rate and mineralization rate of antibiotics (tetracycline and methicillin) that cause bacteria to develop resistance by the chemical-physical pretreatment collaborative plasma disinfection device according to the embodiment of the present invention;

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

[0038] Figure 5 The inactivation efficiency and revival rate of Escherichia coli and Staphylococcus aureus by the chemical-physical pretreatment collaborative plasma disinfection device according to the embodiment of the present invention and other disinfection processes. Specific embodiments

[0039] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present 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 only used to explain the present invention and are not used to limit the present invention.

[0040] Without departing from the scope or spirit of the present invention, various improvements and changes can be made to the specific embodiments of the description of the present invention, which are obvious to those skilled in the art. Other embodiments obtained from the description of the present invention are obvious to those skilled in the art. The description and embodiments of the present invention are only exemplary.

[0041] Regarding the use of "including", "provided with", etc. in this article, they are all open-ended terms, that is, they are intended to include but not limited to.

[0042] Example 1

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

[0044] This embodiment provides a chemical-physical pretreatment collaborative plasma disinfection device. The treatment equipment includes a water storage tank 2, a pretreatment chemical reactor 6, a locally 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 through a water delivery pump line 5, and is internally provided with a water inlet 1 and an ultrasonic level gauge 3; the pretreatment chemical reactor 6 is connected to the locally enhanced electric field treatment disinfection device 9 through a water connection pipeline, and the pretreatment chemical reactor 6 is provided with an electric stirring rod 7 and a plurality of feeding pipes 8; the locally enhanced electric field treatment disinfection device 9 is connected to the dielectric barrier discharge plasma reactor 14 through a water connection pipeline; a water outlet 20 is provided on the dielectric barrier discharge plasma reactor 14.

[0045] In this embodiment, the above-mentioned water inlet 1 accesses the water body to be treated, which is stored in the water storage tank 2. The ultrasonic level gauge 3 can be used to detect the water level in the water storage tank 2 in real time. Start the water delivery pump line 5 to send the water in the water storage tank 2 to the pretreatment chemical reactor 6 for pretreatment. The effluent after pretreatment enters the local enhanced electric field treatment and disinfection device 9. After the local enhanced electric field treatment, the water body is transported to the dielectric barrier discharge plasma reactor 14 for further disinfection, and finally output from the drain pipe.

[0046] In this embodiment, the above-mentioned pretreatment chemical reactor is provided with two feeding pipes 8, and the feeding pipes 8 are used for feeding the H 2 O 2 / HNO 3 mixed solution. Among them, the concentration of H 2 O 2 is 5 mM, and the concentration of HNO 3 is 0.55 mM.

[0047] In this embodiment, the above-mentioned local enhanced electric field treatment and disinfection device 9 is a tubular coaxial electrode device, which is composed of a tubular tank body, a DC power supply 10, a central electrode 11, a coaxial cylindrical copper electrode 12, and a plexiglass bracket 13. The DC power supply provides a working voltage of 2V; the coaxial cylindrical copper electrode 12 is closely attached to the inner surface of the tubular tank body; 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, and the dopamine-coated copper oxide nanowires are loaded on the copper electrode.

[0048] In this embodiment, the above-mentioned dielectric barrier discharge plasma reactor 14 is a tubular coaxial electrode device, including a plasma power supply 15, a quartz dielectric tube 16, a ground electrode 17, a stainless steel mesh high-voltage electrode 18, and a gas supply system 19. The plasma power supply 15 can provide a high-voltage pulse of up to 50 kV (V p-p ), a repetition pulse frequency of 1000 Hz. The quartz dielectric tube 16 includes an outer surface layer and an inner surface layer, and a discharge space is formed between the outer surface layer and the inner surface layer. The space inside the inner surface layer is a water channel, and the ground electrode 17 is arranged at the center of the water channel. The stainless steel mesh high-voltage electrode 18 is wound around the outer surface layer of the quartz dielectric tube 16. The stainless steel mesh high-voltage electrode 18 and the ground electrode 17 are respectively connected to the positive and negative electrodes of the external plasma power supply 15 through metal wires. A plurality of air holes are provided on the inner surface layer of the quartz dielectric tube. 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, and the working gas is air or a nitrogen-oxygen mixed gas.

