CN101434430A - Micro-current electrolysis sterilization algae removing apparatus - Google Patents

Abstract

The invention discloses a micro-current electrolytic sterilization and algae removal device, which comprises a detector that is arranged on the intake pipe of a box body and is used for sensing solution electrical conductivity, wherein, at least more than one group of electrodes are arranged in the box body according to the order of an anode, an auxiliary electrode and a cathode, and a controller is used for judging the degree of the electrical conductivity and controlling the polarity of the electrodes in the box body and circuit connection; and the controller comprises a judging unit which is used for judging the degree of the electrical conductivity and triggering a corresponding seawater electrolytic mode unit, a fresh water electrolytic mode unit and a reversal-electrode electrolytic mode unit to operate according to judging results. The device can be simultaneously applied to sterilization and algae removal in seawater or fresh water, has good sterilization and algae removal effect, can realize automatic desludging and can be applied widely; moreover, an ultrasonicator is added, which effectively destroys various bacteria and algal cells by ultrasonic waves; and the device has simple structure and wide application range.

Description

A kind of micro-current electrolysis device for sterilizing and removing alga

Technical field

The present invention relates to sterilization algae removing equipment, be meant a kind of micro-current electrolysis device for sterilizing and removing alga especially.

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 promptly 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 the place that cyanobacteria carries out nitrogen fixation.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 (Anabaenaflos-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 (Enterococcusgroup), cholera bacteria (Vibrio cholerae) or the like, these thalline 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 the enhancing of people's environment protection idea, this problem seems more and more outstanding.IMO (InternationalMaritime Organization, International Maritime Organizaton) investigation result is found, 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, " nineteen eighty-two United Nations Convention on the Law of the Sea " (UNCLOS that IMO puts into effect, United NationsConference 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 "; 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, and the unnecessary negative influence of avoiding this kind 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.

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, is not suitable for big area eutrophication water such as lake and needs 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 that there is secondary pollution problems in water body; If be applied to ballast water treatment, its residue is still needed by bio-toxicity and toxicity evaluation.

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 seawater or bacterium in fresh water and the microbe filter of suction as 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.

Ultrasonic technology

Ultrasonic wave not only has the intensive vibration, 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 mostly such effect is 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.

The 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.

Biological treating

For the fresh water eutrophication water, people place hope on biological treating, 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 (ALGAL GROWTHINHIBITION EFFECTS AND INDUCEMENT MODES BY PLANT-PRODUCING PHENOLS SATOSHI NAKAI in the work report that 2001 deliver ^*YUTAKA INOUE andMASAAKI HOSOMI, Water Research, Vol.35, Issue 7, and May 2001, Pages 1855-1859) point out, 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.

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.

The 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.

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, with chlorion, the water molecules electrolysis handled in the water body is the material (ClO-with high oxidation activity, 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, thereby reach sterilization algae removal effect, and make the treated water body keep continuing 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 Fig. 1, wherein:

U1: electropotential and polarization overpotential by anodic oxidation reactions constitute, if the polarization phenomena of electrochemical reaction can be ignored, for specific reaction system (reaction density, pH, temperature-resistant), U1 is constant substantially, does not change with current density;

U2: 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;

U3: electropotential and polarization overpotential by cathodic reduction reaction constitute, if the reaction polarization phenomenon can be ignored and do not exist negative electrode to be stain, coat phenomenon by suspended substance and inorganics, for specific reaction system (reaction density, pH, temperature-resistant), U3 is constant substantially, does 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, at least differ more than 60 times with ocean water body, from (1) formula as can be known, put on the voltage U 2 on the water body between anode and the negative electrode, 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 between negative electrode and the 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 ^-Following reaction takes place:

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; In please the patent No. 03156596.4 " built-up type micro-current electroanalysis water technology and device ", 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.We will be applied to the white deposits of the built-up type micro-current electroanalysis water treatment device of sea farming sterile environment, the white fouling of the cathode surface of the built-up type micro-current electroanalysis water treatment device of freshwater aquiculture water treatment, the white fouling of the cathode surface of the self-cleaning sterilizer of water tank that uses with the high building water tank scrapes, carry out field emission electron scanning analysis (SEM) photo and infrared (IR) absorption analysis respectively, result such as Fig. 2 a, 2b, 2c and shown in Figure 3, wherein, the a curve is the Absorption by Sea Water analytic curve among Fig. 3, the b curve is a fresh water absorption analysis curve, and the c curve is the tap water absorption analysis.

