WO2015154714A1 - 日常用水电解制取装置 - Google Patents

日常用水电解制取装置 Download PDF

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WO2015154714A1
WO2015154714A1 PCT/CN2015/076247 CN2015076247W WO2015154714A1 WO 2015154714 A1 WO2015154714 A1 WO 2015154714A1 CN 2015076247 W CN2015076247 W CN 2015076247W WO 2015154714 A1 WO2015154714 A1 WO 2015154714A1
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water
permeable membrane
electrolysis
daily
present
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PCT/CN2015/076247
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English (en)
French (fr)
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肖志邦
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大连双迪创新科技研究院有限公司
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104Devices therefor; Their operating or servicing
    • C02F1/46109Electrodes
    • C02F1/46114Electrodes in particulate form or with conductive and/or non conductive particles between them
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104Devices therefor; Their operating or servicing
    • C02F1/4618Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water
    • C02F2001/46185Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water only anodic or acidic water, e.g. for oxidizing or sterilizing
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104Devices therefor; Their operating or servicing
    • C02F1/4618Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water
    • C02F2001/46195Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water characterised by the oxidation reduction potential [ORP]
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00Apparatus for treatment of water, waste water or sewage
    • C02F2201/46Apparatus for electrochemical processes
    • C02F2201/461Electrolysis apparatus
    • C02F2201/46105Details relating to the electrolytic devices
    • C02F2201/46115Electrolytic cell with membranes or diaphragms
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00Apparatus for treatment of water, waste water or sewage
    • C02F2201/46Apparatus for electrochemical processes
    • C02F2201/461Electrolysis apparatus
    • C02F2201/46105Details relating to the electrolytic devices
    • C02F2201/4616Power supply
    • C02F2201/4617DC only
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00Apparatus for treatment of water, waste water or sewage
    • C02F2201/46Apparatus for electrochemical processes
    • C02F2201/461Electrolysis apparatus
    • C02F2201/46105Details relating to the electrolytic devices
    • C02F2201/4616Power supply
    • C02F2201/46175Electrical pulses
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2307/00Location of water treatment or water treatment device
    • C02F2307/02Location of water treatment or water treatment device as part of a bottle
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2307/00Location of water treatment or water treatment device
    • C02F2307/04Location of water treatment or water treatment device as part of a pitcher or jug
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2307/00Location of water treatment or water treatment device
    • C02F2307/10Location of water treatment or water treatment device as part of a potable water dispenser, e.g. for use in homes or offices
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2307/00Location of water treatment or water treatment device
    • C02F2307/12Location of water treatment or water treatment device as part of household appliances such as dishwashers, laundry washing machines or vacuum cleaners

Definitions

  • the invention relates to a water electrolysis device, belonging to the technical field of water electrolysis equipment, and not belonging to the technical field of sewage treatment.
  • a plasma is a fourth state of a substance composed of a large number of free electrons and ions and which is electrically neutral in its entirety.
  • the so-called water plasma discharge technology is to induce water discharge in a proper way to promote ionization and excitation of water molecules.
  • the common feature is that there are a large number of bubbles in the water, and a large number of strong oxidizing factors ( ⁇ OH, ⁇ H, H 2 O 2 , free oxygen, ozone, etc.) are generated; In other words, ultra-fine bubbles in the water can penetrate deep into the laundry to wash off the dirt; and strong oxidizing factors can effectively degrade various pollutants in the water.
  • the existing water plasma discharge technology has the disadvantages of high initial excitation voltage, serious electrode erosion, and high energy consumption, and it is still difficult to apply in daily water, especially domestic water.
  • Chinese Patent 1 discloses a technique and device for preparing ionized sterilizing water by the so-called "virtual mesh point" underwater discharge method, which is a very useful attempt for water plasma discharge technology for daily life water use.
  • this technology is not only limited by the discharge mechanism and the actual manufacturing process (the spacing between the anode and the cathode cannot be kept small), and the efficiency is difficult to increase, especially the type and quantity of strong oxidizing factors generated by discharge in water according to the specific water demand in different occasions of daily water use. Make corresponding adjustments; therefore, the scope of application is limited.
  • the technology for generating strong oxidizing factors by electrolysis in the treatment of sewage since the sewage and the daily water have a large difference in water quality, and the sewage electrolysis treatment is a high-energy industrial technology, it is completely different from the domestic technology of daily water electrolysis.
  • the existing water treatment technology is only for a single demand and is also difficult to achieve.
  • the generated cold plasma can be uniformly and uniformly released to achieve a technology or device that fully reacts with water; Need a kind A water treatment device capable of generating a large number of safe and usable oxidizing factors with low power consumption and high efficiency, so as to extract water suitable for washing or water having certain sterilizing ability according to different needs of people for daily safety or functionality of water.
  • the technical problem to be solved by the present invention is to provide a device capable of generating a large amount of safe and usable oxidizing factors capable of low-power consumption and high-efficiency electrolysis, thereby extracting water having a detergency and a suitable washing water or water having a certain sterilizing ability.
  • a daily water electrolysis preparation device comprising a water container, at least one pair of cathode electrodes and anode electrodes disposed in the water container, and the cathode electrode And an electrolysis power source supplied by the anode electrode; a water permeable membrane is disposed between the pair of cathode electrodes and the anode electrode, and the water permeable membrane has a water permeability pore diameter of 2 mm or less and 1 nm or more.
  • the water permeable membrane described in the above technical solution is also referred to as a water permeable membrane or a water permeable separator, and refers to a membrane that can penetrate water molecules, and has a water permeability pore diameter ranging from millimeter to nanometer (the present invention defines a water permeable pore size range of 2 mm -1 Nano-permeable membranes, including various filtration membranes used in daily water treatment, such as ultrafiltration membrane (UF), nanofiltration membrane (NF) and microfiltration membrane (MF), etc.
  • UF ultrafiltration membrane
  • NF nanofiltration membrane
  • MF microfiltration membrane
  • the water permeable membrane in the apparatus of the present invention is not a conventionally used ionic membrane, but is a separator which has never been used in the field of water electrolysis, and the inventors have innovatively introduced a water permeable membrane into a water electrolysis apparatus as a yin, A diaphragm between the anode electrodes. Therefore, we believe that the reaction process of the daily water electrolysis preparation device of the present invention generates a new important reaction process in addition to the conventional electrolysis reaction process, that is, the low pressure cold plasma discharge reaction process of the water body.
  • the specific analysis is as follows:
  • the plasma generated in the water is often required to give an initial high voltage of excitation, and one of the main factors affecting the initial voltage is the parameter of the discharge electrode.
  • the electrode material, the discharge pitch, and the electrode diameter have an effect on the initial excitation voltage.
  • the initial excitation voltage decreases. From another point of view, the smaller the electrode diameter, the better the enhancement of the radical generation in the ion channel under the same voltage.
  • the separator has a plurality of pores having a small diameter of water permeability (millimeter or even nanometer), which can be regarded as macroscopically decomposing the discharge reaction in a large range of electrodes. Discharges the tip of an electrode with a myriad of extremely small radius of curvature. This in turn greatly reduces the initial voltage that excites the plasma reaction.
  • the water-permeable film decomposes the two electrodes of the yin and yang into an array-free sub-electrode, but the material and voltage of all the sub-electrodes All the same. This ensures that the overall electric field is evenly distributed in the macroscopic field, and the electric field generated by the electrolysis is more uniform in the rising process. The high efficiency of the discharge reaction is ensured.
  • the present invention compares with the discharge of the counter electrode without a water permeable membrane, and in the case of generating an equal amount of gas, the volume of microbubbles generated by water electrolysis in a myriad of ultrafine pores is much smaller than that of an equivalent area without a water permeable membrane.
  • the volume of bubbles produced by the electrolysis of the electrodes, and the number of bubbles is much larger than it. This effectively increases the specific surface area of the gas-liquid two-phase contact.
