WO2009129670A1 - 一种利用微电流电解灭菌除藻的装置和方法 - Google Patents

一种利用微电流电解灭菌除藻的装置和方法 Download PDF

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Publication number
WO2009129670A1
WO2009129670A1 PCT/CN2008/070783 CN2008070783W WO2009129670A1 WO 2009129670 A1 WO2009129670 A1 WO 2009129670A1 CN 2008070783 W CN2008070783 W CN 2008070783W WO 2009129670 A1 WO2009129670 A1 WO 2009129670A1
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Prior art keywords
electrode
water
cathode
anode
electrolysis
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PCT/CN2008/070783
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English (en)
French (fr)
Inventor
曹学良
曹学磊
杜清华
刘炳言
陈野
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青岛海德威船舶科技有限公司
哈尔滨工程大学
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Application filed by 青岛海德威船舶科技有限公司, 哈尔滨工程大学 filed Critical 青岛海德威船舶科技有限公司
Priority to ES08734141T priority Critical patent/ES2756323T3/es
Priority to JP2011505344A priority patent/JP5127983B2/ja
Priority to PCT/CN2008/070783 priority patent/WO2009129670A1/zh
Priority to US12/680,299 priority patent/US20110036727A1/en
Priority to DK08734141T priority patent/DK2269956T3/da
Priority to EP08734141.8A priority patent/EP2269956B8/en
Priority to KR1020107018436A priority patent/KR101256896B1/ko
Publication of WO2009129670A1 publication Critical patent/WO2009129670A1/zh
Priority to US13/708,608 priority patent/US20130092615A1/en

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
    • C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C02F2001/46142—Catalytic coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4612—Controlling or monitoring
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46125—Electrical variables
    • C02F2201/4613—Inversing polarity
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/05—Conductivity or salinity
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/29—Chlorine compounds

