Ozone generating device for online maintenance of cathode and maintenance method of ozone generating device

Abstract

The invention provides an ozone generation device for online maintenance of a cathode and a maintenance method thereof, the ozone generation device comprises at least one group of ozone generation units, each group of ozone generation units comprises: a first cable, the first cable is provided with a direct current power supply first access end and a direct current power supply second access end; the first diode and the second diode are respectively arranged on the first cable and are positioned between the first access end of the direct-current power supply and the second access end of the direct-current power supply; the first diode and the second diode are opposite in direction; the working anode is connected with the first cable through a second cable; the joint of the second cable and the first cable is located between the first diode and the second diode; two descaling cathodes; and two working cathodes. At the moment, the working anode is still connected with the positive electrode of the working power supply, so that the preparation of ozone is not interrupted while the scale on the working cathode is removed.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of ozone generation, and relates to an ozone generation device, in particular to an ozone generation device for online maintenance of a cathode and a maintenance method based on the same. BACKGROUND

[0002] In addition to the new coronavirus, human living space is also filled with respiratory syncytial virus (RSV), influenza virus, parainfluenza virus (I-IV type), adenovirus, and human interstitial virus. To deal with multiple viruses, ozone (O3) is the most convenient and effective weapon for disinfection and prevention of infection. The reasons are as follows: (1) the bactericidal ability of ozone is much better than that of alcohol, bleach water and vaccine; (2) the bactericidal effect of ozone comes from dissolving the cell wall of the virus, regardless of the type of virus; (3) washing hands or gargling with ozone water can achieve effective sterilization; (4) ozone disinfection has no side effects; (5) electrolysis of water to produce ozone (EO3) can provide on-site, real-time and low-cost ozone water; (6) gargling with ozone water containing 1 ppm O3 can moisten the respiratory tract; (7) the life of O3 in water is up to 20 minutes, and the CT value of 1 ppm, 20 minutes can eliminate any virus attached to the throat; (8) O3 becomes O2 after sterilization, which is beneficial to respiration; (9) the short life of ozone makes it impossible for viruses to develop drug resistance; (10) ozone water will not irritate or harm the respiratory tract and lungs.

[0003] Generally, when electrolyzing water, oxygen is generated at the anode, and hydrogen is generated at the cathode; in the gas generated at the anode, ozone cannot be measured; only when a catalyst is plated on the surface of the anode, a certain concentration of ozone can be obtained. Compared with other common catalysts for generating ozone, such as platinum (Pt), iridium (Ir), boron-doped (B) conductive diamond film, and lead dioxide (β-PbO2), tin dioxide has the advantages of cost and environmental protection. However, tin dioxide cannot be negatively charged like the aforementioned catalysts, and at the same time, the matched cathode is reversed to be positively charged, that is, the cathode can be quickly descaled online: when ozone is generated, tin dioxide must be positively charged, otherwise SnO2 will be reduced to metal Sn in an instant, and black particles will fall off from the surface of the anode, causing permanent damage to the anode.

[0004] The cause of cathode fouling is usually the electrolysis of water on the cathode, as shown in equation (1):

[0005] 2H2O + 2e→ H2 + 2OH - (1)

[0006] The above reaction shows that the cathode surface will gather negatively charged hydroxyl ions (OH - ), thereby attracting calcium and magnesium positive ions (Ca 2+ / Mg 2+) form a precipitate, and scale on the cathode surface. The thickness of the cathode scale depends on water quality, power-on time and current size. Even if the water is treated by reverse osmosis to prepare ozone, the cathode scale is only a matter of time. Once the cathode begins to scale, the function of the anode to produce O3 will decline until the cathode surface is clean. For the user of EO3, automatic online electrode reversal will be the best maintenance-free design. SUMMARY

[0007] To solve the above technical problems, the purpose of the present application is to provide an ozone generating device for online maintenance of a cathode.