  • the various oxidation factors (such as hydroxyl groups) generated by the plasma mainly occur at the contact surface of the gas-liquid two phases.
  • Conventional water plasma discharge technology in order to generate water plasma discharge, often introduces gas into the water through the outside, and applies high-intensity pulse voltage or high temperature conditions.
  • the invention innovates to guide the plasma discharge into the numerous small water storage spaces of the water permeable membrane, and relies on the gas generated by the hydroelectric analysis of hydrogen and oxygen evolution, and enters the membrane to induce the gasification of the water itself, thereby exciting the gas with a very small voltage.
  • the plasma discharge of water is not only due to the improvement of efficiency, but also effectively prevents the deterioration of biological indicators due to excessive current density.
  • the electrode diameter electrode curvature radius
  • the electrolytic gas generation cannot occur or the gas production efficiency is extremely low, and to a certain extent, an infinite number of small curvature radius electrodes in the micropores in the membrane are caused.
  • the tip discharge does not work properly. Therefore, after repeated trials by the inventors, it was confirmed that the water permeability pore diameter ranged from 2 mm to 1 nm.
  • the present invention provides a water permeable membrane outside the conventional electrolysis reaction process by disposing a water permeable membrane having a certain pore diameter between the anode and the anode.
  • the low-pressure cold plasma discharge reaction of the water body is formed in the inner micropores, so that the transient oxidation factor with bactericidal ability can be efficiently generated in water.
  • the specific practical effect is that the water oxidation factor can enhance the washing and removing effect on the pollutants in the water, and at the same time meet the user's needs for water safety and functionality.
  • the improvement of the present invention based on the above technical solution is that the distance between the cathode electrode and the anode electrode is greater than or equal to the thickness of the water permeable membrane and is less than or equal to 20 mm.
  • the membrane can be very thin (for example, ultrafiltration membrane can be 0.1mm ⁇ 0.3mm), the electrolysis voltage under the same working condition can be very low, even if it is only powered by a 3.7V lithium battery, it can form more than 2 amps. Current is not available in the prior art.
  • the distance between the electrodes of the yin and yang is increased, and the generated oxidation factor is correspondingly reduced, especially the generation probability of strong oxidants of ozone is decreased.
  • ozone is produced in large quantities in the passage of oxygen through the discharge area in the form of bubbles.
  • the distance between the electrodes of yin and yang is increased, and the probability of oxygen evolution from the anode into the membrane in the plasma discharge state is reduced, and ozone is reduced in comparison.
  • the oxidative factors produced in water are more represented by hydroxyl-based transient oxidation factors. This is exactly what is needed in some water applications, such as cosmetic water.
  • the distance between the water-use electrode and the anode electrode of the daily life is equal to or greater than the thickness of the water-permeable membrane and less than or equal to 20 mm.
  • a further improvement of the present invention based on the above technical solution is that the water permeable membrane is a non-conductive water permeable membrane. This is because, in most cases, it is desirable to have as many oxidizing factors as possible in the water.
  • the water-permeable separator having a good conductivity is likely to form a composite electrode with a similar electrode at the time of discharge reaction, affecting the effect of the discharge reaction in water and the type of the product, and has many uncontrollable factors. Therefore, a non-conductive water-permeable separator is preferable.
  • a further improvement of the above technical solution of the present invention is that the cathode electrode is provided with a first through hole, and the first through hole has a hole diameter of 1 mm or more.
  • a further improvement of the above technical solution of the present invention is that the water permeable membrane has a second through hole, and the second through hole has a diameter larger than 2 mm.
  • a carbonaceous material film for example, an activated carbon fiber cloth having a certain conductivity
  • the carbonaceous membrane is equivalent to an intermediate electrode
  • the anode side is equivalent to the intermediate cathode (the carbonaceous membrane and the cathode are equivalent to one activated carbon anode-metal cathode pair), and the activated carbon cathode Fenton reaction generates more H 2 O 2 ;
  • the water permeable membrane is a single layer water permeable membrane or a multilayer water permeable membrane.
  • a specific choice of the water permeable membrane is that the single layer water permeable membrane is an ultrafiltration membrane or a single layer water permeable membrane made of a carbonaceous material.
  • the second technical solution of the present invention is that the electrolysis power source is a DC or alternating pulse power source with a high level and a narrow pulse width.
  • the use of a high-frequency narrow pulse width pulse power supply is more conducive to plasma discharge inside the water body between the yin and yang electrodes, resulting in better water production.
  • the present invention provides a kitchen washing sink, which contains the above technical solution of the present invention.
  • the second application of the technical solution of the present invention is that the present invention provides a dishwasher comprising the above technical solution of the present invention.
  • the present invention provides a fruit and vegetable cleaning device, which comprises the above technical solution of the present invention.
  • the fourth application of the technical solution of the present invention is that the present invention provides a washing machine, which comprises the above technical solution of the present invention.
  • the fifth application of the above technical solution of the present invention is that the present invention provides a bathing device, which comprises the above technical solution of the present invention.
  • the sixth application of the technical solution of the present invention is that the present invention provides a toothbrush sterilizer comprising the above technical solution of the present invention.
  • the seventh application of the above technical solution of the present invention is that the present invention provides a nail treatment device or a foot gas treatment device, and the nail treatment device or the athlete's foot treatment device comprises the above technical solution of the present invention.
  • the eighth application of the technical solution of the present invention is: the present invention provides a skin treatment device, a skin care device or a portable skin care spray bottle, the skin treatment device, the skin care device or the portable skin care spray bottle containing the above invention Technical solutions.
  • the present invention provides a medical sausage filling machine comprising the above technical solution of the present invention.
  • the present invention provides an air humidifier comprising the above technical solution of the present invention.
  • FIG. 1 is a schematic view showing the structure of a daily water electrolysis preparation device according to an embodiment of the present invention.
  • FIG. 2 is a schematic view showing the structure of a daily water electrolysis preparation device according to Embodiment 2 of the present invention.
  • FIG. 3 is a schematic view showing the structure of a daily water electrolysis preparation device according to Embodiment 3 of the present invention.
  • Fig. 4 is a schematic view showing the structure of a daily water electrolysis preparation device according to a fourth embodiment of the present invention.
  • Figure 5 is a partial enlarged view of A in Figure 4.
  • Fig. 6 is a schematic view showing the structure of a daily water electrolysis preparation device according to a fifth embodiment of the present invention.
  • Figure 7 is a partial enlarged view of B in Figure 6.
  • Fig. 8 is a schematic view showing the structure of a daily water electrolysis preparation device according to a sixth embodiment of the present invention.
  • Figure 9 is a partial enlarged view of the portion C in Figure 8.
  • Fig. 10 is a schematic view showing the structure of a daily water electrolysis preparation device according to a seventh embodiment of the present invention.
  • Figure 11 is a partial enlarged view of the portion D in Figure 8.
  • Figure 12 is a schematic view showing the structure of a daily water electrolysis preparation device according to an eighth embodiment of the present invention.
  • Figure 13 is a schematic view showing the structure of a daily water electrolysis preparation device according to Embodiment 9 of the present invention.
  • Figure 14 is a schematic view showing the structure of a daily water electrolysis preparation device according to an embodiment of the present invention.
  • the daily water electrolysis preparation device of the present embodiment includes a water container 1, a pair of cathode electrodes 2 and anode electrodes 3 disposed in the water container 1, and power supply for the cathode electrode 2 and the anode electrode 3.
  • the electrolytic power source 4; the water holding container 1 of the present embodiment is an open type container.
  • a water permeable membrane 5 is disposed between the pair of cathode electrodes 2 and the anode electrodes 3.
  • the water permeable membrane 5 of the present embodiment employs a single layer PVDF ultrafiltration membrane (polyvinylidene fluoride membrane) having an average water permeability of 0.03 ⁇ m;
  • the ultrafiltration membrane of the present embodiment may also be an ultrafiltration membrane of other materials, and the average water permeability pore diameter may be between 0.01 and 0.05 micrometers.
