CN101519235A

CN101519235A - Ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga

Info

Publication number: CN101519235A
Application number: CN200810007856A
Authority: CN
Inventors: 王家君
Original assignee: Individual
Current assignee: Beijing Jingsheng Cathay Pacific Technology Co Ltd
Priority date: 2008-02-26
Filing date: 2008-02-26
Publication date: 2009-09-02

Abstract

The invention provides an ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga, consisting of a detection system, a control system, an ultrasonic intensified micro-current electrolysis system. A processing mode of the ultrasonic intensified micro-current electrolysis system is controlled according to the conductivity of water detected by the detection system. The intensified ultrasonic of the ultrasonic reflector is utilized to crush the cell wall of the bacteria, to lighten the scaling phenomenon of the cathode and to prompt the oxidation of the oxidized active matters (ClO<->, OH, H2O2, (O)) generated by micro-current electrolysis to the RNA and DNA of bacteria and microorganism cell in the water, thus inactivating or killing the bacteria and the microorganism cell and achieving the effects of sterilizing and removing alga; and a reticulate auxiliary electrode can lead the device to descale by rearrangeable electrolysis without reducing the activity of the anode and can ensure the reliable and stable running of the device. No medicament is added during the whole process; no secondary pollution is generated; the running and maintenance are simple and convenient; the energy consumption is low; and the device is suitable for quick sterilization and alga-removing process of large-flux fresh water systems and seawater systems.

Description

The ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga

Invention field

The present invention is a kind of ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga, especially can the scale removal of falling the utmost point, adopt the water treatment device of ultrasonic and micro-current electroanalysis kill bacteria and blue-green algae, belong to the environmental protection technology category.

Background technology

Cyanobacteria (cyanobacteria) also claims blue-green algae or blue-green algae (blue-green algae).Do not have nuclear membrane, kernel in their the nucleus structure, belong to prokaryotic organism, do not carry out mitotic division, cell walls is also similar to bacterium, is made up of peptidoglycan, and Gram-negative is so they belong in the prokaryotic micro-organisms.

Cyanobacteria is a unicellular organism, and is individual bigger than bacterium, and general diameter or width are 3-15 μ m.But cyanobacteria seldom with single individual life, normally still flocks together after division, forms thread or single celled colony.When many individualities flock together, can form very big colony, naked eyes are as seen.Cyanobacteria mainly is grown in the water body top layer---and between the 0.5m of underwater, most cyanobacterias are blueness or blue-greenish colour, so people claim still that traditionally it is blue-green algae or blue-green algae.

Cyanobacteria is widely distributed, from the South Pole to the arctic, and all visible its trace from the ocean to the high mountain.They often are grown in rock, bark or grow in pond, lake, breed vigorously, and the color that makes water body changes with the color of cyanobacteria itself.Careless fishy smell or frowst can take place in the kind that has.

Cyanobacteria contains pigmentary system (mainly contain algocyan, contain chlorophyll α, carotene or phycoerythrobilin in addition).Differ owing to contain the ratio of various pigments in every kind of cyanobacteria cell, so, color such as blue, green, red may be.The nutrition of cyanobacteria is simple, does not need VITAMIN, and as nitrogenous source, kind that can fixed nitrogen is a lot of with nitrate or ammonia.Some kind has circular heterocyst (hererocyst), is generally prolonging filament or individually distribution at one end, is that cyanobacteria carries out place, nitrogen fixation ground.Cyanobacteria is put the photosynthesis of oxygen, is obligate photolithotrophy microorganism, and its reaction is as follows

CO ₂+ H ₂O=[CH ₂O] _{Cellular material}+ O ₂(g)

These characteristics are similar to general algae.Its breeding is based on fragmentation, and a few species has spore; Thread cyanobacteria also can grow body and breeds by breaking to form, and does not have sexual propagation.

In water body, enter the material of nitrogenous in a large number and phosphorus, cause body eutrophication, then make the cyanobacteria excessive multiplication, the water surface is covered and make water body form the phenomenon of various different colors, be called " wawter bloom " (water bloom) in fresh water, be called red tide at saline waters.The cyanobacteria of energy formation " wawter bloom " comprises some kinds in the genus such as microcystis kutz (Microcystis), Anabaena (Anabaena), Oscillatoria (Oscillatoria)." wawter bloom " that formed by cyanobacteria often has severe toxicity, as coppery Microcystis aeruginosa (Microcystis aerugeosa) and wawter bloom anabena (Anabaena flos-aguae) etc., poultry or livestock is drunk behind this water less than in one hour even the several minutes and just can be poisoned to death, and can cause that hydrobiont (as fish) is poisoned to death.Thereby hindered water reoxygenation because a large amount of cyanobacterias cover the water surface, simultaneously a large amount of cyanobacteria cause deaths and corruption cause water body thereby anoxic and smelly, the formation vicious cycle.(Ren Nanqi etc. pollute controlling microbial, p38-39, press of Harbin Institute of Technology published in 2002).

In the natural water body, except a large amount of blue-green algaes that body eutrophication produces, many unwanted bacterias and virus etc. are still arranged, as intestinal bacteria (Coliform), enterococcus bacteria (Enterococcus group), kill vibrios (Vibrio cholerae) or the like, these water bodys are in the water ballast that ship's navigation is gathered, might be taken to other waters, be caused eco-catastrophe.Be generally and reduce excessive bending moment of boats and ships and shearing force, alleviate the hull vibrations, nearly all boats and ships all are provided with pumping system.Experiment showed, and have a large amount of bacteriums, pathogenic agent and other some microorganisms non-indigenous in the water ballast that accumulates in for a long time in the water ballast tank.In being rich in the water ballast tank of ferro element, they can be bred rapidly and survive several weeks even longer time.When boats and ships are discharged these external or new microorganisms, can cause local ecotope dysequilibrium.Generally speaking, these microorganisms are harmful, in case the leakage of water ballast takes place, pollute the environment, boats and ships, and the health that threatens personnel also may cause the damage of goods.Along with people to enhancing to the environment protection idea, this problem seems more and more outstanding.IMO (InternationalMaritime Organization, International Maritime Organizaton) investigation result finds that 4 kinds of poisonous algae such as dinoflagellate propagate into China by ballast water for ship, and cause large-area red tide disaster ( Liu Fubin, boats and ships, the 4th phase of in August, 2006).State Environmental Protection Administration in 2004 announces, China since the direct economic loss that biotic intrusion causes up to 57,400,000,000 yuan, wherein the marine organisms invasion is one of main reason.

At this class situation, people carry out many-sided effort very early, in the hope of avoiding harmful organism and pathogenic agent by other waters of water ballast pollution or cause eco-catastrophe.As far back as nineteen eighty-two, IMO has put into effect " nineteen eighty-two United Nations Convention on the Law of the Sea " (UNCLOS, United Nations Conference on the Law of the Sea) the 196th (1) bar regulation, " Marine Environmental Pollution that various countries should take all necessary steps and cause owing to use technology under its administration or control to prevent, to reduce and to control, or owing to deliberately or accidentally cause ocean environment that great and deleterious variation may take place at the external or new species of a certain specific region introducing of ocean environment "; The threat that the target of " Convention on Biological Diversity in 1992 " and the unwanted aquatic organism by Transfer via Ship's Ballast Water and introducing and pathogenic agent cause the protection and the sustainable use of species diversity; 34 (b) bar of world's Sustainable development summit implementation plan in 2002, recognize that boats and ships uncontrolledly discharge the transfer that water ballast and settling have caused unwanted aquatic organism and pathogenic agent, environment, human health, property and resource are damaged or damage, call action of parties to get up to accelerate to formulate the measure that water ballast is introduced the adventive problem that solves; Some countries have acted unilaterally and have entered the risk that unwanted aquatic organism and pathogenic agent are introduced in its harbour to prevent, to reduce to greatest extent and finally to eliminate by boats and ships at present, and caused global extensive concern on this problem, urgent need will be formulated rule and the guide rule that a whole world is suitable for, it is effectively implemented and unified the explanation, continue to advance the development of safer, effective Ballast Management method, thereby continue to prevent, reduce to greatest extent and the final transfer of eliminating unwanted aquatic organism and pathogenic agent; On this basis, IMO formulates " international shipping water ballast and settling control and management contract ", by controlling and manage environment, human health, property and the resource risk that ballast water for ship and settling cause with the transfer that prevents, reduces to greatest extent also final elimination unwanted aquatic organism and pathogenic agent, the unnecessary negative influence of avoiding this control to cause, and the development of encouragement, promotion relevant knowledge and technology; Though this pact U.S. and China is not signature as yet at present, most developed countries sign, and realize the management of water ballast in the global range by this treaty, just a matter of time.

Technology and corresponding the equipment and facility at external unwanted aquatic organism, pathogenic agent invasion are administered and prevented to the blue-green algae of water body in large must possess following feature:

(1), killing microorganisms and pathogenic agent speed must be very fast: otherwise, in water body in large, water after handling enters in the body water once more, if what add is biocide, will be very fast diluted and weaken sterilizing ability, add the microorganism of not killing in a large number, very fast meeting large-scale breeding, regulation effect is very poor; If be applied in the ballast water treatment, water ballast suction and discharging have only the very short time by device, if killing microorganisms and pathogenic agent speed are fast inadequately, the water body after it is handled just can not be up to standard;

(2), kill efficiency height: the discharging water ballast standard of performance of the regular D-2 bar regulation of " international shipping water ballast in 2004 and settling control and management contract " must satisfy:

(a). minimum size is less than 10 more than or equal to 50 microns survived in biology in every cubic metre; And

(b). minimum size is less than 50 microns but be less than 10 more than or equal to 10 microns survived in biology in every milliliter; And

(c). as a kind of HUMAN HEALTH standard, target microorganism should be less than following concentration:

(i). poisonous vibrio cholerae is less than per 100 milliliters 1 colony-forming unit (cfu) or less than 1 cfu of each gram (weight in wet base) zooplankton sample;

(ii). intestinal bacteria: be less than per 100 milliliters of 250cfu; And

(iii). enterococcus bacteria: be less than per 100 milliliters of 100cfu;

(3), can not produce secondary harm to ecotope;

(4), processing power is big: the eutrophication problem in water body in large such as lake, the processing power of sterilization algae removal is one of key factor; Handle for ship ballast water, boats and ships can not stop for a long time, and general requirement unit processing power is at 300M ³More than/the hr.