Definitions

  • the present invention relates to a sterilizing algae removal apparatus and method, and more particularly to an apparatus and method for sterilizing algae by microcurrent electrolysis. Background technique
  • Cyanobacteria are also known as cyanobacteria or blue-green a lgae. Their nuclear structure has no nuclear membrane, nucleolus, is a prokaryote, does not undergo mitosis, and the cell wall is similar to bacteria. It is composed of peptidoglycan and is negative for Gram stain, so they belong to prokaryotic microorganisms. Cyanobacteria are single-celled organisms that are larger than bacteria and generally have a diameter or width of 3 - 15 ⁇ m. However, cyanobacteria rarely live in a single individual, usually after aggregation, to form a filamentous or single-celled population. When many individuals come together, they can form large groups that are visible to the naked eye.
  • the cyanobacteria mainly grow on the surface of the water, that is, below the surface of the water, 0.5 m, most of the cyanobacteria are blue or blue-green. Therefore, people still use it to call it a wide range of blue bacteria, from the south pole to the north pole, from the ocean to the ocean. Traces can be seen in the mountains. They often grow on rocks, bark or in ponds and lakes, and breed vigorously, so that the color of the water changes with the color of the cyanobacteria itself. Some species can produce grassy or mildew. Cyanobacteria contain a pigment system (mainly containing phycocyanin, which also contains chlorophyll alpha, carotene or phycoerythrin).
  • Cyanobacteria are simple in nutrition, do not require vitamins, and use nitrate or ammonia as a nitrogen source. Some species have rounded heterocytes (hererocys t), which are generally extended by filaments or distributed at one end, and are the sites where cyanobacteria carry out nitrogen fixation. Cyanobacteria carry out oxygen-extracting photosynthesis, which is an obligate light-energy inorganic nutrient microorganism, and its response is as follows
  • IM0 develops the International Convention for the Control and Management of Ballast Water and Sediments of Ships, by controlling and managing ships Ballast water and sediment to prevent, minimize and eventually eliminate Environmental, human health, property and resource risks resulting from the transfer of aquatic organisms and pathogens, and avoiding the unnecessary negative effects of such controls, and encouraging and promoting the development of relevant knowledge and technologies; this Convention, although currently in the United States and China Not yet signed, most developed countries have signed, and the implementation of ballast water management under this treaty is only a matter of time.
  • the speed of killing microorganisms and pathogens must be very fast: Otherwise, in a large area of water, when the treated water re-enters the body water, if the biocide is added, it will be diluted quickly and the sterilization capacity will be weakened.
  • ballast water treatment ballast water is pumped in and discharged through the device for only a short time, if the microbes are killed The speed of the pathogen is not fast enough, and the treated water body can not reach the standard;
  • High killing efficiency The discharge ballast specified in Regulation D-2 of the International Convention for the Control and Management of Ballast Water and Sediments of 2004 Water performance standards must meet:
  • the indicator microorganism should be less than the following concentrations:
  • Enterococcus less than 100 cfu per 100 ml;
  • biocide mainly include: (1) biocides, (2) filter fishing and membrane treatment technology, (3) ultrasonic technology, ( 4) high pressure algae killing, (5) biological treatment, (6) ecological management, ( 7 ) ultraviolet sterilization technology, (8) electrolysis to produce active substance sterilization technology.
  • Chinese Patent Application No. 02100332 discloses an oxidized bromine-containing composite biocide-bromochloropropane used in industrial water fields as well as in public places and sewage reuse fields;
  • Chinese Patent Application No. 200510025284 proposes a glutaraldehyde, quaternary ammonium salt An aldehyde compounding high-efficiency biocide;
  • Chinese Patent Application No. 200510025395 discloses a biocide containing isothiazolinone, dodecyldidecylbenzylammonium chloride, used for sewage treatment;
  • WIP0 World Intellectual Property Organization
  • the published international patent WO03002406 uses copper anode electrolysis to produce copper ion sterilization.
  • biocides are biologically toxic and have a long residual time. They can be used in domestic sterilizing treatments in circulating sewage or cooling water systems, and are not suitable for large-area eutrophic water bodies such as lakes and ballast waters that need to be discharged. deal with.
  • US Patent No. 2005016933 uses the addition of C10 2 as a biocide, international patents WO2005061388, US Patent No. US2004099608 and US2003029811, Japanese Patent No. JP200714439K JP2006239556, JP2006263563, respectively, each of which discloses a water treatment technique and corresponding apparatus using filtration and addition of ozone as a biocide,
  • the device and technology without secondary pollution, have certain advantages in the small-flow water body or drinking water sterilization treatment, but the operation cost is 4 ⁇ high for the sterilization and algae removal treatment of large-flow water bodies such as water grabbing water or large-flow water bodies.
  • Ultrasonic ultrasonic technology not only has strong vibration, but also has cavitation and generates a large number of micro-jets, which can make the liquid have a strong impact on the container wall. This function is applied to ultrasonic cleaning and is also used to enhance the reaction effect.
  • the azo dye wastewater treatment method disclosed in Chinese Patent Application No. 200610085548, and the oxidized organotin technology disclosed in German Patent DE19919824, use ultrasonic waves to promote chemical reaction.
  • the micro-regional high pressure generated by ultrasonic cavitation can be used for cell disruption, but this effect is mostly achieved by concentrating ultrasonic energy in a small area. Therefore, the current ultrasonic technology and the corresponding water treatment device, A small-volume water body, and a circulating water body can be used, and the operability is relatively large, such as the acousto-optic sterilizing drinking water treatment device disclosed in Chinese Patent Application No. 200610023241.
  • Japanese patent JP2006007184 applies an ultrasonic transducer (28 ⁇ 200KHz) to the outer wall of the pipeline, and sterilizes and algae-kills the ballast water passing through the pipeline through ultrasonic waves; JP2005021814 provides a corresponding pressure-killing ultrasonic sterilization algae removal device, device The ultrasonic transducer is installed on both sides of the tank, the water passage passes through the tank, and the ultrasonic waves kill the microorganisms in the passing water; neither of these patents considers the ultrasonic wave for mounting on the opposite pipe wall or the casing.
  • Ultrasonic water treatment machine disclosed in 98,236,857, and a circular, continuous ultrasonic treatment pressure water rushing device introduced by the international patent WO03095370 the ultrasonic transducer faces the same problem.
  • the existing ultrasonic treatment devices in addition to the above problems, if ultrasonic treatment is used alone, there is still high energy consumption, high operating cost, and it is difficult to kill. Guaranteed and other unfavorable factors, not operability.
  • High-pressure algae-killing high-pressure sterilization and algae killing are carried out by pressurizing the water body to a certain extent to rupture bacteria and algae cells, such as Japanese patents JP2007021287, JP2005270754, JP2005254138, but for the treatment of cyanobacteria in large-area water bodies, high-pressure algae killing also exists.
  • Bioremediation For freshwater eutrophic waters, people are hoping for bioremediation, but bioremediation may cause biological disasters to native species by introducing alien species.
  • cyanobacteria are actually cyanobacteria, and the toxins produced can cause fish and poultry to die within a few minutes at the ppm level; Satoshi Naka i in a work report published in 2001 (ALGAL GROWTH INHIBITION EFFECTS AND INDUCEMENT MODES BY PLANT- PRODUCING PHENOLS SATOSHI NAKAI*, YUTAKA IN0UE and MASAAKI H0S0MI, Water Research, Vol. 35, Issue 7, May 2001, Pages 1855-1859 ) pointed out that grasses and other aquatic plants can reduce the eutrophication of water to some extent, but Very few plants release phenolic substances that inhibit the growth of cyanobacteria.
  • the ultraviolet sterilization technology is mostly applied to the treatment of small-volume water bodies with low load and circulating water bodies.
  • U.S. Patent Nos. US2004134861 and US2005211639 the international patent line continuously processes the water rushing device; in addition, the combination of ultraviolet radiation and ultrasound can enhance the bactericidal effect, such as the acousto-optic sterilizing drinking water treatment device disclosed in Chinese Patent Application No. 20060112, and 200520087812
  • the disclosed seawater strong ultraviolet disinfection filter applied to cultured seawater treatment; U.S. Patent 5,738,780 combines ultraviolet sterilization with direct current electrolysis for ballast water treatment.
  • these techniques are still limited by the scope of ultraviolet sterilization and sterilization ability, and the bactericidal effect on high-load, large-flow water bodies and large-area water bodies is still unsatisfactory.
  • Electrolysis produces active substance sterilization technology to add salt, and then to produce hypochlorite sterilization by electrolysis.
  • the former has a lot of work, including Chinese patent application No. 200610042972. 2 "A dual function electrolyzed water generation” "A small-sized disinfectant water generator and its use method” disclosed in 200510111126., “Portable water source disinfection machine” disclosed in 200520077629. 2, "Preparation method of high-concentration hypochlorous acid disinfectant water disclosed in 200510023766.
  • the international patent WO2006058261 discloses a pressure rushing water treatment method using electrolysis to produce hypochlorite and a corresponding system, an electrolytic treatment pressure rushing water device disclosed in Japanese Patent No. JP2001000974, and similarly disclosed in Chinese Patent Application No.
  • the electrode spacing of the system satisfies the electrolysis design requirements of ballast water in seawater, and cannot meet the requirements of freshwater system. Because the ship is in the waters and docked ports, some are close to the river estuary and belong to the freshwater area.
  • the electrolysis voltage caused by the difference in conductivity is too large.
  • the voltage applied between the anode and the cathode by the electrolysis system consists of three parts, see Figure 1, where:
  • U1 It consists of the electrode potential of the anodization reaction and the polarization overpotential. If the polarization of the electrochemical reaction is negligible, for a specific reaction system (reaction concentration, pH, temperature constant), U1 is basically unchanged, and does not follow current. Change in density;
  • U2 the pressure drop caused by the resistance of the solution. The lower the conductivity of the solution, the larger the resistance R and the higher the current density.
  • U3 consists of the electrode potential of the cathodic reduction reaction and the polarization overpotential. If the reaction polarization is negligible and there is no contamination and coating of the cathode by suspended matter and inorganic substances, for a specific reaction system (reaction concentration, pH) , the temperature does not change), U3 is basically unchanged, does not change with the change of current density.
  • the electrolysis current I basically needs to be constant above a certain value, if the electrode spacing is d (for all current systems that adopt electrolysis, no change in electrode spacing is considered in the operation of the system.
  • I, d, S are certain values, but different types of water have different conductivity
  • the seawater system is 3000 (S / cm; In the estuary water body, when the tide is low, the water flow is a single flow direction to the ocean. Although it is affected by the ocean tide, the water chemical composition of the intersection area is similar to the river water quality, and the conductivity can be between 50 and 50 (S/cm; At the time, there are both the diarrhea of the river and the retrogression of the trend.
  • the water quality of the junction area is more complicated, and Unstable;
  • the tide has a great influence on the estuary area, and the seawater can be traced back to the deep distance in the estuary.
  • the chemical composition of the water in the intersection shows the characteristics of the sea. Therefore, when the estuary water body is between 50 and 50 (S/cm, at least 60 times different from the ocean water body, it can be known from equation (1) that the voltage U2 applied to the water body between the anode and the cathode has at least More than 60 times difference, it is difficult to ensure that the electrolysis system can meet the requirements of ballast water treatment in different waters in the safe voltage range.
  • the cathode In the fresh water system, the cathode has fouling phenomenon, and the resistance between the cathode and the water body is sharply increased, which affects the electrolysis efficiency. If it is necessary to ensure a constant current, the overall electrolysis voltage rises sharply, and the system cannot operate normally. .
  • the fouling of the electrolysis process at the cathode is mainly CaC0 3 . Since the cathode surface and the cathode region adsorb a large amount of cations to satisfy the charge balance, the cation concentration in the water body is not greatly different, and the Ca 2+ charge is high.
  • the cathode surface and the cathode region are enriched, and the local region reacts with HC0 3 in the water body as follows:
  • Ca 2+ + HC0 3 CaC0 3 (s, + H + (2) Jeffrey A. Franz Effect of the aerobic biodegradation system contamination on the electrode surface of the electrolytic production of oxygen cathode during precipitation / fouling caused ( Water Research, Vol.36, Issue 9, May 2002, Pages 2243-2254) states that the surface precipitation of the cathode is mainly CaC0 3.
  • the water tank self-cleaning sterilizer disclosed in the prior patent 99253589 has a cathode during long-term operation.
  • calcite easily forms a dense structure. It is not easy to fall off on the electrode; aragonite is generally formed by crystallizing and growing in the presence of a template or at a high temperature (above 80 °C), and the electrolysis process does not have such a condition; the vaterite structure is loose and easy. Fall off.
  • aragonite is generally formed by crystallizing and growing in the presence of a template or at a high temperature (above 80 °C), and the electrolysis process does not have such a condition; the vaterite structure is loose and easy. Fall off.
  • white sediment in the combined micro-current electrolyzed water treatment device for marine aquaculture and disinfection environment white scale on the cathode surface of the combined micro-current electrolyzed water treatment device for freshwater aquaculture water treatment, and self-cleaning and disinfection of the water tank used in the high-rise water tank.
  • Figs. 2a, 2b, 2c and Fig. 3 wherein, in Fig. 3, a The curve is the seawater absorption analysis curve, the b curve is the fresh water absorption analysis curve, and the c curve is the tap water absorption analysis. It can be seen from Fig. 2a that the white precipitated particles of the marine aquaculture treatment body are relatively small, mostly spherical; Figures 2b and 2c are the scales on the cathode surface of the electrolytic treatment system for freshwater aquaculture and the water tank used in the high-rise water tank, respectively.
  • the SEM photograph of the white scale on the cathode surface of the self-cleaning sterilizer has a larger particle size; the corresponding IR absorption is shown in Fig. 3, and the curve a is the infrared absorption of the white precipitated particles of the marine aquaculture electrolytic treatment system, except Calcite's in-plane bending vibration v4 characteristic absorption peak 712 cm 1 and carbonate out-of-plane bending vibration v2 absorption peak 875 cm 1 , as well as the characteristic absorption band of the ventilite (vaterite) 745 cm 1 , Infrared absorption of the surface of the cathode of the electrolytic treatment system of freshwater aquaculture, and the infrared absorption of the white surface of the cathode surface of the water tank of the high-rise tank, c is significantly different, b and c are very Similarly, it is a typical calcite infrared absorption; this is consistent with the SEM analysis.
  • an inverted-electrode electrochemical reactor disclosed in Chinese Patent Application No. 200620032114 causes the cathode scale to fall off by means of an inverted pole; this inverted pole method introduces a new problem. Frequent depolarization will cause the anode of the electrolyzer to lose catalytic activity, resulting in a high overpotential of the electrode and a decrease in current efficiency.
  • a system for electrolyzing an oxidizing substance for water treatment generally adopts a catalytically active DSA anode (Dimensionally Stable Anode), which is coated with a platinum group element oxide on the surface of a metal titanium or titanium alloy.
  • H. Beer 65 patent is an oxide of platinum group metal or its alloy selected from platinum, rhodium, ruthenium, iridium, palladium, iridium and ruthenium, with titanium or titanium alloy as the core material/substrate, especially containing more than one type.
  • Non-platinum group metal oxides (such as Ta, Ti), constitute the outer electrode; Italy De Nora Company and the United States Diamond Shamrock Company successfully applied the Beer invention to chlorine reduction production in 1968.
  • the anode for the salt electrolysis has developed a titanium-based platinum group metal oxide electrode, which has high catalytic activity and can be used for more than 15 years.
  • a microcurrent electrolysis sterilization algae removal apparatus comprising: a detector for sensing a conductivity value of a solution installed on a water inlet pipe of a tank, wherein the tank is in accordance with an anode and an auxiliary electrode in the group; The cathode is sequentially installed with at least one set of electrode groups, the controller determines the magnitude of the conductance value, controls the polarity of the electrodes in the box, and the circuit connection; the controller includes: a judging unit for judging the Describe the magnitude of the conductance value, and trigger the corresponding seawater electrolysis mode unit, the fresh water electrolysis mode unit, and the inverted electrolysis mode unit according to the judgment result;
  • the seawater electrolysis mode unit is configured to: after receiving the trigger, turn on the circuit connection of the anode and the cathode, and disconnect the circuit connection of the auxiliary electrode; the fresh water electrolysis mode unit is configured to receive the trigger and then the cathode a circuit in which the polarity is changed to an anode, the polarity of the auxiliary electrode is changed to a cathode, an anode that does not change polarity, an anode that changes polarity by a cathode, and a cathode that changes polarity by an auxiliary electrode
  • the reverse pole mode unit is configured to determine the number of times of operation of the device, and after the running time exceeds the set threshold, change the polarity of the auxiliary electrode to an anode, and turn on the polarity changed by the auxiliary electrode.
  • the microcurrent electrolysis sterilization algae removal apparatus further includes: an ultrasonic generator installed at both ends of the case, and an ultrasonic reflector, wherein the ultrasonic generator includes at least one or more ultrasound A transducer, the electrode set being positioned between the ultrasonic generator and the ultrasonic reflector.
  • the ultrasonic reflector when the shape of the electrode is a sheet shape, the ultrasonic reflector has a triangular prism shape or a circular arc shape, and an edge or a circular arc of the prism protrudes toward the ultrasonic generator;
  • the shape of the ultrasonic reflector when the shape of the electrode is tubular, the shape of the ultrasonic reflector is conical, and the tip of the cone faces the ultrasonic generator.
  • the respective electrodes and the respective ultrasonic transducers when the shape of the electrode is tubular, the respective electrodes and the respective ultrasonic transducers are arranged in an annular shape of the same center.
  • the detector is a conductivity inductive conductivity sensor or a conductivity transducer.
  • the anode is at least one of a metal titanium or a titanium alloy, and the surface thereof is coated with a metal containing Pt, Ir, Ru, Rh, Pd or 0s, and an oxide thereof. At least one of, and a coated electrode (DSA) containing an oxide of at least Ta or Ti.
  • the auxiliary electrode and the cathode are preferably at least one of titanium metal or titanium alloy, and the material of the ultrasonic reflector includes at least plastic, titanium metal, titanium alloy, stainless steel, carbon. A material component of steel or copper alloy.
  • the microcurrent electrolysis sterilization algae removal apparatus further includes: a potentiometer or a residual chlorine electrode installed on the tank outlet pipe for detecting chlorine content in the solution after electrolysis, and The chlorine transmitter; the respective electrolysis unit adjusts the current and voltage values of the electrolysis according to the chlorine content value.
  • a potentiometer or a residual chlorine electrode installed on the tank outlet pipe for detecting chlorine content in the solution after electrolysis, and The chlorine transmitter; the respective electrolysis unit adjusts the current and voltage values of the electrolysis according to the chlorine content value.
  • Still another aspect of the present invention provides a method for sterilizing algae in a water body by microcurrent electrolysis, comprising: 1) detecting a conductance value of the water body;
  • the seawater electrolysis mode unit, the fresh water electrolysis mode unit or the inverted electrolysis mode unit of the controller is activated to control the polarity and circuit connection of the anode, the auxiliary electrode and the cathode in the water body.
  • the circuit connection of the anode and cathode is turned on, and the circuit connection of the auxiliary electrode is disconnected.
  • the polarity of the cathode is changed to an anode
  • the polarity of the auxiliary electrode is changed to a cathode, and the polarity is not changed.
  • the anode of the anode, the anode formed by changing the polarity of the cathode, and the cathode connected by the polarity of the auxiliary electrode are connected.
  • the polarity of the auxiliary electrode is changed to an anode, and the conduction is performed by The auxiliary electrode changes the polarity of the anode and the circuit of the unpolarized cathode is connected, and the circuit connection of the anode of the unpolarized polarity is broken.
  • the body of water can be any suitable body of water, such as sea water or fresh water.
  • the method further comprises applying ultrasonic waves to at least a portion of the body of water.
  • FIG. 1 is a schematic view of an electrolytic body system
  • FIG. 2 is a schematic view of white precipitated particles of a marine aquaculture electrolytic treatment body
  • FIG. 2b Schematic diagram of fouling on the cathode surface of an electrolytic treatment system for freshwater aquaculture
  • Figure 2c shows the white scale of the cathode surface of a water tank self-cleaning sterilizer used in a tall building water tank
  • Figure 3 is a schematic diagram of the IR absorption of different water quality diagrams
  • Figure 4 is a schematic diagram of the micro-current electrolysis sterilization algae removal apparatus
  • Figure 5a is a schematic diagram of the plate-shaped titanium anode structure of the electrode group of the micro-current electrolyzer
  • Figure 5b is micro Schematic diagram of the plate-shaped titanium cathode structure of the electrode group of the current electrolyzer
  • FIG. 5c is a schematic view showing the structure of the plate-type auxiliary electrode of the electrode group of the micro-current electrolyzer
  • FIG. 6 is a schematic diagram of the arrangement of the plate-shaped electrode group in the micro-current electrolyzer;
  • Figure 7B is a partially enlarged schematic view of Figure 7A;
  • Figure 7C is a cross-sectional view of the B-B of Figure 7B;
  • Figure 8 is a structural view of the controller in the device;
  • Figure 9A is an ultrasonic transducer emission
  • Figure 9B is a schematic view of the direction of ultrasonic transmission reflected by the ultrasonic reflector;
  • Figure 10 is a schematic view of the box-type micro-current electrolysis sterilization algae removal device;
  • Figure 11 is a schematic view of the A-A direction of Figure 9;
  • Figure 12A is
  • FIG 13 is a schematic diagram of a control micro-current electrolysis sterilization algaecide device;
  • FIG. 14 is a schematic view of electrode arrangement tank micro-current electrolysis sterilization algaecide device;
  • Figure 15 is a schematic view of the B direction of Figure 9;
  • Figure 16 is a schematic view of the arrangement of the electrode terminal outlets of the rubber pad of the sealed electrode group of the box type micro current electrolysis sterilization algae removal device;
  • Figure 17 is an illustration of the electrode wiring of the electrode sealing cover of the box type micro current electrolysis sterilization algae removal device
  • Figure 18A is a front view of the terminal;
  • Figure 18B is a left side view of the terminal;
  • Figure 19 is a schematic view of the arrangement of the Mitsubishi column;
  • Figure 20 is a schematic view of the arrangement of the ultrasonic generator of the box-type micro-current electrolysis sterilization algae removal device; Schematic diagram of a sealing rubber pad connecting the generator to the cabinet and the ultrasonic generator cover;
  • Figure 22 is a schematic view of the C-direction in Figure 9;
