Over-current sterilization module based on electrolyzed water hydroxyl free radicals, electric appliance and wastewater treatment device

Abstract

The invention provides an overcurrent sterilization module based on hydroxyl free radicals in electrolyzed water, which is characterized by comprising a shell, a water inlet, a water outlet, a water outlet, a water inlet and a water outlet, the at least one electrolysis unit is arranged in the shell and located on a water flow channel between the water inlet and the water outlet, and the electrolysis unit comprises a cathode and a high oxygen evolution overpotential anode; the power supply module is used for supplying power to the electrolysis unit; when the electrolysis unit is in a power-on state, water is electrolyzed on the surface of the high-oxygen-evolution overpotential anode and the adjacent area of the high-oxygen-evolution overpotential anode to generate hydroxyl free radicals, and instant sterilization of the water body is achieved through the hydroxyl free radicals. The invention further provides an electric appliance and a wastewater treatment device comprising the overcurrent sterilization module based on the electrolyzed water hydroxyl free radicals.

Description

Technical Field

[0001] This invention relates to the field of water treatment technology, and in particular to an overflow sterilization module based on hydroxyl radicals. Background Technology

[0002] In fields such as drinking water safety, medical water, and the food industry, efficient and residue-free disinfection of water streams is a core requirement. Electrochemical sterilization technology has been widely used in water treatment due to its advantages such as not requiring the addition of external chemical agents, ease of operation, and environmental friendliness. Current technologies for water electrolysis typically involve electrolyzing chlorine-containing solutions or water with added electrolytes to generate bactericidal substances such as hypochlorous acid or ozone. Sufficient residence time in pipes or storage tanks is required for disinfection to be effective, which results in problems such as chemical residues in the water and low disinfection efficiency. Summary of the Invention

[0003] The purpose of this invention is to overcome the shortcomings of the prior art and provide an overcurrent sterilization module and sterilization method based on hydroxyl radicals from water electrolysis. The module utilizes high oxygen evolution overpotential anodic electrolysis of water to generate hydroxyl radicals, which instantly kill bacteria and viruses in the water by the generated hydroxyl radicals, achieving instantaneous overcurrent sterilization, and the effluent does not contain any residual sterilizing substances.

[0004] The overcurrent sterilization module based on hydroxyl radicals from water electrolysis is characterized by comprising: A housing having an inlet and an outlet; At least one electrolysis unit is disposed within the housing and located in the water flow channel between the inlet and the outlet, the electrolysis unit comprising a cathode and a high oxygen evolution overpotential anode; A power supply module is used to supply power to the electrolysis unit; When the electrolysis unit is energized, it generates hydroxyl radicals by electrolyzing water on the surface of the high oxygen evolution overpotential anode and its adjacent area, thereby achieving instantaneous sterilization of the water through the hydroxyl radicals.

[0005] In one embodiment, a control system is also included, wherein both the power supply module and the electrolysis unit are electrically connected to the control system, and the control module includes a control unit for adjusting the current density and voltage applied to the electrolysis unit to regulate the concentration of hydroxyl radicals.

[0006] In one embodiment, the high oxygen evolution overpotential anode comprises a conductive diamond electrode and a diamond-based composite electrode.

[0007] In one embodiment, the conductive diamond anode is a doped diamond electrode, and the doping element is selected from one or more of boron, nitrogen, phosphorus, and sulfur.

[0008] In one embodiment, the number of electrolysis units is multiple, and the multiple electrolysis units are arranged in a row or arranged opposite each other.

[0009] In one embodiment, the electrolysis unit is provided with a plurality of through holes for guiding water flow through the electrolysis unit.

[0010] In one embodiment, the number of electrolysis units includes multiple units, and the multiple electrolysis units are arranged symmetrically among them.

[0011] In one embodiment, the housing forms two inlets opposite to the two ends of the symmetrically arranged electrolysis units, and the housing forms an outlet corresponding to the middle flow channel formed by the symmetrically arranged electrolysis units. The water flow channel is configured to guide water to flow in from the inlets, flow through the electrolysis units, and then converge into the middle flow channel and flow out from the outlet.