[0008] To achieve the above technical purpose, the present application first provides an ozone generating device for online maintenance of a cathode, which comprises at least one set of ozone generating units, each set of the ozone generating units comprising:

[0009] a first cable having a direct current power first access end and a direct current power second access end;

[0010] a first diode and a second diode, which are respectively installed on the first cable and located between the direct current power first access end and the direct current power second access end; the first diode and the second diode are opposite in direction;

[0011] a working anode connected to the first cable through a second cable; the connection of the second cable to the first cable is located between the first diode and the second diode;

[0012] two descaling cathodes, which are respectively connected to the first cable through a third cable; the connection of the third cable to the first cable is located between the direct current power first access end and the first diode; the third cable is provided with a third diode opposite in direction to the first diode;

[0013] two working cathodes, which are respectively located between the working anode and the corresponding two descaling cathodes, and are respectively connected to the first cable through a fourth cable; the connection of the fourth cable to the first cable is located between the direct current power second access end and the second diode; each of the fourth cables is connected with a fourth diode and a fifth diode arranged in parallel and opposite in direction.

[0014] Optimally, the gap between the working anode and the working cathode and between the working cathode and the corresponding descaling cathode is 0.5-2 mm.

[0015] Further, the gap is provided with an insulating gasket of corresponding thickness.

[0016] Optimally, the working anode is a titanium substrate and its surface is coated with a mixture coating of antimony oxide, nickel oxide and tin oxide.

[0017] Further, the working cathode and the descaling cathode are independently 304 stainless steel plates.

[0018] Optimally, the first access end of the direct current power source and the second access end of the direct current power source access working power or / and recovery power, the working voltage of the working power and the recovery power is ≤24V, the pulse frequency of the PWM is 100Hz-10000Hz.

[0019] Another object of the present application is to provide a maintenance method for the above-mentioned ozone generator with online maintenance cathode, comprising the following steps:

[0020] The working anode is connected to the positive pole of the working power source, the two working cathodes are connected to the negative pole of the working power source, and electricity is supplied to produce ozone; when the surface of the working cathode has deposits accumulated, the two descaling cathodes are used to maintain and recover the activity of the working cathode in a polarity reversal manner.

[0021] Optimally, the polarity reversal is that the negative pole of the recovery power source is connected to the descaling cathode, the positive pole of the recovery power source is connected to the working cathode, and the working anode is disconnected from the current, so that ozone is produced while the working cathode is cleaned.

[0022] Optimally, the polarity reversal can be determined by measuring the change of resistance or current, or controlled according to the set time.

[0023] Further, the working power source and the recovery power source are the same power source.

[0024] The present application is an ozone generator with online maintenance cathode, the working cathode is arranged next to the working anode, and the descaling cathode is arranged at the outermost side, so that when ozone is produced, the working anode is connected to the positive pole of the working power source, and the working cathode is connected in parallel to the negative pole of the working power source; when the surface of the working cathode has deposits gradually accumulated, the descaling cathode is connected in parallel to the negative voltage, the working anode and the working cathode are applied with positive voltage, the polarity of the working cathode is reversed, the accumulated deposits on the working cathode are removed, and the surface of the working cathode is regenerated; at this time, the working anode still maintains connection with the positive pole of the working power source, the accumulated deposits on the working cathode are removed, and the production of ozone is ensured not to be interrupted. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 It is the overall framework diagram of the ozone generator with online maintenance cathode of the present application;

[0026] Figure 2 It is the principle schematic diagram of the ozone generator with online maintenance cathode of the present application;

[0027] Figure 3 The principle schematic diagram of the ozone generating device of the application for on-line maintenance of cathode in mode 1;

[0028] Figure 4 The principle schematic diagram of the ozone generating device of the application for on-line maintenance of cathode in mode 2. DETAILED DESCRIPTION

[0029] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the drawings in the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the application.

