WO2015154706A1 - Dispositif d'épuration auxiliaire pour épurateur d'eau - Google Patents

Dispositif d'épuration auxiliaire pour épurateur d'eau Download PDF

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Publication number
WO2015154706A1
WO2015154706A1 PCT/CN2015/076239 CN2015076239W WO2015154706A1 WO 2015154706 A1 WO2015154706 A1 WO 2015154706A1 CN 2015076239 W CN2015076239 W CN 2015076239W WO 2015154706 A1 WO2015154706 A1 WO 2015154706A1
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Prior art keywords
water
permeable membrane
water purifier
anode electrode
cathode
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PCT/CN2015/076239
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English (en)
Chinese (zh)
Inventor
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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Publication of WO2015154706A1 publication Critical patent/WO2015154706A1/fr

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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

Definitions

  • the invention relates to a water purifier auxiliary purification device, belonging to the technical field of water electrolysis equipment.
  • the residual chlorine in the water interacts with residual organic matter, which may generate new harmful substances (such as strong carcinogen chloroform, etc.) that are not in the source water.
  • new harmful substances such as strong carcinogen chloroform, etc.
  • the toxic by-products caused by the above residual chlorine cannot be removed by a simple method such as boiling water.
  • the existing water purifiers on the market that deal with the “faucet water” are all physical treatment processes that use media to adsorb or use harmful membranes of various pore sizes to intercept and filter harmful substances in the water. Since the activated carbon-based adsorbent material is easily saturated and the various filter membranes are easily contaminated by bacteria or blocked or damaged by organic matter, the actual situation is not sufficient to purify the pollutants in the water as expected by the theoretical design. However, the physical water treatment process also has the advantage that no toxic by-products are formed. In contrast, although the chemical water treatment process has many advantages such as being cheap, simple, and efficient, it has not been widely used in daily water treatment. The reason is that the chemical water treatment process requires sufficient reaction time.
  • the water purifier In daily water use, the water purifier is only a few seconds from the start-up to the effluent. The residence time of the pollutants in the water purifier is too short to complete the relevant chemical reaction treatment.
  • the chemical water treatment process may be accompanied by certain The toxic side effects.
  • the chemical oxidation reaction process can strongly inactivate bacteria, deeply degrade organic matter, and remove various harmful substances in water, the various strong oxidation factors generated by chemical oxidation are basically non-selective and uncontrollable. Improperly, it is very likely to produce new substances that are not in the source water, which in turn jeopardizes the safety of drinking water. Because of this, in the daily life of drinking water purification treatment, the application of chemical water treatment process can be said to be cautious.
  • the technical problem to be solved by the invention is to propose a water purifier auxiliary device with better sterilizing ability, which can extract water rich in hydrogen and low in oxidation-reduction potential suitable for human drinking.
  • a water purifier auxiliary purification device comprising a water container provided with a water inlet, the water inlet being connected with the water purifier; characterized in that: The housing of the water container is provided with a cathode electrode and an anode electrode, and further comprises an electrolytic power source for supplying power to the cathode electrode and the anode electrode; a water permeable membrane is disposed between the pair of cathode electrodes and the anode electrode, and the water permeability
  • the separator covers the anode electrode, and the distance ⁇ between the water-permeable membrane and the cathode electrode ranges from 0 ⁇ ⁇ ⁇ 10 mm, and the water-permeable membrane of the water-permeable membrane has a water-permeable pore diameter of 2 mm or more and 1 nm or more.
  • the water permeable membrane of the present invention is also called a water permeable membrane, and refers to a water permeability pore diameter ranging from millimeters to nanometers, including various filtration membranes used in daily water treatment, such as ultrafiltration membrane (UF), nanofiltration membrane (NF) and microfiltration. Filter membrane (MF), etc.
  • UF ultrafiltration membrane
  • NF nanofiltration membrane
  • MF Filter membrane
  • the water permeable membrane is covered on the anode electrode, which means that the water permeable membrane and the anode electrode are substantially zero-pitch.
  • 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 the permeable membrane into a water electrolysis apparatus as a yin. , a separator between the anode electrodes.