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

[0050] All bacterial cultures (Escherichia coli resistant to tetracycline, Staphylococcus aureus resistant to methicillin, Bacillus subtilis, Listeria innocua, Candida albicans, and bacteriophage MS2) were cultured in Luria-Bertani broth at 37 °C until the logarithmic growth phase was reached. The target microorganisms (bacteria at ~10 6 CFU mL -1 or viruses at ~10 6 PFU mL -1 ) were diluted into a solution composed of 5 mM phosphate buffered saline and 10 mM NaHCO 3 to adjust the salinity and maintain the pH buffering capacity.

[0051] Select the prepared bacterial suspension as the test water body and treat it using the water body disinfection method proposed by the present invention:

[0052] A chemical-physical pretreatment collaborative plasma disinfection method that allows the water body to be treated to pass through a pretreatment chemical reactor, a locally enhanced electric field disinfection device, and a dielectric barrier discharge plasma reactor; the water body is softened by a H 2 O 2 / HNO 3 mixture to the cell walls of resistant bacteria and resistance genes in the water body, and then perform a locally enhanced electric field treatment to cause electroporation of the cell walls, and then perform a non-thermal plasma treatment, so that the cell inclusions are oxidized by highly reactive active particles, and the cell walls and cell membranes are decomposed under the attack of highly reactive active particles, realizing the removal of resistant bacteria and resistance genes; the specific operation steps are as follows:

[0053] S1: Pass the prepared bacterial suspension into the water body storage tank 2 through the water body inlet, and pump the water body in the water body storage tank 2 into the pretreatment chemical reactor 6 through the water body delivery pump path 5;

[0054] S2: Open the feeding pipe 8 and the electric stirring rod 7 of the pretreatment chemical reactor, so that a mixed solution of 5 mM H 2 O 2 and 0.5 HNO 3 is loaded into the prepared bacterial suspension;

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

[0056] S4: Introduce the configured bacterial suspension obtained in S3 into the dielectric barrier discharge plasma reactor 14, turn on the plasma power supply 15, apply a high-voltage alternating current voltage between the two electrodes to generate non-thermal plasma for treatment, and finally discharge the treated water body.

[0057] During operation, the hydraulic retention times of the pretreatment chemical reactor, the locally enhanced electric field treatment and disinfection device, and the dielectric barrier discharge plasma reactor are 15 - 20 s, 10 - 15 s, and 20 - 25 s respectively, the fluxes are 20 - 30 m³h⁻¹m⁻², 30 - 40 m³h⁻¹m⁻², and 15 - 25 m³h⁻¹m⁻² respectively, and the energy consumptions of the water body disinfection equipment are 5 - 10 Whm⁻³, 15 - 20 Whm⁻³, and 35 - 50 Whm⁻³ respectively. Based on the above parameters, the chemical pretreatment reactor can complete 60% of the organic matter oxidation in 10 s and achieve more than 90% cell wall softening in 15 - 20 s; the locally enhanced electric field reactor can complete 3 - 5 pulse treatments within 10 s, and the plasma reactor can complete DNA strand breakage in 25 s.

[0058] The standard spread plate method and the double agar layer method are used to measure the concentrations of bacteria and viruses. By Figure 2 It can be concluded that two ARBs, namely Escherichia coli resistant to tetracycline (Gram-negative) and Staphylococcus aureus resistant to methicillin (Gram-positive), are completely inactivated. Other typical bacteria and even viruses, such as Bacillus subtilis, Listeria innocua, Candida albicans, and phage MS2, can also be effectively inactivated (>99.999%) by this water body disinfection equipment.

[0059] In addition to bacteria, antibiotics that cause bacteria to develop resistance, including tetracycline and methicillin, can also be effectively degraded in this water body disinfection equipment ( Figure 3 ). The removal rate and mineralization rate of antibiotics are as high as ~99.9% and ~66% respectively. Highly reactive active particles react with antibiotic molecules, causing them to rapidly transform into various intermediate products in a short time. These intermediate products can be further oxidized and finally decomposed into CO 2 , H 2 O, etc. In addition, this water body disinfection equipment can effectively disinfect actual water bodies such as lake water, river water, and groundwater (>99.99%), and has excellent stability during long-term (>50 days) continuous operation ( Figure 4 ).