  • Figure 23A is a schematic view showing the structure of the ultrasonic-enhanced micro-current electrolysis system of the tubular micro-current electrolysis sterilization algae removal apparatus;
  • FIG. 23B is a partially enlarged schematic view of FIG. 23A;
  • FIG. 24 is a schematic view showing the structure of a plastic rod flange including a rod-shaped titanium anode and an electrode lead;
  • FIG. 25 is a schematic view showing a structure of a plastic flange having a fixed rod-shaped titanium anode and no electrode lead;
  • Figure 26 is a schematic view showing the structure of a plastic flange including a lead wire for fixing a porous tubular auxiliary electrode;
  • Figure 27 is a schematic view showing the structure of a plastic flange which does not include electrode leads for fixing a porous tubular auxiliary electrode.
  • FIG. 4 A schematic diagram of Embodiment 1 of some embodiments of the present invention can be seen in FIG. 4, including: the detector detects the conductance in the water inlet conduit, and the controller determines the conductance detected by the detector,
  • the ultrasonically enhanced microcurrent electrolyzer under different conductance controls operates in the corresponding mode.
  • the detector can be a conductivity sensor or a conductivity meter.
  • the conductivity sensor uses an inductive conductivity sensor. Since the sensor works in a closed loop in a solution, an induced current is generated. By measuring the magnitude of the current, the conductivity of the solution is obtained, and the pollution resistance is strong. Ensure that the system operates stably in a complex water quality environment.
  • the conductivity meter and the potentiometer can respectively use the conductivity transmitter and the residual chlorine transmitter to facilitate industrial control.
  • the ultrasonic enhanced micro-current electrolyzer comprises: a DC electrolysis power source, an electrolysis electrode set, a box body, and an electrode lead connection terminal, an ultrasonic generator, and an ultrasonic reflector.
  • the DC power supply adopts linear DC power supply, the access terminal is 110V or 220V AC power, the output is DC power, the electrolysis current can be adjusted according to the need, the output voltage is controlled within the safe range of 36V; the electrode group is made of metal titanium and titanium alloy as the core material.
  • the coating electrode is equidistantly arranged;
  • the casing comprises a casing, a seal, a fixing member and a connecting flange, and the casing and the flange are made of a plastic member;
  • the ultrasonic generator comprises a casing, a transducer, and a power ultrasonic generator.
  • the electrolysis electrode group in the micro-current electrolyzer can realize the effect of sterilization and algae elimination, and an ultrasonic generator can be added according to the actual situation to achieve the breakage of bacteria and algae cells.
  • the electrode set of the ultrasonic enhanced microcurrent electrolyzer comprises:
  • Anode a metal titanium or titanium alloy is used as a substrate to coat a surface thereof with at least one metal Pt, Ir, Ru, Rh, Pd, 0s or an oxide thereof, and at least one Ta or Ti
  • the oxide electrode acts as the anode - the titanium anode (DSA anode), and Pt, Ir, Ru, Rh, Pd, 0s, Ta, Ti can provide the catalytic active center of the ⁇ f empty orbit to facilitate the electron transfer and avoid the pole
  • the phenomenon is beneficial to the formation of highly active oxidizing substances; in order to avoid excessive current flow through the junction between the electrode and the lead, it is easy to cause blow-out in operation, and the plate-shaped anode has at least two terminals at the anode.
  • Cathode an electrode member coated with at least one oxide of Ta and Ti on the surface of a metal titanium or titanium alloy; it can ensure that the properties of the electrode are changed as an anode in a fresh water system with low conductivity Catalytic activity, while the oxides of Ta and Ti have low hydrogen absorption capacity and will not fall off when used as a cathode. Similarly, in order to avoid excessive current passing between the electrodes and the leads, it is easy to cause blow-out in the work.
  • the cathode has at least two terminals and is evenly distributed on the cathode. See the schematic diagram of the cathode structure of Fig. 5b. A through hole is formed in the terminal, and can be connected with the wire by screw fastening; the tubular cathode can be contacted by the ring to solve the problem of excessive local current at the contact point.
  • Auxiliary electrode a metal titanium or titanium alloy mesh having an average pore diameter of not less than 3 legs, and an oxide layer of at least one of Ta and Ti coated on the surface thereof as an outer electrode member to ensure descaling and descaling as an anode When the electrode material is not corroded; likewise, in order to avoid excessive current flow between the electrode and the lead wire, it is easy to cause blow-out in operation, and the plate-shaped auxiliary electrode has at least two terminals and is uniformly distributed on the auxiliary electrode. Referring to the schematic diagram of the auxiliary electrode structure of Fig.
  • a through hole is formed in the terminal, and the wire can be connected with the wire by screw fastening;
  • the tubular auxiliary electrode can solve the problem of excessive local current of the point contact through the annular contact;
  • the electrodes in the electrode group can be arranged by the plate electrode according to the order of the auxiliary electrode between the cathode and the anode, forming the electrode group of the micro-current electrolysis system; the arrangement of the electrode group composed of the plate electrode is shown in Fig. 6, and all the electrodes are used. Double-coated electrode, because the anode cost is relatively high, in the last group of arrangements, the mark A is the anode, the mark C is the cathode, the mark B is the auxiliary electrode, and the cathode C is the outermost side to ensure the device. Space utilization and cost reduction. In some embodiments a plastic positioning bracket is used, see Figures 7A, 7B, 7C, Figure
  • FIG. 7B is an enlarged schematic view of Fig. 7A
  • Fig. 7C is a cross-sectional view of B-B of Fig. 7B.
  • the electrode is fixed by a plastic positioning bracket. Since the conductivity of seawater is different from that of freshwater, in some embodiments different electrodes are selected by the controller to select different electrolysis modes through different conductances.
  • the schematic diagram of the controller can be seen in Figure 8, including The determination unit and the electrolysis mode unit, the electrolysis mode unit is divided into a seawater electrolysis mode unit, a fresh water electrolysis mode unit, and an inverted electrolysis mode unit.
  • the seawater electrolysis mode unit controls the auxiliary electrode B not working, and the electrolysis between the anode A and the cathode C is performed.
  • Electrolytic oxidation of chloride ions and water molecules in water to high oxidizing activity C10-, ⁇ , ⁇ 2 0 2 , (0)
  • oxidation of RNA and DNA of bacteria and algae in water Function, inactivation and death, thereby achieving the effect of sterilization and algae elimination, and maintaining the disinfection of the treated water body continuously
  • the diffusion and oxidative sterilization effect of the active material generated by electrolysis is not affected by the presence of the auxiliary electrode B; when the judging unit judges the conductance detected by the detector In the fresh water body with a rate less than 150 (S/cm, the fresh water electrolysis mode unit is triggered, the fresh water electrolysis mode unit controls the auxiliary electrode B as the cathode, and the original cathode C acts as the anode.
  • the properties of the original anode A are unchanged, and the corresponding electrode spacing
  • the electrolytic treatment of the low-conductivity freshwater body can greatly reduce the working voltage; in the higher-hardness water body, if the auxiliary electrode B works for a long time, the surface
  • the sedimentary carbonate reverse electrolysis mode unit can perform reverse electrolysis by changing the polarity of the original cathode C (one of the anodes when the fresh water system works) and the auxiliary electrode B according to the number of operations and the running time reaching a certain threshold.
  • the electrolysis mode unit changes the auxiliary electrode B to the anode, and serves as the original cathode C of one of the anodes.
  • the pole is changed to the cathode again, and the scale is removed electrically.
  • the original anode A does not work, and the catalytic activity of the anode A can be effectively protected, thereby ensuring the long-term stability and reliability of the operation of the device.
  • the scheme according to the law of long-term operation of the water tank, it operates in the same fresh water body, and uses constant current electrolysis. If the electrolysis potential is increased by 20% under the condition of constant current, it indicates that the cathode is definitely fouled during electrolysis.
  • the depolarization is performed by the reverse electrolysis mode, and the current density of the inverted electrolysis is not more than 20 mA/cm2.
  • the electrolysis time of the inverted pole does not need to be more than 1 hour; while in the seawater system, it is not necessary to use the reverse electrode to remove the scale.
  • the electrode group adopts the tubular electrode the same order can be followed: the auxiliary electrode is placed at the cathode and the anode.
  • the electrodes are equidistantly arranged in a radial direction, and are fixed by a plastic flange with a uniform support rib of no more than six to reduce water resistance.
  • an ultrasonic generator and an ultrasonic reflector for destroying bacteria and algae cells may also be included in the device.
  • the ultrasonic generator includes a housing, a transducer, a power supply, and a plurality of ultrasonic transducer arrays, It is evenly arranged in the shell and arranged in parallel with the arrangement direction of the plate electrode groups to increase the intensity of the ultrasonic waves and ensure uniform distribution of the ultrasonic field in the water body of the processing device; in the microcurrent electrolysis system of the tubular electrode group, it is preferable to adopt The rings are evenly arranged.
  • the ultrasonic reflector may be made of plastic, titanium metal, titanium alloy, stainless steel, carbon steel or copper alloy. To prevent corrosion of the material during system operation, titanium, titanium alloy, plastic Best for components.
  • the ultrasonic reflector may be a triangular prism or a semi-cylindrical body.
  • One cylinder of the triangular prism is connected to the casing and parallel to the electrode, and one edge of the triangular prism is perpendicular to the ultrasonic transmission direction of the ultrasonic generator; the semi-cylindrical body will The plane of the column is connected with the box body and parallel with the electrolysis electrode, and the curved surface is perpendicular to the ultrasonic wave transmission direction of the ultrasonic generator; this can ensure the effective change of the reflection direction of the ultrasonic wave, strengthen the cleaning effect of the electrode, and reduce the scaling phenomenon.
  • the ability to ultrasonically break bacteria and microbial cell walls is increased; among them, a triangular prism structure is preferably used to improve the uniformity of the ultrasonic field distribution.
  • the ultrasonic reflector is preferably a conical structure.
  • the structural diagram of the plate electrode in the device can be seen in FIG. 10, the box ultrasonic enhanced micro-current electrolysis sterilization algae removal device is connected to the water inlet flange 1, and the inductive conductance is arranged in the water inlet pipe.
  • the sensor 2 has a plate electrode assembly 4 in the box housing 5, and a plate electrode assembly 4 is provided with a plastic electrode fixing bracket 3 for fixing the plate electrode;
  • the box housing 5 is connected with the water flange 6 and is in the outlet
  • a residual chlorine electrode 7 and a residual chlorine transmitter are disposed on the water pipe;
  • an ultrasonic reflector 9 is installed in the device, and an electrode group sealing rubber pad 10 is mounted outside the plate electrode group 4, and is fixed on the box casing 5 through the cover plate 15,
  • And fixed by the fastener 11, the titanium anode 12, the cathode 13, and the titanium mesh auxiliary electrode 14 are mounted on the plastic electrode fixing bracket 3, and the ultrasonic generator housing 16 is installed at one end of the device, and the ultrasonic transducer is installed in the housing 16
  • a sealing rubber pad 18 is connected between the ultrasonic generator housing 16 and the casing, and is fixed by the ultrasonic generator cover 19.
  • the InPro7250HT inductive conductivity sensor 2 made of PEEK (polyetheretherketone) and the METTLER TOLEDO transmitter form the conductance detection and signal transmission part of the inlet water body, connecting the signal output terminal to the controller; using SZ283
  • the residual chlorine electrode 7 and the Italian B & C (CL3630 residual chlorine transmitter) form the residual chlorine detection and signal transmission part, and connect the signal output end to the controller.
  • the device employs U-PVC (polychlorinated) having a thickness of preferably 15 legs Made of vinyl) sheet.
  • the interior preferably has a box-shaped housing 5 having a net size of 1580 mm x 600 mm x 515 mm.
  • the outer diameter of the inlet connection flange 2 and the outlet connection flange 6 is preferably 350 legs, an inner diameter of 200 mm, and 8 bolt holes having a bore diameter of 22 mm are evenly distributed.
  • the ring with a diameter of 295 mm is connected to the water inlet pipe and the water outlet pipe by M20 fastening bolts, as shown in Fig. 11, and Fig. 11 is a schematic view in the direction A in Fig. 9.
  • the plate electrode group 4 is preferably a titanium anode 12 having a length of 800 mm, a width of 500, and a thickness of ⁇ 2.5.
  • the surface of the leg is coated with Ir, Rh oxide and TiO 2 ; preferably 800 mm long, 500 wide, and ⁇ 2. 5 mm.
  • the surface is coated with a coating of the oxide of Ta, Ti as a cathode 13; preferably a length of 800 legs, a width of 500nun, a thickness of ⁇ ⁇ . 3nun, a core material of metal titanium, a mesh (center distance) of 4. 5 legs xl2. 5mm, surface coating
  • a titanium mesh electrode covering the oxide of Ta, Ti serves as the auxiliary electrode 14; all electrodes have two terminals, see Figs. 12A to 12C, respectively.
  • 6 anodes, 7 cathodes, 12 mesh auxiliary electrodes are arranged on the plastic fixing bracket 3 according to the sequence center distance of the cathode, the auxiliary electrode and the anode.
  • the fixing groove of the fixing bracket has 15 legs from the bottom of the box.
  • the height of the plate electrode is 15 feet and is completely left in the plate of the case. Inside (the thickness of the plate forming the box is 15 legs), so that the electrode can be accurately positioned, and under the action of flowing water, no displacement and displacement occur; the electrode is inserted into the box from the mounting slot of the box, and the other side The two ends are embedded with the plastic fixing bracket 3, the mounting slot is 803 mm long and 3 legs wide for easy installation and positioning, see Fig. 15; between the mounting notch and the electrode sealing cover 15, a sealing rubber pad 10 with a thickness of 5 legs is added.
  • each electrode terminal uses a thick steel leg with a thickness of 4 legs, an outer diameter of 25 mm, a 17 mm x 3 mm through hole at the center, and a M30 bolt 31 with a central aperture of 18 mm and a height of 50 legs.
  • the sealing is fastened, and the electric wire is screwed to the electrode through the screw hole of the electrode terminal, and the electrode terminal, the metal pressing piece 30, and the hollow fastening bolt 31 constitute a terminal, as shown in Figs. 18A and 18B.
  • the electrodes in the plate electrode group 4 are connected to a linear constant current DC power source, as shown in FIG. 13, the linear constant current power supply output terminals i, iii, and v are positive output terminals, ii and iv are negative electrode output terminals; and the cathode 13 passes through the connection terminals.
  • auxiliary electrode 14 is respectively connected to the output terminals iv, V of the linear constant current DC power supply through the connection terminal 29, and the output terminals i, iii of the linear constant current DC power supply are respectively v is the positive output ⁇ >, ii, iv is the negative output.
  • the controller turns on the i, ii output terminal of the linear constant current DC power supply; in the fresh water system electrolysis operation (the conductivity is less than 150 (S/cm), the controller turns on the linear constant current DC power supply i, iii, iv output terminal; When the reverse pole descaling operation, the controller turns on the ii and V output terminals of the linear constant current DC power supply; the device can be stably and reliably operated in fresh water and seawater.
  • Ultrasonic reflector 9 A PVC-made Mitsubishi column with a 50-legged, 15-legged isosceles triangle and a length of 515 legs is used.
  • Each electrolysis unit in the controller determines the electrolysis mode according to the measured conductivity, and adjusts the electrolysis current and voltage according to the residual chlorine size; the voltage of the linear constant current DC power source, The current signal is transmitted to the controller, and the inverted electrolysis mode unit in the controller determines whether an inverted pole is needed; the controller can also select a corresponding number of ultrasonic transducers 17 to operate according to the predetermined power to perform the power of the ultrasonic generator. control.
  • the tubular micro-current electrolysis sterilization algae removal apparatus comprises a water inlet flange, an inductive conductivity sensor 2, a water outlet flange 6, a residual chlorine electrode 7, a residual chlorine transmitter, and an ultrasonic reflector.
  • the ultrasonic generator 33 and the ultrasonic reflector 41 are fastened together with the electrode group by bolts through the plastic tee 34, the intermediate sealing rubber pad 40, and the mounting of the sealing rubber pad 40 can be seen in Fig. 23B.
  • the shape of the ultrasonic reflector 41 is conical, and the tip of the cone faces the ultrasonic generator.
  • the tubular electrodes may be arranged in an annular shape. At this time, each of the ultrasonic transducers is also arranged in an annular shape and is concentric with the center of the tubular electrode.
  • the inlet connection flange 1 and the outlet connection flange 6 can be connected to the inlet pipe and the outlet pipe by fastening bolts, respectively.
  • the flanges 35-1, 35-2 are used to fix the rod-shaped titanium anode 39, see Fig. 23A, Fig. 23B, Fig. 24, Fig. 25, in order to reduce the water resistance, the plastic flange of the fixed electrode is uniformly distributed by not more than six.
  • the support ribs, the thickness of the flanges 35-1, 35-2 is generally not less than 12mm, and the flange 35-1 with the electrode lead 50 is drilled with a ⁇ 3.5 ⁇ ⁇ 5. Omm along the center of one of the support ribs.
  • the through hole of the fixed circular groove of the electrode is fixed, the depth of the fixed circular groove is 5 ⁇ 6mm, and the electrode lead is connected with the rod-shaped titanium anode 39 and the output terminal i of the linear constant current DC power supply, and the electrode and the plastic flange 35-1 are circularly grooved.
  • the gap between them is sealed with waterproof insulating glue, and the other end is fitted with a fixed circular groove of plastic flange 35-2 without electrode lead, which does not need to be bonded for easy disassembly; flange 36-1, 36-2
  • For fixing the porous tubular auxiliary electrode 37 see Fig. 23A, Fig. 23B, Fig. 26, Fig.
  • the plastic flange of the same fixed electrode adopts not more than six uniform supporting ribs, and the flange thickness is not Less than 12 legs, the diameter of the ring supporting the electrode is within the inner diameter of the porous tubular auxiliary electrode ⁇ - 2 legs ⁇ outside Between the diameter ⁇ + 2 ⁇ , a circular groove with a depth of 6 ⁇ 8mm is opened according to the diameter and thickness of the porous tubular auxiliary electrode for fixing the anode, and the flange 36-1 with the electrode lead is along the center of one of the support ribs The position is drilled with a circular groove through hole having a diameter of ⁇ 3.5 ⁇ ⁇ 5.0 leg to the fixed electrode, and the electrode lead is connected with the porous tubular auxiliary electrode 37, and the electrode lead is connected with the output terminals iv, V of the DC constant current power supply, and then The gap between the electrode and the groove of the plastic flange 36-1 is sealed with a waterproof insulating glue, and the other end of the other end of the
  • the tubular cathode 38 as the water pipe body passes through the lead terminal 42 with the copper gasket and the DC constant current power source.
  • the output terminals ii, iii are connected, and the porous tubular cathode 37 and the tubular cathode 38 are coaxial with the rod-shaped titanium anode 39.
  • the output terminals i, iii, and v of the linear constant current DC power supply are the positive output terminals, and ii and iv are the negative output terminals.
  • the controller turns on the i, iii, iv output terminals of the linear constant current DC power supply;
  • the controller is connected to the ii, V output terminals of the linear constant current DC power supply; the device can be stably and reliably transported in fresh water and sea water bodies.
  • the connection mode and control mode between the controller and the detector, the power supply of the ultrasonic generator, and the linear constant current DC power supply are the same as those in the first embodiment, and are not described herein again.
  • the linear constant current DC power supply in the device adopts a linear power supply with model specification of 0-30V/800A; the thickness of the leg is 1.5 legs, the mesh (center distance) is 3.0 legs X 6. Omm, the width of the drink net is 10nun, 1.5 legs thick
  • test water body is tap water, water quality indicators see Table 1; Table 1, experimental tap water quality:
  • GB15979 For the determination method, refer to GB15979, using 1.000 ml of water samples before and after treatment by microcurrent electrolysis sterilization algae removal apparatus, and sterilized agar medium, and incubated at 35 ⁇ 2 °C for 48 hours to count bacteria. The number of colonies, the bactericidal efficiency ⁇ was calculated by the formula (18), and three sets of parallel samples were taken to obtain an average value.
  • ⁇ is the number of colonies of water sample after electrolytic treatment
  • ⁇ is the number of colonies of the water sample before the electrolytic treatment.
  • the method for determining the algae killing method is approximated by chlorophyll change, and the treated water body is naturally placed for 24 hours with the untreated water body, and then the chlorophyll content in the two water bodies is tested to approximate the killing effect on the cyanobacteria. Although most algae cannot determine the life-and-death, the killed microorganisms are filtered into the filtrate and contribute to the determination of chlorophyll. Test results: (1), tap water body test:
  • the original tubular cathode 38 and the rod-shaped titanium anode 39 are both used as the electrolytic anode, and the auxiliary electrode 37 is used as the cathode, and the raw water is tested with reference to GB15979, respectively.
  • the bactericidal efficiency ⁇ is calculated according to the formula (18), and the results are shown in Table 5, which indicates that the water is treated by the box-type ultrasonic enhanced micro-current electrolysis sterilization algae removal device, and the working voltage is not more than 30V, which is good. It is a germicidal effect. Table 5, sterilization effect under different current density conditions
  • the sterilization and algae removal treatment of the marine farm adopts a box type micro-current electrolysis sterilization algae removal device with a treatment capacity of 300M3/hr, and the water body pump is treated according to the flow rate of 300M3/hr to the feeding device to the titanium anode 12 and The cathode 13 is operated, the auxiliary electrode is not working, the current density is 16 mA/cm2, and the operating voltage is 6.4 V.
  • the treated water body flows back to the culture tank along a channel of about 100 meters long at the edge of the pool, and runs for 6 hours per day, running 32.
  • the sterilization and algae removal treatment of the freshwater aquaculture pond adopts a box type micro-current electrolysis sterilization algae removal device with a treatment capacity of 300M3/hr, and the water body water pump is treated according to the flow rate increase device of 300M3/hr, the titanium anode 12 and the original
  • the cathode 13 is used as an electrolytic anode, and the auxiliary electrode 14 is used as a cathode.
  • the current density is 10 mA/cm2, and the operating voltage is 9.6 V.
  • the treated water body flows along the side of the pool at a distance of about 65 meters to the other end of the culture tank. , run 4 hours a day, run for 30 days, refer to GB15979 to test the total number of aerobic bacteria in the raw water and treated water on the first and last days, and compare the raw water chlorophyll with the treated water for 24 hours.
  • the chlorophyll in the water was presumed to kill algae. The results are shown in Table 7. The growth of algae was effectively inhibited during the operation of the device.
  • the device in the invention can obviously obtain the sterilization and algae removal effect of the device of the invention by the above test, and can be simultaneously applied to seawater or fresh water for sterilization and algae removal, and can realize automatic descaling, and has wide application range;
  • the ultrasonic generator is added to effectively destroy various bacteria and algae cells by ultrasonic waves; the device is simple and has a wide range of applications. All modifications, equivalents, improvements, etc., made within the spirit and scope of the present invention are intended to be included within the scope of the present invention.