  • the normal reaction to water electrolysis is that the cathode hydrogen evolution (gas), the anodic oxygen evolution (gas), the H + ions tend to the cathode region, and the OH - ions tend to the anode region.
  • a water permeable membrane is disposed between the anode and the cathode, and the electrolytic cell is divided into two reaction spaces of a cathode chamber and an anode chamber.
  • the distance ⁇ between the water-permeable membrane and the cathode electrode is greater than zero, that is, the volume of the cathode chamber is greater than zero, the hydrogen evolution reaction of the cathode proceeds normally, hydrogen gas is generated, and the oxidation-reduction potential of the cathode chamber and the entire container water is decreased.
  • the innumerable micropore storage space of the diaphragm is equivalent to one micro water resistance in parallel in the electrolysis current path of the cathode and the anode electrode. Because the distance ⁇ between the cathode electrode and the membrane is small, the water resistance drop of the cathode chamber can be neglected, and the external electrolytic voltage mainly acts on the water-permeable membrane, and the unit voltage intensity in each micropore is extremely high.
  • the water-permeable pore size of the water-permeable separator is small (micron or nanometer), and the high-energy electrons released from the cathode are dense in the micropores, which is equivalent to decomposing a large discharge electrode (cathode) into an infinite number of small radii of curvature. electrode. Therefore, not only the electrolytic oxidation-reduction reaction of water in the micropores of the water-permeable membrane can be sufficiently performed, and O 2 migrated from the anode to the pores of the membrane is bombarded by high-energy electrons and a strong electric field generates oxygen bubbles, and stimulates a chain reaction to induce a water body. Self-gasification, forming a continuous and stable plasma discharge in the micropores, generating a large number of oxidation factors, and finally diffusing into the container water through the cathode region.
  • the present invention provides an innovative effect of providing a water permeable membrane between the cathode and the anode electrode, and covering the anode with the water permeable membrane and controlling the distance between the water permeable membrane and the cathode electrode, the direct effects of which are:
  • the device of the invention can not only obtain beneficial water with low redox-rich hydrogen-rich potential, but also generate a considerable amount of strong oxidizing factor in water, which has greater sterilization and purification capability than other existing hydrogen-rich water preparation techniques. Upgrade
  • the water-permeable separator can usually be very thin (for example, the thickness of the ultrafiltration membrane can be 0.1mm to 0.5mm). After the separator is added between the anode and the cathode, the spacing between the anode and the cathode can be stably maintained at substantially equal to the isolation.
  • the thickness range of the film, 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 an operating current of 2 amps or more, which cannot be done by the prior art;
  • the plasma discharge efficient reaction factor and the like make the actual power consumption of the device of the present invention much lower than that of the similar device.
  • When covering the carbon material anode it is also effective to prevent the carbon particles from peeling off and causing a short circuit.
  • the permeable pore size of the water permeable membrane further affects the effect of the apparatus of the present invention in treating water.
  • the water permeable pore size is small, the effect of suppressing the oxygen evolution reaction of the anode is good, and the decrease of the water permeability pore diameter is equivalent to the decrease of the radius of curvature of the discharge electrode, which is also favorable for the plasma discharge; however, the water permeability pore size is too small, and the oxygen is oxidized to the anode.
  • the permeable pore size selection of the membrane is also related to various factors such as the mechanical strength of the membrane.
  • the water permeable membrane is a single layer water permeable membrane or a multilayer water permeable membrane.
  • the single-layer water-permeable membrane is preferably an ultrafiltration membrane or a water-permeable membrane made of a carbonaceous material;
  • the multilayer water-permeable membrane is at least two layers superposed and laminated, wherein a layer of the water-permeable membrane close to the anode electrode is used.
  • the normal hydrogen evolution reaction can be ensured, and the harmful substances in the water are adsorbed to the activated carbon membrane for oxidative degradation, and the oxidizing substances in the water are not inhibited too much, and the biological indicators are prevented from being deteriorated. It is especially suitable for the treatment of domestic water for the purpose of “drinking”. Further, if the water permeable membrane is at least two layers superposed and laminated, and wherein one of the water permeable membranes adjacent to the anode electrode has conductivity and a micron-sized pore diameter (for example, made of conductive ceramic or activated carbon fiber), Will bring further changes as follows:
  • the inhibition of oxygen evolution on the anode can be enhanced, and on the other hand, the pollutants in the source water can be adsorbed in the pores of the conductive ceramic or activated carbon fiber, and subjected to direct oxidation and indirect oxidation of the anode. Degraded by deep degradation.