The improvement technical system of existing body eutrophication and blue-green algae, and ballast water treatment technical system, mainly contain: (1) medicament of killing livestock, (2) filter screen drags for collection and membrane technology, (3) ultrasonic technique, (4) high pressure algae removal, (5) biological treating, (6) ecological management, (7) ultraviolet sterilising technology, (8) electrolysis produces the active substance sterilising technology.

1, the medicament of killing livestock

Chinese patent application number 02100332 discloses a kind of brominated composite biocide of oxidized form-bromine chlorine prestige that is applied to service water field and public place, reusing sewage field; Chinese patent application number 200510025284 releases are a kind of by glutaraldehyde, the composite efficient aldehyde insecticide that quaternary amine constitutes; Chinese patent application numbers 200510025395 discloses a kind of biocide that contains isothiazolinone, dodecyl dimethyl benzyl ammonium chloride, is used for sewage disposal; The disclosed international monopoly WO03002406 of WIPO (World Intellectual Property Organization) adopts the sterilization of copper anode generating cu ions electrolytically; The bio-toxicity of this class biocide is bigger, and the residence time is long, still can be applied to the germicidal treatment in circulating sewage or the cooling water system at home; Be not suitable for big area eutrophication water such as lake and need discharged ballast water to handle.

U.S. Pat 2005016933 adopts adds ClO ₂As biocide, international monopoly WO2005061388, U.S. Pat 2004099608 and US2003029811, Japanese Patent JP2007144391, JP2006239556, JP2006263563, disclose respectively and adopted filtration and add water technology and the corresponding device thereof of ozone as biocide, this class device and technology, there is not secondary pollution, in low discharge water body or tap water germicidal treatment, certain advantage is arranged, but the sterilization algae removing for big flow water body such as water ballast or large watershed water body is handled, and running cost is very high.

Usually, add the medicament of killing livestock, fine to the little water body effect of local, but be difficult to keep the long period, at 1-2 after week in summer, generally need dosing again.For administering big area, eutrophication water exists running cost height, biocide water body to be existed factors such as secondary pollution; If be applied to ballast water treatment, its residue is still needed by bio-toxicity and toxicity evaluation.

2, filter screen drags for collection and membrane technology

Filter screen drags for collection and filters this class mechanical means and remove blue-green algae, as the summer of present Kunming Dianchi lake at the blue-green algae large-scale outbreak, and for the improvement of water body in large, but an utterly inadequate amount, difficulty becomes effective; This technology and corresponding device thereof can not effectively be removed unwanted bacteria (poisonous vibrio cholerae, intestinal bacteria, enterococcus bacteria etc.) and virus, can't satisfy the requirement of ballast water treatment, are unsuitable for ballast water treatment.How this technical scheme is as the supplementary means of filtering macrobead suspended substance or silt in the water treatment.

At present, developed country adopts membrane technology and corresponding device thereof more, and filtering microorganism, planktonic organism and bacterium are as Japanese Patent JP2005342626, JP20060099157, JP2006223997, JP2005342626, international monopoly WO2007114198, all adopt membrane technique with suction as seawater or the bacterium in the fresh water and the microbe filter of water ballast, this class technology needs higher pressure with device, and power consumption is big, and film is easy to contaminated and obstruction; Administer and the quick big flow water body of mobile for the blue-green algae of water body in large, running cost is higher, and processing power can not satisfy corresponding requirement.

3, ultrasonic technique

Ultrasonic not only have intensive to vibrate, but also have cavatition and produce a large amount of microjets, can make liquid that wall of container is produced the intensive shock action, such function is applied to ultrasonic cleaning, also be applied to the intensified response effect, as Chinese patent application number 200510117457 a kind of interior electrolysis wastewater treatment process and the devices of being announced based on ultrasonication, the method and the device thereof of a kind of ultrasonic wave water treatment of being announced with Chinese application number 99120675 are applied to strengthen flocculating effect; As Chinese patent application number 200610085548 method for treating wastewater of azo dye of being announced and German patent DE 19919824 disclosed oxidation organotin technology, adopt ultrasonic wave to promote the carrying out of chemical reaction.The microcell high pressure that ultrasonic cavitation produces, can be used for the fragmentation of cell, but such effect, mostly be that ultrasonic energy is converged in the less zone and could realize, therefore, present ultrasonic technique and corresponding water treatment device, for the small volume water body, and can adopt the water body that circulates, it is bigger to implement operability, as Chinese patent application number 200610023241 acousto-optic sterilization treatment device for drinking water of being announced.

(28～200KHz) are added on pipeline outer wall to Japanese Patent JP2006007184, will carry out sterilization algae removal by the water ballast of pipeline by ultrasonic wave and handle with ultrasonic transducer; JP2005021814 then provides corresponding water ballast tubular ultrasonic device for sterilizing and removing alga, in the device ultrasonic transducer is installed on the casing both sides, and the water route is passed through from casing, microorganism killing in the water body that ultrasonic wave will be passed through; These two parts of patents are not all considered hyperacoustic damage for the ultrasonic transducer piezoelectric ceramics that is installed on opposite tube wall or casing, and can not ignore equally the damage of piezoelectric ceramics perpendicular to the reflection echo of ultrasonic transducer, otherwise directly influence the life-span of ultrasonic transducer, thereby reduce the operation stability and the reliability of device.A kind of annular that ultrasonic wave water treatment machine that number of patent application 98236857 is announced and international monopoly WO03095370 are released, successive supersound process water ballast device, its ultrasonic transducer faces same problem.

But administer and the quick big flow water body of mobile for the blue-green algae of water body in large, existing ultrasonic processing apparatus is except the problems referred to above, if adopt ultrasonic technique to handle separately, remain at energy consumption high the running cost height, killing effect is difficult to unfavorable factors such as assurance, does not possess operability.

4, high pressure algae removal

High pressure sterilization and algae removal, be to adopt water body is pressurized to a certain degree, make the cell rupture of bacterium and algae, as Japanese Patent JP2007021287, JP2005270754, JP2005254138 but administer for the blue-green algae of water body in large, there is the energy consumption height equally in the high pressure algae removal, unfavorable factors such as running cost height do not possess operability; At ballast water treatment, also there is the problem of processing power and running cost.

5, biological treating

For the fresh water eutrophication water, people wish in biological treating the phase, but biological treating might cause biological disaster to local species because of introducing adventive.And blue-green algae is actual to be cyanobacteria, and the toxin of generation just can make fish, poultry dead in several minutes in the ppm level; Satoshi Nakai is at 2001 work of delivering (ALGAL GROWTH INHIBITIONEFFECTS AND INDUCEMENT MODES BY PLANT-PRODUCING PHENOLS SATOSHINAKAI ^*, YUTAKA INOUE and MASAAKI HOSOMI, Water Research, Vol.35, Issue 7, May2001, Pages 1855-1859) and point out that grass and other waterplant can reduce the eutrophication degree of water quality to a certain extent, but rarer plant can discharge the aldehydes matter of the growth that can suppress cyanobacteria.For the red tide of seawer system, biological treating is unpractical.Biological process still is in the exploratory stage to the improvement of algae at present, still unmatchful in the world extensive eutrophication water adopts the successful precedent of biological control blue-green algae, and, be difficult to blue-green algae be realized overall the inhibition with a kind of or limited several microorganisms, phage because the cyanobacteria kind that blue-green algae comprised is more.In addition, consider that from processing speed and efficient the biological treating technology is not suitable for the processing of water ballast.

6, ecological management

Polluting under the controlled situation in external source, recover aquatic higher plant to improve the self-purification capacity of water body, is the key of lake eutrophication improvement and ecological recovery.But this method responding time is longer, is difficult to realize in a short time the blue-green algae control of eutrophication water.And the blue algae bloom of eutrophication water can cover the water surface, hinders water reoxygenation, and simultaneously a large amount of cyanobacteria cause deaths and corruption consume the dissolved oxygen of water body and make water body smelly, cause fish kills and other hydrocoles death, the formation vicious cycle.Equally, the ecological management technology is not suitable for the processing of water ballast.

7, ultraviolet sterilising technology

Because water body itself to ultraviolet strong absorption effect, makes the scope of rentschlerization and sterilization ability be restricted, general ultraviolet disinfection technology is applied to handle lower small volume water body of load and the water body that circulates more.As Chinese patent application number 20051114 disclosed ultraviolet ray water treatment sterilization systems, 200610093390 disclosed household drinking water treating machines.

U.S. Pat 2004134861 and US2005211639, international monopoly WO2004002895 and WO2005110607 release the ultraviolet treatment of ballast water device continuously that adopts many group ultraviolet lamps to produce respectively; In addition, ultraviolet irradiation and combination of ultrasound, can strengthen sterilization effect, as Chinese patent application number 20060112 disclosed acousto-optic sterilization treatment device for drinking water and the 200520087812 disclosed sea filter device with mighty ultraviolet disinfection that are applied to the breeding seawater processing; U.S. Pat 5738780 combines ultra-violet sterilization and dc electrolysis, is applied to ballast water treatment.But these technology still are subjected to the restriction of the scope and the sterilization ability of rentschlerization, for the sterilization effect of high loading, big flow water body and water body in large, and still can not be satisfactory.

8, electrolysis produces the active substance sterilising technology

To add salt, produce the technology and the device of hypochlorous acid sterilization then by electrolysis, forefathers have many work, comprise Chinese patent application number 200610042972.2 disclosed " a kind of two-functional electrolytic generators ", disclosed 200510111126.7 " a kind of small-sized disinfected water generator and using method thereof ", disclosed 200520077629.2 " portable water source sterilizing machine ", disclosed 200510023766.2 " preparation method of high concentration hypochlorous acid disinfecting liquid ", than directly adding chlorinated lime, throw in dioxide peroxide, schemes such as hydrogen peroxide are convenient, save cost, but can increase the salinity of water of handling, especially for the big area lake, the sterilization of the eutrophication water of reservoir, algae removal is handled, under the long-term operation condition, the measure that all add medicament and increase water salinity all is unacceptable.