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Description

一种利用微电流电解灭菌除藻的装置和方法 技术领域 本发明涉及灭菌除藻设备和方法，特别是指一种利用微电流电解 灭菌除藻的装置和方法。 背景技术
蓝细菌 ( cyanobacteria ) 亦称蓝藻或蓝绿藻 (blue-green a lgae)。 它们的细胞核结构中无核膜、核仁， 属原核生物， 不进行有 丝分裂， 细胞壁也与细菌相似， 由肽聚糖组成， 革兰氏染色阴性， 故 它们归属于原核微生物中。 蓝细菌为单细胞生物， 个体比细菌大， 一般直径或宽度为 3 - 15μπι。 但是， 蓝细菌很少以单一个体生活， 通常是在分裂后仍聚集 在一起， 形成丝状或单细胞的群体。 当许多个体聚集在一起， 可形成 很大的群体， 肉眼可见。蓝细菌主要生长在水体表层， 即水面下 0. 5m 之间， 多数蓝细菌为蓝色或蓝绿色， 所以， 人们习惯上仍然称它为蓝 蓝细菌分布广泛， 从南极到北极， 从海洋到高山均可见其踪迹。 它们常生长在岩石、树皮或在池塘、 湖泊中生长， 繁殖旺盛， 使水体 的颜色随蓝细菌本身的颜色而变化。 有的种类能发生草腥味或霉臭 味。 蓝细菌含有色素系统（主要含有藻蓝素， 此外还含有叶绿素 α、 胡萝卜素或藻红素）。 由于每种蓝细菌细胞内所含有各种色素的比例 不一， 所以， 可能呈蓝、 绿、 红等颜色。 蓝细菌的营养简单， 不需要 维生素， 以硝酸盐或氨作为氮源， 能固氮的种很多。 某些种具有圓形 的异形胞（hererocys t ), —般延着丝状体或在一端单个地分布， 是 蓝细菌进行固氮作用的场所。蓝细菌进行放氧性的光合作用，为专性 光能无机营养微生物， 其反应如下
C02 + H20 = [CH20]细胞物质 + 02 (g) 这些特点与一般藻类相似。其繁殖以裂殖为主，少数种类有孢子； 丝状蓝细菌还可通过断裂形成断殖体进行繁殖， 没有有性繁殖。
当水体中排入大量含氮和磷的物质，导致水体富营养化，则使蓝 细菌过度繁殖，将水面覆盖并使水体形成各种不同色彩的现象，在淡 水域称为"水华"（water bloom), 在海水域称为赤潮。 能形成"水华" 的蓝细菌包括微嚢藻属（Microcystis), 鱼腥藻属（ Anabaena )、 颤 藻属（Oscillatoria)等属中的一些种。 由蓝细菌形成的"水华"往往 有剧毒， 如铜色微嚢藻 （Microcystis aerugeosa ) 和水华鱼腥藻 ( Anabaena flos-aguae)等， 家禽或家畜饮用这种水后不到一小时 甚至几分钟内就可中毒死亡， 而且也能引起水生生物（如鱼类）中毒 死亡。 由于大量蓝细菌将水面覆盖从而阻碍了水体复氧， 同时大量蓝 细菌因死亡而腐败， 致使水体因而缺氧而发臭， 形成恶性循环。 （任 南琪等， 污染控制微生物学， p38 - 39，哈尔滨工业大学出版社， 2002 年出版）。
天然水体中，除了水体富营养化产生的大量蓝藻以外， 尚有许多 有害细菌和病毒等，如大脉杆菌（ Col i form)、脉道球菌（ Enterococcus group), 霍乱菌 (Vibrio cholerae)等等， 这些菌体在船舶航行所 采集的压载水中， 有可能被带往其它水域， 引发生态灾难。 通常为减 小船舶过大的弯曲力矩和剪切力，减轻船体震动， 几乎所有的船舶都 设有压载水系统。实验证明，长期积存在压载水抢中的压载水中存在 大量的细菌、病原体和其他的一些非本地的微生物。在富含铁元素的 压载水抢中，它们可以迅速繁殖并存活几周甚至更长的时间。 当船舶 将这些外来的或新的微生物排出时， 会造成当地的生态环境平衡失 调。 一般而言， 这些微生物对人体有害， 一旦发生压载水的泄漏， 会 污染环境、 船舶， 威胁人员的健康， 也可能造成货物的损坏。 随着人 们环境保护观念的增强， 这个问题显得越来越突出。 IM0 ( International Maritime Organization, 国际海事组织)调查结 果发现， 4种曱藻等有毒藻类是通过船舶压载水传播到中国的， 并造 成大面积的赤潮灾害 （刘富斌， 船舶， 2006年 8月.第 4期）。 2004 年国家环保总局公布， 我国由于生物入侵造成的直接经济损失高达 574亿元， 其中海洋生物入侵是主要成因之一。 针对这类情况，人们很早就进行多方面的努力， 以期避免有害生 物和病原体通过压载水污染其它水域或造成生态灾难。早在 1982年， IM0出台的 《1982年联合国海洋法公约》 (UNCL0S, United Nations Conference on the Law of the Sea )第 196 ( 1 )条规定， "各国应 采取一切必要措施以防止、减少和控制由于在其管辖或控制下使用技 术而造成的海洋环境污染，或由于故意或偶然在海洋环境某一特定区 域引入外来的或新的物种致使海洋环境可能发生重大和有害的变 化"； 2002年世界可持续发展峰会实施计划的 34 ( b )条， 意识到船 舶无控制地排放压载水和沉积物已经造成有害水生物和病原体的转 移， 对环境、人类健康、 财产和资源造成伤害或损坏， 号召各方行动 起来加快制定解决压载水引入外来生物问题的措施；目前一些国家已 经采取单边行动以防止、最大限度地减少并最终消除通过船舶进入其 港口引入有害水生物和病原体的风险，且这一问题上引起了全世界的 广泛关注， 急需要制定一个全球适用的规则以及导则，使其有效实施 并统一解释， 继续推进更安全、有效的压载水管理方法的发展， 从而 继续防止、 最大限度地减少并最终消除有害水生物和病原体的转移； 在此基础上， IM0制定《国际船舶压载水和沉积物控制与管理公约》， 通过控制和管理船舶压载水和沉积物以防止、最大限度地减少并最终 消除有害水生物和病原体的转移造成的环境、人类健康、财产及资源 风险， 并避免此种控制造成的不必要的消极影响， 并且鼓励、促进相 关知识和技术的发展；这个公约虽然美国和我国目前尚未签字， 多数 发达国家已经签字，全球范围内按此条约实现压载水的管理，只是一 个时间问题。 针对大面积水体的蓝藻治理和防止外来有害水生物、病原体入侵 的技术及相应的装备和设施， 必须具备以下特征：
( 1 )、 杀灭微生物和病原体速度必须很快： 否则， 在大面积水体 中， 当处理后的水再次进入本体水中， 如果加入的是杀生剂， 就会很 快被稀释而减弱杀菌能力，加上大量未杀灭的微生物，很快会大规模 繁殖， 治理效果很差； 如果应用于压舱水处理中， 压舱水抽入和排放 通过装置只有很短的时间，如果杀灭微生物和病原体速度不够快，其 处理后的水体就不能达标； ( 2 )、 杀灭效率高： 《2004年国际船舶压载水和沉积物控制与管 理公约》 的规则 D- 2条规定的排放压载水性能标准必须满足：
(a) . 每立方米中最小尺寸大于或等于 50微米的可生存生物少 于 10个； 且
(b) . 每毫升中最小尺寸小于 50微米但大于或等于 10微米的可 生存生物少于 10个； 且
(c) .作为一种人体健康标准， 指标微生物应小于下述浓度：
(0.有毒霍乱弧菌少于每 100毫升 1个菌落形成单位（cfu )或 小于每一克（湿重）浮游动物样品 1个 cfu; (i i) . 大肠杆菌： 少于每 100毫升 250 cfu; 及
(i i i) . 肠道球菌： 少于每 100毫升 100 cfu;
( 3 )、 对生态环境不能产生二次危害；
( 4 )、 处理能力大： 大面积水体如湖泊的富营养化问题， 杀菌灭 藻的处理能力是关键因素之一；对于船舶压舱水处理，船舶不可能长 时间停留， 一般要求单机处理能力在 300M3/hr以上。
现有的水体富营养化和蓝藻的治理技术体系，以及压舱水处理技 术体系， 主要有： ( 1 )杀生药剂， （2 )滤网捞集和膜处理技术， （3 ) 超声技术， （ 4 )高压灭藻， （ 5 )生物治理， （ 6 )生态治理， （ 7 )紫外 灭菌技术， （8 ) 电解产生活性物质灭菌技术。 杀生药剂
中国专利申请号 02100332公开一种应用于工业水领域以及公共 场所、污水回用领域的氧化型含溴复合杀生剂-溴氯威； 中国专利申 请号 200510025284推出一种由戊二醛， 季胺盐构成的醛类复合高效 杀生剂；中国专利申请号 200510025395公开了一种含有异噻唑啉酮、 氯化十二烷基二曱基苄基铵、 用于污水处理的杀生剂； WIP0 (世界知 识产权组织）公开的国际专利 WO03002406 采用铜阳极电解产生铜离 子杀菌。 这类杀生剂的生物毒性较大， 残留时间长， 在国内尚可以应 用于循环式污水或冷却水系统中的杀菌处理，不适合于湖泊等大面积 富营养化水体和需要排放的压舱水处理。
美国专利 US2005016933 采用添加 C102作为杀生剂， 国际专利 WO2005061388, 美国专利 US2004099608和 US2003029811、 日本专利 JP200714439K JP2006239556、 JP2006263563, 分别公开了采用过滤 和添加臭氧作为杀生剂的水处理技术和相应的装置， 这类装置和技 术， 没有二次污染， 在小流量水体或饮用水杀菌处理中有一定优势， 但对于压抢水等大流量水体或大流域水体的灭菌除藻处理，运行成本 4艮高。
通常， 加入杀生药剂， 对局域小水体效果很好， 但难以维持较长 时间， 在夏季 1-2周后， 一般又需加药。 对于治理大面积， 富营养化 水体存在运行成本高、杀生剂对水体存在二次污染等问题；如果应用 于压抢水处理， 其残留物尚需通过生物毒性和毒理评价。 滤网捞集和膜处理技术 滤网捞集、以及过滤这类机械方法清除蓝藻，如目前昆明滇池在 蓝藻大规模爆发的夏季， 对于大面积水体的治理， 不过杯水车薪， 难 见成效； 这种技术和相应的装置， 不可能有效除去有害细菌（有毒霍 乱弧菌、 大肠杆菌、 肠道球菌等）和病毒， 无法满足压抢水处理的要 求， 不适于压抢水处理。 这种技术方案， 多作为水处理中过滤大颗粒 悬浮物或泥沙的辅助手段。 目前， 发达国家多采用膜处理技术和相应的装置， 过滤微生物、 浮游生物和细菌， 如日本专利 JP2005342626 , JP20060099157 , JP2006223997 , JP2005342626 , 国际专利 WO2007114198 , 均采用膜 技术将抽入作为压舱水的海水或淡水中的细菌和微生物过滤，这类技 术和装置需要较高的压力， 耗能大， 并且膜很容易被污染和堵塞； 对 于大面积水体的蓝藻治理和快速流动的大流量水体， 运行成本较高， 处理能力不可能满足相应的要求。 超声波技术 超声波不但有强烈的振动，而且还具有空化作用并产生大量的微 射流，可以使液体对容器壁产生强烈的冲击作用，这样的功能被应用 于超声清洗， 也被应用于增强反应效果， 如中国专利申请号 200510117457 所公布的一种基于超声作用的内电解废水处理方法和 装置， 和中国申请号 99120675所公布的一种超声波水处理的方法及 其装置， 应用于增强絮凝效果； 如中国专利申请号 200610085548所 公布的偶氮染料废水处理方法， 和德国专利 DE19919824所公开的氧 化有机锡技术，采用超声波促进化学反应的进行。超声空化作用产生 的微区高压，可以用于细胞的破碎，但这样的效果多是将超声能量汇 聚在较小的区域内才能实现， 因此， 目前的超声技术和相应的水处理 装置， 对于小体积水体， 并可以采用循环流动的水体， 实施可操作性 比较大， 如中国专利申请号 200610023241所公布的声光杀菌饮用水 处理装置。
日本专利 JP2006007184将超声换能器 ( 28 ~ 200KHz )加于管道 外壁， 通过超声波将通过管道的压舱水进行杀菌灭藻处理； JP2005021814 则提供相应的压抢水管式超声灭菌除藻装置， 装置中 将超声换能器安装于箱体两侧，水路从箱体中通过，超声波将经过的 水体中微生物杀灭；这两份专利均没有考虑到超声波的对于安装于对 面管壁或箱体的超声换能器压电陶瓷的损伤，而且垂直于超声换能器 的反射回波对压电陶瓷的损伤同样不能忽略，否则直接影响超声换能 器的寿命， 从而降低装置的运行稳定性和可靠性。 专利申请号
98236857所公布的超声波水处理机，和国际专利 WO03095370所推出 的一种环形、连续的超声处理压抢水装置，其超声换能器面临同样的 问题。 但对于大面积水体的蓝藻治理和快速流动的大流量水体，现有的 超声处理装置， 除了上述问题之外， 如果单独采用超声技术处理， 尚 存在能耗高，运行成本高， 杀灭效果难以保证等不利因素， 不具备可 操作性。 高压灭藻 高压杀菌和灭藻，是采用将水体加压到一定程度，使细菌和藻类 的细胞破裂， 如日 本专利 JP2007021287、 JP2005270754、 JP2005254138,但对于大面积水体的蓝藻治理， 高压灭藻同样存在能 耗高， 运行成本高等不利因素， 不具备可操作性； 针对压抢水处理， 也存在处理能力和运行成本的问题。 生物治理 对于淡水富营养化水体，人们寄希望于生物治理，但生物治理有 可能因引入外来生物对本地物种造成生物灾难。而且，蓝藻实际是蓝 细菌， 产生的毒素在 ppm 级就可以使鱼类、 家禽在数分钟内死亡； Satoshi Naka i 在 2001 发表的工作报告中 （ ALGAL GROWTH INHIBITION EFFECTS AND INDUCEMENT MODES BY PLANT- PRODUCING PHENOLS SATOSHI NAKAI* , YUTAKA IN0UE and MASAAKI H0S0MI , Water Research, Vol. 35 , Issue 7， May 2001， Pages 1855-1859 )指 出， 草和其他水生植物可以在一定程度上减少水质的富营养化程度， 但较少有植物能释放可以抑制蓝细菌的生长的酚类物质。对于海水体 系的赤潮，生物治理是不现实的。 目前生物法对藻类的治理尚处于探 索阶段，国际上尚无对大规模富营养化水体采用生物防治蓝藻的成功 先例， 而且由于蓝藻所包含的蓝细菌种属较多，难以用一种或有限的 几种微生物、噬菌体对蓝藻实现总体抑制。 另外， 从处理速度和效率 考虑， 生物治理技术不适合压抢水的处理。 生态治理 在外源污染得到控制的情况下，恢复水生高等植物以提高水体的 自净能力，是湖泊富营养化治理和生态恢复的关键。但这种方法见效 时间较长，难以在短期内实现富营养化水体的蓝藻控制。而富营养化 水体的蓝藻爆发， 会将水面覆盖， 阻碍水体复氧， 同时大量蓝细菌因 死亡而腐败， 消耗水体的溶解氧而使水体发臭，导致鱼类死亡和其他 水生动物死亡， 形成恶性循环。 同样， 生态治理技术不适合压抢水的 处理。 紫外灭菌技术
由于水体本身对紫外线的强烈吸收作用，使得紫外线灭菌作用的 范围和灭菌能力受到制约，一般紫外线灭菌技术多应用于处理负荷较 低的小体积水体和循环流动的水体。 如中国专利申请号 20051114所 公开的紫外线水处理灭菌系统、 200610093390 所公开的家庭饮用水 处理机。
美国 专利 US2004134861 和 US2005211639、 国 际专利 线连续处理压抢水装置； 另外， 紫外线辐照与超声结合， 可以加强杀 菌效果， 如中国专利申请号 20060112所公开的声光杀菌饮用水处理 装置， 和 200520087812所公开的应用于养殖海水处理的海水强力紫 外线消毒过滤器；美国专利 US5738780将紫外线杀菌与直流电解结合 在一起，应用于压舱水处理。但这些技术仍然受到紫外线灭菌作用的 范围和灭菌能力的制约，对于高负荷、大流量水体和大面积水体的杀 菌效果， 还是不能令人满意。
电解产生活性物质灭菌技术 以添加食盐、 然后通过电解产生次氯酸消毒灭菌的技术和装置， 前人有许多工作，包括中国专利申请号 200610042972. 2公开的 "一种 双功能电解水生成器"、 200510111126. 7公开的 "一种小型消毒水生 成器及其使用方法"、 200520077629. 2公开的 "便携式水源消毒机"、 200510023766. 2公开的 "高浓度次氯酸消毒水的制备方法"， 比直接 添加漂白粉、 二氧化氯、 双氧水等方案要便捷、 节省成本， 但会 增大所处理水体的盐度，尤其对于大面积湖泊、水库的富营养化水体 的杀菌、 灭藻处理， 长期运转条件下， 所有添加药剂和增大水体盐度 的措施， 均是不可接受的。
国际专利 WO2006058261公开了一种采用电解产生次氯酸盐的压 抢水处理方法和相应的系统、 日本专利 JP2001000974公开的电解处 理压抢水装置、 和与此类似的还有中国专利申请号 200510046991公 开的船舶压载水 （压舱水） 电解处理系统、 中国专利申请号 200480027174公开的处理水贮存器的电解装置， 将处理水体中的氯 离子、水分子电解为具有高氧化活性的物质 （C10-，· 0Η， Η202, (0) )， 对水体中的细菌和藻类的细胞、 RNA、 DNA进行氧化作用， 使其失活 和死亡，从而达到灭菌灭藻效果，并使处理过的水体保持持续消毒作 用。 这种方法和系统存在两种缺陷：
( 1 )、体系的电极间距满足压舱水在海水中的电解设计要求，不 能满足淡水体系的要求， 因为船舶在^水域和停靠的港口，有的是 靠近江河口，属于淡水区域，二者由于水体电导率差异而引起的电解 电压变化太大。 电解体系施加于阳极和阴极之间的电压有三部分构成， 参见 图 1 , 其中：
U1: 由阳极氧化反应的电极电位和极化超电势构成，如果电化学 反应的极化现象可以忽略， 对于特定的反应体系（反应浓度、 pH、 温 度不变）， U1基本不变， 不随电流密度改变而变化；
U2: 溶液的电阻引起的压降， 溶液电导率越低， 则电阻 R越大， 随电流密度的增大而升高；
U3: 由阴极还原反应的电极电位和极化超电势构成，如果反应极 化现象可以忽略并且不存在阴极被悬浮物和无机物沾污、 包覆现象， 对于特定的反应体系 （反应浓度、 pH、 温度不变）， U3基本不变， 不 随电流密度改变而变化。 要保证体系一定的杀菌、灭藻能力， 电解电流 I基本上要求恒定 在一定数值之上， 如果电极间距为 d (对于目前所有公开采取电解法 的体系， 均没有在体系运行中考虑改变电极间距的设计）， 电极面积 为 S， 水体电导率为 μ， 则存在如下关系： d/
U2 = IR = Ix ( /( 〃）） ( 1 ) 对于一定的电解系统， 由于 I、 d、 S为确定值， 但不同类型的水 有不同的电导率， 海水体系为 3000( S/cm; 河口水体， 退潮时， 水 流表现为向海洋的单一流向， 虽受海洋潮汐影响，此时交汇区的水化 学组成近似于江河水质， 电导率可以在 50— 50( S/cm之间；平潮时， 既有河流的下泻， 也有潮流的上溯， 此时交汇区的水质较复杂， 而且 不稳定； 涨潮时， 潮汐对河口区影响大， 海水可上溯到河口内很深的 距离， 此时交汇区中水的化学组成则表现出海水特征。 因此， 当河口 水体的在 50— 50( S/cm之间时， 至少与海洋水体相差 60倍以上， 从（1)式可知， 施加于阳极和阴极之间的水体上的电压 U2， 至少有 60倍以上的差别， 很难保证电解系统在安全电压范围内可以满足船 舶运行于不同水域对压舱水处理的要求。