  • the second technical solution of the present invention is that the specific coverage of the water permeable membrane and the anode electrode may cover the entire surface of the anode electrode or a part of the surface covering the anode electrode; In the case of a face, it is preferable to cover the surface (also the main reaction surface) of the anode electrode on the side opposite to the cathode electrode.
  • the third technical solution of the present invention is as follows: the cathode electrode is provided with a first through hole, and the first through hole has a diameter of 1 mm or more.
  • the water permeable membrane is provided with a second through hole, and the second through hole has a diameter larger than 2 mm.
  • the second through hole is formed in the water permeable membrane, which is substantially equivalent to generating a small area of the membrane-free electrolysis, or equivalent to introducing a conventional membrane-free electrolysis reaction, and the water treatment effect of the device of the present invention can be appropriately changed. For example, the pH of the water is adjusted.
  • the second through hole is different from the water permeable hole of the water permeable membrane in that the water permeable hole is inherent to the purchased diaphragm itself, and the second through hole is separately fabricated.
  • the above technical solution of the present invention is perfect: when the water container of the device of the present invention is made of a metal material (for example, stainless steel), the housing of the water container can be directly used as a cathode electrode.
  • a metal material for example, stainless steel
  • the above technical solution of the present invention is perfected in that the water inlet of the water container is connected to the water purifier through the sewage outlet of the external water purifier.
  • the water inlet of the water container is connected to the water purifier through an inlet pipe or an outlet pipe connected to the water purifier.
  • the electrolysis power source is a high-frequency narrow pulse width DC pulse power source or an alternating pulse power source whose forward voltage level is greater than a reverse voltage level.
  • FIG. 1 is a schematic structural view of a water purifier auxiliary purification device according to a first embodiment of the present invention.
  • FIG. 2 is a schematic structural view of a water purifier auxiliary purification device according to a second embodiment of the present invention.
  • FIG. 3 is a schematic structural view of a water purifier auxiliary purification device according to a third embodiment of the present invention.
  • FIG. 4 is a schematic view showing the structure of a positive electrode and a negative electrode and a water permeable membrane in the fourth embodiment of the present invention.
  • Fig. 5 is a schematic view showing the structure of a positive electrode and a negative electrode and a water permeable membrane according to a fifth embodiment of the present invention.
  • Fig. 6 is a schematic view showing the structure of a positive electrode and a negative electrode and a water permeable membrane in a sixth embodiment of the present invention.
  • the water purifier auxiliary purifying device of this embodiment is shown in Fig. 1 (including the water container 1 provided with the water inlet 9, the water inlet 9 of the water container 1 is connected to the sewage outlet 6 of the existing water purifier 7, and the water purifier 7
  • the inlet pipe 10-1 and the outlet pipe 10-2 are provided.
  • the housing of the water container 1 is provided with a cathode electrode 2 and an anode electrode 3, and a cathode electrode 2 and an anode electrode 3
  • a water permeable membrane 5 is disposed between the water permeable membrane 5 and the water permeable membrane 5 covering the entire surface of the anode electrode 3.
  • the water-permeable membrane 5 of the present embodiment employs a single-layer PVDF ultrafiltration membrane having an average water permeability of 0.03 ⁇ m and a thickness of 0.1 mm.
  • the ultrafiltration membrane of the present embodiment may also adopt a water permeable filter membrane of other materials, and the average water permeability pore diameter may be between 0.1 and 0.05 micrometers.
  • the cathode electrode 2 of the present embodiment is an inert electrode made of a titanium-based platinum group oxide (coating thickness: 0.8 mm), and the anode electrode 3 is made of a carbonaceous material such as graphite or activated carbon, and the anode and the cathode are both wafers. Shape, no holes on the surface.