International monopoly WO2006058261 discloses a kind of ballast water treatment method and corresponding system, Japanese Patent JP2001000974 disclosed electrolysis treatment water ballast device and electrolyzer that also has Chinese patent application number 200510046991 disclosed ballast water for ship (water ballast) electrolytic treatment systems, Chinese patent application number 200480027174 disclosed treating water reservoirs similarly that adopts electrolysis to produce hypochlorite, is the material (ClO with high oxidation activity with chlorion, the water molecules electrolysis of handling in the water body ^-, OH, H ₂O ₂, (O)), cell, RNA, the DNA of bacterium in the water body and algae carried out oxygenizement, make its inactivation and death, make its inactivation and death, thereby reach sterilization algae removal effect, and make the maintenance of treated water body continue disinfection.

There are two kinds of defectives in this method and system:

(1), the interelectrode distance of system satisfies the electrolysis design requirements of water ballast in seawater, can not satisfy the requirement of fresh water system, because boats and ships are at the harbour of shipping waters and stop, has plenty of close rivers mouth, belong to fresh water zone, the two is owing to the electrolysis voltage that water body specific conductivity difference causes changes too greatly.

The voltage that electrolysis system puts between anode and the negative electrode has three parts to constitute, referring to figure (1), wherein: U ₁: the electropotential of anodic oxidation reactions and polarization overpotential constitute, if the polarization phenomena of electrochemical reaction can ignore, for specific reaction system (reaction density, pH, temperature-resistant), U ₁Substantially constant, do not change with current density; U ₂: the pressure drop that the resistance of solution causes, electrical conductivity of solution are low more, and then resistance R is big more, raise with the increase of current density; U ₃: the electropotential of cathodic reduction reaction and polarization overpotential constitute, if the reaction polarization phenomenon can be ignored and do not exist negative electrode to be stain, coat phenomenon, for specific reaction system (reaction density, pH, temperature-resistant), U by suspended substance and inorganics ₃Substantially constant, do not change with current density.

Want the certain sterilization of guarantee system, algae removal ability, Faradaic current I requires constant on certain numerical value basically, if interelectrode distance is that d is (for all openly take the system of electrolytic process at present, all less than the design that changes interelectrode distance in system consideration in service), electrode area is S, the water body specific conductivity is μ, then has following relation:

U ₂＝IR＝I×(d/(S×μ)) (1)

For certain electrolytic system, owing to I, d, S are determined value, but dissimilar water has different specific conductivity, and seawer system is 30000 μ S/cm; The river mouth water body, at ebb tide, current show as the single flow direction to the ocean, though influenced by oceanic tide, the water chemistry composition in the district that crosses this moment is similar to river water quality, specific conductivity can be between 50-500 μ S/cm; During slack tide, dropping of existing river also has tracing back of trend, and the water quality in the district that crosses this moment is complicated, and unstable; At the incoming tide, morning and evening tides is big to Hekou District influence, the seawater very dark distance in the river mouth of tracking, and the chemical constitution of the Qu Zhongshui that crosses this moment then shows the seawater feature.Therefore, when the river mouth water body between 50-500 μ S/cm the time, differ more than 60 times with ocean water body at least, from (1) formula as can be known, put on the voltage U on the water body between anode and the negative electrode ₂, have the difference more than 60 times at least, be difficult to guarantee that electrolytic system can satisfy boats and ships and run on the requirement of different waters to ballast water treatment in the safety voltage scope.

(2), there is scale formation in negative electrode in the fresh water system, and cause the resistance of negative electrode between water body sharply to increase, influence electrolytic efficiency, guarantee current constant if desired, then Zheng Ti electrolysis voltage sharply raises, and system can't normally be moved.

In the fresh water system, electrolytic process mainly is CaCO in the fouling of negative electrode ₃, because cathode surface and cathode zone adsorb a large amount of positively charged ions to satisfy charge balance, cation concn does not have very big difference, Ca in the water body ²⁺Electric charge is higher, at cathode surface and cathode zone enrichment, the HCO in this regional area and water body ₃ ^-Launch following reaction:

Ca ²⁺+HCO ₃ ^-＝CaCO _3(s)+H ⁺ (2)

Jeffrey A.Franz is at research (the Water Research of the pollution of producing the electrode surface that cathode deposition/fouling causes in the oxygen process about electrolysis to the influence of aerobic biodegradation system, Vol.36, Issue 9, May 2002, Pages 2243-2254) points out in that the cathode surface precipitation is mainly CaCO ₃Formerly apply for a patent the self-cleaning sterilizer of 99253589 disclosed water tanks in the long-time running process, negative electrode has tangible CaCO ₃Precipitation is used in the area that hardness is higher, even because the CaCO that reaction (2) produces ₃Precipitation causes the electrolysis line clogging; The number of applying for a patent formerly 03156596.4 " built-up type micro-current electroanalysis water technology and device " in person, though in the process that ultrasound probe counter electrode surface is cleaned, scale problems is eased, but might produce adverse influence to the aquatic ecological system, in the long-time running process, still there is slight scale formation in cathode surface; Though this device can be realized the blue-green algae of big area eutrophication water is effectively administered and inhibition, organizes parallel electrode more, makes erecting stage (ship, floating drum) in moving process, causes to turn to difficulty; And hydrocoles (fish) enters between the electrode easily, causes electric shock, and forms electric pole short circuit; The water that this device is fixed in the tank sea farming carries out electrolysis sterilization, disinfects by tank, handle seawater passes through to install electrolyzer with the flow velocity of 1.0～1.5m/s tank, white precipitate (bottom land ionization electrode edge 2cm) in a small amount appears in (more than at least 3 months) its bottom land after the long-time running, but the not precipitated covering of cathode surface.Chinese patent application number 200520114686.3 " the blue-green algae controlling devices " released face similar CaCO equally ₃Deposition and scale problems.

CaCO ₃There are three kinds of crystal formations: calcite (calcite), aragonite (aragonite) and ball aragonite (vaterite), calcite (calcite) forms dense structure easily, difficult drop-off on electrode; Aragonite (aragonite) generally could form in (more than 80 ℃) crystallization in the presence of the template or under the high temperature, growth, and electrolytic process does not possess such condition; Ball aragonite (vaterite) short texture comes off easily.The white fouling that we will be applied to the cathode surface of the white fouling of cathode surface of built-up type micro-current electroanalysis water treatment device of white deposits, freshwater aquiculture water treatment of the built-up type micro-current electroanalysis water treatment device of sea farming sterile environment and the self-cleaning sterilizer of water tank that the high building water tank uses scrapes, carry out field emission electron scanning analysis (SEM) photo and infrared (IR) absorption analysis respectively, the result is shown in figure (2a, 2b, 2c) and figure (3).

From figure (2a) as can be seen, the white precipitate particle of sea farming electrolysis treatment system is less relatively, and major part is spherical; Figure (2b) and figure (2c) are respectively the SEM photo of white fouling of cathode surface of the self-cleaning sterilizer of water tank of the fouling of cathode surface of electrolysis treatment system of freshwater aquiculture and the use of high building water tank, and particle is bigger; Corresponding therewith IR absorbs spectrogram (3) and shows, curve a be sea farming electrolysis treatment system white precipitate particulate infrared absorption spectrum, except the carbonate in-plane bending vibration v of calcite (calcite) ₄Charateristic avsorption band 712cm ^-1With carbonate out-of-plane deformation vibration v ₂Absorption peak 875cm ^-1Outside, also have the characteristic absorption band 745cm of ball aragonite (vaterite) ^-1With the infrared absorption spectrum c of the cathode surface white fouling of the infrared absorption spectrum b of the cathode surface fouling of the electrolysis treatment system of freshwater aquiculture and the self-cleaning sterilizer of water tank that the high building water tank uses remarkable difference is arranged, b and c are quite similar, belong to typical calcite (calcite) infrared absorption spectrum; This conforms to the analytical results of SEM.

At solving negative electrode scale problems in the electrolytic process, the electrochemical reactor of Chinese patent application number 200620032114 disclosed a kind of operations of falling the utmost point comes off the negative electrode fouling by means of the utmost point; This method of falling the utmost point is introduced a new problem again, and the frequently pole-reversing scale removal will make the anode loss of catalytic activity of electrolyzer, causes electrode to produce very high overvoltage, and current efficiency descends.

At present, electrolysis produces oxidizing substance to carry out the system of water treatment, the general DSA anode (Dimensionally Stable Anode) that all adopts with catalytic activity, be with metal titanium or titanium alloy be matrix at a kind of electrode materials of its surface-coated with platinum group element oxide, be Dutch Henri Bernard Beer (1909-1994) invention.H.Beer 65 patents be a kind of be core/base material with titanium or titanium alloy, from platinum, iridium, rhodium, palladium, ruthenium, osmium, select the oxide compound of platinum metals or its alloy, the non-platinum group metal oxide (as Ta, Ti) that particularly contains more than one is formed outer electrode; Italy De Nora company and U.S. Diamond Shamrock company successfully were applied to the Beer invention in the chlor-alkali production in nineteen sixty-eight.Its salt electrolysis has been developed titanium base platinum group metal oxide electrode with anode, the catalytic activity height, and can use more than 15 years.DSA has lasted 40 years so far and has put in order after late 1960s comes out.Zhang Zhaoxian points out (electroplate and cover with paint, lacquer, colour wash, etc., 2007 the 26th the 1st phases of volume) in about " coated electrode 40 years " literary composition, the development that the titanium anodic is born and has greatly advanced salt electrolysis to produce is described as chlorine industry one big technological revolution.The invention of DSA is one of the most great invention of 20th century electrochemical industry, is to the electrochemical field epoch-making contribution.But kind electrode, if use as negative electrode, then because Pt, Ir, Ru, Rh, Pd and Ti are strong hydrogen-absorbing material, the H that cathodic reaction produces ₂Adsorbed by Pt, Ir, Ru, Rh, Pd and Ti, cause volumetric expansion to cause between coating and the core and peel off, cause coating and active substance to come off loss of catalytic activity.