[0030] Embodiment 1

[0031] The embodiment provides a preparation method of the working anode C, and specifically as follows:

[0032] (a) dissolve stannous oxalate (SnC2O4), antimony nitrate (Sb(NO3)5) (obtained by oxidizing Sb2O3 with concentrated nitric acid) and nickel acetate (Ni(CH3COO)2) in pure water to form a clear mixed solution (the molar ratio of stannous oxalate, antimony oxide and nickel acetate is 800:3:1, and the amount of stannous oxalate is 8 mol); if there is a precipitate in the mixed solution, it can be removed by a centrifuge;

[0033] (b) uniformly coat the mixed solution (also can be realized in the way of brush coating or spray coating) on the surface of a titanium (Ti) sheet (50 cm x 50 cm) by using a dispensing machine; after drying (at a temperature of 100-120°C), pyrolysis (at a temperature of 200-250°C for 20-40 min) and sintering (at a temperature of 530-580°C for 50-90 min) heat treatment, the three metals are changed into a composite of ceramic oxides (containing SnO2, Sb2O5 and NiO; that is, the working anode C is a titanium base material and the surface of the working anode C is coated with a mixed coating layer of antimony oxide, nickel oxide and tin oxide), so as to form a Ni, Sb-SnO2 catalyst for generating ozone on the surface of the titanium sheet, thereby obtaining the anode sheet of EO3 (each batch of anode sheet needs to be subjected to ozone concentration verification, adhesion / surface resistance test, electron microscope surface structure and accelerated aging life test, so that the product has an ozone production capacity of more than 2 mg O 2 / cm 3 omin above at a power density of 20 mW / cm 2 .

[0034] Embodiment 2

[0035] The embodiment provides an ozone generator device for on-line maintenance of a cathode, which comprises at least one set of ozone generation units. Figure 1 and Figure 2 As shown in the figure, the ozone generation units can be multiple sets, and when the ozone generation units are multiple sets, the multiple sets can be connected in parallel; at this time, the sets can be recovered in sequence, and the working cathode waiting for recovery can still continue to produce ozone with the working anode. In the embodiment, the ozone generation units are one set. Each set of ozone generation units mainly comprises a first diode 4, a second diode 5, a working anode C, a descaling cathode A, a descaling cathode E, a working cathode B and a working cathode D.

[0036] The first cable has a direct current power supply first access end 10 and a direct current power supply second access end 11, and the direct current power supply first access end 10 and the direct current power supply second access end 11 are respectively used for connecting the positive pole and the negative pole of a direct current power supply (a working power supply or a recovery power supply). The first diode 4 and the second diode 5 are respectively installed on the first cable and located between the direct current power supply first access end 10 and the direct current power supply second access end 11, and the first diode 4 and the second diode 5 are opposite in direction (at this time, the direction of the first diode 4 is the same as the direction of the current in the first cable, so the current can flow through the first diode 4 but cannot flow through the second diode 5).

[0037] The working anode C is connected with the first cable through a second cable (when powered, the second cable is electrically connected with the first cable; the same below); the connection position of the second cable with the first cable is located between the first diode 4 and the second diode 5. The descaling cathode A and the descaling cathode E are respectively connected with the first cable through a third cable; the connection position of the third cable with the first cable is located between the direct current power supply first access end 10 and the first diode 4; the third diode 1 and the third diode 9 opposite in direction are installed on the third cable (that is, one third diode 1 or one third diode 9 is installed on one third cable); the working cathode B and the working cathode D are respectively located between the working anode C and the descaling cathode A and between the working anode C and the descaling cathode E, and are respectively connected with the first cable through a fourth cable; the connection position of the fourth cable with the first cable is located between the direct current power supply second access end 11 and the second diode 5; the fourth diode 2 (or the fourth diode 6) and the fifth diode 3 (or the fifth diode 7) opposite in direction are connected on each fourth cable.