  • the distance ⁇ between the water permeable membrane 5 and the cathode and the anode electrode is 1 mm, and both ends of the membrane 5 are separated from the cathode and the anode electrode by a small length.
  • the cathode electrode 2 and the anode electrode 3 of the present embodiment each use an inert electrode made of a titanium-based platinum group oxide (coating thickness: 0.8 mm), the cathode electrode 2 has a circular sheet shape, and the anode electrode 3 has a rectangular sheet. shape.
  • the surfaces of the cathode electrode and the anode electrode are not open.
  • the electrolysis power source 4 of the embodiment adopts a DC pulse power source with a high-level narrow pulse width regulation voltage of 30 volts, and an alternating pulse power source can also be used.
  • the cathode electrode 2 and the anode electrode 3 of the present embodiment are placed in parallel in the water in the water holding container 1, and the cathode electrode 2 is positioned above the anode electrode 3.
  • the water electrolysis experiment is carried out by using the daily water electrolysis device of the present embodiment.
  • the volume of the water container is 200 ⁇ 80 ⁇ 120 mm
  • the source water is the water of the RO pure water machine
  • TDS 3 mg/L
  • the water container is filled with water of about 1.5 liters.
  • the electrolysis time was 30 minutes, and the water sample was taken every 5 minutes.
  • the bubble from the water is zero - the maximum relative bubble content in the experiment is divided into 0 to 5 grades;
  • the color is the yellowest - the corresponding oxidation factor in the water is the most, set to 5;
  • the degree of color change from colorless to color yellow is set to 1, 2, 3, and 4 levels.
  • the water permeable membrane 5 of the present embodiment was subjected to water electrolysis separately from the three cases in which the water permeable membrane 5 was removed or replaced with an ionic membrane, and the comparative experimental conditions were:
  • This embodiment uses a PVDF ultrafiltration membrane of the water-permeable membrane 5;
  • the electrolysis current was 300 mA in both cases and electrolysis was carried out for 15 minutes.
  • the results of Experiment 2 are shown in Table 2.
  • the daily water electrolysis apparatus of this embodiment is basically the same as that of the first embodiment.
  • the variation different from the first embodiment is: 1) the hydrophobic membrane 5 is closely attached to the cathode electrode 2 and the anode electrode 3 at the same time, and the diaphragm 5 The distance from the anode and cathode is 0; 2) The two ends of the diaphragm 5 are longer than the longer ones of the anode and the anode.
  • Other experimental conditions and detection methods are the same as in the first embodiment. The experimental results are shown in Table 4 below:
  • the daily water electrolysis preparation device of the present embodiment is basically the same as that of the first embodiment.
  • the variation different from the first embodiment is: 1) the water container 1 is a closed container, and the water inlet 6 and the outlet are provided.
  • the distance ⁇ 1 between the separator 5 and the anode electrode 3 is 8 mm; 5) The distance ⁇ 2 between the water permeable membrane 5 and the cathode electrode 2 is 0.5 mm.
  • the water electrolysis experiment of the daily water electrolysis apparatus of the present embodiment was carried out, and the experimental conditions and detection methods were the same as those of the second embodiment.
  • Add a hydrogen peroxide test select the hydrogen peroxide rapid detection reagent commonly used in the market, and observe the yellowing degree of the water color by titrating the speed test agent into the water, and classify it into 5 levels to qualitatively determine the hydrogen peroxide content in the water:
  • Colorless - the corresponding hydrogen peroxide in the water is basically zero, set to 0;
  • the color is orange - corresponding to the most hydrogen peroxide in the water, set to 5;
  • the degree of color change from colorless to color yellow is set to 1, 2, 3, and 4 levels.
  • the amount of oxidation factor in the water increases proportionally with the increase of electrolysis time, and the content of hydrogen peroxide in the water also increases step by step compared with the source water.
  • the daily water electrolysis preparation device of the embodiment is basically the same as that of the second embodiment.
  • the variation different from the second embodiment is: 1) the first through hole 8 is opened in the cathode electrode 2, Through hole diameter is 1mm; 2) water permeable membrane 5 3 is the same length as the cathode electrode 2 and the anode electrode 3; 3) the water-permeable membrane 5 is in close contact with the anode electrode 3 but separated from the cathode electrode 2, and the distance ⁇ between the water-permeable membrane 5 and the cathode electrode 2 is 2 mm.
  • the daily water electrolysis preparation device of the present embodiment is subjected to a water electrolysis experiment.
  • 24 first through holes having a diameter of ⁇ 3 mm are uniformly distributed on the cathode electrode, and the electrolysis time is 20 minutes.
  • Other experimental conditions, detection methods and implementation are performed. In the same example, the experimental results are shown in Table 6 below:
  • the daily water electrolysis preparation device of this embodiment is basically the same as that of the fourth embodiment, as shown in FIG. 6 and FIG. 7, and the variation with the fourth embodiment is: 1) the water permeable membrane 5 is opened with a second pass having a diameter of ⁇ 2.1 mm.
  • the hole 9, the second through hole 9 and the first through hole 8 are of the same number and substantially concentrically aligned; 2) the distance ⁇ between the water permeable membrane 5 and the cathode electrode 2 is 3 mm.
  • the daily water electrolysis preparation device of the present embodiment was subjected to a water electrolysis experiment, and the electrolysis time was 20 minutes.
  • Other experimental conditions and detection methods were the same as those in the fourth embodiment.
  • the experimental results are shown in Table 7 below:
  • the present embodiment is evolved on the basis of the third embodiment.
  • the different changes are: 1) the water permeable membrane 5 is composed of an activated carbon fiber membrane (felt) 5-1 and an ultrafiltration membrane stack 5 -2 plus a composite two-layer water permeable membrane, the activated carbon fiber membrane 5-1 is adjacent to the anode electrode 3 (toward the anode electrode 3) and covers the entire surface of the anode electrode 3, facing the cathode electrode 2 (facing away from the anode electrode 3)
  • the ultrafiltration membrane 5-2 covers a part of the surface of the anode electrode 3 (the entire surface of the anode electrode toward the side of the cathode electrode 2), and both ends of the ultrafiltration membrane 5-2 slightly exceed the anode electrode; 2) the water permeable membrane 5 and The pitch ⁇ of the cathode electrode 2 is 5 mm; 3)
  • the anode electrode of the anode electrode 3 and the cathode electrode 2 are made of a titanium-based platinum group oxide (coating thickness
  • the daily water electrolysis preparation device of the present embodiment is a variation based on the sixth embodiment, as shown in FIG. 10 and FIG. 11, which differs from the sixth embodiment in that: 1) the super-anode electrode 2 (reverse from the anode electrode 3)
  • the filter membrane 5-2 also covers the entire surface of the anode electrode 3 like the activated carbon fiber membrane 5-1; 2) a first through hole 8 of ⁇ 2 mm is opened on the cathode electrode 2; 3) in the water permeable membrane 5 (including activated carbon fiber)
  • the film (felt) 5-1 and the ultrafiltration membrane 5-2) have a diameter ⁇ toward one side of the cathode electrode 2 2.5mm second through hole 9.
  • the daily water electrolysis preparation device of the present embodiment is shown in FIG. 12, which is a variation based on the second embodiment.
  • the difference from the second embodiment is as follows: 1) the cathode electrode 2 and the anode electrode 3 are both wafer plane electrodes, and the size thereof Both have a diameter of 48 mm and a thickness of 1 mm; 2) the cathode electrode 2 is uniformly provided with a comb-shaped first through hole 8; 3) the water permeable membrane 5 has the following three options and settings:
  • membrane 1 Single-layer PVDF ultrafiltration membrane (numbered as membrane 1#), with an average water permeability of 0.03 ⁇ m and a thickness of 0.5 mm, without pores, close to the yin and yang electrodes.