(2)、在淡水体系中阴极存在结垢现象，并致使阴极与水体之间 的电阻急剧增大， 影响电解效率， 如果需要保证电流恒定， 则整体的 电解电压急剧升高， 体系无法正常运行。 在淡水体系中， 电解过程在阴极的结垢主要是 CaC03， 由于阴极 表面和阴极区域吸附大量的阳离子以满足电荷平衡，水体中阳离子浓 度没有很大的差异， Ca2+电荷较高， 在阴极表面和阴极区域富集， 在 该局部区域与水体中的 HC03发生如下反应：
Ca2+ + HC03" =CaC03(s, + H+ (2) Jeffrey A. Franz在关于电解产氧过程中阴极沉淀 /结垢引起的 电极表面的污染对好氧生物降解体系影响的研究 （Water Research, Vol.36, Issue 9， May 2002， Pages 2243-2254 ) 中指出， 阴极 表面沉淀主要为 CaC03。在先申请专利 99253589所公开的水箱自洁消 毒器在长期运行过程中， 阴极有明显的 CaC03沉淀， 在硬度较高的地 区使用， 甚至因为反应 (2)产生的 CaC03沉淀造成电解管路堵塞； 在申请专利号 03156596.4"组合式微电流电解水处理技术和装置"， 虽然超声探头对电极表面进行清洗的过程中，可以使结垢问题得到緩 解， 但对水生生态体系有可能产生不利的影响， 长期运行过程中， 阴 极表面仍然存在轻微结垢现象；该装置虽然可以实现对大面积富营养 化水体的蓝藻有效的治理和抑制， 但多组平行的电极， 使安装平台 (船、浮筒）在移动过程中， 造成转向困难； 而且， 水生动物（鱼类） 容易进入电极之间， 遭致电击， 并形成电极短路； 这种装置固定于水 槽中将海水养殖的水通过水槽进行电解灭菌、消毒处理，处理海水以 1.0-1.5m/ s的流速通过安装电解装置的水槽， 长期运行后 (至少 3 个月以上）其槽底出现小量的白色沉淀（槽底离电极边缘 2cm)， 但 阴极表面不被沉淀覆盖。 中国专利申请号 200520114686.3所推出的 "蓝藻治理装置"， 同样面临类似的 CaC03沉积和结垢问题。
CaC03存在三种晶型： 方解石 （calcite)、 文石 （aragonite)和 球文石 （vaterite), 方解石 （ calcite )容易形成比较致密的结构， 在电极上不易脱落； 文石 （aragonite) —般在模板存在下或者高温 下 （80°C以上）结晶、 生长才能形成， 电解过程不具备这样的条件； 球文石（ vaterite)结构疏松， 容易脱落。 我们将应用于海水养殖消 毒环境的组合式微电流电解水处理装置的白色沉积物、淡水养殖水处 理的组合式微电流电解水处理装置的阴极表面的白色结垢、和高楼水 箱使用的水箱自洁消毒器的阴极表面的白色结垢刮下，分别进行场发 射电子扫描分析 (SEM)照片和红外（IR)吸收分析， 结果如图 2a、 2b、 2c和图 3所示， 其中， 图 3中 a曲线是海水吸收分析曲线， b 曲线是淡水吸收分析曲线， c曲线是自来水吸收分析。 从图 2a可以看出， 海水养殖电解处理体的白色沉淀颗粒相对较 小， 大部分为球形； 图 2b和图 2c分别为淡水养殖的电解处理体系的 阴极表面的结垢和高楼水箱使用的水箱自洁消毒器的阴极表面的白 色结垢的 SEM照片， 颗粒较大； 与此对应的 IR吸收 i普图 3表明， 曲 线 a为海水养殖电解处理体系的白色沉淀颗粒的红外吸收 i普，除了方 解石 （calcite) 的碳酸根面内弯曲振动 v4特征吸收峰 712 cm1和碳 酸根面外弯曲振动 v2吸收峰 875 cm1之外， 还有球文石 （vaterite) 的特征吸收带 745 cm1, 与淡水养殖的电解处理体系的阴极表面结垢 的红外吸收 i普 b、和高楼水箱使用的水箱自洁消毒器的阴极表面白色 结垢的红外吸收 i普； c有显著区别， b和 c十分相似， 属于典型的方 解石 （calcite)红外吸收 i普； 这与 SEM的分析结果相符。 针对解决电解过程中阴极结垢问题， 中国专利申请号 200620032114 所公开的一种倒极运行的电化学反应器， 借助于倒极 使阴极结垢脱落； 这种倒极方法又引入一个新问题， 频繁倒极除垢， 将使电解装置的阳极丧失催化活性，导致电极产生很高的超电势， 电 流效率下降。 目前， 电解产生氧化性物质以进行水处理的体系，一般均采用具 有催化活性的 DSA阳极（Dimensionally Stable Anode) , 是以金属钛 或钛合金为基体在其表面涂覆以铂族元素氧化物的一种电极材料，是 荷兰人 Henri Bernard Beer (1909— 1994)发明的。 H. Beer 65 专 利是一种以钛或钛合金为芯材 /基材， 从铂、 铱、 铑、 钯、 钌、 锇中 选择铂族金属或其合金的氧化物，特别是含有一种以上的非铂族金属 氧化物 （如 Ta、 Ti)， 组成外层电极； 意大利 De Nora公司和美国 Diamond Shamrock公司于 1968年成功地将 Beer发明应用于氯减生 产中。其食盐电解用阳极开发了钛基铂族金属氧化物电极，催化活性 高， 而且能使用 15年以上。 DSA自 20世纪 60年代末问世后， 至今 已经历时 40年整。张招贤在关于 "涂层电极 40年"一文中指出（电镀 与涂饰， 2007年第 26卷第 1期）， 钛阳极的诞生极大地推进了食盐 电解生产的发展， 被誉为氯碱工业一大技术革命。 DSA 的发明是 20 世纪电化学工业最重大的发明之一， 是对电化学领域划时代的贡献。 但这种电极， 如果作为阴极使用， 则由于 Pt、 Ir、 Ru、 Rh、 Pd和 Ti 均为强吸氢材料， 阴极反应产生的 H2被 Pt、 Ir、 Ru、 Rh、 Pd和 Ti 所吸附，致使体积膨胀引起涂层与芯材之间剥离，导致涂层和活性物 质脱落， 丧失催化活性。 由于大面积富营养化水体和大流量压抢水处理技术所存在上述 的缺陷，导致无法同时适用于淡水和海水体系、不能有效杀灭细菌和 蓝藻、 运行成本高、 会造成二次污染。 有鉴于此，本领域中仍然需要一种微电流电解灭菌除藻装置， 以 解决上述水处理技术中，无法同时适用于淡水和海水体系、不能有效 杀灭细菌和蓝藻的问题。 发明内容 本发明的一个方面提供一种微电流电解灭菌除藻装置， 包括： 安装在箱体的进水管道上感应溶液电导值的检测器，所述箱体内 按照组内阳极、 辅助电极、 阴极的顺序安装至少一组以上的电极组， 控制器判断所述电导值的大小，控制所述箱体内电极的极性、及电路 连接； 所述控制器内包括： 判断单元，用于判断所述电导值的大小，并按照判断结果触发相 应的海水电解模式单元、淡水电解模式单元、和倒极电解模式单元工 作；
所述海水电解模式单元，用于接收触发后，导通所述阳极和阴极 的电路连接， 断开辅助电极的电路连接； 所述淡水电解模式单元，用于接收触发后，将所述阴极的极性改 为阳极， 将所述辅助电极的极性改为阴极， 导通未改变极性的阳极、 由阴极改变极性而成的阳极、和由辅助电极改变极性而成的阴极的电 路连接； 所述倒极模式单元，用于判断装置的运行次数、运行时间超过设 定阈值后，将所述辅助电极的极性改为阳极，导通由所述辅助电极改 变极性而成的阳极和未改变极性的阴极的电路连接，断开未改变极性 的阳极的电路连接。 在本发明的一些实施方案中，所述电极组内的电极形状为片状电 极或管状电极。 在本发明的一些实施方案中，所述微电流电解灭菌除藻装置还包 括： 安装在所述箱体两端的超声发生器、及超声波反射体， 所述超声 发生器内包括至少一个以上超声换能器，所述电极组的位置在所述超 声发生器和超声波反射体之间。 在本发明的一些实施方案中，所述电极形状为片状时，所述超声 波反射体的形状为三棱柱形或者圓弧形，棱柱的棱边或圓弧朝向超声 发生器的方向凸出； 所述电极形状为管状时，所述超声波反射体的形状为圓锥形， 圓 锥的顶尖朝向超声发生器。 在本发明的一些实施方案中，所述电极形状为管状时，所述各个 电极、 各个超声换能器呈同一圓心的圓环状排列。 在本发明的一些实施方案中，所述检测器为电导率感应式电导传 感器或电导变送器。 在本发明的一些实施方案中，所述的阳极至少是以金属钛或钛合 金的一种为基体， 在其表面涂覆含有金属 Pt、 Ir、 Ru、 Rh、 Pd或 0s、 及其氧化物中至少一种， 和含有至少 Ta或 Ti 的氧化物的涂层电极 ( DSA )。 在本发明的一些实施方案中，所述辅助电极和阴极至少是以金属 钛或钛合金的一种为优选的， 所述超声反射体的材料至少包括塑料、 金属钛、 钛合金、 不锈钢、 碳钢或铜合金的一种材料构件。 在本发明的一些实施方案中，所述微电流电解灭菌除藻装置还包 括：安装在所述箱体出水管道上用于检测电解后溶液中氯含量的电位 计或余氯电极、及余氯变送器； 所述各个电解单元按照所述氯含量值 调节电解的电流、 电压值。 本发明的另一个方面提供上述微电流电解灭菌除藻装置在水体中 灭菌除藻的用途。 在一些情况下， 所述水体是海水或淡水。
本发明的再另一个方面提供一种利用微电流电解在水体中灭菌除 藻的方法， 包括： 1)检测所述水体的电导值；
2)传送所述电导值至判断单元；
3) 判断所述电导值；
4)按照判断结果触发控制器的海水电解模式单元、淡水电解模式 单元或倒极电解模式单元工作， 以便控制水体中的阳极、 辅助电 极和阴极的极性及电路连接。 在本发明方法的一些实施方案中， 其中当所述海水电解模式单元 工作时，导通所述阳极、阴极的电路连接，断开辅助电极的电路连接。 在本发明方法的一些实施方案中， 其中当所述淡水电解模式单元 工作时，将所述阴极的极性改为阳极，将所述辅助电极的极性改为阴 极， 导通未改变极性的阳极、 由阴极改变极性而成的阳极、和由辅助 电极改变极性而成的阴极的电路连接。 在本发明方法的一些实施方案中， 其中当所述倒极模式单元工作 时， 判断装置的运行次数、运行时间超过设定阈值后， 将所述辅助电 极的极性改为阳极，导通由辅助电极改变极性而成的阳极和未改变极 性的阴极的电路连接， 断开未改变极性的阳极的电路连接。 在本发明方法的一些实施方案中， 其中所述水体可以是任何合适 的水体， 例如海水或淡水。 在本发明方法的一些实施方案中， 其中所述方法还包括对至少部 分水体施加超声波。
在本发明方法的一些实施方案中，其中所述方法还包括检测电解 后水体中的氯含量，以及按照所述氯含量值调节电解的电流、电压值。 本发明中的装置和方法可同时应用到海水或淡水中灭菌除藻，具 有良好的杀菌除藻效果， 并可实现自动除垢， 且应用范围广； 并加入 超声发生器， 通过超声波有效破坏各种细菌和藻类细胞； 设备简单， 且应用范围广泛。 附图说明 图 1是电解体系统的示意图； 图 2a海水养殖电解处理体的白色沉淀颗粒示意图；
图 2b淡水养殖的电解处理体系的阴极表面的结垢示意图； 图 2c高楼水箱使用的水箱自洁消毒器的阴极表面的白色结垢示 意图；
图 3是不同水质 IR吸收 i普图的曲线示意图； 图 4是微电流电解灭菌除藻装置的示意图； 图 5a是微电流电解器的电极组的板状钛阳极结构示意图； 图 5b是微电流电解器的电极组的板状钛阴极结构示意图； 图 5c是微电流电解器的电极组的平板式辅助电极结构示意图； 图 6是微电流电解器中板状电极组排列示意图； 图 7A是塑料电极固定支架结构示意图； 图 7B是图 7A中部分放大的示意图； 图 7C是图 7B中 B- B的剖视图； 图 8是该装置中控制器的结构图； 图 9A是超声换能器发射的超声波传输方向示意图； 图 9B是超声反射体所反射的超声波传输方向示意图； 图 10是箱式微电流电解灭菌除藻装置示意图； 图 11是图 9中 A- A向的示意图； 图 12A是 800腿 x500腿饮阳极 ( δ = 2. Omm )结构图； 图 12B是 800腿 x500腿钛阴极（δ = 2. Omm )结构图； 图 12C是 800腿 χ500腿钛网辅助电极（δ = 1. 3nun )结构图； 图 13是微电流电解灭菌除藻装置的控制原理图； 图 14是箱式微电流电解灭菌除藻装置的电极排列结构示意图； 图 15是图 9中 B向的示意图； 图 16是箱式微电流电解灭菌除藻装置密封电极组橡胶垫的电极 接线端出口排列结构示意图；
图 17是箱式微电流电解灭菌除藻装置电极密封盖板电极接线示 意图；
图 18 A是接线端子的主视图； 图 18B是接线端子的左视图； 图 19是三菱柱排列结构示意图； 图 20是箱式微电流电解灭菌除藻装置超声发生器排列示意图； 图 21是超声发生器与箱体、 超声发生器盖板连接的密封橡胶垫 结构示意图；
图 22是图 9中 C向的示意图； 图 23A是管式微电流电解灭菌除藻装置的超声强化微电流电解 系统结构示意图；
图 23B是图 23A中的局部放大示意图； 图 24是固定棒状钛阳极、包含电极引线的塑料法兰结构示意图； 图 25是固定棒状钛阳极、 不包含电极引线的塑料法兰结构示意 图；
图 26是为固定多孔管状辅助电极、 包含电极引线的塑料法兰结 构示意图；
图 27是为固定多孔管状辅助电极、 不包含电极引线的塑料法兰 结构示意图。 具体实施方式 为清楚说明本发明的装置，下面结合附图并给出实施例和详细说 明， 然而这些附图和实施例仅用于说明的目的而并非用于限制本发 明。
作为本发明某些实施方案的实施例 1的原理图可参见图 4，包括： 检测器检测进水管路中的电导， 控制器判断检测器所检测到的电导， 不同的电导下控制超声强化微电流电解器在相应的模式下工作。 其中，检测器可采用电导率传感器或电导仪。 电导率传感器采用 感应式电导率传感器，由于这种传感器的工作原理是在溶液中的封闭 回路中，产生一个感应电流，通过测量电流的大小得到溶液的电导率， 其抗污染性很强，可以保证系统在复杂的水质环境中运行稳定。 电导 仪、 电位计分别可以采用电导变送器、 余氯变送器， 便于工控。 超声强化微电流电解器中包括： 直流电解电源、 电解电极组、 箱 体、 和电极引线连接端子、 超声发生器、 超声反射体组成。 其中直流电源采用线性直流电源，接入端为 110V或 220V交流电， 输出为直流电， 可以根据需要调节电解电流， 输出电压控制在 36V 的安全范围内；电极组由金属钛和钛合金为芯材的涂层电极等距离排 列组成； 箱体包括外壳、 密封件、 固定件和连接法兰， 外壳、 法兰采 用塑料构件； 超声发生器包括壳体、 换能器、 电源超声发生器。 微电流电解器中电解电极组可实现灭菌灭藻的作用，并可根据实 际情况添加超声发生器， 实现对细菌和藻类细胞的破碎。 在一些实施方案中， 超声强化微电流电解器的电极组内主要包 括：
( 1 ) 阳极： 采用金属钛或钛合金为基体在其表面涂覆至少含有 一种金属 Pt、 Ir、 Ru、 Rh、 Pd、 0s或及其氧化物、 和含有至少一种 Ta、或 Ti的氧化物的电极作为阳极——钛阳极（DSA阳极）， Pt、 Ir、 Ru、 Rh、 Pd、 0s、 Ta、 Ti均能提供^ f 空轨道的催化活性中心的有 利于实现电子转移，避免极化现象，并有利于高活性氧化性物质的生 成；为了避免电极与引线之间接点所通过的电流过大而容易在工作中 产生烧断现象， 板状阳极至少有 2个接线端， 在阳极上均匀分布， 参 见图 5a的钛阳极结构示意图， 在接线端上开有通孔， 可以与电线连 接采用螺钉紧固；管状阳极可以通过环状接触以解决接触点局部电流 过大问题。
( 2 ) 阴极： 采用金属钛或钛合金为基体在其表面涂覆至少一种 Ta、 Ti 的氧化物的电极构件； 可以保证在电导率较低的淡水体系中 转化电极性质作为阳极时具有一定的催化活性， 同时 Ta、 Ti的氧化 物吸氢能力低， 不会在作为阴极使用时脱落； 同样， 为了避免电极与 引线之间通过的电流过大而容易在工作中产生烧断现象，板状阴极至 少有 2个接线端，在阴极上均匀分布，参见图 5b的阴极结构示意图， 在接线端上开有通孔，可以与电线连接采用螺钉紧固； 管状阴极可以 通过环状接触以解决接触点局部电流过大问题。
( 3 )辅助电极：采用平均孔径不小于 3腿的金属钛或钛合金网、 其表面涂覆至少一种 Ta、 Ti的氧化物作为外层的电极构件， 保证在 倒极除垢作为阳极使用时， 电极材料不会被腐蚀； 同样， 为了避免电 极与引线之间通过的电流过大而容易在工作中产生烧断现象，板状辅 助电极至少有 2个接线端， 在辅助电极上均匀分布， 参见图 5c的辅 助电极结构示意图，在接线端上开有通孔，可以与电线连接采用螺钉 紧固；管状辅助电极可以通过环状接触以解决点接触局部电流过大问 题； 对于板状钛阳极、 阴极和辅助电极， 在电极长度不大于 1200mm 的条件下，接线端子以 2到 3个为上，接线端子太多对系统的密封和 外形美观均有影响。
电极组中的电极可采用板状电极按照辅助电极在阴极、阳极之间 的循序等距离排列，组成微电流电解系统的电极组；板状电极构成的 电极组排列参见图 6 , 所有电极均采用双面涂覆的电极， 由于阳极造 价相对较高， 可以使最后一组的排列中， 标记 A处为阳极， 标记 C 为阴极， 标记 B为辅助电极， 以阴极 C为最外侧， 以保证装置的空间 利用率和降低成本。 在一些实施方案中采用塑料定位支架， 参见图 7A、 7B、 7C， 图
7B是图 7A中的放大示意图， 图 7C是图 7B中 B- B的剖视图。 通过塑 料定位支架将电极固定。 由于海水与淡水的电导不同， 因此，在一些实施方案中通过不同 的电导由控制器选择不同的电解模式控制超声强化微电流电解器中 不同的电极工作， 控制器的示意图可参见图 8， 包括判断单元和电解 模式单元，电解模式单元分为海水电解模式单元、淡水电解模式单元、 倒极电解模式单元。 当判断单元判断出检测器检测的电导率大于 150( S/cm 的海水 水体，触发海水电解模式单元工作，海水电解模式单元控制辅助电极 B不工作， 通过阳极 A和阴极 C之间的电解作用， 将处理水体中的氯 离子、 水分子电解为具有高氧化活性的物质（C10- , ΟΗ, Η202, (0) )， 对水体中的细菌和藻类的细胞的 RNA、 DNA进行氧化作用， 使其失活 和死亡，从而达到灭菌灭藻效果，并使处理过的水体的保持持续消毒 作用； 由于辅助电极 B的大量的通孔和超声波的共同作用，使电解产 生的活性物质的扩散和氧化杀菌效果不会因为辅助电极 B存在而受 影响； 当判断单元判断出检测器检测的电导率小于 150( S/cm 的淡水 水体中，触发淡水电解模式单元工作，淡水电解模式单元控制辅助电 极 B作为阴极， 原来的阴极 C均作为阳极， 原阳极 A的性质不变，相 应的电极间距为原来的二分之一， 根据 ( 1 ) 式可知， 对于低电导率 的淡水水体的电解处理可以大大降低的工作电压； 在硬度较高的水体中，如果辅助电极 B工作较长时间，表面沉积 碳酸 倒极电解模式单元可根据运行次数、运行时间到达一定阈值 时， 通过改变原来阴极 C (淡水体系工作时为阳极之一）与辅助电极 B的极性——进行倒极电解，倒极电解模式单元将辅助电极 B改为阳 极， 作为阳极之一的原阴极 C (淡水体系工作时为阳极）再次改为阴 极， 电解除垢， 在倒极除垢过程中， 原阳极 A不工作， 可以有效地保 护阳极 A的催化活性， 从而保证装置运行的长期稳定性和可靠性。 在一些实施方案中，根据水箱长期运行的规律，在相同的淡水水 体中运行， 采用恒电流电解， 如果在电流不变的条件下， 电解电位升 高 20 % , 则表明电解过程中阴极肯定结垢， 以采用在相同电解电流、 在相同的淡水水体中电解运行时电解电位（U1 + U2 + U3 )升高 20 % 时， 采用倒极电解模式除垢， 倒极电解的电流密度不大于 20mA/cm2， 倒极电解时间不需大于 1小时即可； 而在海水体系中运行，无需采用 倒极电解除垢。 当电极组采用管状电极时，可以按照同样的顺序：将辅助电极安 在阴极、 阳极之间， 各电极等距离沿径向同轴排列构成， 采用带有均 布的支撑筋不多于 6根的塑料法兰固定， 以减少水阻。 在一些实施方案中，装置中还可包括用于破坏细菌和藻类细胞的 超声发生器及超声反射体。超声发生器包括壳体、换能器、电源组成， 采用多个超声换能器阵列，在壳体中均匀布置，并与板状电极组排列 方向均布平行排列， 以增大超声波的强度，保证处理装置的水体中超 声场分布均匀；在管状电极组的微电流电解体系中， 宜采用环形均布 排列。