[0038] In the embodiment, the gap between the working anode C and the working cathode B (or the working cathode D) and the gap between the working cathode B (the working cathode D) and the corresponding descaling cathode A (or the descaling cathode E) are 0.5 mm-2 mm; the corresponding thickness of the insulating gasket is arranged at the gap; and the anode and the cathode can be prevented from being short. The entire ozone generation unit can also be fixed by titanium bolts and titanium nuts. The working cathode B, the working cathode D, the descaling cathode A and the descaling cathode E are all independently made of 304 stainless steel plates.

[0039] The working principle of the ozone generation device with the online maintenance cathode is as follows.

[0040] Mode 1

[0041] When the first access end 10 of the direct current power supply accesses the positive pole of the power supply and the second access end 11 of the direct current power supply accesses the negative pole of the power supply:

[0042] The descaling cathode A and the descaling cathode E are affected by the one-way conduction characteristics of the third diode 1 and the third diode 9, so no current passes through the descaling cathode A and the descaling cathode E; the current passes through the first diode 4 from the positive pole of the power supply, passes through the working anode C, passes through the water (a conductor) and flows to the working cathode B and the working cathode D, respectively passes through the fourth diode 2 and the fourth diode 6, and returns to the negative pole of the power supply. In this mode, the descaling cathode A, the descaling cathode E, the working cathode B and the working cathode D are negative poles, and the working anode C is a positive pole.

[0043] Mode 2

[0044] When the first access end 10 of the direct current power supply accesses the negative pole of the power supply and the second access end 11 of the direct current power supply accesses the positive pole of the power supply:

[0045] Since the working cathode B, the working anode C and the working cathode D are connected in parallel to the power supply, the current flows from the positive pole of the power supply, respectively through the fifth diode 3 to the working cathode B, the second diode 5 to the working anode C and the fifth diode 7 to the working cathode D; since the working cathode B, the working anode C and the working cathode D are all positive poles and are connected in parallel in the circuit and have the same voltage, no current passes through the water between the working cathode B and the working anode C and between the working cathode B and the working cathode D; the current passing through the working cathode B and the working cathode D passes through the descaling cathode A and the descaling cathode E on both sides as a conductor, respectively passes through the third diode 1 and the third diode 9, and returns to the negative pole of the power supply. In this mode, the descaling cathode A and the descaling cathode E are negative poles, and the working cathode B, the working anode C and the working cathode D are positive poles.

[0046] In the embodiment, the first DC power access end 10 and the second DC power access end 11 access working power or / and recovery power, the working voltage of the working power and the recovery power is less than or equal to 24V (when high-concentration ozone is prepared with large current, the large current is provided by the super capacitor without exceeding 24V), the pulse frequency of the PWM is 100Hz-10000Hz; the working power and the recovery power can be the same power source, or different power sources can be used.

[0047] The test results are as follows: the ozone concentration is similar to that of continuous electrolysis for 5 minutes; and after 3 or 4 continuous cycles, the stainless steel does not have fouling phenomenon. The electrolysis time and the descaling time are adjustable, and can be adjusted according to the situation. The above-mentioned circuit design can be realized at very low cost.

[0048] As can be known from the working principle of the above-mentioned ozone generating device, the working anode C is always positive, otherwise the catalyst on the surface thereof will form unstable stannous ions (Sn 2+ ), which are oxidized to SnO or SnO2 white precipitate when heated and water, so that the catalyst loses the ability to generate ozone. In the present application, when the surface of the working cathode B and the working cathode D has gradually accumulated deposits, the descaling cathode A and the descaling cathode E are connected in parallel with negative voltage, the working anode C is applied with positive voltage with the working cathode B and the working cathode D, the polarity of the working cathode B and the working cathode D is reversed, and the accumulated fouling on the working cathode B and the working cathode D is removed, so that the surface of the working cathode is regenerated. In the present application, the descaling cathode is connected in parallel to the negative electrode of the recovery power source, the positive electrode of the recovery power source is connected with the parallel working cathode, and the working anode is still connected with the positive electrode of the working power source. While removing the accumulated fouling on the working cathode, the preparation of ozone is not interrupted, and only the yield of ozone is slightly reduced.