  • the cathode electrode 2 and the anode electrode 3 are powered by a DC electrolysis power source 4, and the electrolysis power source 4 is an alternating-current DC pulse power source with a high-level narrow pulse width regulation voltage of 24 volts, and the forward pulse level is greater than the reverse pulse. Level.
  • the water purifier auxiliary purifying device of the embodiment can form a large amount of ultra-micro bubbles mainly composed of hydrogen in the water, and the ultra-micro hydrogen bubbles float up to the water purifier 7 to wash the filter film in the existing water purifier 7 ( Or the outer surface of the activated carbon) 8 prevents the outer surface of the filter membrane (or activated carbon) 8 from scaling, reduces the concentration polarization, and removes the contaminants in the source water by flocculation and precipitation.
  • the strong oxidizing factor produced by the device sterilizes the water and prevents premature saturation of the activated carbon, which greatly prolongs the replacement cycle of the activated carbon.
  • the water purifier auxiliary purifying device of the embodiment is used for docking with a commercially available conventional ultrafiltration water purifier having a nominal flow rate of 380 liters/hour (the water inlet sealing sleeve of the water container 1 is connected to the water purifier of the water purifier). Port 6) was subjected to a water electrolysis experiment.
  • 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 purifier auxiliary purifying apparatus of the present embodiment is an improvement on the basis of the first embodiment.
  • the variation with the first embodiment is: 1) the water receiving container 1 is disposed in the water inlet pipe of the water purifier 7. At 10-1, such a large amount of hydrogen-based ultra-microbubbles and strong oxidizing factors formed in the water purifier auxiliary purification device can enter the water purifier under the action of water pressure, and also play the role of sterilization and cleaning.
  • the water container 1 can also be connected in series with the inlet pipe 10-1 (the water outlet is opened in the water container 1). Further, the water container 1 can also be connected or connected to the outlet pipe 10-2. Pick up.
  • the anode electrode 3 was changed to an inert electrode of a titanium-based platinum group oxide (coating thickness: 0.8 mm).
  • the distance ⁇ between the water permeable membrane 5 and the cathode electrode 2 is 3 mm.
  • a comparative experiment is performed to adjust the coverage of the anode 3 by the water permeable membrane 5: in the first mode, as shown in FIG. 2, the water permeable membrane 5 completely covers the entire surface of the anode electrode 3; The diaphragm 5 covers only the surface of the anode electrode 3 facing the 2/3 side of the cathode electrode 2 (not shown), and the other structural parameters are unchanged in both modes.
  • the experimental conditions were also the same as in the first embodiment.
  • the two kinds of coverage methods of the permeable membrane 5 for the anode electrode 3 were tested separately, and the test results are shown in Table 2 below:
  • the hydrogen content in the water and bubbles increases, the oxidation-reduction potential decreases, the alkalinity strengthens, and the oxidation factor decreases; on the contrary, the oxidation factor in the water increases.
  • the water purifier auxiliary purifying device of this embodiment is an improvement on the basis of the first embodiment.
  • the variation with the first embodiment is: 1) the water container 1 is made of stainless steel and serves as a cathode electrode. 2; 2) The distance ⁇ between the water permeable membrane 5 and the cathode electrode 2 is 2 mm.
  • the water purifier auxiliary purification 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 first embodiment.
  • the experimental results are shown in Table 3 below:
  • the water purifier auxiliary purifying apparatus of this embodiment is an improvement based on the first embodiment.
  • the variation with the first embodiment is: 1) the cathode electrode 2 is uniformly provided with 24 diameters of ⁇ 1 mm. a through hole; 2) the distance ⁇ between the water permeable membrane 5 and the cathode electrode 2 is 4 mm; 3) the anode electrode 3 is changed to an inert electrode coated with a platinum group oxide (coating thickness: 0.8 mm); 4) permeable to water Part of the surface of the diaphragm 5 covering the anode electrode 3 The face (the entire surface of the anode electrode 3 facing the side of the cathode electrode 2).
  • the water purifier auxiliary purification 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 first embodiment.