[0012] In one embodiment, the electrolysis unit further includes a solid electrolyte membrane disposed between the conductive diamond anode and the cathode.

[0013] In one embodiment, the system further includes a circulation pipeline, the two ends of which are connected to the inlet and the outlet, respectively, and a circulation pump is installed on the circulation pipeline.

[0014] In one embodiment, a water storage container is provided on the circulation pipeline.

[0015] An electrical appliance comprising the overcurrent sterilization module based on hydroxyl radicals from water electrolysis as described in any of the above embodiments.

[0016] A wastewater treatment device includes the overcurrent sterilization module based on hydroxyl radical electrolysis of water as described in any of the above embodiments.

[0017] The beneficial effects of this invention are: (1) Instantaneous in-situ sterilization: Based on the extremely short lifespan of hydroxyl radicals, their generation area is located in the electrode near the anode surface. When the water to be treated flows through the electrolysis unit, hydroxyl radicals are generated by electrolysis as the water flows over the anode surface. The hydroxyl radicals instantly oxidize and inactivate bacteria, viruses, etc. in the water. That is, they are generated as soon as they flow through the unit and act immediately upon generation, achieving instantaneous in-situ sterilization.

[0018] (2) Direct water electrolysis: A high oxygen evolution overpotential anode is used, which has an extremely high oxygen evolution overpotential and can directly electrolyze water to generate a high concentration of hydroxyl radicals. This characteristic makes the module of this application particularly suitable for application scenarios with high water quality requirements, such as medical water, food processing water, and high-end drinking water.

[0019] (3) No chemical residue: The half-life of hydroxyl radicals is 10.-9 -10 -8 The s-type disinfectant primarily exists only in the near-electrode region and rapidly degrades into harmless substances such as H2O and O2 after leaving this region. The module's effluent contains no disinfectant residue, ensuring the purity and immediate safety of the effluent. Attached Figure Description

[0020] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0021] Figure 1 This is a schematic diagram of the structure of an overflow sterilization module according to an embodiment of the present invention.

[0022] Figure 2 This is a schematic diagram of the overflow sterilization module according to another embodiment of the present invention.

[0023] Figure 3 This is a schematic diagram of a device with an overflow sterilization module according to an embodiment of the present invention. Detailed Implementation

[0025] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0026] This invention provides an overcurrent sterilization module 1 based on hydroxyl radicals from water electrolysis, specifically, as follows: Figure 1 and 2 As shown, including: The housing 100, the power module 300, and at least one electrolysis unit.

[0027] The housing 100 has an inlet 110 and an outlet 120; the electrolysis unit is disposed inside the housing 100 and located in the water flow channel between the inlet 110 and the outlet 120, and the electrolysis unit includes a high oxygen evolution overpotential anode 210 and a cathode 220; the power module 300 is used to supply power to the electrolysis unit. When the electrolysis unit is energized, hydroxyl radicals are generated by electrolyzing water on the surface of the high oxygen evolution overpotential anode 210 and its adjacent area, and the water is instantly sterilized by the hydroxyl radicals.

[0028] In this embodiment, the anode 210 is a high oxygen evolution overpotential anode for electrolyzing water. For example, the anode 210 and cathode 220 are electrically connected to the power module 300 via wires. The internal space of the housing 100 forms a water flow channel, through which water flows in from the inlet 110, is guided by the water flow channel to flow between the high oxygen evolution overpotential anode 210 and cathode 220, and then flows out from the outlet 120.

[0029] During operation, the power module applies voltage to the electrolysis unit. The water to be treated flows in through the inlet and, as it flows over the surface of the high oxygen evolution overpotential anode and its adjacent area, is electrolyzed to generate hydroxyl radicals: H₂O → ·OH + H⁺ + e⁻ - The generated hydroxyl radicals instantly act on bacteria, viruses, and other microorganisms in the vicinity of the electrode, oxidizing and inactivating them.