At at present for big area eutrophication water and the big existing above-mentioned defective of flow ballast water treatment technology, for provide a kind of can be applicable to fresh water and seawer system, can effectively low fast kill bacteria and blue-green algae, running cost low, do not cause secondary pollution, easy to use, stable performance water treatment device, the spy finishes the present invention.

Summary of the invention

The purpose of this invention is to provide a kind of can be applicable to fresh water and seawer system, can effectively low fast kill bacteria and blue-green algae, satisfied big area eutrophication water are handled and big flow ballast water treatment requires, running cost is low, do not cause secondary pollution, the ultrasonic intensified self-descaling micro-current electrolysis sterilization algae removing water treatment device of easy to use, stable performance.

Technical conceive of the present invention is:

Water body enters detection system by the road, detect the specific conductivity of water body, Controlling System determines the electrolysis mode of ultrasound-enhanced micro-current electroanalysis system according to the specific conductivity of being surveyed, water body is discharged after ultrasound-enhanced micro-current electroanalysis system handles, ultrasonic transducer is evenly arranged in a side of system, the ultrasonic wave that is produced, ultrasound reflectors reflection through its opposite one side, and change ultrasonic transmission direction along the reflection of former road, promote bacterium and microbial cell wall in the water body to break, strengthen electrolysis and produce the oxidisability active substance bacterium, the killing effect of blue-green algae reduces the scale formation that negative electrode shows; Contain a large amount of organic special water bodys that pollute (chemical oxygen demand COD and biological oxygen demand BOD are very high) for running into, Controlling System can also suitably be revised electrolytic parameter according to the redox potential in the water body of outflow micro-current electroanalysis system, to guarantee treatment effect, referring to figure (4).

Micro-current electroanalysis produces the machine-processed as follows of oxidisability active substance:

Beyond the heavy metal and organic pollutant do not considered in the water body, the micro-current electroanalysis reaction that is taken place in the natural water body mainly is:

The reaction that takes place in A, anode and the positive column

2Cl ^-＝＝＝Cl ₂+2e (3)

4OH ^-＝＝＝2H ₂O+O ₂+2e (4)

Be rich on the catalysis electrode of metal Pt, Ir, Ru, Rh, Pd, can provide d, f unoccupied orbital catalytic active center help realizing transfer transport, avoid polarization phenomena, and help the generation of highly reactive form of oxygen voltinism material, referring to reaction (3～11).Catalytic oxidation has:

·OH-Cat＝＝＝＝＝O-Cat+H ⁺+e (6)

The active substance complex reaction on catalysis electrode surface

2·OH-Cat＝＝＝＝＝H ₂O ₂+Cat (8)

2O-Cat＝＝＝＝＝O _2(g)+Cat (9)

2·Cl-Cat＝＝＝＝＝Cl ₂ (10)

2·OH-Cat＝＝＝＝＝H ₂O+O-Cat (11)

Reaction in the water body of positive column

Cl ₂+H ₂O＝＝＝＝＝ClO ^-+Cl ^-+2H ⁺ (12)

3HClO＝＝＝＝＝ClO ₃ ^-+2Cl ^-+3H ⁺ (13)

H ₂O ₂+2H ⁺＝＝＝2H ₂O+O _2(g) (14)

B, cathodic reaction

2H ⁺+2e＝＝＝H _2(g) (15)

H ₂O ₂+H _2(g)＝＝＝2H ₂O (16)

2HClO+H _2(g)＝＝＝＝＝2HCl+2H ₂O (17)

Above-mentioned Cat represents the catalytic active center that d, f unoccupied orbital can be provided of electrode.The Chinese patent application number 03826068 disclosed free radical aqueous solution has confirmed the generation of free radical activity material in the electrolytic process with spectrum (ESR).The H that cathodic reduction produces _{2 (g)}, with the oxidizing substance reaction that is diffused into the cathodic area, as reaction formula (16) and (17), the oxidisability active substance that electrolysis produces in the consumption system will cause current efficiency to descend; Because quite a few H of electrolysis initial stage _{2 (g)}Adsorbed by negative electrode, the consumption of the oxidisability active substance that electrolysis is produced seldom; Work as H _{2 (g)}Absorption when reaching capacity, H is arranged _{2 (g)}Be released in the water body, but H in fact _{2 (g)}Solubleness in water body is very little, and very fast formation bubble is overflowed from water, and the oxidisability active substance has very big solubleness in water, so, although the H that electrolysis produces _{2 (g)}Separate without special means, it produces the consumption of active substance to electrolysis and produces the influence of sterilization algae removal effect very for a short time, and test shows that electrolytic current density is not more than 10mA/cm ²Under the condition, for the micro-current electroanalysis system, the oxidisability active substance that electrolysis produces in reaction formula (16) and (17) institute consumption system can be ignored.

This shows that adopt ultrasound-enhanced, micro-current electrolysis sterilization algae removing, whole process does not need to add any medicament, and water body is not caused secondary pollution.Operation, easy maintenance, energy consumption is low.

Core novelty of the present invention is and can regulates electrolysis mode according to water electric conductivity, the scale removal of falling the utmost point and do not reduce anode-catalyzed activity, the ultrasound-enhanced micro-current electroanalysis system that is fit to the sterilization algae removing of the very big water body of specific conductivity difference, utilize ultrasound reflectors to strengthen the ultrasonication bacteria cell wall, alleviate scale formation, weaken the piezoelectric vibrator influence of ultrasonic reflection to ultrasonic transducer, give the fresh water that the ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga can adapt to big area and big flow, seawer system quick sterilization algae removal processing power, and can be when the fresh water system be worked, can not influence DSA anodic catalytic activity by the scale removal of falling the utmost point, ensuring equipment reliability of operation and stability.

Technical scheme of the present invention is as follows:

A kind of ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga is characterized in that device is made of detection system, Controlling System, ultrasound-enhanced micro-current electroanalysis system, referring to figure (4); Discharge after water route process detection system, the ultrasound-enhanced micro-current electroanalysis system handles, the entire treatment process is carried out under the control of Controlling System; The specific conductivity of the water body that Controlling System is surveyed according to detection system determines the electrolysis mode of ultrasound-enhanced micro-current electroanalysis system.

1, detection system:

Detection system mainly is made up of conductivity sensor, conductivity meter, potentiometer, redox electrode assembly or chlorine residue electrode.

Wherein conductivity sensor adopts induction conductivity sensor, because the principle of work of this transmitter is in the loop in solution, produce an induced current, obtain the specific conductivity of solution by the size of measuring electric current, its resistance to crocking is very strong, and the system that can guarantee is stable in the water quality environment of complexity.

Conductivity meter, potentiometer can adopt conductivity transmitter, chlorine residue transmitter respectively, are convenient to industry control.

2, ultrasound-enhanced micro-current electroanalysis system:

Ultrasound-enhanced micro-current electroanalysis system mainly is made up of dc electrolysis power supply, electrolysis electrode group, casing and contact conductor splicing ear, ultra-sonic generator, ultrasound reflectors; Wherein direct supply adopts the linear DC power supply, and incoming end is 110V or 220V alternating-current, is output as direct current, can regulate Faradaic current as required, and output voltage is controlled in the safety range of 36V; The electrode group is equidistant the rearranging of coated electrode of core by metal titanium and titanium alloy; Casing comprises shell, sealing member, mounting block and joint flange, and shell, flange adopt plastic member; Ultra-sonic generator comprises housing, transverter, power supply composition, can adopt a plurality of ultrasonic transducers evenly to arrange to increase hyperacoustic intensity, and the ultrasonic field in the assurance treatment unit is evenly distributed, and the power input that ultrasonic transducer is provided can be to be 110V or 220V alternating-current.

The principal character of the electrode group of ultrasound-enhanced micro-current electroanalysis system is:

(1), titanium anode: the electrode of oxide compound that to adopt metal titanium or titanium alloy be matrix contains a kind of metal Pt, Ir, Ru, Rh, Pd, Os and oxide compound thereof at least and contain at least a Ta, Ti in its surface-coated is as anode---titanium anode (DSA anode), Pt, Ir, Ru, Rh, Pd, Os, Ta, Ti all can provide d, f unoccupied orbital catalytic active center help realizing transfer transport, avoid polarization phenomena, and help the generation of highly reactive form of oxygen voltinism material; Excessive and produce at work easily and blow phenomenon for fear of electric current that contact passed through between electrode and the lead-in wire, plate-shaped anode has 2 terminals at least, uniform distribution on anode, titanium anode construction synoptic diagram referring to figure (5a), on terminals, open by through hole, can be connected with electric wire and adopt screw fastening; Sheath can be by the ring-type contact to solve point of contact local current problems of too;

(2), negative electrode: adopting metal titanium or titanium alloy is the electrode member of matrix at the oxide compound of at least a Ta of its surface-coated, Ti; Can guarantee to have certain catalytic activity in the lower fresh water system transfer polarizing electrode character of specific conductivity during as anode, the oxide compound hydrogen-absorbing ability of Ta, Ti is low simultaneously, can not come off when using as negative electrode; Equally, excessive and produce at work easily and blow phenomenon for fear of the electric current that passes through between electrode and the lead-in wire, plate-like cathodes has 2 terminals at least, uniform distribution on negative electrode, cathode construction synoptic diagram referring to figure (5b), on terminals, open by through hole, can be connected with electric wire and adopt screw fastening; Sleeve cathode can be by the ring-type contact to solve point of contact local current problems of too;

(3), supporting electrode: adopt oxide compound that mean pore size is not less than the metal titanium of 3mm or titanium alloy reticulated, at least a Ta of its surface-coated, Ti as outer field electrode member, guarantee that electrode materials can not be corroded when the scale removal of falling the utmost point is used as anode; Equally, excessive and produce at work easily and blow phenomenon for fear of the electric current that passes through between electrode and the lead-in wire, tabular supporting electrode has 2 terminals at least, uniform distribution on supporting electrode, auxiliary electrode structure synoptic diagram referring to figure (5c), on terminals, open by through hole, can be connected with electric wire and adopt screw fastening; The tubulose supporting electrode can be by the ring-type contact to solve some contact local current problems of too;

For tabular titanium anode, negative electrode and supporting electrode, be not more than at electrode length under the condition of 1200mm, connection terminal is last with 2 to 3, connection terminal is all influential to the sealing and the good looking appearance of system too much.