[0049] The maintenance method of the above-mentioned ozone generating device with online maintenance cathode includes the following steps:

[0050] The working anode C is connected to the positive electrode of the working power source, and the two working cathodes (the working cathode B and the working cathode D) are connected to the negative electrode of the working power source, and electricity is supplied to prepare ozone; when the surface of the working cathode B and the working cathode D has accumulated deposits, the two descaling cathodes (the descaling cathode A and the descaling cathode E) are used to maintain and restore the activity of the working cathode B and the working cathode D in a polarity reversal manner.

[0051] The polarity reversal is as follows: the negative pole of the recovery power source is connected with the descaling cathode A and the descaling cathode E, the positive pole of the recovery power source is connected with the working cathode B and the working cathode D, and the working anode C is disconnected from the current. The working cathode is cleaned at the same time, and ozone is also prepared. Specifically, when the descaling is 0.25 A, the water amount is 500 ml, the water temperature is 10°C, and the ozone concentration in the water is 0.33 mg / L after 5 min; when the descaling is 0.4 A, the water amount is 500 ml, the water temperature is 10°C, and the ozone concentration in the water is 1.1 mg / L after 5 min. Before descaling, the electrode normally operates under the conditions of a water amount of 500 ml, a descaling of 0.25 A, a water temperature of 10°C, and an ozone concentration of 1.9 mg / L after 5 min of operation. After descaling, the electrode operates under the same conditions, and the ozone concentration is 1.9 mg / L (although theoretically, the anode should not have an electrolysis reaction without current; however, there may be an electric field around the electrolysis module after the module is powered on, and there is an electron flow, so that an electrolysis reaction occurs with the working anode edge part, resulting in the generation of ozone (0.33 mg / L vs. 1.9 mg / L). In the maintenance state, the working anode in the middle still generates current with the descaling cathode on the outermost side, and ozone is generated during the experiment, which proves that the anode is still working, and the current may be transmitted at the edge of the electrode, so the concentration is not high, but this is a good thing, at least in the maintenance state, it still has a certain effect). The polarity reversal can be determined by measuring the resistance or current change, or controlled according to the set time.

[0052] The polarity reversal descaling frequency of the application can be automatically executed by program control in cooperation with an online monitor. The online monitor can be used to monitor the pollution of the working cathode: when the resistance on the surface of the cathode is greater than a predetermined value or the current is less than a set value, the descaling recovery program is started, and the execution is performed to the preset time. The descaling frequency can also be adjusted to perform the working time (electrolysis of water to produce ozone) and the descaling time, respectively.

[0053] The method of on-line maintenance of cathode of the present invention, by restoring the positive electrode connection of the power supply to the working cathode to make it positive, and restoring the negative electrode connection of the power supply to the descaling cathode. The working cathode is reversed from the cathode during ozone production to the anode in the restoration state. At this time, the high positive voltage will quickly decompose the deposits such as calcium carbonate (CaCO3) on the working cathode, and the decomposition time required depends on the thickness and intensity of the scaling. The product of the electric decomposition, calcium oxide (CaO), will be washed away from the working cathode by the flowing water, leaving a clean electrode surface to produce ozone. According to the number of working cathodes, they can be divided into groups, and some scaling working cathode groups can be restored while the remaining working cathode groups can still produce ozone, so that the method of the present invention can clean the cathodes without affecting the production of ozone. The method of on-line maintenance of cathode of the present invention is applied to consumer goods, which belong to non-continuous operation, and the maintenance of cathode plates only needs to be carried out during shutdown, so the method of the present invention can only be used for maintenance of cathodes. In industrial ozone production, the ozone machine runs continuously for 5 hours (water quality will affect the scaling time), and the cathode plates begin to scale. The application of the method of the present invention can maintain the cathode plates while producing ozone.