在超声发生器产生的超声波传输过程中， 参见图 9A、 图 9B， 虽 然有发散作用，但如果遇到与前进方向垂直的平面，将有相当一部分 能量沿原路反射回去，超声反射体构成的反射平面或曲面与超声波行 进的方向成一定角度，从而改变超声波的反射方向，强化对电极的清 洗作用， 减轻结垢现象； 另一方面， 增加了超声波在处理装置的水体 中的传播路程， 从而增大超声作用使细菌和微生物的细胞破碎的机 会；再者避免超声波直接沿原路反射， 以免造成对超声换能器压电振 子的损伤， 延长使用寿命。 在一些实施方案中，所述的超声波反射体，可以为塑料、金属钛、 钛合金、 不锈钢、碳钢或铜合金等材料， 为防止系统运行时材料的腐 蚀， 以金属钛、 钛合金、 塑料为构件最佳。 超声波反射体的可以是三棱柱或半圓柱体，三棱柱的一个柱面与 箱体衔接，并且与电极平行，三棱柱的一条棱与超声发生器发射的超 声波传输方向垂直； 半圓柱体则将柱平面与箱体衔接，并且与电解电 极平行， 曲面与超声发生器发射的超声波传输方向垂直；这样可以保 证有效的改变超声波的反射方向，强化对电极的清洗作用，减轻结垢 现象， 同时， 增大超声破碎细菌和微生物细胞壁的能力； 其中， 优选 采用三棱柱结构， 以提高超声场分布均匀性。对于管状电极体系， 超 声反射体采用圓锥型的结构为佳。 在一些实施方案中， 该装置中采用板状电极的结构图可参见图 10， 箱式超声强化微电流电解灭菌除藻装置连接进水法兰 1， 在进水 管道中设置有感应式电导传感器 2，该装置的箱式壳体 5中具有板式 电极组 4，板式电极组 4中设置有固定板式电极的塑料电极固定支架 3; 箱式壳体 5上连接出水法兰 6，并在出水管路上设置有余氯电极 7 及余氯变送器； 装置内安装有超声反射体 9， 板式电极组 4外安装有 电极组密封橡胶垫 10， 通过盖板 15固定在箱式壳体 5上， 并通过紧 固件 11固定， 钛阳极 12、 阴极 13、 钛网辅助电极 14安装在塑料电 极固定支架 3上， 装置的一端安装有超声发生器壳体 16 , 壳体 16内 安装有超声换能器 17 ,超声发生器壳体 16与箱体之间连接有密封橡 胶垫 18 , 并通过超声发生器盖板 19固定。 采用 PEEK (聚醚醚酮）制成的 InPro7250HT感应式电导传感器 2 和梅特勒-托利多变送器构成进水水体的电导检测和信号传输部分， 将信号输出端与控制器连接； 采用 SZ283余氯电极 7和意大利 B &C ( CL3630余氯变送器）构成余氯检测和信号传输部分， 将信号输出 端与控制器连接。 在一些实施方案中， 装置采用厚度优选为 15腿的 U- PVC (聚氯 乙烯）板制成。 内部优选净尺寸为 1580mmx 600mmx515mm的箱式壳 体 5， 进水连接法兰 2和出水连接法兰 6的外径优选为 350腿、 内径 为 200mm、8个为孔径为 22mm的螺栓孔均布在直径为 295mm的圓环上， 采用 M20紧固螺栓分别与进水管道、 出水管道连接， 如图 11所示， 图 11为图 9中 A向的示意图。 板式电极组 4优选采用长 800mm、 宽 500、 厚度 δ2. 5腿表面涂覆 Ir、Rh氧化物和 Ti02的钛阳极 12;优选长 800mm、宽 500、厚度 δ2. 5mm, 芯材为金属钛表面涂覆 Ta、 Ti的氧化物的电极作为阴极 13; 优选长 800腿、 宽 500nun、 厚度 δΐ. 3nun、 芯材为金属钛、 网孔（中心距）为 4. 5腿 xl2. 5mm、 表面涂覆 Ta、 Ti的氧化物的钛网电极作为辅助电极 14; 所有电极均有两个接线端， 分别参见图 12A至图 12C。 采用 6块阳极、 7块阴极、 12块网状辅助电极按照阴极、辅助电 极、阳极的循序中心距相间 25腿等距离排列插在塑料固定支架 3上， 固定支架的固定槽离箱底有 15腿， 保证运行期间水体中沉积的少量 沉积物不会导致电极之间短路， 参见图 7和图 14， 由于箱体净高为 500mm,使板状电极有 15腿的高度完全留在箱体的板内（构成箱体的 板厚度为 15腿）， 从而保证电极可以准确定位， 并且在流水作用下， 不会发生错动和移位； 电极从箱体的安装槽口插入箱内，另一侧的两 端嵌入塑料固定支架 3， 安装槽口长 803mm、 宽 3腿， 便于安装定位， 参见图 15; 安装槽口与电极密封盖板 15之间， 加厚度为 5腿的密封 橡胶垫 10， 用 M8螺栓经 Φ10腿的通孔 25紧固； 在密封橡胶垫对应 于电极接线端处划口，作为密封电极组橡胶垫的电极接线端出口 26， 使电极接线端通过， 同时保证密封效果， 参见图 16、 图 17; 每个电 极接线端用厚 4腿、 外径为 25mm、 中心开有 17mmx3mm通孔的不锋钢 压片 30和中心孔径为 18mm、 高 50腿的 M30螺栓 31紧固密封， 将电 线用螺丝经电极接线端的螺孔与电极连接， 电极接线端、 金属压片 30、 中空紧固螺栓 31构成接线端子， 如图 18A、 图 18B所示。 板式电极组 4内的电极与线性恒流直流电源连接，如图 13所示， 线性恒流电源输出端 i、 i i i、 v为正极输出端， i i、 iv为负极输出 端； 阴极 13通过接线端子 28分别与线性恒流直流电源的输出端 i i、 i i i连接，辅助电极 14通过接线端子 29分别与线性恒流直流电源的 输出端 iv、 V连接， 线性恒流直流电源的输出端 i、 i i i、 v为正极输 出 ^>， i i、 iv为负极输出端。 在一些实施方案中， 在海水体系电解运行时 （电导率大于 150( S/cm )， 控制器接通线性恒流直流电源的 i、 i i 输出端子； 在 淡水体系电解运行时（电导率小于 150( S/cm )， 控制器接通线性恒 流直流电源的 i、 i i i、 iv输出端子； 倒极除垢运行时， 控制器接通 线性恒流直流电源的 i i、 V输出端子； 可以使装置在淡水、 海水水体 中稳定、 可靠地运行。 超声反射体 9采用 PVC制成底面为 50腿、 高 15腿等腰三角形、 长为 515腿 的三菱柱， 12个相同的三菱柱按照与电极平行的方向排 列， 焊接在箱式壳体 5上， 参见图 9、 图 19; 将 10个 TYH- 50- 25型 功率 50W、 工作频率 25KHz的超声换能器 17 , 用 AB胶粘结在厚度为 2腿的 Crl8Ni 9Ti不锈钢超声发生器壳体 16上，均匀分布，参见图 9、 图 20， 在箱式壳体 5、 超声发生器壳体 16、 和超声发生器面板 19之 间， 各加一个厚度为 3. 5mm的密封橡胶垫密封垫 18 , 参见图 21， 用 Μ20χ60螺栓经 Φ22腿的通孔 32将它们紧固在一起， 保证密封效果， 超声换能器 17的电线经超声发生器面板 19的中心孔导出， 参见图 22 , 与超声发生器的电源 21连接。 在一些实施方案中， 电导变送器的输出端与控制器的输入端连 接， 控制器的输出端与超声发生器的电源 21、 线性直流恒流电源连 接， 线性恒流直流电源采用型号规格为 0-30V/800A线性电源； 通过 控制器的指令对进水水质的电导率、排水水质中余氯进行检测，控制 器中各个电解单元根据所测的电导率决定电解模式，根据余氯大小调 节电解电流、 电压； 线性恒流直流电源的电压、 电流信号传输给控制 器，控制器中倒极电解模式单元决定是否需要进行倒极；控制器还可 以根据预定的功率选择相应组数的超声换能器 17工作， 以对超声发 生器的功率进行控制。
上面的详细描述了板式电极组的装置，下面详细描述管式电极组 的微电流电解灭菌除藻装置。 如图 23A所示，管式微电流电解灭菌除藻装置，主体包括连接进 水法兰 1、 感应式电导传感器 2、 出水法兰 6、 余氯电极 7、 余氯变送 器、超声反射体、电导变送器、超声发生器电源、线性恒流直流电源、 控制器、 超声发生器 33, 带法兰的三通 34 , 固定棒状钛阳极塑料法 兰 35 - 1、 35 - 2 , 固定多孔管状辅助电极塑料法兰 36 - 1、 36 - 2 , 表面包覆 Ti02的多孔管状辅助电极 37， 同时作为水路管体的表面包 覆 Ti02的管状阴极 38 , 含有金属 Pt、 Ir氧化物的棒状钛阳极 39, 密封垫 40, 圓锥形不锈钢超声反射体 41 , 带有金属垫片的引线端子 42组成。 超声发生器 33和超声反射体 41通过塑料三通 34、 中间添 加密封橡胶垫 40与电极组用螺栓紧固在一起，密封橡胶垫 40的安装 可参见图 23B。 超声波反射体 41的形状为圓锥形， 圓锥的顶尖朝向 超声发生器。 管状电极可以按圓环状排列， 此时， 各个超声换能器也 按圓环状排列， 且与管状电极的圓心为同心。 进水连接法兰 1和出水连接法兰 6可以用紧固螺栓分别与进水管 道、 出水管道连接。 法兰 35- 1、 35- 2用于固定棒状钛阳极 39, 参 见图 23A、 图 23B、 图 24、 图 25， 为减少水阻， 固定电极的塑料法兰 采用不多于六根的均布的支撑筋， 法兰 35- 1、 35- 2的厚度一般为 不小于 12mm, 带有电极引线 50的法兰 35 - 1， 沿其一根支撑筋的中 心位置钻有 Φ3.5 ~Φ5. Omm直达电极固定圓槽的通孔， 固定圓槽的 深度为 5~6mm, 布设电极引线与棒状钛阳极 39和线性恒流直流电源 的输出端子 i连接，将电极与塑料法兰 35- 1圓槽之间的间隙用防水 绝缘胶粘结密封，其另一端与不带电极引线的塑料法兰 35- 2的固定 圓槽嵌合， 不必粘结， 便于拆卸； 法兰 36- 1、 36- 2用于固定多孔 管状辅助电极 37, 参见图 23A、 图 23B、 图 26、 图 27， 为减少水阻， 同样固定电极的塑料法兰采用不多于六根的均布的支撑筋，法兰厚度 不小于 12腿， 支撑电极的圓环的直径在多孔管状辅助电极的内直径 Φ- 2腿~外直径 Φ + 2πιιη之间， 按多孔管状辅助电极的直径和厚度 开设深度为 6 ~ 8mm的环行凹槽用于固定阳极， 带有电极引线的法兰 36- 1, 沿其一根支撑筋的中心位置钻有直径 Φ3.5 ~ Φ5.0腿直达固 定电极的环行凹槽通孔，布设电极引线与多孔管状辅助电极 37连接， 其电极引线与直流恒流电源的输出端子 iv、 V连接，然后将电极与塑 料法兰 36 - 1环行凹槽之间的间隙用防水绝缘胶粘结密封，辅助电极 37的另一端与不带电极引线的塑料法兰 36- 2的环行凹槽嵌合， 不 必粘结， 便于拆卸； 在各法兰之间， 加密封垫 40， 用螺栓将整个装 置紧固在一起， 作为水路管体的管状阴极 38通过带铜垫片的引线端 子 42与直流恒流电源的输出端子 ii、 iii连接， 多孔管状阴极 37 及管状阴极 38与棒状钛阳极 39同轴。 线性恒流直流电源的输出端 i、 iii、 v 为正极输出端， ii、 iv 为负极输出端； 在海水体系电解运行时（电导率大于 150( S/cm)， 控制器接通线性恒流直流电源的 i、 ii输出端子；在淡水体系电解运 行时（电导率小于 150( S/cm), 控制器接通线性恒流直流电源的 i、 iii、 iv输出端子； 倒极除垢运行时， 控制器接通线性恒流直流电源 的 ii、 V输出端子； 可以使装置在淡水、 海水水体中稳定、 可靠地运 控制器与检测器、超声发生器的电源、线性恒流直流电源之间的 连接方式、 控制模式与实施例 1相同， 此处不再赘述。 该装置中的线性恒流直流电源采用型号规格为 0-30V/800A线性 电源； 将厚度为 1.5腿、 网孔（中心距）为 3.0腿 X 6. Omm的饮网用 宽 10nun、 厚 1.5腿的钛条, 焊接成接近 ( O=60mm, 长 1030腿）的多 孔钛管， 经空气中 120X:加热 3小时并按照 l~2X:/min降温速率降 至室温的处理，使其表面均匀包覆 Ti02，作为多孔管状辅助电极 37; 将钛管（ Φ=108πιπι, δ=6.5腿，长 1000腿）， 用同样的方法处理后， 作 为阴极 38, 用表面涂覆 Pt、 Ir氧化物的棒状钛阳极 39 ( Φ=20腿， 长 1060mm)， 功率 40W的超声发生器作为主体配置， 可以实现处理流 量为 30M3/hr的水体灭菌除藻。 对使用本发明中装置进行淡水、 海水中灭菌除藻分析结果如下： 试验与使用条件：
( 1 )、 50M3不锈钢水箱，试验水体为自来水，水质指标参见表 1; 表 1、 实验用自来水水质:
Figure imgf000025_0001
( 2 )、 海水养殖池水体， 面积 0.8km2, 试验期间（32天）海水水 质指标见表 2; 表 2、 试验用海水水质
Figure imgf000025_0002
( 3)、 淡水养殖池， 水域面积 2200m2, 试验期间（30天）淡水水 质指标见表 3。 表 3、 试验用淡水水质
CI- (ppm) 硬度 CaC03 减度 CaC03 H 电 导 率
( pm) ( pm) μ8/ cm
25 ~ 36 430 ~ 480 450 ~ 510 7.7~ 8.2 950 - 1080 结果计算:
结果的测定方法， 参照 GB15979 , 采用经过微电流电解灭菌除藻 装置处理前后的水样各 1. 00ml，用经过灭菌的琼脂培养基，置于 35±2 °C培养 48 小时， 计数细菌菌落数目， 以 （18 ) 式计算杀菌效率 η， 测试取 3组平行样， 求取平均值。
Figure imgf000026_0001
其中： Ν为电解处理后的水样的菌落数，
Μ为电解处理前的水样的菌落数。 灭藻结果的测定方法，采用叶绿素变化进行近似估计，将处理后 的水体， 与未经处理的水体， 自然放置 24小时， 然后测试两种水体 中的叶绿素含量，近似评价对蓝藻的杀灭效果，尽管多数藻类无法确 定死活、 已经杀死的微生物经过滤进入滤液也对叶绿素的测定有贡 献。 试验结果： ( 1 )、 自来水水体试验：
Α、采用板式电极的处理能力为 300M3/hr的箱式微电流电解灭菌 除藻装置， 用 50M3的自来水进行灭菌试验， 水体水泵按照 250M3/hr 的流量输送进入装置处理， 按 3种电流密度各运行， 钛阳极 12和原 阴极 13均作为电解阳极，以辅助电极 14作为阴极，分别参照 GB15979 测试原水和处理后的水体中细菌总数，根据 ( 18 )式计算杀菌效率 η， 结果列于表 4，表明经箱式超声强化微电流电解灭菌除藻装置处理水 体， 工作电压不大于 30V, 具有良好是杀菌效果。 表 4、 不同电流密度条件下杀菌效果
Figure imgf000026_0002
B、 采用处理能力为 30M3/hr的管式微电流电解灭菌除藻装置， 用 50 M3的自来水进行灭菌试验， 同样用水泵按照 30M3/hr的流量输 送进入装置处理，按 3种电流密度各运行 （因为阳极直径不同， 以电 流密度无法准确描述电解工况， 以总电流 35A、 18A、 7A来描述更确 切一些， 分别对应管阳极 38 的近似电流密度为 5. 0 mA/cm2、 2. 5 mA/cm2、 1. 0 mA/cm2) , 原管状阴极 38和棒状钛阳极 39均作为电解 阳极， 以辅助电极 37作为阴极， 分别参照 GB15979测试原水和处理 后的水体中细菌总数， 根据（18 )式计算杀菌效率 η， 结果列于表 5， 表明经箱式超声强化微电流电解灭菌除藻装置处理水体，工作电压不 大于 30V, 具有良好是杀菌效果。 表 5、 不同电流密度条件下杀菌效果
Figure imgf000027_0001
( 2 )、 海水养殖场的灭菌除藻处理 采用处理能力为 300M3/hr的箱式微电流电解灭菌除藻装置， 水 体水泵按照 300M3/hr的流量提升送入装置处理，以钛阳极 12和阴极 13工作， 辅助电极不工作， 采用电流密度为 16mA/cm2 , 运行电压为 6. 4V,处理后的水体沿池边约 100米长的水渠流回到养殖池，每天运 行 6小时， 运行 32天， 参照 GB15979测试分别第一天和最后一天原 水和处理后的水体中需氧菌总数 ( Tota l aerobi c count )， 和对比原 水叶绿素与处理水 24小时后的水体中的叶绿素推测对藻类的杀灭作 用， 结果列于表 6， 装置运行过程中有效地抑制了藻类的生长。 表 6、 海水养殖池杀菌灭藻效果（电流密度为 16. 0mA/cm2 )
Figure imgf000027_0002
在 32天的运行过程中，运行电压稳定在 3. 2±0. 2V的范围内，十 分稳定，也佐证了海水体系中，微电流电解系统的阴极表面不会形成 CaC03的结论。 ( 3 )、 淡水养殖池的灭菌除藻处理 采用处理能力为 300M3/hr的箱式微电流电解灭菌除藻装置， 水 体水泵按照 300M3/hr的流量提升送入装置处理，钛阳极 12和原阴极 13均作为电解阳极， 以辅助电极 14作为阴极， 采用电流密度为 10 mA/cm2 , 运行电压为 9. 6V, 处理后的水体沿池边约 65米长的水渠流 到养殖池的另一端， 每天运行 4小时， 运行 30天， 参照 GB15979测 试分别第一天和最后一天原水和处理后的水体中需氧菌总数（ To t a 1 aerobic count ), 和对比原水叶绿素与处理水 24小时后的水体中的 叶绿素推测对藻类的杀灭作用， 结果列于表 7， 装置运行过程中有效 地抑制了藻类的生长。 其中运行到第 22天时， 运行电压已经逐渐升高至 12. 2V， 以电 流密度为 8mA/cm2 , 将辅助电极 14作为阳极， 与原阴极 13进行倒极 电解 20分钟； 随后恢复正常运行， 运行电压恢复为 9. 6V, —直到第 30天， 运行电压恢复为 12V。 表 7、 淡水养殖池杀菌灭藻效果（电流密度为 10. 0mA/cm2 )
Figure imgf000028_0001
本发明中的装置，通过上述的试验可明显得出本发明装置的杀菌 除藻效果，且可同时应用到海水或淡水中灭菌除藻，并可实现自动除 垢， 且应用范围广； 并加入超声发生器， 通过超声波有效破坏各种细 菌和藻类细胞； 设备简单， 且应用范围广泛。对于本发明各个实施例 中所阐述的装置， 凡在本发明的精神和原则之内， 所作的任何修改、 等同替换、 改进等， 均应包含在本发明的保护范围之内。