(4), electrode array: plate electrode is formed the electrode group of micro-current electroanalysis system according to the equidistant in proper order arrangement of supporting electrode between negative electrode, anode; The electrode group that plate electrode constitutes is arranged referring to figure (6), and all electrodes all adopt the electrode of dual coating, because the anode cost is higher relatively, can make in the arrangement of last group, and be outermost with the negative electrode, with the space availability ratio of assurance device with reduce cost; Adopt the plastics locating support,, electrode is fixed referring to figure (7a, 7b, 7c); In the seawater water body of specific conductivity greater than 1500 μ S/cm, the electrolysis mode of employing is: supporting electrode B does not work, and by the electrolytic action between anode A and the negative electrode C, is the material (ClO with high oxidation activity with chlorion, the water molecules electrolysis of handling in the water body ^-.OH, H ₂O ₂, (O)), RNA, the DNA of the cell of bacterium in the water body and algae carried out oxygenizement, make its inactivation and death, thereby reach sterilization algae removal effect, and make the maintenance of treated water body continue disinfection; Because a large amount of through holes and the hyperacoustic acting in conjunction of supporting electrode B, make the diffusion and the oxidation disinfection effect of the active substance that electrolysis produces can be not influenced because supporting electrode B exists; In the fresh water water body of specific conductivity less than 1500 μ S/cm, the electrolysis mode that adopts is: supporting electrode B is as negative electrode, negative electrode C originally is all as anode, the character of former anode A is constant, the corresponding electrode spacing is original 1/2nd, according to (1) formula as can be known, the operating voltage that can reduce greatly for the electrolysis treatment of the fresh water water body of low conductivity; If the supporting electrode B work long period in the higher water body of hardness, surface deposition lime carbonate, by changing the polarity of original negative electrode C (during the work of fresh water system is one of anode) and supporting electrode B---carry out the electrolysis of falling the utmost point, the electrolysis mode that is adopted is: change supporting electrode B into anode, former negative electrode C (during the work of fresh water system is anode) as one of anode changes negative electrode once more into, electrolytic descaling, in the scale removal of falling utmost point process, former anode A does not work, can protect the catalytic activity of anode A effectively, thus the permanent stability and the reliability of assurance device operation; Rule according to the water tank long-time running, in identical fresh water water body, move, adopt constant-current electrolysis, if under the constant condition of electric current, electrolytic potential raises 20%, then show negative electrode fouling certainly in the electrolytic process, electrolytic potential (U when electrolysis moves at identical Faradaic current, in identical fresh water water body with employing ₁+ U ₂+ U ₃) raise 20% o'clock, adopting the electrolysis mode of falling utmost point scale removal, extremely electrolytic current density is not more than 5mA/cm ², the electrolysis time of falling the utmost point is to get final product in 20-40 minutes; And in seawer system, move, need not to adopt the electrolytic descaling of falling the utmost point.

The hollow edged electrode group can be according to same order: supporting electrode is positioned between negative electrode, the anode, and the equidistant radially arranged in co-axial alignment of each electrode constitutes, and adopts to have no more than 6 plastics flange of uniform brace rod and fixes, to reduce water resistance.

(5) ultra-sonic generator:

Ultra-sonic generator comprises housing, transverter, power supply composition, adopt a plurality of ultrasonic transducer displays, in housing, evenly arrange, with uniform being arranged in parallel of plate electrode group orientation, to increase hyperacoustic intensity, ultrasonic field is evenly distributed in the water body of assurance treatment unit; In the micro-current electroanalysis system of hollow edged electrode group, should adopt annular uniform arrangement.

(6) ultrasound reflectors

The ultrasonic reflection body structure is referring to figure (8a, 8b).In hyperacoustic transmission course that ultra-sonic generator produces, referring to figure (8a), though disperse function is arranged, if but run into and the vertical plane of working direction, will there be quite a few energy to reflect back along former road, the direction that the plane of reflection that ultrasound reflectors constitutes or curved surface and ultrasonic wave are advanced is angled, thereby change hyperacoustic reflection direction, strengthen the cleanup action of counter electrode, alleviate scale formation, referring to figure (8b); On the other hand, increase the propagation distance of ultrasonic wave in the water body of treatment unit, thereby increased the chance that ultrasonication makes bacterium and microbial cell fragmentation; Moreover avoid ultrasonic wave directly along the reflection of former road, in order to avoid cause damage, increase the service life to the ultrasonic transducer piezoelectric vibrator.

Described ultrasound reflector can be plastics, metal titanium, titanium alloy, stainless steel, carbon steel, Cu alloy material member, and the corrosion of material is good with metal titanium, titanium alloy, plastic member when moving for anti-locking system.

Corresponding to the plate electrode system, ultrasound reflectors can be triangular prism and semicylinder, a trequetrous cylinder is connected with casing, and parallel with electrode, a trequetrous rib is vertical with the transmission direction of ultrasonic transducer ultrasonic waves transmitted; Semicylinder then is connected the post plane with casing, and parallel with electrolysis electrode, and curved surface is vertical with the transmission direction of ultrasonic transducer ultrasonic waves transmitted; Can guarantee effectively to change hyperacoustic reflection direction like this, strengthen the cleanup action of counter electrode, alleviate scale formation, simultaneously, increase the ability of ultrasonication bacterium and microorganism wall; Wherein, preferably adopt the triangular prism structure, to improve the ultrasonic field distributing homogeneity.

For the hollow edged electrode system, it is good that ultrasound reflectors adopts the structure of triangular pyramid type.

3, Controlling System

Form by MPU and serial trip switch, the specific conductivity of the water body of measuring according to detection system, the redox potential in the water outlet water body, electrolysis operational mode, Faradaic current intensity, the electrolytic descaling of falling the utmost point time of control ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga, thereby guarantee system steady running.

Effect of the present invention and advantage are as follows:

1, the induction conductivity sensor of the detection system of water route process detects the specific conductivity of water body, whether greater than the electrolysis mode of 1500 μ S/cm determination devices, handle by the sterilization algae removing that is suitable for very big fresh water of specific conductivity difference and seawer system according to specific conductivity for Controlling System;

When 2, water body enters ultrasound-enhanced micro-current electroanalysis system, the material (ClO of the high oxidation activity that is generated by little electric current catalytic electrolysis ^-.OH, H ₂O ₂, (O)), cell, RNA, the DNA of bacterium in the water body and algae carried out oxygenizement, make its inactivation and death, make its inactivation and death, thereby reach sterilization algae removal effect, how not add medicament, non-secondary pollution;

3, the ultrasonic wave of ultra-sonic generator generation is after the ultrasound reflectors reflection, changed the ultrasonic reflections direction, prolong the stroke of ultrasonic wave in handling water body, improve the ultrasonic field distributing homogeneity, thereby the cell walls to bacterium in the water body and algae has the intensive crushing effect, strengthen the quick killing effect of the material of high oxidation activity, and counter electrode there is the intensive cleanup action, alleviates the electrode scale formation water body bacterium, blue-green algae; The ultrasonic wave of diminished reflex improves operation stability and reliability to the infringement of ultrasonic transducer piezoelectric vibrator;

4, by means of netted supporting electrode, make device be suitable for fresh water, seawer system sterilization, remove algae and handle, can reduce the operating voltage of electrolysis treatment of the fresh water water body of low conductivity greatly; Long period operation in the higher water body of hardness, if supporting electrode generation fouling, surface deposition lime carbonate are by the electrolytic descaling of falling the utmost point, in the scale removal of falling utmost point process, do not damage titanium anodic catalytic activity, thus the permanent stability and the reliability of assurance device operation;

5, the electrode group of the micro-current electroanalysis layout that can adopt board-like electrode to be arranged in parallel is looked after the radially coaxial equidistant alignment placement of electrode, and can adopt configuration in parallel according to handling flow, be suitable for the processing of the different big flow water body of processing power;

6, the navigation maneuvering ability to erecting stage does not cause negative impact, and can combine with the water pump water lift, and with the draining energy utilized, as water-jet propulsion power.

In sum, the present invention is simple in structure, erecting stage there is not harsh requirement, navigation maneuvering ability is not caused negative impact, be suitable for handling in the sterilization algae removal of big area eutrophication water, big flow water body and water ballast, treating processes does not have a negative impact to aquatic ecological, and the easy installation and maintenance of equipment, running cost suit, do not cause secondary pollution, have excellent operation stability and reliability.