  • the first layer adopts PVDF ultrafiltration membrane, the average permeability pore diameter is 0.03 micron, the thickness is 0.5mm, no opening, close to the anode electrode;
  • the second layer Using a 0.2 mm PVDF ultrafiltration membrane with an average permeability of 0.05 ⁇ m, the thickness is 0.5 mm, and is cut into a wafer film of the same size as the cathode electrode 2 and having a comb-shaped second through hole 9, which is closely attached to the cathode electrode;
  • the hole 9 is perpendicular to the position of the comb-shaped first through hole 8.
  • the first layer is made of activated carbon fiber cloth, the specific surface area is 1200 m 2 /g, and the thickness is about 1.8 mm after pressing with water to adhere to the anode electrode;
  • the second layer (intermediate layer) adopts PVDF ultrafiltration membrane with an average permeability of 0.03 ⁇ m and a thickness of 0.5 mm without opening.
  • the third layer adopts an average permeability pore size of 0.05 ⁇ m PVDF ultrafiltration membrane with a thickness of 0.5 mm.
  • the wafer film of the same size as the cathode electrode 2 and having the comb-shaped second through hole 9 is in close contact with the cathode electrode; the comb-shaped second through hole 9 is perpendicular to the position of the comb-shaped first through hole 8.
  • the daily water electrolysis preparation device of the present embodiment selects different water permeable membranes 5 for water electrolysis experiments as follows:
  • the volume of the water container 1 is 100 ⁇ 100 ⁇ 300 mm
  • the above-mentioned single-layer separator and combined separator were each electrolyzed for 15 minutes, and the electrolysis current was maintained at 300 mA during the electrolysis.
  • the experimental results are shown in Table 9.
  • This embodiment is a sterile water storage container, see Fig. 13.
  • the aseptic water storage container of the present embodiment has evolved from the eighth embodiment, and the changes different from the eighth embodiment are:
  • the water-permeable membrane 5 is made of a carbon fiber membrane having an average hydrophobic pore size of 150 ⁇ m, a membrane thickness of 2 mm, and a diameter D of 42 mm, and the surface is uniformly distributed with the cathode-shaped first through-hole 8 Comb-shaped second through holes 9 perpendicular to each other;
  • the anode electrode 3 is installed at the bottom of the water container 1, and the cathode electrode 2 is concentrically passed through the permeable membrane 5 and the anode electrode 3 and the bottom surface of the water container 1 via the positioning screw 10 (the outer jacket and the insulating sheath), and is also fixed.
  • the water permeable membrane 5 is pressed;
  • a plastic outer frame 11 fixed by a screw 12 is attached to the outer periphery of the anode electrode 3 for pressing the water-permeable membrane 5 covering the anode electrode 3 against the bottom surface of the water container 1 to achieve a positive
  • the bottom surface of the positive electrode 3 is in close contact with the bottom surface of the water container 1, so that the water permeable membrane 5 covers all surfaces except the bottom surface of the anode electrode 3, the cathode electrode 2, the carbon fiber membrane and the anode electrode. 3 no gap superposition combination;
  • Two equally spaced anode screws 13 are welded to the bottom surface of the anode electrode 3 and the cathode 2 positioning screw 10 at a position of 90 degrees, and the positive and negative electrodes of the externally supplied electrolytic power source are respectively connected to the positioning screw 10 and the anode screw 13.
  • the commercially available barrel of purified water is filled into the container, and the concentration of bacteria in the water of the E. coli group is about 95,000 pieces/cm 3 ; the power supply to the yin and yang electrode group is maintained, and the electrolysis is maintained. The current is 10 mA. After 25 minutes of electrolysis, the water sample is taken again, and the total number of bacteria in the container water is reduced to zero.
  • an electrolytic unit device suitable for preparing washing water see FIG. 14, is an evolution from the embodiment 9, and the variation different from the embodiment 9 is:
  • the water permeable membrane 5 is formed by superposing a two-layer membrane, and the first layer is a polysulfone ultrafiltration membrane 5-1 facing the cathode 2 (average water permeability pore diameter 0.02 ⁇ m, thickness 0.5 mm, sheared to the cathode electrode 2 The same wafer), the second layer is a PVDF ultrafiltration membrane 5-2 close to the full coverage of the anode electrode (average permeability pore diameter 0.05 ⁇ m, thickness 0.5 mm, no opening);
  • the comb-shaped first through hole 8 of the cathode electrode 2 is changed to a uniformly ⁇ 3 mm round hole; the first layer of the polysulfone ultrafiltration membrane 5-1 of the corresponding water-permeable membrane 5 is disposed concentrically with the first through hole 8
  • This embodiment provides a kitchen washing tank which employs the daily water electrolysis apparatus of the above embodiment.
  • the present embodiment provides a dishwasher which employs the daily water electrolysis apparatus of the above embodiment.
  • Example thirteen
  • the present embodiment provides a fruit and vegetable cleaning device which adopts the daily water electrolysis preparation device of the above embodiment.
  • the present embodiment provides a washing machine which employs the daily water electrolysis apparatus of the above embodiment.
  • Example fifteen
  • This embodiment provides a bathing apparatus which employs the daily water electrolysis apparatus of the above embodiment.
  • the present embodiment provides a toothbrush sterilizer which employs the daily water electrolysis apparatus of the above embodiment.
  • the present embodiment provides a nail treatment apparatus which employs the daily water electrolysis apparatus of the above embodiment.
  • the present embodiment provides a beriberi treatment apparatus which employs the daily water electrolysis preparation apparatus of the above embodiment.
  • the present embodiment provides a skin treatment apparatus which employs the daily water electrolysis apparatus of the above embodiment.
  • the present embodiment provides a skin care device which employs the daily water electrolysis preparation device of the above embodiment.
  • the present embodiment provides a portable skin care spray bottle which employs the daily water electrolysis preparation device of the above embodiment.
  • the present embodiment provides a medical sausage filling machine which employs the daily water electrolysis preparation device of the above embodiment.
  • the present embodiment provides an air humidifier which employs the daily water electrolysis apparatus of the above embodiment.
  • the daily water electrolysis preparation device of the present invention is not limited to the specific technical solutions described in the above embodiments, for example: 1) the anode electrode 3 and the cathode electrode 2 may also be two pairs; 2) the electrolysis power source 4 may also be an AC pulse power source.
  • the water permeable membrane 4 may also be a stack of three or more layers of different materials; 4) the shape of the cathode electrode 2 and the anode electrode 3 may also be other shapes other than a circle and a square;
  • the activated carbon fiber membrane 5-1 near the anode electrode 3 may be, or a water-permeable membrane made of graphite or other carbon material; 6) the technical solutions of the above various embodiments of the present invention may be Cross-combination forms new technical solutions; and so on. All technical solutions formed by equivalent replacement are the scope of protection required by the present invention.