  • the experimental results are shown in Table 3 below:
  • the water purifier auxiliary purification device of the present embodiment is an improvement on the basis of the fourth embodiment, and the variation with the first embodiment is: 1) as shown in FIG. 5, the water permeable membrane 5 is made of an activated carbon fiber membrane (felt) 5- 1 and a super-filtration membrane 5-2 superposed and laminated to form a two-layer water-permeable membrane, the activated carbon fiber membrane 5-1 is close 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 ( The ultrafiltration membrane 5-2 facing away from the anode electrode 3) covers a part of the surface of the anode electrode 3 (the entire surface of the anode electrode 3 toward the side of the cathode electrode 2), and both ends of the ultrafiltration membrane 5-2 slightly exceed the anode electrode; 2) The distance ⁇ between the water permeable membrane 5 and the cathode electrode 2 is 5 mm; 3) the anode electrode 3 is changed to the same inertness as the
  • the water purifier auxiliary purification device of the present embodiment was subjected to a water electrolysis experiment, and the electrolysis time was 20 minutes.
  • the other experimental conditions were the same as those in the first embodiment.
  • the experimental results are shown in Table 4 below:
  • the water purifying device auxiliary purifying device of the present embodiment has a water permeability diaphragm 5 which is a two-layer water permeable material formed by superimposing an activated carbon fiber membrane (fel) 5-1 and an ultrafiltration membrane 5-2.
  • the separator can therefore adsorb a large amount of oxidizing factors in water, thereby making water which is more suitable for human consumption and rich in hydrogen and low in oxidation-reduction potential.
  • the water purifier auxiliary purification device of the present embodiment is an improvement on the basis of the fifth embodiment, and the variation of the fifth embodiment is: 1) the activated carbon fiber membrane (felt) 5-1 is replaced by a water permeable membrane made of a conductive ceramic; 2) As shown in Fig. 6, the ultrafiltration membrane 5-2 facing the cathode electrode 2 (reverse from the anode electrode 3) covers the three side surfaces of the anode electrode 3; 3) the distance ⁇ between the water permeable membrane and the cathode electrode 2 is 9 mm .
  • the water purifier auxiliary purification device of the present invention is not limited to the specific technical solutions described in the above embodiments, such as: 1) the anode electrode 3 may be an inert electrode of other materials; 2) the distance ⁇ between the water permeable membrane 5 and the cathode electrode 2 It may be any spacing of 0 ⁇ 10mm, such as 7mm, 8mm or 10mm, etc.; 3) The water permeable membrane 5 may also be a stack of three or more layers of different materials; 4) the cathode electrode 2 and the anode electrode 3 The shape may also be various shapes including a circle and a square; 5) The technical solutions of the above-described various embodiments of the present invention may be cross-combined with each other to form a new technical solution; All technical solutions formed by equivalent replacement are the scope of protection required by the present invention.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Water Treatment By Sorption (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne un dispositif d'épuration auxiliaire pour un épurateur d'eau, qui relève du domaine technique des dispositifs électrolytiques. Le dispositif comprend un récipient contenant de l'eau (1) doté d'une admission d'eau (9), l'admission d'eau (9) étant en communication avec un épurateur d'eau (7) ; le récipient contenant de l'eau (1), dans le boîtier, est pourvu d'une cathode (2) et d'une anode (3), et comprend également une source d'énergie d'électrolyse (4) qui fournit de l'énergie pour la cathode (2) et l'anode (3) ; une membrane perméable à l'eau (5) est disposée entre la cathode (2) et l'anode (3) appariées ; l'anode (3) est recouverte de la membrane perméable à l'eau (5) ; la distance δ entre la membrane perméable à l'eau (5) et la cathode (2) est dans la plage de 0 ≤ δ ≤ 10.
PCT/CN2015/076239 2014-04-12 2015-04-10 Dispositif d'épuration auxiliaire pour épurateur d'eau WO2015154706A1 (fr)

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WO2008016671A2 (fr) * 2006-08-01 2008-02-07 Quos, Inc. Systèmes multifonctionnels de filtration et de purification d'eau
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Publication number Priority date Publication date Assignee Title
CN113929188A (zh) * 2020-06-29 2022-01-14 佛山市顺德区美的饮水机制造有限公司 电极结构、净化结构和电极制备方法

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