Description of drawings

The voltage distribution schematic diagram of Fig. 1, electrolysis of solutions process;

The microscopic appearance of negative electrode fouling is analyzed SEM photo (instrument JEOL JSM-6700F, sweep voltage 3KV) in figure (2a, 2b, 2c), the water body electrolytic process, wherein:

The white precipitate particle SEM photo (5000 times of enlargement ratios) of figure (2a) sea farming electrolysis treatment system,

The SEM photo (8000 times of enlargement ratios) of the fouling of the cathode surface of the electrolysis treatment system of figure (2b) freshwater aquiculture,

The SEM photo (3000 times of enlargement ratios) of the white fouling of the cathode surface of the self-cleaning sterilizer of water tank that figure (2c) high building water tank uses;

The infrared absorption spectrum of negative electrode fouling in Fig. 3, the water body electrolytic process, wherein curve a, b, c are respectively the infrared absorption spectrum of white fouling of cathode surface of fouling, the self-cleaning sterilizer of water tank that the high building water tank uses of cathode surface of electrolysis treatment system of white precipitate particle, the freshwater aquiculture of sea farming electrolysis treatment system, and X-coordinate is a wave number;

Fig. 4, ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga treatment scheme synoptic diagram;

The electrode structure synoptic diagram of the electrode group of Fig. 5, ultrasound-enhanced micro-current electroanalysis system, wherein:

Figure (5a) tabular titanium anode,

Figure (5b) plate-like cathodes,

Figure (5c) flat netted supporting electrode;

Fig. 6, ultrasound-enhanced micro-current electroanalysis system plate electrode group are arranged synoptic diagram;

Fig. 7, plastic electrode fixing rack structure synoptic diagram, wherein: figure (7a) is a front view, figure (7b), (7c) are respectively the partial enlarged drawing of different directions;

Fig. 8, the ultrasonic wave transmission direction synoptic diagram between electrolysis electrode, wherein: figure (8a) is a ultrasonic transducer ultrasonic waves transmitted transmission direction synoptic diagram, figure (8b) is the ultrasonic transmission direction synoptic diagram that ultrasound reflectors reflected;

Fig. 9, box ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga synoptic diagram;

Figure 10, the ultrasound-enhanced micro-current electroanalysis A-A of system are to view;

Figure 11,800mm * 500mm titanium anode (structure iron of δ=2.0mm);

Figure 12,800mm * 500mm titanium negative electrode (structure iron of δ=2.0mm);

Figure 13,800mm * 500mm titanium net supporting electrode (structure iron of δ=1.3mm);

The electrode arranging structure synoptic diagram of Figure 14, box ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga;

Figure 15, box ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga electrode mounting groove mouth structure synoptic diagram (the box ultrasound-enhanced micro-current electroanalysis B-B of system is to view);

The electrode terminal outlet arrangement architecture synoptic diagram of Figure 16, box ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga enclosed electrode group rubber pad;

Figure 17, box ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga electrode seal cover board electrode connection synoptic diagram;

Figure 18, connection terminal structure synoptic diagram, wherein:

Figure (18a), (18b) are respectively the sectional view of connection terminal when being mutually 90 °, and figure (18c) is the metal sheeting front view;

Figure 19, Mitsubishi's cylindricality ultrasound reflectors structural representation, wherein:

Figure (19a) is the structure iron of triangular prism length direction, and figure (19b) is a triangular prism arrangement architecture synoptic diagram;

Figure 20, box ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga ultra-sonic generator are arranged synoptic diagram;

The sealing rubber pad structural representation that Figure 21, ultra-sonic generator are connected with casing, ultra-sonic generator cover plate;

Figure 22, C-C are to box ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga ultra-sonic generator faceplate view;

The ultrasound-enhanced micro-current electroanalysis system architecture synoptic diagram of Figure 23, tubular ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga;

Figure 24, fixing bar-shaped titanium anode, comprise the plastics flange structural representation of contact conductor;

Figure 25, for fixing bar-shaped titanium anode, do not comprise the plastics flange structural representation of contact conductor;

Figure 26, for fixing perforated tubular supporting electrode, comprise the plastics flange structural representation of contact conductor;

Figure 27, for fixing perforated tubular supporting electrode, do not comprise the plastics flange structural representation of contact conductor.

Reference numeral lists as follows:

1, the water inlet joint flange, 2, conductivity sensor, 3, the plastic electrode fixed support, 4, the electrode group, 5, box-type shell, 6, the water outlet joint flange, 7, the chlorine residue electrode, 8, the chlorine residue transmitter, 9, ultrasound reflectors, 10, enclosed electrode group rubber pad, 11, fastening piece, 12, the titanium anode, 13, negative electrode, 14, supporting electrode, 15, the electrode seal cover board, 16, the ultra-sonic generator housing, 17, ultrasonic transducer, 18, ultra-sonic generator and casing, the sealing rubber pad that the ultra-sonic generator cover plate connects, 19, the ultra-sonic generator panel, 20, conductivity transmitter, 21, the ultra-sonic generator power supply, 22, linear constant current direct supply, 23, Controlling System, 24, electrode is installed notch, 25, the fixed via of electrode seal cover board, 26, the electrode terminal outlet of enclosed electrode group rubber pad, 27, titanium anode connection terminal, 28, the cathode connection terminal, 29, the supporting electrode connection terminal, 30, the metal sheeting of electrode connection terminal, 31, the hollow standing bolt, 32, go out the fastening screw that water generator is connected with casing; 33-ultra-sonic generator, 34, the plastic three-way of flange connection, 35-1,35-2 are fixing bar-shaped titanium anode plastics flange, 36-1,36-2 are fixing perforated tubular supporting electrode plastics flange, 37, the perforated tubular supporting electrode, 38, negative electrode, 39, titanium anode bar, 40, gasket, 41, conical ultrasound reflectors, 42, have a lead terminal of metallic gasket.

Embodiment

Below in conjunction with specific embodiments and the drawings the present invention is further described:

Embodiment 1, processing flow are 300M ³The box ultrasound-enhanced micro-current electrolysis device for sterilizing and removing alga of/hr

With reference to figure (9), box ultrasound-enhanced micro-current electrolysis device for sterilizing and removing alga is by connecting water-in flange 1, induction type conductivity sensor 2, plastic electrode fixed support 3, electrode group 4, box-type shell 5, water-output flange 6, chlorine residue electrode 7, chlorine residue transmitter 8, ultrasound reflectors 9, electrode group sealing rubber pad 10, fastening piece 11, titanium anode 12, negative electrode 13, titanium net supporting electrode 14, cover plate 15, ultra-sonic generator housing 16, ultrasonic transducer 17, the sealing rubber pad 18 that ultra-sonic generator is connected with casing, ultra-sonic generator cover plate 19, conductivity transmitter 20, ultra-sonic generator power supply 21, linear constant current direct supply 22, Controlling System 23, the electrode connection terminal is formed.

The InPro7250HT induction type conductivity sensor 2 and the plum Teller-electricity of Tuo benefit transmitter 20 formation water inlet water bodys that adopt PEEK (polyether-ether-ketone) to make are led and are detected and the signal hop, signal output part is connected with Controlling System 23; Adopt SZ283 chlorine residue electrode 7 and Italian B﹠amp; C (CL3630 chlorine residue transmitter) 8 constitutes chlorine residue detection and signal hop, signal output part is connected the detection system of this two portions constituent apparatus with Controlling System 23.

Device employing thickness is that U-PVC (polyvinyl chloride) plate of 15mm is made the box-type shell 5 that inner dead size is 1580mm * 600mm * 515mm, the external diameter of water inlet joint flange 2 and water outlet joint flange 6 be 350mm, internal diameter be 200mm, 8 for the aperture be that the bolt hole of 22mm is distributed on the annulus that diameter is 295mm, adopt the M20 holding bolt to be connected with inlet channel, outlet conduit respectively, referring to figure (10).

Electrode group 4 adopts long 800mm, wide by 500, (thickness δ 2.5mm) surface-coated Ir, Rh oxide compound and TiO ₂Titanium anode 12; With the electrode of long 800mm, wide by 500, oxide compound that (thickness δ 2.5mm), core are metal titanium surface-coated Ta, Ti as negative electrode 13; With long 800mm, wide by 500, (thickness δ 1.3mm), core is that metal titanium, mesh (width between centers) are that the titanium net electrode of oxide compound of 4.5mm * 12.5mm, surface-coated Ta, Ti is as supporting electrode 14; All electrodes all have two terminals, respectively referring to figure (11), (12), (13) (above three kinds of electrodes are all available from Shenyang Zhong Kehui friend development in science and technology company limited).Adopt 6 anodes, 7 negative electrodes, 12 netted supporting electrodes are according to negative electrode, supporting electrode, the anodic equidistant arrangement of the alternate 25mm of width between centers in proper order is inserted on the plastics fixed support 3, support bracket fastened pickup groove has 15mm at the bottom of case, guarantee that sedimentary a small amount of settling can not cause short circuit between the electrode in the run duration water body, referring to figure (7) and (14), because the casing clear height is 500mm, make plate electrode have the height of 15mm to stay (plate thickness that constitutes casing is 15mm) in the plate of casing fully, thereby the assurance electrode can accurately be located, and under fluviation, the changing of the relative positions and displacement can not take place; Electrode inserts in the case from the installation notch of casing, and the two ends of opposite side embed plastics fixed support 3, and the long 803mm of notch, wide 3mm are installed, and is convenient to install the location, referring to figure (15); Install between notch and the electrode seal cover board 15, adding thickness is the sealing rubber pad 10 of 5mm, fastening through the through hole 25 of Φ 10mm with the M8 bolt; Corresponding to electrode terminal place designated port, the electrode terminal outlet 26 as enclosed electrode group rubber pad is passed through electrode terminal, guarantees sealing effectiveness simultaneously, referring to figure (16), (17) at sealing rubber pad; Each electrode terminal is that 25mm, center have the stainless steel compressing tablet 30 of 17mm * 3mm through hole and M30 bolt 31 fit sealings that central aperture is 18mm, high 50mm with thick 4mm, external diameter, electric wire is connected with electrode through the screw of electrode terminal with screw, and electrode terminal, metal sheeting 30, hollow holding bolt 31 constitute connection terminal; Titanium anode 12 is connected with the output terminal i of linear constant current direct supply 22 by connection terminal 27, negative electrode 13 is connected with output terminal ii, the iii of linear constant current direct supply 22 respectively by connection terminal 28, supporting electrode 14 is connected with output terminal iv, the v of linear constant current direct supply 22 respectively by connection terminal 29, output terminal i, iii, the v of linear constant current direct supply 22 are cathode output end, and ii, iv are cathode output end; When the seawer system electrolysis moves (specific conductivity is greater than 1500 μ S/cm), Controlling System is connected i, the ii output terminal of linear constant current direct supply 22; When the electrolysis of fresh water system moves (specific conductivity is less than 1500 μ S/cm), Controlling System is connected i, iii, the iv output terminal of linear constant current direct supply 22; During the scale removal of falling utmost point operation, Controlling System is connected ii, the v output terminal of linear constant current direct supply 22; Can make stable in fresh water, seawater water body, the operation reliably of device.Ultrasound reflectors 9 adopts PVC to make the bottom surface to be 50mm, high 15mm isosceles triangle, longly be the triangular prism of 515mm that 12 identical triangular prisms are arranged according to the direction parallel with electrode, are welded on the box-type shell 5, referring to scheming (9), (19); With 10 TYH-50-25 type power 50W, the ultrasonic transducer 17 of operating frequency 25KHz, with the AB glue bond is on the 1Cr18Ni9Ti stainless steel ultra-sonic generator housing 16 of 2mm at thickness, uniform distribution, referring to figure (9), (20), at box-type shell 5, ultra-sonic generator housing 16, and between the ultra-sonic generator panel 19, the sealing rubber pad gasket 18 that respectively to add a thickness be 3.5mm, referring to figure (21), fasten them together with the through hole 32 of M20 * 60 bolts through Φ 22mm, guarantee sealing effectiveness, the electric wire of ultrasonic transducer 17 is derived through the centre hole of ultra-sonic generator panel 19, referring to figure (22), is connected with the power supply 21 of ultra-sonic generator.