[0060] Comparative Example 1

[0061] Select the prepared bacterial suspension as the test water body, and conduct a comparative test on the hydraulic retention time in the disinfection device of the present invention while keeping other conditions unchanged. The hydraulic retention times of the prepared bacterial suspension in the pretreatment chemical reactor, the locally enhanced electric field treatment disinfection device, and the dielectric barrier discharge plasma reactor are 30 s, 15 s, and 25 s respectively.

[0062] Comparative Example 2

[0063] Select the prepared bacterial suspension as the test water body, and conduct a comparative test on the hydraulic retention time in the disinfection device of the present invention while keeping other conditions unchanged. The hydraulic retention times of the prepared bacterial suspension in the pretreatment chemical reactor, the locally enhanced electric field treatment disinfection device, and the dielectric barrier discharge plasma reactor are 20 s, 25 s, and 25 s respectively.

[0064] Comparative Example 3

[0065] Select the prepared bacterial suspension as the test water body, and conduct a comparative test on the hydraulic retention time in the disinfection device of the present invention while keeping other conditions unchanged. The hydraulic retention times of the prepared bacterial suspension in the pretreatment chemical reactor, the locally enhanced electric field treatment disinfection device, and the dielectric barrier discharge plasma reactor are 30 s, 25 s, and 25 s respectively.

[0066] Table 1 shows the comparative results of the pretreatment chemical reactor, the locally enhanced electric field treatment disinfection device, and the dielectric barrier discharge plasma reactor in the disinfection device of the present invention when the hydraulic retention time is too long. It can be seen that in the chemical pretreatment stage, the H2O2 / HNO3 mixture partially decomposes (especially under acidic conditions) due to the too long retention time within 30 s, resulting in a decrease in oxidation ability. In addition, some microorganisms initiate a stress repair mechanism, leading to a decrease in the subsequent electroporation efficiency. When the locally 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 self-repair through membrane fluidity (such as lipid layer reorganization), weakening the oxidation efficiency of subsequent plasma active particles (such as ·OH, O3) on intracellular substances. Any deviation in the hydraulic retention time of any single step (especially in the chemical and electric field stages) will disrupt the "oxidation - perforation - oxidation" synergistic chain, resulting in a decrease in disinfection efficiency and an increase in energy consumption.

[0067] Table 1

[0068]

[0069] Comparative Example 4

[0070] Select the prepared bacterial suspension as the test water body, and only use the ultraviolet disinfection method alone to treat the prepared bacterial suspension. The prepared bacterial suspension is irradiated with ultraviolet light at an intensity of 300 μW / cm 2 , and the ultraviolet dose is 180 mJ / cm2 The illumination time is 5 min under the conditions.

[0071] Comparative Example 5

[0072] Select the same prepared bacterial suspension as in the examples as the test water body, and only use sodium hypochlorite alone to treat the prepared bacterial suspension. Transport the finished sodium hypochlorite solution into the prepared bacterial suspension and mix for 30 min for disinfection, and the dosage is 2 mg / L.

[0073] Comparative Example 6

[0074] Select the same prepared bacterial suspension as in the examples as the test water body, and only use the Fenton oxidation method alone to treat the prepared bacterial suspension. Transport the Fenton reagent into the prepared bacterial suspension and mix for 20 min for disinfection.

[0075] Comparative Example 7

[0076] Select the same prepared bacterial suspension as in the examples as the test water body, and only use the photocatalysis method alone to treat the prepared bacterial suspension. Pass the prepared bacterial suspension into the P25 titanium dioxide photoelectrocatalytic oxidation water purification device. Utilize P25 nano-TiO 2 Under the action of ultraviolet light, the prepared bacterial suspension is disinfected for 15 min by the catalyst.

[0077] Comparative Example 8

[0078] Select the same prepared bacterial suspension as in the examples as the test water body, and only use the ozone disinfection method alone to treat the prepared bacterial suspension. Pass the prepared bacterial suspension into the ozone generator. Add the generated ozone gas to the prepared bacterial suspension and mix thoroughly for 10 min for disinfection.

[0079] Figure 5 The inactivation efficiency and resuscitation rate of Escherichia coli and Staphylococcus aureus by the device in the examples of the present invention and other disinfection processes. It can be seen that the high disinfection rate of chemical-physical pretreatment combined with plasma is hundreds of times 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 m -3 -1 kWh m -3 ) to achieve the same treatment level.