Claims

权 利 要 求
1、 一种微电流电解灭菌除藻装置， 包括： 安装在箱体的进水管道上 感应溶液电导值的检测器， 所述箱体内按照组内阳极、辅助电极、 阴 极的顺序安装至少一组以上的电极组， 控制器判断所述电导值的大 小、 控制所述箱体内电极的极性及电路连接； 所述控制器内包括： 判断单元，用于判断所述电导值的大小，并按照判断结果触发相应的 海水电解模式单元、 淡水电解模式单元、 倒极电解模式单元工作； 所述海水电解模式单元， 用于接收触发后， 导通所述阳极、 阴极的电 路连接， 断开辅助电极的电路连接；
所述淡水电解模式单元，用于接收触发后，将所述阴极的极性改为阳 极， 将所述辅助电极的极性改为阴极， 导通未改变极性的阳极、 由阴 极改变极性而成的阳极、和由辅助电极改变极性而成的阴极的电路连 接；
所述倒极模式单元，用于判断装置的运行次数、运行时间超过设定阈 值后，将所述辅助电极的极性改为阳极，导通由辅助电极改变极性而 成的阳极和未改变极性的阴极的电路连接，断开未改变极性的阳极的 电路连接。
2、 根据权利要求 1所述的装置， 其中所述电极组内的电极形状为片 状电极或管状电极。
3、 根据权利要求 2所述的装置， 其中所述装置还包括： 安装在所述 箱体两端的超声发生器、及超声波反射体，所述超声发生器内包括至 少一个以上超声换能器，所述电极组的位置在所述超声发生器和超声 波反射体之间。
4、 根据权利要求 3所述的装置， 其中当所述电极形状为片状时， 所 述超声波反射体的形状为三棱柱形或者圓弧形，棱柱的棱边或圓弧朝 向超声发生器的方向凸出； 当所述电极形状为管状时，所述超声波反 射体的形状为圓锥形， 圓锥的顶尖朝向超声发生器。
5、 根据权利要求 4所述的装置， 其中所述电极形状为管状时， 所述 各个电极、 各个超声换能器呈同一圓心的圓环状排列。
6、根据权利要求 1 ~ 5中任何一项所述的装置，其中所述检测器为电 导率感应式电导传感器或电导变送器。
7、根据权利要求 1 ~ 6中任何一项所述的装置，其中所述的阳极是以 金属钛或钛合金的至少一种为基体， 在其表面涂覆含有金属 Pt、 Ir、 Ru、 Rh、 Pd或 Os、 及其氧化物中的至少一种和至少一种 Ta或 Ti 的氧化物的涂层的电极（DSA )。
8、根据权利要求 1 ~ 7中任何一项所述的装置，其中所述辅助电极和 阴极是以金属钛或钛合金的至少一种为基体，在其表面涂覆至少一种 Ta或 Ti的氧化物的电极构件。
9、根据权利要求 3 ~ 8中任何一项所述的装置，其中所述超声波反射 体的材料包括塑料、金属钛、钛合金、 不锈钢、碳钢或铜合金中的至 少一种。
10、 根据权利要求 1 ~ 9中任何一项所述的装置， 其中所述装置还包 括：安装在所述箱体出水管道上用于检测电解后溶液中氯含量的电位 计或余氯电极以及余氯变送器；所述各个电解单元按照所述氯含量值 调节电解的电流值和电压值。
11、 根据权利要求 1~10任何一项的微电流电解灭菌除藻装置在海水 或淡水中灭菌除藻的用途。
12、 一种利用微电流电解在水体中灭菌除藻的方法， 包括：
1)检测所述水体的电导值； 2)传送所述电导值至判断单元；
3) 判断所述电导值；
4)按照判断结果触发控制器的海水电解模式单元、淡水电解模式 单元或倒极电解模式单元工作， 以便控制水体中的阳极、 辅助电 极和阴极的极性及电路连接。
13、根据权利要求 12的方法，其中当所述海水电解模式单元工作时， 导通所述阳极、 阴极的电路连接， 断开辅助电极的电路连接。
14、根据权利要求 12的方法，其中当所述淡水电解模式单元工作时， 将所述阴极的极性改为阳极，将所述辅助电极的极性改为阴极，导通 未改变极性的阳极、由阴极改变极性而成的阳极和由辅助电极改变极 性而成的阴极的电路连接。
15、 根据权利要求 12的方法， 其中当所述倒极模式单元工作时， 判 断装置的运行次数、运行时间超过设定阈值后，将所述辅助电极的极 性改为阳极，导通由辅助电极改变极性而成的阳极和未改变极性的阴 极的电路连接， 断开未改变极性的阳极的电路连接。
16、 根据权利要求 12 ~ 15任何一项的方法， 其中所述水体是海水或 淡水。
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120048728A1 (en) * 2010-08-27 2012-03-01 C. Uyemura & Co., Ltd. Electrolytic regeneration device
NL2005505C2 (nl) * 2010-10-12 2012-04-16 Luykx Patenten B V Werkwijze, inrichting en systeem voor het beperken van biologische groei.
CN102976530A (zh) * 2012-11-30 2013-03-20 吴江市万事达环保溶剂有限公司 化工生产污水处理回用装置
CN103241907A (zh) * 2013-05-28 2013-08-14 无锡百奥源生态环保科技有限公司 一种有机含油脂废水的处理方法和装置
CN103265147A (zh) * 2013-05-28 2013-08-28 浩蓝环保股份有限公司 一种脱氮除磷的污水处理装置