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Abstract

一种日常用水电解制取装置,属于水电解设备技术领域。该装置包括盛水容器(1)、设于盛水容器内的至少一对阴电极(2)和阳电极(3)、用于对阴电极(2)和阳电极(3)供电的电解电源(4);成对的阴电极(2)和阳电极(3)之间设有透水性隔膜(5),所述透水性隔膜(5)的透水孔径小于等于2毫米且大于等于1纳米。该装置对水电解时可低耗、高效的生成大量安全可用的氧化因子并可以有效调节水中氧化因子,从而强化对水中污染物的洗涤清除效果。

Description

日常用水电解制取装置 技术领域
本发明涉及一种水电解装置,属于水电解设备技术领域,不属于污水处理技术领域。
背景技术
现实中,日常用水(不含污水)尤其是生活用水所受污染越来越严重。现有以介质吸附或采用各种孔径的过滤膜将水中的有害物加以拦截滤除的物理方式处理工艺,由于吸附材料很容易饱和失效,而各种过滤膜又很容易被细菌污染或有机物阻塞或破损,实际情况是并不能达到理论设计所期望的水质净化效果,甚至连细菌超标问题都难以解决,有必要引入新的水质强效净化技术。另一方面,伴随社会的进步,人们也对日常用水提出一些功能性需求。例如,期望能够增强水的洗涤能力、清除被洗涤物中的污物、以节能减排,等等。针对上述对日常用水的需求,比较适宜的是水体等离子放电技术。
等离子体是由大量自由电子和离子组成、且在整体上表现为电中性的物质第四态。所谓水体等离子放电技术,乃是通过适当方式诱发水中放电,促使水分子发生电离与激发。水体等离子放电技术具体形式有多种变化,共同特征是,水中存在大量气泡,以及生成大量强氧化因子(·OH、·H、H2O2、游离氧、臭氧等等);显然对洗涤而言,水中的超微气泡可深度渗透到洗涤物内部将污垢冲洗剥落;而强氧化因子可将水体中的各种污染物高效降解。然而,现有水体等离子放电技术存在初始激发电压较高、电极侵蚀较严重、能耗过高等不足,尚难以在日常用水尤其是生活用水中应用。
中国专利1(ZL200480007381.0)公示了一种以所谓“虚拟网孔点”水中放电方法制取离子化杀菌水的技术与装置,对于水体等离子放电技术用于日常生活用水作了十分有益的尝试。然而,该技术不仅受放电机理及实际制造工艺限制(阴阳电极间距不能保持很小)效率难以提高,尤其是不能根据日常用水不同场合的具体用水需求,对水中放电生成的强氧化因子类型及数量做相应调整;故应用范围有限。
至于污水处理中通过电解生成强氧化因子的技术,由于污水与日常用水在水质上差距甚大,且污水电解处理属于高能耗工业技术,因此与日常用水电解的民用技术完全不同。
发明内容
通过上述背景技术的描述可以知道,现有水处理技术只针对单一需求而且也难以达到,目前尚没有一种可以同时满足人们对日常用水的安全和功能性需求的水处理装置。在日常用水领域,需要寻求一种低功耗、高效和用水安全的微放电水体冷等离子体发生,同时能将产生的冷等离子体充分均匀释放而达到与水充分反应的技术或装置;或者说,需要一种 可以低功耗、高效产生大量安全可用氧化因子的水处理装置,以便根据人们对日常用水的安全或功能性的不同需求,制取出去污力强适宜洗涤的水或具有一定杀菌能力的水。
因此,本发明要解决的技术问题是:提出一种能够低功耗和高效电解产生大量安全可用氧化因子,从而制取出去污力强适宜洗涤的水或具有一定杀菌能力的水的装置。
为了解决上述技术问题,本发明申请公开的技术方案是:一种日常用水电解制取装置,包括盛水容器、设于盛水容器内的至少一对阴电极和阳电极、用于对阴电极和阳电极供电的电解电源;成对的阴电极和阳电极之间设有透水性隔膜,所述透水性隔膜的透水孔径小于等于2毫米且大于等于1纳米。
上述技术方案中所述透水性隔膜也叫透水膜或透水性隔离膜,是指可以穿透水分子的隔膜,其透水孔径从毫米级到纳米级(本发明限定透水孔径范围是2毫米-1纳米)的透水隔膜,包括日常水处理使用的各种过滤膜,如:超滤膜(UF)、纳滤膜(NF)和微滤膜(MF),等。
上述本发明公开的日常用水电解制取装置技术方案的工作机理及有益效果陈述如下。
本发明装置中所述透水性隔膜并非常规采用的离子膜,而是在水电解领域中从未用过的的一种隔膜,本发明人创新地将透水性隔膜引入水电解装置中作为阴、阳电极间的隔膜。由此我们认为本发明的日常用水电解制取装置在工作时的反应过程除了常规电解反应过程以外,产生了一个新的重要反应过程,即水体低压冷等离子放电反应过程。具体分析如下:
1、电极尖端直径曲率与透水膜孔隙直径的等效模型
在水体放电中,诱发水中等离子体产生往往需要给予一个激发的初始高电压,影响初始电压主要因素之一即为放电电极的参数。在同等条件下电极材质、放电间距、电极直径(电极曲率半径)对初始激发电压都有影响。随着电极直径的减小,起始激发电压降低。从另一个角度说,在外加相同电压条件下,电极直径越小越有利于增强离子体通道中自由基产生的剧烈程度。在本发明中,阴阳电极之间有一层透水性隔膜,隔膜拥有无数个透水直径很小(毫米级乃至纳米级)的孔隙,从宏观看可视为将大范围电极的水中放电反应等效分解为无数个极小曲率半径电极的尖端放电。进而极大的降低了激发等离子体反应的初始电压。
水中电解时会生成大量超微气泡,其中有氢气泡也有氧气泡。而气泡的局部放电能大大增加反应活性分子的生成并且易于产生羟基等自由基,从而提高水中放电的反应效率。但是在气泡中产生放电需要气泡中的场强高于水中,要求整体电场较均匀;在本发明中,透水膜将阴阳两组大电极分解为无数组子电极,但是所有子电极的材质、电压均相同。这就保证在宏观领域整体电场均匀排布,电解所产生的气泡在上升过程中所受电场较均匀, 保证了放电反应的高效率。
2、增大接触面积,提高水中反应效率
众所周知,总体积相同的同等物体,被分成的个体越多总体的比表面积越大。同理,本发明与不加透水隔膜的对电极放电情况对比,在产生等量气体的情况下,在无数个超微孔隙内水电解所产生的微气泡体积远远小于同等面积不加透水隔膜对电极电解所产生的气泡体积,而气泡数量也远远多于它。这就有效增加了气液两相接触的比表面积。而我们知道,等离子体次生成的各种氧化因子(如:羟基)主要发生在气液两相的接触面。也就是说:气液两相的接触面积越大,氧化因子的生成越多和反应越充分,水中有机物的降解、微生物杀菌效果更加优良,更进一步提高了水中放电反应的最终效率。
传统的水体等离子放电技术,为产生水体等离子放电,往往通过外部向水中导入气体,并施以加高强度脉冲电压或高温条件。本发明则创新将等离子放电引导到透水性隔膜的无数微小蓄水空间进行,依靠对水电解析氢、析氧反应生成的气体,进入膜中诱发水体自身气化,进而以极小电压激发出高效的水体等离子放电,其意义不仅在于效率的提高,还有效防止了因电流密度过大易导致生物性指标的恶化。
本发明装置中,如果透水性隔膜透水孔径过大(即微孔空间过大)等效于变相增大了电极直径(电极曲率半径)致使水中放电起始激发电压增高,并且使产生气泡体积变大减小了气液两相接触反应的比表面积。而透水性隔膜透水孔径过小(即微孔空间过小),会使电解产气无法发生或是产气效率极其低下,小到一定程度会导致隔膜内各微孔中无数个小曲率半径电极的尖端放电无法正常进行。因此,经过发明人的反复试验,确定透水孔径范围是2毫米-1纳米。