[0030] The beneficial effects of this invention are: (1) Instantaneous in-situ sterilization: Based on the extremely short lifespan of hydroxyl radicals, their generation area is located in the near-electrode region near the anode surface with high oxygen evolution overpotential. When the water to be treated flows through the electrolysis unit, hydroxyl radicals are generated by electrolysis as the water flows over the anode surface. The hydroxyl radicals instantly oxidize and inactivate bacteria, viruses, etc. in the water. That is, they are generated as soon as they flow through the anode and act immediately upon generation, achieving instantaneous in-situ sterilization.

[0031] (2) Direct electrolysis of water: A high oxygen evolution overpotential anode is used, which has an extremely high oxygen evolution overpotential, directly electrolyzing water to generate a high concentration of hydroxyl radicals. This characteristic makes the module of this application particularly suitable for application scenarios with high water quality requirements, such as medical water, food processing water, and high-end drinking water.

[0032] (3) No chemical residue: The half-life of hydroxyl radicals is 10. -9 —10 -8 The s-type disinfectant primarily exists only in the near-electrode region and rapidly degrades into harmless substances such as H2O and O2 after leaving this region. The module's effluent contains no disinfectant residue, ensuring the purity and immediate safety of the effluent.

[0033] Hydroxyl radicals kill microorganisms primarily through the following pathways: disrupting the integrity of cell walls and cell membranes, leading to leakage of intracellular substances; oxidizing key enzymes and structural proteins within microorganisms, causing them to become inactive; and attacking DNA or RNA molecules, damaging genetic material, and preventing microbial reproduction.

[0034] Furthermore, experiments have verified that the ozone concentration detected by the module of this invention is 0.1-0.25 mg / L, and the water body is instantly disinfected mainly by the strong oxidizing properties of hydroxyl radicals.

[0035] The main pathway for the generation of hydroxyl radicals on the anode surface is: H2o→·OH + H + + e - That is, for every 1 mol of electrons transferred, 1 mol of hydroxyl radicals are generated. In one embodiment of this application, the electrolysis unit has dimensions of 12mm x 11mm, the water flow rate is 2.5L / min, the applied current is 0.5A, and the voltage is 12V. Therefore, the electron flow rate is I / F = 5.18 * 10⁻⁶. -6 mol e - / s (F is Faraday's constant).

[0036] Assuming the efficiency of hydroxyl radical generation in the reaction is 100%, according to the reaction equation, 1 mol of electrons needs to be transferred to generate 1 mol of ·OH. Therefore, the yield of hydroxyl radicals can be calculated as: 5.18 * 10⁻⁶. -6 mol / s = 0.088 mg / s (mass flow rate); Concentration of hydroxyl radicals on the surface of the electrolytic anode:

[0037] Using *E. coli*, a common bacterium in water, as the target, the contact time (t) required to achieve a 99.99% (4-log) inactivation rate was estimated. Based on the simplified first-order reaction kinetic equation:

[0038] To achieve 4-log inactivation, ln(N / N0) = -9.21, and the rate constant K for the carboxyl group = 10. 10 M -1 S -1 Substituting into the above equation, we get:

[0039] The results showed that 99.99% of Escherichia coli could be inactivated in just 7.41 μs at an electrolysis current of 0.5 A.

[0040] Since the conversion rate of hydroxyl radicals is difficult to reach the theoretical value of 100%, in the above calculation, if the generation efficiency of hydroxyl radicals is 50%, the result is t=14.8μs, and if the generation efficiency of hydroxyl radicals is 70%, the result is t=10.6μs.

[0041] Since the generation rate of hydroxyl radicals is directly proportional to the current, as the current increases, the concentration of hydroxyl radicals increases, and the corresponding contact time and inactivation rate also increase. Conversely, as the flow rate increases, the concentration of hydroxyl radicals decreases proportionally, and the corresponding contact time and inactivation rate also decrease. For pure water, according to the national standard GB / T6682-2008, the total bacterial count in the water should be between 0 and 100 CFU / ml. At a current of 0.1A, the concentration of hydroxyl radicals generated by the overcurrent sterilization module is sufficient to achieve instantaneous bacterial elimination. For tap water, the total bacterial count in the raw water (untreated water) is 10... 4 ~ 10 5 With a CUF / ml, instantaneous disinfection can be achieved by increasing the module voltage to above 0.5A. For treated water, the national standard limits the total bacterial count to 0~100CUF / ml. Under these conditions, the concentration of hydroxyl radicals generated by the electrolytic disinfection module is sufficient to achieve instantaneous bacterial disinfection.