[0080] Comparative Example 9

[0081] The components in the disinfection device of the present invention, namely the pretreatment chemical reactor, the locally enhanced electric field treatment disinfection device, and the dielectric barrier discharge plasma reactor, were subjected to a comparative test under other unchanged conditions. 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 ~ represents the unconnected device).

[0082] Table 2

[0083]

[0084]

[0085] It can be seen from Table 2 that the optimal operation steps in the technical solution of the present invention are: pretreatment chemical reactor → locally enhanced electric field treatment disinfection device → dielectric barrier discharge plasma reactor in this process.

[0086] Analyzing the reason for this phenomenon theoretically: The role of the pretreatment chemical reactor in the present invention is to use H 2 O 2 / HNO 3 to pretreat and weaken ARB, effectively reducing the defense ability of the bacterial outer wall in ARB against electroporation. At the same time, preloading HNO 3 and H 2 O 2 into the water body will induce the generation of more highly reactive reactive species in the subsequent non-thermal plasma treatment, and the productivity is increased by more than 100 times; the role of the locally enhanced electric field treatment disinfection device is to use the combined action of electroporation and physical puncture and tearing caused by nano-tips on ARB, making it easy for ARB to be pierced by electroporation; while the dielectric barrier discharge plasma reactor in-situ generates a large number of highly reactive active particles (such as O 3 、·O 2 - 、·OH and 1 O 2 ) to pour into the cell interior. Bacterial inclusions (including nuclear bodies, cytoplasm, etc.) will be effectively oxidized and decomposed by the active particles. At the same time, the cell wall and cell membrane will also be gradually decomposed under the attack of the active particles, resulting in the destruction of the entire cell structure from the inside out.

[0087] The above embodiments are the preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the described embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in 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 local enhanced electric field 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 liquid softens the cell walls of resistant bacteria and resistance genes in the water body, and then performs local enhanced electric field treatment to cause electroporation of the cell walls, and then performs non-thermal plasma treatment in a dielectric barrier discharge plasma reactor, so that the cell contents are oxidized by highly reactive active particles, and the cell walls and cell membranes are decomposed under the attack of highly reactive active particles, thereby achieving the removal of resistant bacteria and resistance genes.

2. The chemical-physical pretreatment synergistic plasma disinfection method according to claim 1, characterized in that: In the H2O2 / HNO3 mixed solution, 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 hydraulic retention time of the pretreatment chemical reactor is 15-20s and the flux is 20-30m 3 h -1 m -2 .

4. The chemical-physical pretreatment synergistic plasma disinfection method according to claim 2, characterized in that: The hydraulic retention time of the local enhanced electric field treatment disinfection device is 10-15s, and the flux is 30-40m 3 h -1 m -2 .

5. The chemical-physical pretreatment synergistic plasma disinfection method according to claim 3, characterized in that: The hydraulic retention time of the dielectric barrier discharge plasma reactor is 20-25s, and the flux is 15-25m 3 h -1 m -2 .

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

7. A chemical-physical pretreatment synergistic plasma disinfection device for implementing the chemical-physical pretreatment synergistic plasma disinfection method according to any one of claims 1 to 6, characterized in that: It includes a pretreatment chemical reactor, a local enhanced electric field treatment disinfection device and a dielectric barrier discharge plasma reactor which are connected in sequence; The pretreatment chemical reactor is provided with a feeding pipe; the feeding pipe is used to feed H2O2 / HNO3 mixed solution; The local enhanced electric field treatment disinfection device comprises a tank body, a cylindrical outer electrode arranged on the inner surface of the tank body, and a central electrode fixed in the middle of the tank body; the central electrode comprises a copper electrode and dopamine-coated copper oxide nanowires, and the dopamine-coated copper oxide nanowires are loaded on the copper electrode; The dielectric barrier discharge plasma reactor comprises a quartz dielectric tube, a grounding electrode, a high-voltage electrode and a gas supply system; the quartz dielectric tube comprises an outer surface layer and an inner surface layer, a discharge space is formed between the outer surface layer and the inner surface layer, and a plurality of aeration holes are arranged 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 arranged at the center position of the water channel.

8. The chemical-physical pretreatment synergistic plasma disinfection device according to claim 7, characterized in that: In the dielectric barrier discharge plasma reactor, a water channel is filled with a catalyst.

9. The chemical-physical pretreatment synergistic plasma disinfection device according to claim 8, characterized in that: The catalyst is borosilicate glass beads, alumina, zirconia or cerium oxide.

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

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