概括上述本发明的日常用水电解制取装置技术方案的有益效果是:本发明通过将具有一定孔径的透水性隔膜设置在阴、阳极之间,在常规电解反应过程以外带来了在透水性隔膜内微孔中形成水体低压冷等离子放电反应,从而可以高效的在水中生成具杀菌能力的暂态氧化因子。具体实用效果是:水中氧化因子可强化对水中污染物的洗涤清除效果,同时满足用户对于用水安全和功能性等多方面需求。
本发明在上述技术方案基础上的改进是:所述阴电极和阳电极的间距大于等于所述透水性隔膜的厚度且小于等于20毫米。
本发明装置中,同等电压情况下,阴阳电极间的距离越小(极端情况下阴阳电极间的距离=膜的厚度)水中电场强度越大,电极间的等离子通道更易形成,冷等离子体产生效率更高,生成的氧化因子越多。而且膜可以很薄(例如超滤膜可做到0.1mm~0.3mm),同等工況下的电解电压可以很低,甚至仅仅以一块3.7V锂电池供电,可以形成2安培以上的工 作电流,现有技术是无法做到的。反之,拉大阴阳电极间的距离,生成的氧化因子相应减少,尤其是臭氧类强氧化剂的生成几率下降了。我们知道,臭氧大量产生于氧气以气泡形式通过放电区域。阴阳电极间距离增大,阳极析出氧气进入处于等离子放电状态的膜中的几率减少,对比而言臭氧就减少了。水中所生成的氧化因子,更多地表现为羟基类暂态氧化因子。这在某些用水场合(例如美容用水)恰恰是所需的。但是间距过大又带来效率的降低,甚至膜中放电过程无法进行。因此,经过发明人的反复试验,日常生活用水阴电极和阳电极的间距大于等于所述透水性隔膜的厚度且小于等于20毫米为最佳。
本发明在上述技术方案基础上的进一步改进是:所述透水性隔膜是非导电性的透水性隔膜。这是因为,多数情况下,希望水中产生的氧化因子越多越好。导电性较好的透水性隔膜在放电反应时容易与相近的电极形成复合电极而影响水中放电反应的效果和生成物的种类,不可控因素较多,因此优选非导电性的透水性隔膜。
上述本发明技术方案的更进一步改进是:所述阴电极上开有第一通孔,所述第一通孔的孔径大于等于1毫米。通过这样的改进,可以有利于阴极反应更充分进行,并将阴电极与隔膜之间区域产生的氢气泡更好导出。
上述本发明技术方案的再进一步改进是:所述透水性隔膜开有第二通孔,所述第二通孔的孔径大于2毫米。通过这样的改进可以有利于产生的气泡更好的导出,尤其是在阴阳电极与透水性隔膜间距较小时其气泡导出效果更好。第二通孔与透水性隔膜的透水孔区别在于:透水孔是采购的隔膜自身固有的,第二通孔则是另外单独制作的。
在某些用水场合希望水中生成的氧化因子中,过氧化氢的成分能多一些,则可选用碳质材料膜(例如具有一定导电性的活性炭纤维布)。此时碳质隔膜等效于一个中间电极,靠阳极侧等效于中间阴极(而碳质隔膜与阴极间则等效于一个活性炭阳极-金属阴极对),基于活性炭阴极Fenton反应生成较多的H2O2;进一步地,我们可以通过两层以上不同性状隔膜的优化组合,控制水中氧化因子的生成情况,即可以有效调节和控制氧化因子生成量。因此,上述本发明技术方案完善一是:所述透水性隔膜是单层透水性隔膜或者是多层透水性隔膜。其中透水性隔膜的具体选择是:所述单层透水性隔膜是超滤膜或采用碳质材料制成的单层透水性隔膜。
上述本发明技术方案的完善二是:所述电解电源是高电平窄脉宽的直流或交变脉冲电源。采用高电平窄脉宽的脉冲电源更加有利于阴阳电极间水体内部的等离子放电,得到更好的制水效果。
作为上述本发明技术方案的应用拓展之一是:本发明提出一种厨房清洗水槽,该厨房清洗水槽含有上述本发明技术方案。
作为上述本发明技术方案的应用拓展之二是:本发明提出一种洗碗机,该洗碗机含有上述本发明技术方案。
作为上述本发明技术方案的应用拓展之三是:本发明提出一种果蔬清洗装置,该果蔬清洗装置含有上述本发明技术方案。
作为上述本发明技术方案的应用拓展之四是:本发明提出一种洗衣机,该洗衣机含有上述本发明技术方案。
作为上述本发明技术方案的应用拓展之五是:本发明提出一种洗浴装置,该洗浴装置含有上述本发明技术方案。
作为上述本发明技术方案的应用拓展之六是:本发明提出一种牙刷消毒器,该牙刷消毒器含有上述本发明技术方案。
作为上述本发明技术方案的应用拓展之七是:本发明提出一种指甲治疗仪或脚气治疗仪,该指甲治疗仪或脚气治疗仪含有上述本发明技术方案。
作为上述本发明技术方案的应用拓展之八是:本发明提出一种皮肤治疗仪、皮肤护理装置或便携式皮肤护理喷瓶,该皮肤治疗仪、皮肤护理装置或便携式皮肤护理喷瓶含有上述本发明技术方案。
作为上述本发明技术方案的应用拓展之九是:本发明提出一种医用灌肠机,该医用灌肠机含有上述本发明技术方案。
作为上述本发明技术方案的应用拓展之十是:本发明提出一种空气加湿器,该空气加湿器含有上述本发明技术方案。
附图说明
下面结合附图对本发明的日常用水电解制取装置作进一步说明。
图1是本发明实施例一日常用水电解制取装置的结构示意图。
图2是本发明实施例二日常用水电解制取装置的结构示意图。
图3是本发明实施例三日常用水电解制取装置的结构示意图。
图4是本发明实施例四日常用水电解制取装置的结构示意图。
图5是图4中A处的局部放大图。
图6是本发明实施例五日常用水电解制取装置的结构示意图。
图7是图6中B处的局部放大图。
图8是本发明实施例六日常用水电解制取装置的结构示意图。
图9是图8中C处的局部放大图。
图10是本发明实施例七日常用水电解制取装置的结构示意图。
图11是图8中D处的局部放大图
图12是本发明实施例八日常用水电解制取装置的结构示意图。
图13是本发明实施例九日常用水电解制取装置的结构示意图。
图14是本发明实施例十日常用水电解制取装置的结构示意图。
具体实施方式
实施例一
本实施例的日常用水电解制取装置参见图1,包括盛水容器1、设于盛水容器1内的一对阴电极2和阳电极3、用于对阴电极2和阳电极3供电的电解电源4;本实施例的盛水容器1为敞开式容器。在一对阴电极2和阳电极3之间设有透水性隔膜5,本实施例的透水性隔膜5采用平均透水孔径0.03微米的单层PVDF超滤膜(聚偏二氟乙烯膜);当然本实施例的超滤膜也可以采用其他材质的超滤膜,平均透水孔径在0.01~0.05微米之间均可。
透水性隔膜5与阴、阳电极的间距δ都是1mm,而且隔膜5两端分别超出阴、阳电极一小段。
本实施例的阴电极2和阳电极3均采用钛基覆涂铂族氧化物(涂层厚度为0.8毫米)制成的惰性电极,阴电极2呈圆形片状,阳电极3呈长方形片状。阴电极和阳电极的表面均不开孔。
本实施例的电解电源4采用高电平窄脉宽稳压30伏的直流脉冲电源,也可以采用交变脉冲电源。
本实施例的阴电极2和阳电极3在盛水容器1内的水中平行放置,阴电极2位于阳电极3的上方。
一、实验1
采用本实施例的日常用水电解装置进行水电解实验,盛水容器容积为200×80×120毫米,源水是RO纯水机的出水,TDS=3mg/L,盛水容器注水约1.5升,电解时间为30分钟,每5分钟取水样测定一次。
以下实验中,水中气泡量(强度)以及水中氧化因子多少采用定性观测方法
①水中气泡量(强度)的目测分级:
从水中气泡为零~实验中相对气泡含量最大,分为0~5级;
②水中氧化因子的测定
如前所述,由于氧化因子在水中存留时间极为短暂,现有的检测方法(例如化学反应法和捕获法)的分析选择性和可信度还难以令人满意。同时考虑到本发明装置系专用于日常用水的处理,侧重关心的是氧化因子的变化趋势级宏观作用。因此为简化重复实验工作 量,专门研发了定性了解水中氧化因子总量的滴定液。通过自制滴定液滴定到水中后,观察水体颜色的变黄程度,分为5级,定性判定水中氧化因子含量:
无色——对应水中氧化因子基本为零,设为0级;
颜色最黄——对应水中氧化因子相对最多,设为5级;
从无色到颜色最黄中间颜色变化的程度不同分设为1、2、3和4级。
实验1结果如下表1:
表1
Figure PCTCN2015076247-appb-000001
实验结果分析
随电解时间的增加,水中氧化因子量均呈正比例增长。
二、实验2
无膜/离子膜/透水性膜的对比
将本实施例的透水性隔膜5与拿掉透水性隔膜5或更换为离子膜的三种情况分别进行水电解,对比实验条件是:
1)拿掉阴极2与阳极3之间的透水性隔膜5,使阴极2与阳极3之间形成无隔膜状态,阴极2与阳极3之间的间距为2.0毫米(用绝缘垫圈定位,保持间距不变);
2)透水性隔膜5改成中性离子膜,膜5与阴阳极间距δ分别是1毫米;
3)本实施例采用PVDF超滤膜的透水性隔膜5;
4)实验源水为市售RO纯水机的出水,TDS=3mg/L,pH=6.8,向容器注入水约1升。
保持三种情况下电解电流均为300毫安,电解15分钟,实验2结果示于表2。
表2
Figure PCTCN2015076247-appb-000002
Figure PCTCN2015076247-appb-000003
三、实验3
测验阴极与透水性隔膜之间间距δ范围变化对装置工作特性的影响
将本实施例的阴极2与透水性隔膜5之间的间距δ分别调整为:δ=10、7、4、1、0毫米五种情况。其他实验条件与上述实验2相同,实验3结果示于表3。
表3
Figure PCTCN2015076247-appb-000004
实施例二
本实施例的日常用水电解装置与实施例一基本相同,如图2所示,与实施例一不同的变化是:1)疏水性隔膜5同时紧贴在阴电极2和阳电极3上,隔膜5与阴阳极的间距为0;2)隔膜5两端分别超出阴、阳电极更长的一段。
将本实施例的日常用水电解装置进行水电解实验,源水为市供自来水,ORP=+320mv,pH=7.1,TDS=48mg/L,电解时间为20分钟,每5分钟取水样测定一次。其他实验条件和检测方法与实施例一相同,实验结果如下表4:
表4
Figure PCTCN2015076247-appb-000005
实施例三
本实施例的日常用水电解制取装置与实施例一基本相同,如图3所示,与实施例一不同的变化是:1)盛水容器1为封闭式容器,设有进水口6和出水口7;2)阳电极3是采用石墨、活性炭等碳质材料制成的惰性电极;3)透水性隔膜是采用石墨、活性炭等碳质材料制成的单层透水性隔膜;4)透水性隔膜5与阳电极3的间距δ1是8mm;5)透水性隔膜5与阴电极2的间距δ2是0.5mm。
将本实施例的日常用水电解装置进行水电解实验,实验条件和检测方法与实施例二相同。增加一项双氧水的测定,选用市面上常用的双氧水快速检测试剂,通过将速测试剂滴定到水中后,观察水体颜色的变黄程度,分为5级,定性判定水中过氧化氢的含量:
无色——对应水中过氧化氢基本为零,设为0级;
颜色呈桔黄——对应水中过氧化氢相对最多,设为5级;
从无色到颜色最黄中间颜色变化的程度不同分设为1、2、3和4级。
实验结果如下表5:
表5
Figure PCTCN2015076247-appb-000006
实验结果分析
选用碳质材料做隔膜后,随电解时间的增加,水中氧化因子量均呈正比例增长,水中的过氧化氢的含量也在逐级增高比源水增加很多。
实施例四
本实施例的日常用水电解制取装置与实施例二基本相同,如图4和图5所示,与实施例二不同的变化是:1)在阴电极2上开有第一通孔8,通孔孔径取1mm;2)透水性隔膜5 与阴电极2、阳电极3同长;3)透水性隔膜5紧贴阳电极3但与阴电极2分离,透水性隔膜5与阴电极2的间距δ是2mm。
将本实施例的日常用水电解制取装置进行水电解实验,本实施例在阴电极上均布开有24个直径φ3mm的第一通孔,电解时间20分钟,其他实验条件和检测方法与实施例一相同,实验结果如下表6:
表6
Figure PCTCN2015076247-appb-000007
实施例五
本实施例的日常用水电解制取装置与实施例四基本相同,如图6和图7所示,与实施例四的变化是:1)透水性隔膜5开有直径φ2.1mm的第二通孔9,第二通孔9与第一通孔8数量相同且基本同心对齐;2)透水性隔膜5与阴电极2的间距δ是3mm。
将本实施例的日常用水电解制取装置进行水电解实验,电解时间20分钟,其他实验条件和检测方法与实施例四相同,实验结果如下表7:
表7
Figure PCTCN2015076247-appb-000008
实施例六
本实施例如图8和图9所示,是在实施例三基础上演变而来,不同的变化是:1)透水性隔膜5是由活性炭纤维膜(毡)5-1和超滤膜叠5-2加复合而成的二层透水性隔膜,活性炭纤维膜5-1靠近阳电极3(朝向阳电极3)并且包覆阳电极3的全部表面,朝向阴电极2(背离阳电极3)的超滤膜5-2包覆阳电极3的部分表面(阳电极朝向阴电极2一侧的全部表面),并且超滤膜5-2的两端略微超出阳电极;2)透水性隔膜5与阴电极2的间距δ是5mm;3)阳电极3与阴电极2相同的采用钛基覆涂铂族氧化物(涂层厚度为0.8毫米)制成的惰性电极,呈圆形片状。
实施例七
本实施例的日常用水电解制取装置是实施例六基础上的变化,如图10和图11所示,与实施例六不同的是:1)朝向阴电极2(背离阳电极3)的超滤膜5-2也和活性炭纤维膜5-1一样包覆阳电极3的全部表面;2)在阴电极2上开有φ2mm第一通孔8;3)在透水性隔膜5(包括活性炭纤维膜(毡)5-1和超滤膜5-2)朝向阴电极2的一侧面上开有直径φ 2.5mm的第二通孔9。
实施例八
本实施例的日常用水电解制取装置如图12所示,是实施例二基础上的变化,与实施例二不同的是:1)阴电极2和阳电极3均为圆片平面电极,尺寸均为直径48毫米,厚度1毫米;2)阴电极2均布开有梳状第一通孔8;3)透水性隔膜5有以下三种选择和设置:
①单层PVDF超滤膜(编号为膜1#),平均透水孔径0.03微米,厚度为0.5mm,不开孔,紧贴阴阳电极。
②两层膜叠加组合(编号为膜2#+膜1#):第一层采用PVDF超滤膜,平均透水孔径0.03微米,厚度为0.5mm,不开孔,紧贴阳电极;第二层采用平均透水孔径0.05微米PVDF超滤膜片,厚度0.5mm,剪切成与阴电极2相同尺寸并开有梳状第二通孔9的圆片膜,紧贴阴电极;梳状第二通孔9与梳状第一通孔8位置方向相垂直。
③三层膜叠加组合(编号为膜3#+膜2#+膜1#):第一层采用活性炭纤维布,比表面积1200m2/g,浸水紧压后厚度约1.8毫米紧贴阳电极;第二层(中间层)采用PVDF超滤膜,平均透水孔径0.03微米,厚度为0.5mm,不开孔;第三层采用平均透水孔径0.05微米PVDF超滤膜片,厚度0.5mm,剪切成与阴电极2相同尺寸并开有梳状第二通孔9的圆片膜,紧贴阴电极;梳状第二通孔9与梳状第一通孔8位置方向相垂直。
关于透水性隔膜单层或多层组合对本实施例装置工作特性的影响的实验
本实施例的日常用水电解制取装置分别选择不同透水性隔膜5进行水电解实验如下:
1、实验条件
1.1盛水容器1的容积为100×100×300毫米
1.2电解电源4,采用直流稳压电源;
1.3其他实验条件和检测方法与实施例一相同。