[0042] It is worth noting that the generation efficiency of hydroxyl radicals is constrained by multiple factors, including the intrinsic properties of the electrode material, competition from oxygen evolution side reactions, solution mass transfer conditions, and radical self-quenching. Conventional electrodes struggle to generate large quantities of hydroxyl radicals because ordinary electrodes (such as Pt) have low oxygen evolution overpotentials, making it easier for water to be directly oxidized into oxygen or hypochlorous acid. This application employs a high oxygen evolution overpotential anode. Because a higher oxygen evolution overpotential results in a wider potential window for ·OH generation, the oxygen evolution side reactions are more thoroughly suppressed, and water is forced to take a single-electron path to generate ·OH, thus achieving a higher ·OH yield.

[0043] Based on the above, the sterilization module of this application can achieve instantaneous disinfection by inactivating bacteria with hydroxyl radicals in a time of up to nanoseconds.

[0044] Table 1 shows the bacterial killing effect of the overcurrent sterilization module of this application under different currents (with an efficiency of 50%~70%).

[0045] Current (A) Flow rate (L / min) Free radical concentration (μM) Required contact time (μs) <![CDATA[Theoretical inactivation rate (log 10 ).]]> 0.3 0.5 186.6 ~ 261.2 4 ~ 5 <![CDATA[2.3 × 10 4 ~ 3.3 × 10 4 ]]> 0.3 1 93.3 ~ 130.5 7 ~ 10 5.8 × 10³ ~ 8.2 × 10³ 0.3 1.5 62.2 ~ 87.1 11 ~ 15 2.6 × 10³ ~ 3.6 × 10³ 0.3 2 46.6 ~ 65.3 14 ~ 20 1.5 × 10³ ~ 2.0 × 10³ 0.3 2.5 37.3 ~ 52.2 18 ~ 25 935.0 ~ 1.3 × 10³ 0.5 0.5 310.9 ~ 435.3 2 ~ 3 <![CDATA[3.9 × 10 4 ~ 5.4 × 10 4 ]]> 0.5 1 155.4 ~ 217.6 4 ~ 6 <![CDATA[9.7 × 10³ ~ 1.4 × 10 4 <!-- 4 -->]]> 0.5 1.5 103.7 ~ 145.1 6 ~ 9 4.3 × 10³ ~ 6.0 × 10³ 0.5 2 77.8 ~ 108.8 8 ~ 12 2.4 × 10³ ~ 3.4 × 10³ 0.5 2.5 62.2 ~ 87.1 11 ~ 15 1.6 × 10³ ~ 2.2 × 10³ 0.7 0.5 435.3 ~ 609.3 2 ~ 2 <![CDATA[5.5 × 10 4 ~ 7.6 × 10 4 ]]> 0.7 1 217.7 ~ 304.7 3 ~ 4 <![CDATA[1.4 × 10 4 ~ 1.9 × 10 4 ]]> 0.7 1.5 145.1 ~ 203.1 5 ~ 6 6.0 × 10³ ~ 8.5 × 10³ 0.7 2 108.8 ~ 152.3 6 ~ 8 3.4 × 10³ ~ 4.8 × 10³ 0.7 2.5 87.0 ~ 121.9 8 ~ 11 2.2 × 10³ ~ 3.1 × 10³ Table 1 The water body used in this application can be municipal tap water, purified water, etc.

[0046] In one embodiment, the conductive diamond anode 210 is a doped diamond electrode, and the doping element is selected from one or more of boron, nitrogen, phosphorus, and sulfur. For example, the conductive diamond anode 210 is boron-doped diamond, or nitrogen-doped diamond. In this embodiment, these are not described in detail.