The output terminal of conductivity transmitter 20 is connected with the input terminus of Controlling System 23, the output terminal of Controlling System is connected with the input control end of the power supply of ultra-sonic generator 21, linear DC constant current power supply 22, and it is the 0-30V/500A linear power supply that linear constant current direct supply 22 adopts model specification; Detection system is implemented online detection according to the instruction of Controlling System to specific conductivity, the chlorine residue of influent quality, and Controlling System is according to the specific conductivity decision electrolysis mode of being surveyed, according to chlorine residue size adjustment Faradaic current; Voltage, the current signal of linear constant current direct supply 22 are transferred to Controlling System 23, and whether estimate needs to carry out down the utmost point; Controlling System can also select several groups of ultrasonic transducer work to control with the power to ultra-sonic generator.

In the use, the treatment scheme according to figure (4) can realize 300M ³The water body sterilization algae removing of/hr.

Embodiment 2, processing flow are 30M ³The tubular ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga of/hr

As shown in figure 23, tubular ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga, main body comprises connection water-in flange 1, induction type conductivity sensor 2, water-output flange 6, chlorine residue electrode 7, chlorine residue transmitter 8, ultrasound reflectors 9, conductivity transmitter 20, ultra-sonic generator power supply 21, linear constant current direct supply 22, Controlling System 23, ultra-sonic generator 33, flanged (FLGD) threeway 34, fixing bar-shaped titanium anode plastics flange 35-1,35-2, fixing perforated tubular supporting electrode plastics flange 36-1,36-2, the surface coats TiO ₂Perforated tubular supporting electrode 37, simultaneously the surface as the water route body coats TiO ₂Sleeve cathode 38, contain the bar-shaped titanium anode 39 of metal Pt, Ir oxide compound, gasket 40, conical stainless steel ultrasound reflectors 41, the lead terminal 42 that has metallic gasket is formed.Ultra-sonic generator 33 ultrasound reflectors 41 by plastic three-way 34, middle interpolation sealing rubber pad 40 and electrode group with bolted together.

The InPro7250HT induction type conductivity sensor 2 and the plum Teller-electricity of Tuo benefit transmitter 20 formation water inlet water bodys that adopt PEEK (polyether-ether-ketone) to make are led and are detected and the signal hop, signal output part is connected with Controlling System 23; Adopt SZ283 chlorine residue electrode 7 and BCCL7685 analyser 8 to constitute chlorine residue detection and signal hop, signal output part is connected the detection system of this two portions constituent apparatus with Controlling System 23.

Water inlet joint flange 2 can be connected with inlet channel, outlet conduit respectively with holding bolt with water outlet joint flange 6.

Flange 35-1,35-2 are used for fixing bar-shaped titanium anode 39, referring to figure (23), (24), (25), for reducing water resistance, the plastics flange of fixed electorde adopt the no more than six roots of sensation uniform brace rod, flange 35-1,35-2 thickness is generally and is not less than 12mm, the flange 35-1 that has contact conductor, central position along one root brace rod is drilled with the fixedly through hole of garden groove of the through electrode of Φ 3.5～5.0mm, fixedly the degree of depth of garden groove is 5～6mm, laying contact conductor is connected with the output terminal i of bar-shaped titanium anode 39 and linear constant current direct supply 22, gap between electrode and plastics flange 35-1 garden groove is sealed with the waterproof insulation glue bond, its the other end is chimeric with the fixedly garden groove of the plastics flange 35-2 of the lead-in wire of belt electrode not, needn't bond, be convenient to dismounting; Flange 36-1,36-2 is used for fixing perforated tubular supporting electrode 37, referring to figure (23), (26), (27), for reducing water resistance, the plastics flange of same fixed electorde adopt the no more than six roots of sensation uniform brace rod, thickness of flange is not less than 12mm, and the diameter of the garden ring of support electrode is in the diameter of phi of perforated tubular supporting electrode _In-2mm～Φ _OutwardBetween+the 2mm, digging the degree of depth by the diameter of perforated tubular supporting electrode and thickness is that the annular recess of 6～8mm is used for fixing anode, the flange 36-1 that has contact conductor, be drilled with the annular recess through hole of the through fixed electorde of Φ 3.5～5.0mm along the central position of one root brace rod, laying contact conductor is connected with perforated tubular supporting electrode 37, the output terminal iv of its contact conductor and dc constant flowing power 22, v connects, then the gap between electrode and plastics flange 36-1 annular recess is sealed with the waterproof insulation glue bond, the other end of supporting electrode 37 is chimeric with the annular recess of the plastics flange 36-2 of the lead-in wire of belt electrode not, needn't bond, be convenient to dismounting; Between each flange, add gasket 40, with bolt whole device is tightened together, sleeve cathode 38 as the water route body is connected with output terminal ii, the iii of dc constant flowing power 22 by the lead terminal 42 of being with copper backing, perforated tubular negative electrode 37, sleeve cathode 38, coaxial with bar-shaped titanium anode 39.

Output terminal i, iii, the v of linear constant current direct supply 22 are cathode output end, and ii, iv are cathode output end; When the seawer system electrolysis moves (specific conductivity is greater than 1500 μ S/cm), Controlling System 23 is connected i, the ii output terminal of linear constant current direct supply 22; When the electrolysis of fresh water system moves (specific conductivity is less than 1500 μ S/cm), Controlling System is connected i, iii, the iv output terminal of linear constant current direct supply 22; During the scale removal of falling utmost point operation, Controlling System is connected ii, the v output terminal of linear constant current direct supply 22; Can make stable in fresh water, seawater water body, the operation reliably of device.

Controlling System 23 and the power supply 21 of detection system, ultra-sonic generator, mode of connection, master mode between the linear constant current direct supply are identical with embodiment 1.

It is the 0-30V/150A linear power supply that linear constant current direct supply 22 adopts model specification; With thickness is that 1.5mm, mesh (width between centers) are the titanium net of 3.0mm * 6.0mm (trade mark TA2, available from precious titanium) with the titanium bar of wide 10mm, thick 1.5mm, be welded near (Φ=60mm, long 1030mm) POROUS TITANIUM pipe, 120 ℃ of heating 3 hours and reduce to the processing of room temperature according to 1～2 ℃/min rate of temperature fall in air make its coated with uniform TiO ₂, as perforated tubular supporting electrode 37; With the trade mark is titanium pipe (Φ=108mm of TA2, δ=6.5mm, long 1000mm), use the same method after the processing,, use the bar-shaped titanium anode 39 (Φ=20mm of surface-coated Pt, Ir oxide compound as negative electrode 38, long 1060mm) (available from Shenyang Zhong Kehui friend development in science and technology company limited), power 50W operating frequency is that the ultra-sonic generator of 28KHz disposes as main body, and according to the treatment scheme of figure (4), can realize handling flow is 30M ³The water body sterilization algae removing of/hr.

As follows to using the present invention to carry out in fresh water, the seawater sterilization algae removing analytical results:

1, test and working conditions:

(1), 50M ³Stainless steel water tank, the test water body is a tap water, water-quality guideline is referring to table 1;

Table 1, experiment tap water quality

Cl-(ppm)	Hardness CaCO ₃(ppm)	Basicity CaCO ₃(ppm)	pH	Specific conductivity μ S/cm
Cl-(ppm)	Hardness CaCO ₃(ppm)	Basicity CaCO ₃(ppm)	pH	Specific conductivity μ S/cm	30～48	320～380	350～370	8.0～8.5	750～800

(2), the seawater-culture pond water body, area 0.8km ², duration of test (32 days) seawater quality index sees Table 2;

Table 2, test seawater quality

Salinity (S ‰)	COD(ppm)	DO(ppm)	pH	Specific conductivity μ S/cm
Salinity (S ‰)	COD(ppm)	DO(ppm)	pH	Specific conductivity μ S/cm	30.1～31.5	0.60～0.65	7.8～8.2	7.9～8.3	33200～34300

(3), the freshwater aquiculture pond, water surface area 2200m ², duration of test (30 days) fresh water water-quality guideline sees Table 3.

Table 3, test fresh water water quality

Cl-(ppm)	Hardness CaCO ₃(ppm)	Basicity CaCO ₃(ppm)	pH	Specific conductivity μ S/cm
Cl-(ppm)	Hardness CaCO ₃(ppm)	Basicity CaCO ₃(ppm)	pH	Specific conductivity μ S/cm	25～36	430～480	450～510	7.7～8.2	950～1080

2, the result calculates:

Result's measuring method, with reference to GB15979, adopt each 1.00ml of water sample that handles front and back through the ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga, with nutrient agar through sterilization, place 35 ± 2 ℃ to cultivate 48 hours, the enumeration of bacterial colonies number calculates germ-killing efficiency η with (18) formula, 3 groups of parallel samples, averaged are got in test.