[0054] The above examples are only for illustrating the technical concept and characteristics of the present invention, and the purpose is to enable those skilled in the art to understand the content of the present invention and to implement it, and it cannot limit the protection scope of the present invention. Any equivalent changes or modifications made in accordance with the spirit and essence of the present invention shall be covered within the protection scope of the present invention.

Claims

1. An ozone generating apparatus for on-line maintenance of a cathode, comprising at least one set of ozone generating cells, characterized in that, Each group of the ozone generating units comprises: a first cable having a first DC power access end (10) and a second DC power access end (11); a first diode (4) and a second diode (5) mounted on the first cable respectively between the first DC power access end (10) and the second DC power access end (11); the first diode (4) and the second diode (5) are opposite in direction; a working anode (C) connected to the first cable through a second cable; the connection between the second cable and the first cable is located between the first diode (4) and the second diode (5); two descaling cathodes (A, E) connected to the first cable through a third cable respectively; the connection between the third cable and the first cable is located between the first DC power access end (10) and the first diode (4); a third diode (1, 9) opposite in direction to the first diode (4) is mounted on the third cable; two working cathodes (B, D) located between the working anode (C) and the two descaling cathodes (A, E) respectively, and connected to the first cable through a fourth cable respectively; the connection between the fourth cable and the first cable is located between the second DC power access end (11) and the second diode (5); a fourth diode (2, 6) and a fifth diode (3, 7) opposite in direction and arranged in parallel are connected to each fourth cable.

2. The ozone generating apparatus for on-line maintenance of a cathode according to claim 1, characterized in that: The gap between the working anode (C) and the working cathodes (B, D) and between the working cathodes (B, D) and the corresponding descaling cathodes (A, E) is 0.5-2 mm.

3. The ozone generating apparatus for on-line maintenance of a cathode according to claim 2, characterized in that: An insulating gasket with a corresponding thickness is arranged at the gap.

4. The ozone generating apparatus for on-line maintenance of a cathode according to claim 1, characterized by: The working anode (C) is a titanium substrate coated with a mixture of antimony oxide, nickel oxide and tin oxide.

5. The ozone generating device of claim 4, wherein: The working cathodes (B, D) and the descaling cathodes (A, E) are 304 stainless steel plates independent of each other.

6. The ozone generating apparatus of claim 1, wherein: The first DC power access end (10) and the second DC power access end (11) are connected to a working power source or / and a recovery power source; the working voltage of the working power source and the recovery power source is ≤24 V, and the pulse frequency of PWM is 100-10,000 Hz.

7. The maintenance method of the ozone generating apparatus of the on-line maintenance cathode according to any one of claims 1 to 6, characterized by, The method comprises the following steps: connecting the working anode (C) to the positive pole of the working power source, connecting the two working cathodes (B, D) to the negative pole of the working power source, and electrifying to produce ozone; when the surface of the working cathodes (B, D) has deposits accumulated, the two descaling cathodes (A, E) are used to maintain and recover the activity of the working cathodes (B, D) in a polarity reversal manner.

8. The maintenance method of the ozone generating apparatus of claim 7, wherein the ozone generating apparatus is maintained on-line. The polarity reversal is that the negative pole of the recovery power source is connected with the descaling cathode (A, E), the positive pole of the recovery power source is connected with the working cathode (B, D), and the working anode (C) is disconnected from the current, so that the working cathode is cleaned and ozone is prepared at the same time.

9. The maintenance method for the ozone generator with online cathode maintenance according to claim 7, characterized in that: The polarity reversal can be determined by measuring resistance or current change, or controlled according to a set time.

10. The maintenance method for the ozone generator with online cathode maintenance according to claim 8, characterized in that: The working power source and the recovery power source are the same power source.

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