[0047] For example, the conductive diamond anode 210 can be a monolithic conductive diamond electrode, or it can be an electrode with a conductive diamond film formed on the surface of a substrate. In this embodiment, these are not described in detail.

[0048] In a preferred embodiment, there are multiple electrolysis units, which are arranged in a row or relative to each other. For example, multiple electrolysis units are arranged sequentially, or multiple electrolysis units are arranged with relative intervals. Alternatively, multiple electrolysis units are arranged sequentially and with relative intervals. These are not described exhaustively in this embodiment.

[0049] For example, the electrolysis units are arranged along the direction of the inlet water flow, or the electrolysis units are arranged perpendicular to the direction of the inlet water flow.

[0050] In one embodiment, the electrolysis unit is provided with multiple through holes to guide water flow through the electrolysis unit. Water flows into the water channel inside the housing 100 from the inlet 110, is guided to the electrode surface, passes through the through holes, and increases the water contact surface. Since instantaneous disinfection can be achieved, the through holes can accelerate the water flow rate and facilitate the adjustment of different flow rates.

[0051] Based on the above embodiments, in one embodiment, the number of electrolysis units includes multiple units, and the multiple electrolysis units are symmetrically arranged. Further, the housing 100 forms two inlets 110 opposite to the two ends of the symmetrically arranged electrolysis units, and the housing 100 forms an outlet 120 corresponding to the middle flow channel formed by the symmetrically arranged electrolysis units. The water flow channel is configured to guide water to flow in from the inlets 110, pass through the electrolysis units, and then converge in the middle flow channel to flow out from the outlet 120. In this embodiment, the water entering from the first inlet 110 and the second inlet 110 flows from both ends towards the middle under water pressure, that is, the water flows sequentially through the through holes on each electrolysis unit, and is electrolyzed to generate hydroxyl radicals when flowing through the electrode surface area of ​​each electrolysis unit, achieving instantaneous sterilization. Finally, the water flows converge in the middle flow channel in the middle of the housing 100 and is discharged from the outlet 120. The symmetrical arrangement, water inlet at both ends, water outlet in the middle, and multiple perforated electrolysis units significantly extend the water flow path and increase the water's residence time and contact area near the electrodes, thus ensuring excellent sterilization effect even under high flow rate or high microbial load conditions.

[0052] In one embodiment, the electrolysis unit further includes a solid electrolyte membrane disposed between the conductive diamond anode 210 and the cathode 220.

[0053] In one embodiment, the structure of this application further includes a circulation pipeline, the two ends of which are respectively connected to the inlet 110 and the outlet 120, and a circulation pump is installed on the circulation pipeline. In a preferred embodiment, a water storage container is installed on the circulation pipeline. In this embodiment, the circulation pump causes the water to circulate between the circulation pipeline and the flow sterilization module 1, and multiple cycles ensure that the water fully contacts the electrode surface to achieve comprehensive sterilization. By controlling the circulation time and electrolysis parameters, thorough sterilization of water with different initial microbial loads can be achieved.

[0054] In one embodiment, the structure of this application further includes a control module 420. Both the power supply module and the electrolysis unit are electrically connected to the control system. The control module includes a control unit for adjusting the current density and voltage applied to the electrolysis unit to regulate the concentration of hydroxyl radicals. That is, the control module optimizes parameters to adapt to different water flow rates and water qualities, adjusting the current density to regulate the concentration of hydroxyl radicals generated, thereby ensuring stable and compliant disinfection of the water.

[0055] Preferably, the present invention also provides an electrical appliance, such as Figure 3 As shown, it includes the machine body 430 and the overcurrent sterilization module 1 based on electrolyzed water hydroxyl radicals as described in any of the above embodiments. The electrical appliances, such as humidifiers, air purifiers, floor scrubbers, and water purifiers, are not described in detail in this embodiment.