η＝{(M-N)/M}×100％(18)

Wherein: N is the colony number of the water sample after the electrolysis treatment,

M is the colony number of the water sample before the electrolysis treatment.

Algae removal result's measuring method, adopt chlorophyll to change and carry out approximate evaluation, with the water body after handling, with undressed water body, naturally placed 24 hours, test two kinds of chlorophyll contents in the water body then, the approximate killing effect of estimating blue-green algae also has contribution to chlorophyllous mensuration although the microorganism that most algae can't be determined anyway, kill enters filtrate after filtration.

3, test-results:

(1), tap water water body test:

The processing power of A, employing embodiment 1 is 300M ³The box ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga of/hr, the flow process of reference drawing (4) is used 50M ³Tap water carry out sterile test, the water body water pump is according to 250M ³The flow volume delivery access to plant of/hr is handled, by each operation of 3 kinds of current densities, titanium anode 12 and former negative electrode 13 are all as electrolytic anode, as negative electrode, total plate count in the water body after testing former water and handle with reference to GB15979 is respectively calculated germ-killing efficiency η according to (18) formula with supporting electrode 14, the results are shown in table 4, show through box ultrasound-enhanced micro-current electrolysis device for sterilizing and removing alga and handle water body, operating voltage is not more than 30V, and having well is sterilization effect.

Sterilization effect under table 4, the different current density condition

Current density mA/cm ²	Intestinal bacteria	Streptococcus aureus	Bacillus subtilus	Operating voltage (V)
Current density mA/cm ²	Intestinal bacteria	Streptococcus aureus	Bacillus subtilus	Operating voltage (V)	1.0	99.2	93.7	92.3	3.6
5.0	100	99.9	99.9	5.3	1.0	99.2	93.7	92.3	3.6
5.0	100	99.9	99.9	5.3	8.0	100	100	100	6.5

The processing power of B, employing embodiment 2 is 30M ³The tubular ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga of/hr is used 50M ³Tap water carry out sterile test, use water pump according to 30M equally ³The flow volume delivery access to plant of/hr is handled, by each operation (because anode diameter difference of 3 kinds of current densities, can't accurate description electrolysis operating mode with current density, describe more definitely with total current 35A, 18A, 7A, the approximate current density of respective tube anode 38 is 5.0mA/cm respectively ², 2.5mA/cm ², 1.0mA/cm ²), former sleeve cathode 38 and bar-shaped titanium anode 39 are all as electrolytic anode, with supporting electrode 37 as negative electrode, total plate count in the water body after testing former water and handle with reference to GB15979 respectively, calculate germ-killing efficiency η according to (18) formula, the results are shown in table 5, show through box ultrasound-enhanced micro-current electrolysis device for sterilizing and removing alga and handle water body, operating voltage is not more than 30V, and having well is sterilization effect.

Sterilization effect under table 5, the different current density condition

The current density mA/cm of tube anode 38 correspondences ²	Intestinal bacteria	Streptococcus aureus	Bacillus subtilus	Operating voltage (V)
	Intestinal bacteria	Streptococcus aureus	Bacillus subtilus	Operating voltage (V)	1.0	99.5	93.2	90.2	5.8
2.5	99.9	100	98.5	8.3	1.0	99.5	93.2	90.2	5.8
2.5	99.9	100	98.5	8.3	5.0	100	100	100	15.8

(2), the sterilization algae removing of marine park is handled

Adopting the processing power of embodiment 1 is 300M ³The box ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga of/hr, the flow process of reference drawing (4), the water body water pump is according to 300M ³The flow enhancement feeder of/hr is handled, and with titanium anode 12 and negative electrode 13 work, supporting electrode is not worked, and the employing current density is 8mA/cm ²Running voltage is 3.2V, water body after the processing flow back into along the about 100 meters long water channels of pool side and cultures the pond, move 6 hours every day, move 32 days, with reference to GB15979 test respectively first day and the last day former water and handle after water body in aerophil sum (Total aerobic count) and contrast former water chlorophyll with the water body for the treatment of water after 24 hours in the chlorophyll supposition to the killing action of algae, the results are shown in table 6, suppressed algae grows effectively in the device operational process.

(current density is 10.0mA/cm for table 6, seawater-culture pond sterilization algae removal effect ²)

In 32 days operational process, running voltage is stabilized in the scope of 3.2 ± 0.2V, and is very stable, also proved in the seawer system, and the cathode surface of micro-current electroanalysis system can not form CaCO ₃Conclusion.

(3), the sterilization algae removing in freshwater aquiculture pond is handled

Adopting the processing power of embodiment 1 is 300M ³The box ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga of/hr, the flow process of reference drawing (4), the water body water pump is according to 300M ³The flow enhancement feeder of/hr is handled, and titanium anode 12 and former negative electrode 13 are all as electrolytic anode, and as negative electrode, the employing current density is 5mA/cm with supporting electrode 14 ²Running voltage is 4.8V, water body after the processing flows to the other end of culturing the pond along the about 65 meters long water channels of pool side, move 4 hours every day, move 30 days, with reference to GB15979 test respectively first day and the last day former water and handle after water body in aerophil sum (Total aerobiccount) and contrast former water chlorophyll with the water body for the treatment of water after 24 hours in the chlorophyll supposition to the killing action of algae, the results are shown in table 7, suppressed algae grows effectively in the device operational process.

When wherein running to the 22nd day, running voltage has been increased to 5.6V gradually, is 2.5mA/cm with the current density ², supporting electrode 14 as anode, was carried out the electrolysis of falling the utmost point 20 minutes with former negative electrode 13; Recover normal operation subsequently, running voltage reverts to 4.9V, until the 30th day, running voltage reverts to 5.3V.

(current density is 5.0mA/cm for table 7, freshwater aquiculture pond sterilization algae removal effect ²)

Should be pointed out that the above embodiment can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.Therefore, although this specification sheets has been described in detail the present invention with reference to drawings and Examples,, it will be appreciated by those skilled in the art that still and can make amendment or be equal to replacement the present invention; And all do not break away from the technical scheme and the improvement thereof of the spirit and scope of the present invention, and it all should be encompassed in the middle of the protection domain of patent of the present invention.

Claims

1, of the present invention is a kind of ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga, it is characterized in that device is made of detection system, Controlling System, ultrasound-enhanced micro-current electroanalysis system, wherein:

(1), detection system is made up of conductivity sensor, conductivity meter, potentiometer, redox electrode assembly or chlorine residue electrode;

(2), ultrasound-enhanced micro-current electroanalysis system mainly is made up of dc electrolysis power supply, electrolysis electrode group, casing and contact conductor splicing ear, ultra-sonic generator, ultrasound reflectors;

(3), Controlling System is made of MPU, trip switch.

2, ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga according to claim 1 is characterized in that described detection system is an induction conductivity sensor by conductivity sensor.

3, ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga according to claim 1, the conductivity meter that it is characterized in that described detection system is a conductivity transmitter.

4, ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga according to claim 1 is characterized in that the current potential of described detection system is counted the chlorine residue transmitter.

5, ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga according to claim 1 is characterized in that the dc electrolysis power supply of described ultrasound-enhanced micro-current electroanalysis system is the linear DC power supply.

6, ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga according to claim 1 is characterized in that the electrolysis electrode group of described ultrasound-enhanced micro-current electroanalysis system is made of according to the in proper order equidistant arrangement of supporting electrode between negative electrode, anode titanium anode, negative electrode and netted supporting electrode.

7, ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga according to claim 1 is characterized in that the ultra-sonic generator of described ultrasound-enhanced micro-current electroanalysis system is made up of housing, ultrasonic transducer, power supply.

8, ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga according to claim 1 is characterized in that the ultrasound reflectors of described ultrasound-enhanced micro-current electroanalysis system is a triangulo column.

9, ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga according to claim 1 is characterized in that the ultrasound reflectors of described ultrasound-enhanced micro-current electroanalysis system is a cone.

10, according to claim 1,4 described ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga, it is characterized in that described titanium anode is at least is matrix with a kind of of metal titanium, titanium alloy, contain a kind of metal Pt, Ir, Ru, Rh, Pd, Os and oxide compound thereof at least and contain the coated electrode (DSA) of the oxide compound of at least a Ta, Ti in its surface-coated.

11, according to claim 1,4 described ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga, it is characterized in that described negative electrode is at least is matrix with a kind of of metal titanium, titanium alloy, at the electrode member of the oxide compound of at least a Ta of its surface-coated, Ti.

12, according to claim 1,4 described ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga, it is characterized in that described supporting electrode is that the mean pore size metal titanium that is not less than 3mm, titanium alloy reticulated a kind of is matrix at least, at the electrode member of the oxide compound of at least a Ta of its surface-coated, Ti.

13, according to claim 1,10,11,12 described ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga, it is characterized in that described ultrasound-enhanced micro-current electroanalysis system is handling in the seawater water body of specific conductivity greater than 1500 μ S/cm, netted supporting electrode is not worked, the electrolysis between titanium anode and negative electrode; Handle the fresh water water body of specific conductivity less than 1500 μ S/cm, supporting electrode is a negative electrode, and former cathode titanium anode carries out electrolysis as anode.

14, according to claim 1,10,11,12 described ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga, it is characterized in that described ultrasound-enhanced micro-current electroanalysis system is when the electrolytic descaling of falling the utmost point, supporting electrode is an anode, and with catholyte, the titanium anode is not worked.

15, according to claim 1,5 described ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga, it is characterized in that described ultrasonic transducer in the housing of ultra-sonic generator along the uniform array of plate electrode group orientation.

16,, it is characterized in that described ultrasonic transducer adopts annular uniform arrangement with the axle center that the hollow edged electrode group is arranged as the center of circle in the housing of ultra-sonic generator according to claim 1,5 described ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga.

17,, it is characterized in that described ultrasound reflectors is the material members of a kind of plastics, metal titanium, titanium alloy, stainless steel, carbon steel, copper alloy at least according to claim 1,6,7 described ultrasonic intensified self-descaling micro-current electrolysis device for sterilizing and removing alga.