源水为市供自来水,TDS=160mg/L,pH=7.5,向容器注入水约1升。分别以上述单层隔膜及组合隔膜,各电解15分钟,电解过程中电解电流均保持为300毫安,实验结果示于表9。
表9
Figure PCTCN2015076247-appb-000009
Figure PCTCN2015076247-appb-000010
实施例九
本实施例是一种无菌蓄水容器,参见图13。本实施例的无菌蓄水容器是从实施例八进行演变而来,与实施例八不同的变化是:
1)透水性隔膜5采用碳纤维制成的膜片,平均疏水孔径为150微米,膜片厚2毫米,直径D=42毫米,表面均布开有与阴电极梳状第一通孔8位置方向相互垂直的梳状第二通孔9;
2)阳电极3安装在盛水容器1底部,阴电极2经定位螺杆10(外套加绝缘护套)同心穿过透水性隔膜5和阳电极3与盛水容器1底面后固定,同时也将透水性隔膜5压紧;
3)在阳电极3外周边加有一个用螺杆12固定的的塑料外框11,用于将覆盖在阳电极3上的透水性隔膜5压紧在盛水容器1底面,以做到对阳电极3的可靠包覆,本实施例阳电极3的底面紧贴盛水容器1底面,因此透水性隔膜5包覆阳电极3除了底面以外的全部表面,阴电极2、碳纤维膜片和阳电极3无间隙叠加组合;
4)在阳电极3底面与阴极2定位螺杆10相对90度位置焊接有两个均分的阳极螺杆13,外部供电电解电源的正负极引线分别连接到定位螺杆10和阳极螺杆13上。
为检验本实施例装置的灭菌效果,将市售桶装纯净水注满容器,并加入大肠杆菌群取样检测容器水中细菌浓度约达9.5万个/cm3;对阴阳电极组供电,维持电解电流为10毫安,电解25分钟后再次取水样检测结果,容器水中细菌总数降为零。
实施例十
本实施例一种适宜制取洗涤用水的电解单元装置,参见图14,是从实施例九进行演变而来,与实施例九不同的变化是:
1)透水性隔膜5由二层膜叠加组合而成,第一层是朝向阴极2的聚砜超滤膜片5-1(平均透水孔径0.02微米,厚度0.5mm,剪切成与阴电极2相同圆片),第二层是紧贴全覆盖阳电极的PVDF超滤膜5-2(平均透水孔径0.05微米,厚度为0.5mm,不开孔);
2)阴电极2的梳状第一通孔8改为均布的φ3mm圆孔;相应的透水性隔膜5的第一层聚砜超滤膜片5-1设置与第一通孔8同心大小的圆形第二通孔9。
为检验本实施例单元装置的制水效果,进行了如下试验:
1)将本实施例装置固定在一塑料容器底部(阴极朝上),注入市供自来水约20升;
2)按国标GB-T 4288-2003家用电动洗衣机中附录A方法,分别制备出A、B双份、三 种污染样布(炭黑油污染布,蛋白污染布,皮脂污染布);
3)分别将上述三种污染样布放入容器内,经外部直流稳压电源对实施例装置提供12V的电解电压,电解20分钟,分别电解三次。实测各电解期间电解电流约在2~8A范围变化;
4)停止电解后,用手搓洗上述经电解浸泡的三种污染样布各5分钟,之后用清水漂净;漂洗后的三种样布标注为:“炭黑样布A”,“蛋白样布A”,“皮脂样布A”;
5)另外,使用一台市售mini洗衣机(小鸭牌),注入市供自来水约20升,加入洗衣粉,按标准洗涤程序,分别洗涤三种污染样布各20分钟,漂洗甩干后,标注三种样布为:“炭黑样布B”,“蛋白样布B”,“皮脂样布B”;
6)目测对比两种方法的洗净程度,结果证明,经本发明装置清洗的三种A类污染样布,洗净程度均明显高于洗衣粉机洗方式的B类污染样布。若设洗衣机机洗后的B类样布洗净度为1,则A、B两种洗涤效果对比约为1.5:1。
上述实验结果表明,经本发明装置处理后的水,洗涤能力大为提高。
实施例十一
本实施例是提供一种厨房清洗水槽,该水槽采用了上述实施例的日常用水电解制取装置。
实施例十二
本实施例是提供一种洗碗机,该洗碗机采用了上述实施例的日常用水电解制取装置。实施例十三
本实施例是提供一种果蔬清洗装置,该果蔬清洗装置采用了上述实施例的日常用水电解制取装置。
实施例十四
本实施例是提供一种洗衣机,该洗衣机采用了上述实施例的日常用水电解制取装置。实施例十五
本实施例是提供一种洗浴装置,该洗浴装置采用了上述实施例的日常用水电解制取装置。
实施例十六
本实施例是提供一种牙刷消毒器,该牙刷消毒器采用了上述实施例的日常用水电解制取装置。
实施例十七
本实施例是提供一种指甲治疗仪,该指甲治疗仪采用了上述实施例的日常用水电解制取装置。
实施例十八
本实施例是提供一种脚气治疗仪,该脚气治疗仪采用了上述实施例的日常用水电解制取装置。
实施例十九
本实施例是提供一种皮肤治疗仪,该皮肤治疗仪采用了上述实施例的日常用水电解制取装置。
实施例二十
本实施例是提供一种皮肤护理装置,该皮肤护理装置采用了上述实施例的日常用水电解制取装置。
实施例二十一
本实施例是提供一种便携式皮肤护理喷瓶,该便携式皮肤护理喷瓶采用了上述实施例的日常用水电解制取装置。
实施例二十二
本实施例是提供一种医用灌肠机,该医用灌肠机采用了上述实施例的日常用水电解制取装置。
实施例二十三
本实施例是提供一种空气加湿器,该空气加湿器采用了上述实施例的日常用水电解制取装置。
本发明的日常用水电解制取装置不局限于上述实施例所述的具体技术方案,比如:1)阳电极3和阴电极2也可以是二对;2)电解电源4也可以是交流脉冲电源;3)透水性隔膜4也可以是三层或更多层不同材质的隔膜叠加而成;4)阴电极2和阳电极3的形状也可以是除了圆形和方形的其他各种形状;5)实施例六中,靠近阳电极3的活性炭纤维膜5-1也可以是,或者是由石墨或其他碳材料制成的透水性隔膜;6)本发明的上述各个实施例的技术方案彼此可以交叉组合形成新的技术方案;等等。凡采用等同替换形成的技术方案均为本发明要求的保护范围。

Claims (10)

  1. 一种日常用水电解制取装置,包括盛水容器、设于盛水容器内的至少一对阴电极和阳电极、用于对阴电极和阳电极供电的电解电源;其特征在于:成对的阴电极和阳电极之间设有透水性隔膜,所述透水性隔膜的透水孔径小于等于2毫米且大于等于1纳米。
  2. 根据权利要求1所述日常用水电解制取装置,其特征在于:所述阴电极和阳电极的间距大于等于所述透水性隔膜的厚度且小于等于20毫米。
  3. 根据权利要求1所述日常用水电解制取装置,其特征在于:所述透水性隔膜是非导电性的透水性隔膜。
  4. 根据权利要求2所述日常用水电解制取装置,其特征在于:所述透水性隔膜是非导电性的透水性隔膜。
  5. 根据权利要求4所述日常用水电解制取装置,其特征在于:所述阴电极上开有第一通孔,所述第一通孔的孔径大于等于1毫米。
  6. 根据权利要求4所述日常用水电解制取装置,其特征在于:所述透水性隔膜开有第二通孔,所述第二通孔的孔径大于2毫米。
  7. 根据权利要求4所述日常用水电解制取装置,其特征在于:所述透水性隔膜是单层透水性隔膜。
  8. 根据权利要求4所述日常用水电解制取装置,其特征在于:所述透水性隔膜是多层透水性隔膜。
  9. 根据权利要求7所述日常用水电解制取装置,其特征在于:所述单层透水性隔膜是超滤膜或采用碳质材料制成的单层透水性隔膜。
  10. 根据权利要求4所述日常用水电解制取装置,其特征在于:所述电解电源是高电平窄脉宽的直流或交变脉冲电源。
PCT/CN2015/076247 2014-04-12 2015-04-10 日常用水电解制取装置 WO2015154714A1 (zh)

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