[0056] Specifically, for example, the electrical appliance is a humidifier, including a humidifier body 430 and the overcurrent sterilization module 1 based on electrolyzed water hydroxyl radicals as described in any of the above embodiments. In this embodiment, the working method is as follows: the water pump 410 draws water from the humidifier's water tank into the sterilization system circuit and then into the overcurrent sterilization module for instantaneous sterilization. After this instantaneous sterilization, the treated water flows out and back into the water tank, thus completing the cyclical sterilization of the water in the tank. The treated water is then drawn into the atomization module through the water suction module for atomized humidification.

[0057] Preferably, the present invention also provides a wastewater treatment device, including the flow-through sterilization module based on hydroxyl radical electrolysis of water as described in any of the above embodiments. The wastewater is treated by the flow-through sterilization module.

Claims

1. A flow-through sterilization module based on hydroxyl radicals from water electrolysis, characterized in that, include: A housing having an inlet and an outlet; At least one electrolysis unit is disposed within the housing and located in the water flow channel between the inlet and the outlet, the electrolysis unit comprising a cathode and a high oxygen evolution overpotential anode; A power supply module is used to supply power to the electrolysis unit; When the electrolysis unit is energized, it generates hydroxyl radicals by electrolyzing water on the surface of the high oxygen evolution overpotential anode and its adjacent area, thereby achieving instantaneous sterilization of the water through the hydroxyl radicals.

2. The overcurrent sterilization module based on hydroxyl radicals from water electrolysis according to claim 1, characterized in that, It also includes a control system, wherein the power supply module and the electrolysis unit are both electrically connected to the control system, and the control module includes a control unit for adjusting the current density and voltage applied to the electrolysis unit to regulate the concentration of hydroxyl radicals.

3. The overcurrent sterilization module based on hydroxyl radicals from water electrolysis according to claim 1, characterized in that, The high oxygen evolution overpotential anode includes a conductive diamond electrode and a diamond-based composite electrode.

4. The overcurrent sterilization module based on water electrolysis hydroxyl radicals according to claim 3, wherein the conductive diamond is doped diamond, and the doping element is selected from one or more of boron, nitrogen, phosphorus, and sulfur.

5. The overcurrent sterilization module based on hydroxyl radicals from water electrolysis according to claim 1, characterized in that, The number of electrolysis units is multiple, and the multiple electrolysis units are arranged in a row or relative to each other.

6. The overcurrent sterilization module based on hydroxyl radicals from water electrolysis according to claim 1, characterized in that, The electrolysis unit is provided with multiple through holes to guide water flow through the electrolysis unit.

7. The overcurrent sterilization module based on hydroxyl radicals from water electrolysis according to claim 6, characterized in that, The number of electrolysis units includes multiple units, and the multiple electrolysis units are arranged symmetrically among them.

8. The overcurrent sterilization module based on hydroxyl radicals from water electrolysis according to claim 7, characterized in that, The shell forms two water inlets opposite to the two ends of the symmetrically arranged electrolysis units, and the shell forms an outlet corresponding to the middle flow channel formed by the symmetrically arranged electrolysis units. The water flow channel is configured to guide water to flow in from the water inlets, flow through the electrolysis units, and then converge into the middle flow channel and flow out from the outlet.

9. The overcurrent sterilization module based on hydroxyl radicals from water electrolysis according to claim 1, characterized in that, The electrolysis unit also includes a solid electrolyte membrane disposed between the conductive diamond anode and the cathode.

10. The overcurrent sterilization module based on hydroxyl radicals from water electrolysis according to claim 1, characterized in that, It also includes a circulation pipeline, the two ends of which are connected to the inlet and the outlet, respectively, and a circulation pump is installed on the circulation pipeline.

11. The overcurrent sterilization module based on hydroxyl radicals from water electrolysis according to claim 1, characterized in that, A water storage container is installed on the circulation pipeline.

12. An electrical appliance, characterized in that, Includes the overcurrent sterilization module based on hydroxyl radicals from water electrolysis as described in claims 1-11.

13. A wastewater treatment device, characterized in that, Includes the overcurrent sterilization module based on hydroxyl radicals from water electrolysis as described in claims 1-11.

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