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101786748B (zh) * 2010-03-30 2012-06-13 青岛海德威科技有限公司 一种高效灭活和节能的船舶压载水处理方法和系统
US9896355B2 (en) * 2014-01-22 2018-02-20 Michael Green Method and apparatus for an expandable industrial waste water treatment system
KR101610485B1 (ko) 2014-08-12 2016-04-20 두산중공업 주식회사 감지 조류 제거 시스템 및 방법
US9902625B2 (en) 2014-09-03 2018-02-27 International Business Machines Corporation Removal of HAB-produced toxins from bodies of water
CN104817140B (zh) * 2015-04-22 2017-06-20 南京水思环保科技有限公司 全氟酮生产过程中含乙腈的高盐废水回收处理方法
CN105329990B (zh) * 2015-10-28 2017-06-23 中海油天津化工研究设计院有限公司 一种超声波强化电催化氧化处理反渗透浓水的装置及方法
JP2018095080A (ja) * 2016-12-13 2018-06-21 三浦工業株式会社 バラスト水処理装置
CN107500389A (zh) * 2017-09-26 2017-12-22 陈雷 一种地表水除藻净水器
CN109264817A (zh) * 2018-11-13 2019-01-25 深圳市周行环保科技有限公司 一种控制藻类生长和抑制微囊藻毒素的方法
KR102450345B1 (ko) * 2020-05-29 2022-09-30 동의대학교 산학협력단 병원균의 탐지 및 살균 장치
CN112340826A (zh) * 2020-11-23 2021-02-09 同济大学 一种快速削减放江污染的管道混凝方法
CN114314747B (zh) * 2022-01-18 2024-03-01 福州大学 一种集储藻与超声抑藻于一体的太阳能浮游装置及方法

Citations (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6125687A (ja) * 1984-07-13 1986-02-04 Hitachi Plant Eng & Constr Co Ltd 有機性廃液の電解処理装置
US5738780A (en) 1995-08-02 1998-04-14 Amway Corporation Voltage converter for water treatment system UV bulb
DE19919824A1 (de) 1999-04-30 2000-11-02 Sas Sonderabfallservice Gmbh Verfahren zum Abbau von zinnorganischen Verbindungen, insbesondere Tri-, Di,- und Monobutylzinn, in Flüssigkeiten und Schlämmen
JP2001000974A (ja) 1999-06-23 2001-01-09 Konica Corp バラスト水の処理方法、及び船舶
CN2457123Y (zh) * 2000-12-08 2001-10-31 常州高德卡本净化技术开发有限公司 液体处理装置的控制装置
WO2003002406A1 (en) 2001-06-29 2003-01-09 Wilson Taylor & Company Ltd Management of water ballast in marine vessels
US20030029811A1 (en) 2000-11-06 2003-02-13 Larry Russell Ballast water treatment for exotic species control
WO2003095370A1 (en) 1999-07-13 2003-11-20 Oceanit Laboratories, Inc. Ship ballast water ultrasonic treatment
WO2004002895A2 (en) 2002-06-29 2004-01-08 The Marenco Group Ballast water treatment systems including related apparatus and methods
US20040099608A1 (en) 2002-11-18 2004-05-27 Leffler Charles E. Ballast water treatment system
US20040134861A1 (en) 2001-03-16 2004-07-15 Brodie Paul F. Ship ballast water sterilization method and system
US20050016933A1 (en) 2001-11-28 2005-01-27 Tom Perlich Methods, apparatus, and compositions for controlling organisms in ballast water
JP2005021814A (ja) 2003-07-03 2005-01-27 Sasakura Engineering Co Ltd バラスト水の処理方法及び装置
WO2005061388A1 (en) 2003-11-20 2005-07-07 Marine Environmental Partners, Inc. Ballast water treatment system
JP2005254138A (ja) 2004-03-11 2005-09-22 Jfe Engineering Kk 液圧発生方法及び装置、バラスト水処理方法及び装置、該装置を搭載した船舶
JP2005270754A (ja) 2004-03-24 2005-10-06 Shusuke Akiyama パルスパワー生成衝撃波によるバラスト水処理法
WO2005110607A1 (en) 2004-05-19 2005-11-24 Reederei Hesse Gmbh & Co. Kg Treatment of ballast water
JP2005342626A (ja) 2004-06-03 2005-12-15 Jfe Engineering Kk バラスト水処理方法及び装置、該装置を搭載した船舶
CN2748475Y (zh) * 2004-11-01 2005-12-28 活水企业发展（上海）有限公司 调整电解池进水含盐量的管路连接设备
JP2006007184A (ja) 2004-06-29 2006-01-12 Ki System:Kk バラスト水の処理方法及び装置
WO2006009339A1 (en) 2004-07-23 2006-01-26 Lg Electronics Inc. Condenser of refrigerator
JP2006099157A (ja) 2004-09-28 2006-04-13 Hitachi Ltd 情報処理装置
WO2006058261A2 (en) 2004-11-29 2006-06-01 Severn Trent De Nora, Llc System and method for treatment of ballast water
JP2006223997A (ja) 2005-02-17 2006-08-31 Mitsui Eng & Shipbuild Co Ltd バラスト水の取水・処理装置
JP2006239556A (ja) 2005-03-03 2006-09-14 Mitsui Eng & Shipbuild Co Ltd バラスト水の処理方法
JP2006239531A (ja) * 2005-03-02 2006-09-14 Hideo Hayakawa 次亜塩素酸ナトリウム塩を用いた水の浄化方法
JP2006263563A (ja) 2005-03-23 2006-10-05 Mitsui Eng & Shipbuild Co Ltd バラスト水中の微生物等の殺減装置
JP2007014439A (ja) 2005-07-06 2007-01-25 Pentax Corp 超音波内視鏡の吸引操作弁
JP2007021287A (ja) 2005-07-12 2007-02-01 Katsuhiro Nakayama バラスト水の処理方法
WO2007114198A1 (ja) 2006-03-31 2007-10-11 Mitsui Engineering & Shipbuilding Co., Ltd. 膜モジュールを用いたバラスト水の膜処理方法及び膜処理装置

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4955366A (en) * 1987-11-27 1990-09-11 Olympus Optical Co., Ltd. Ultrasonic therapeutical apparatus
US5102515A (en) * 1990-07-20 1992-04-07 Ibbott Jack Kenneth Method and apparatus for treating fluid
US5389214A (en) * 1992-06-19 1995-02-14 Water Regeneration Systems, Inc. Fluid treatment system employing electrically reconfigurable electrode arrangement
JPH0648886U (ja) * 1992-12-07 1994-07-05 九州日立マクセル株式会社 加振機能を有する整水器
JP3518907B2 (ja) * 1994-10-06 2004-04-12 ホシザキ電機株式会社 電解水生成装置
JP3547819B2 (ja) * 1994-11-29 2004-07-28 ホシザキ電機株式会社 電解水生成装置
JPH1087381A (ja) * 1996-06-28 1998-04-07 Konica Corp 多孔性炭素質電極の処理方法、炭素質固定床型三次元電極電解槽及び水処理方法
JP3267904B2 (ja) * 1997-08-20 2002-03-25 株式会社マリン技研 水域浄化装置
JP3906088B2 (ja) * 2002-02-04 2007-04-18 三洋電機株式会社 水処理装置
US6780306B2 (en) * 2002-02-12 2004-08-24 Bioelectromagnetics, Inc. Electroionic water disinfection apparatus
CN1594121A (zh) * 2003-09-10 2005-03-16 王家君 组合式微电流电解水处理技术和装置
KR100542895B1 (ko) * 2003-12-22 2006-01-11 재단법인 포항산업과학연구원 차아염소산나트륨을 이용한 전해식 밸러스트수 처리방법및 처리장치
JP2005205343A (ja) * 2004-01-23 2005-08-04 Nippon Savcor Kk 液体の電解防汚処理方法
EP1751063A1 (en) * 2004-05-11 2007-02-14 Metafil AS Ballast water system
KR100630279B1 (ko) * 2004-09-16 2006-09-29 에스아이비(주) 전기분해 응집부상방식 수처리장치
US8163141B2 (en) * 2004-11-10 2012-04-24 Chlorking, Inc. Chlorination system for swimming pools and the like
JP2006289304A (ja) * 2005-04-13 2006-10-26 Denkai Giken:Kk 電気化学的水処理電極ユニット、電気化学的水処理電極構造体及び電気化学的水処理装置
KR100597254B1 (ko) * 2005-09-14 2006-07-06 한국해양연구원 선박용 밸러스트수의 전해 소독장치
WO2007126189A1 (en) * 2006-04-28 2007-11-08 Dolki Korea, Ltd Apparatus for removing red tide and apparatus for preventing water in pool from decaying
DE102006025194A1 (de) * 2006-05-29 2007-12-06 Endress + Hauser Conducta Gesellschaft für Mess- und Regeltechnik mbH + Co. KG Induktiver Leitfähigkeitssensor
US20100187122A1 (en) * 2007-04-05 2010-07-29 Vadim Zolotarsky Method and system of electrolytic treatment
WO2009023241A1 (en) * 2007-08-15 2009-02-19 Siemens Water Technologies Corp. Method and system for treating ballast water
JP5011084B2 (ja) * 2007-12-18 2012-08-29 有限会社スプリング 水中の微生物を殺減する装置及び水中の微生物を殺減する方法

Patent Citations (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6125687A (ja) * 1984-07-13 1986-02-04 Hitachi Plant Eng & Constr Co Ltd 有機性廃液の電解処理装置
US5738780A (en) 1995-08-02 1998-04-14 Amway Corporation Voltage converter for water treatment system UV bulb
DE19919824A1 (de) 1999-04-30 2000-11-02 Sas Sonderabfallservice Gmbh Verfahren zum Abbau von zinnorganischen Verbindungen, insbesondere Tri-, Di,- und Monobutylzinn, in Flüssigkeiten und Schlämmen
JP2001000974A (ja) 1999-06-23 2001-01-09 Konica Corp バラスト水の処理方法、及び船舶
WO2003095370A1 (en) 1999-07-13 2003-11-20 Oceanit Laboratories, Inc. Ship ballast water ultrasonic treatment
US20030029811A1 (en) 2000-11-06 2003-02-13 Larry Russell Ballast water treatment for exotic species control
CN2457123Y (zh) * 2000-12-08 2001-10-31 常州高德卡本净化技术开发有限公司 液体处理装置的控制装置
US20040134861A1 (en) 2001-03-16 2004-07-15 Brodie Paul F. Ship ballast water sterilization method and system
WO2003002406A1 (en) 2001-06-29 2003-01-09 Wilson Taylor & Company Ltd Management of water ballast in marine vessels
US20050016933A1 (en) 2001-11-28 2005-01-27 Tom Perlich Methods, apparatus, and compositions for controlling organisms in ballast water
US20050211639A1 (en) 2002-06-29 2005-09-29 Hap Nguyen Ballast water treatment systems including related apparatus and methods
WO2004002895A2 (en) 2002-06-29 2004-01-08 The Marenco Group Ballast water treatment systems including related apparatus and methods
US20040099608A1 (en) 2002-11-18 2004-05-27 Leffler Charles E. Ballast water treatment system
JP2005021814A (ja) 2003-07-03 2005-01-27 Sasakura Engineering Co Ltd バラスト水の処理方法及び装置
WO2005061388A1 (en) 2003-11-20 2005-07-07 Marine Environmental Partners, Inc. Ballast water treatment system
JP2005254138A (ja) 2004-03-11 2005-09-22 Jfe Engineering Kk 液圧発生方法及び装置、バラスト水処理方法及び装置、該装置を搭載した船舶
JP2005270754A (ja) 2004-03-24 2005-10-06 Shusuke Akiyama パルスパワー生成衝撃波によるバラスト水処理法
WO2005110607A1 (en) 2004-05-19 2005-11-24 Reederei Hesse Gmbh & Co. Kg Treatment of ballast water
JP2005342626A (ja) 2004-06-03 2005-12-15 Jfe Engineering Kk バラスト水処理方法及び装置、該装置を搭載した船舶
JP2006007184A (ja) 2004-06-29 2006-01-12 Ki System:Kk バラスト水の処理方法及び装置
WO2006009339A1 (en) 2004-07-23 2006-01-26 Lg Electronics Inc. Condenser of refrigerator
JP2006099157A (ja) 2004-09-28 2006-04-13 Hitachi Ltd 情報処理装置
CN2748475Y (zh) * 2004-11-01 2005-12-28 活水企业发展（上海）有限公司 调整电解池进水含盐量的管路连接设备
WO2006058261A2 (en) 2004-11-29 2006-06-01 Severn Trent De Nora, Llc System and method for treatment of ballast water
JP2006223997A (ja) 2005-02-17 2006-08-31 Mitsui Eng & Shipbuild Co Ltd バラスト水の取水・処理装置
JP2006239531A (ja) * 2005-03-02 2006-09-14 Hideo Hayakawa 次亜塩素酸ナトリウム塩を用いた水の浄化方法
JP2006239556A (ja) 2005-03-03 2006-09-14 Mitsui Eng & Shipbuild Co Ltd バラスト水の処理方法
JP2006263563A (ja) 2005-03-23 2006-10-05 Mitsui Eng & Shipbuild Co Ltd バラスト水中の微生物等の殺減装置
JP2007014439A (ja) 2005-07-06 2007-01-25 Pentax Corp 超音波内視鏡の吸引操作弁
JP2007021287A (ja) 2005-07-12 2007-02-01 Katsuhiro Nakayama バラスト水の処理方法
WO2007114198A1 (ja) 2006-03-31 2007-10-11 Mitsui Engineering & Shipbuilding Co., Ltd. 膜モジュールを用いたバラスト水の膜処理方法及び膜処理装置

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
LIU FUBIN, SHIPS, 4 August 2006 (2006-08-04)
REN NANQI ET AL.: "Microbiology of pollution control", 2002, PRESS OF HARBIN INSTITUTE OF TECHNOLOGY, pages: 38 - 39
WATER RESEARCH, vol. 36, no. 9, May 2002 (2002-05-01), pages 2243 - 2254
YUTAKA INOUE; MASAAKI HOSOMI: "ALGAL GROWTH INHIBITION EFFECTS AND INDUCEMENT MODES BY PLANT- PRODUCING PHENOLS SATOSHI NAKAI*", WATER RESEARCH, vol. 35, no. 7, May 2001 (2001-05-01), pages 1855 - 1859
ZHANG ZHAOXIAN: "Coated electrode with a history of 40 years", ELECTROPLATING & FINISHING, vol. 26, no. 1, 2007

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120048728A1 (en) * 2010-08-27 2012-03-01 C. Uyemura & Co., Ltd. Electrolytic regeneration device
US9045836B2 (en) * 2010-08-27 2015-06-02 C. Uyemura & Co., Ltd. Electrolytic regeneration device
NL2005505C2 (nl) * 2010-10-12 2012-04-16 Luykx Patenten B V Werkwijze, inrichting en systeem voor het beperken van biologische groei.
WO2012050447A3 (en) * 2010-10-12 2012-12-27 Luykx Patenten B.V. Method, device and system for limiting biological growth
CN102976530A (zh) * 2012-11-30 2013-03-20 吴江市万事达环保溶剂有限公司 化工生产污水处理回用装置
CN103241907A (zh) * 2013-05-28 2013-08-14 无锡百奥源生态环保科技有限公司 一种有机含油脂废水的处理方法和装置
CN103265147A (zh) * 2013-05-28 2013-08-28 浩蓝环保股份有限公司 一种脱氮除磷的污水处理装置

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