From Fig. 2 a as can be seen, the white precipitate particle of sea farming electrolysis treatment body is less relatively, and major part is spherical; Fig. 2 b and Fig. 2 c are respectively the SEM photo of white fouling of the cathode surface of the fouling of cathode surface of electrolysis treatment system of freshwater aquiculture and the self-cleaning sterilizer of water tank that the high building water tank uses, and particle is bigger; Dui Ying IR absorption spectrum Fig. 3 shows therewith, and curve a is the white precipitate particulate infrared absorption spectrum of sea farming electrolysis treatment system, except the carbonate in-plane bending vibration v4 charateristic avsorption band 712cm of calcite (calcite) ^-1With carbonate out-of-plane deformation vibration v2 absorption peak 875cm ^-1Outside, also have the characteristic absorption band 745cm of ball aragonite (vaterite) ^-1, with the infrared absorption spectrum 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; C has remarkable difference, and b and c are quite similar, belongs 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.The H.Beer65 patent 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, particularly contain more than one non-platinum group metal oxide (as Ta, Ti), form 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.

Because big area eutrophication water and the big existing above-mentioned defective of flow ballast water treatment technology, cause being applicable to simultaneously fresh water and seawer system, effectively kill bacteria and blue-green algae, running cost height, can cause secondary pollution.

Summary of the invention

In view of this, the invention reside in provides a kind of micro-current electrolysis device for sterilizing and removing alga, to solve in the above-mentioned water technology, can't be applicable to fresh water and seawer system, the effective problem of kill bacteria and blue-green algae simultaneously.

For addressing the above problem, the invention provides a kind of micro-current electrolysis device for sterilizing and removing alga, comprising:

Be installed in the detector of induction solution conductivity value on the inlet channel of casing, the interior order according to group inner anode, supporting electrode, negative electrode of described casing is installed the electrode group more than at least one group, controller is judged the size of described electric conductivity value, control electrode in the described casing polarity, and circuit connect;

Comprise in the described controller:

Judging unit is used to judge the size of described electric conductivity value, and triggers corresponding seawater electrolysis mode unit, fresh water electrolysis mode unit, the electrolysis mode of falling utmost point cell operation according to judged result;

Described seawater electrolysis mode unit, after being used for receiving triggering, the circuit of the described anode of conducting, negative electrode connects, and the circuit that disconnects supporting electrode connects;

Described fresh water electrolysis mode unit after being used for receive triggering, changes the polarity of described negative electrode into anode, changes the polarity of described supporting electrode into negative electrode, and the circuit that conducting do not change the polar anode, change polar anode, negative electrode connects;

The described mode unit of falling the utmost point, after the number of run, working time that is used for judgment means surpasses setting threshold, change the polarity of described supporting electrode into anode, conducting changes the polar anode, does not change the circuit connection of polar negative electrode, disconnects not changing the connection of polar anodic circuit.

Preferably, the electrode shape in the described electrode group is pellet electrode or hollow edged electrode.

Preferably, also comprise:

Be installed in ultra-sonic generator, and the ultrasound reflector of described tank ends, comprise at least more than one ultrasonic transducer in the described ultra-sonic generator, the position of described electrode group is between described ultra-sonic generator and ultrasound reflector.

Preferably,

When described electrode shape is sheet, described ultrasound reflector be shaped as triangular prism shaped or circular arc, prismatical seamed edge or circular arc protrude towards the direction of ultra-sonic generator;

When described electrode shape is tubulose, described ultrasound reflector be shaped as taper shape, circular cone top towards ultra-sonic generator.

Preferably, when described electrode shape was tubulose, described each electrode, each ultrasonic transducer were the circular arrangement in the same center of circle.

Preferably, described detector is specific conductivity induction type conductivity sensor or conductivity transmitter.

Preferably, described titanium anode is to be matrix with a kind of of metal titanium or titanium alloy at least, contain in metal Pt, Ir, Ru, Rh, Pd or Os and the oxide compound thereof at least a and contain the coated electrode (DSA) of the oxide compound of Ta at least or Ti in its surface-coated.

Preferably, described supporting electrode and negative electrode are to serve as preferred with metal titanium or titanium alloy a kind of at least, and the material of described ultrasound reflectors comprises a kind of material members of plastics, metal titanium, titanium alloy, stainless steel, carbon steel or copper alloy at least.

Preferably, also comprise:

Be installed in the potentiometer that is used for detecting solution cl content after the electrolysis on the described casing outlet conduit or chlorine residue electrode, and chlorine residue transmitter;

Described each electrolysis cells is regulated electrolytic electric current, magnitude of voltage according to described cl content value.

Device among the present invention can be applied to sterilization algae removing in seawater or the fresh water simultaneously, and have good sterilizing and algae-removing effect, and can realize automatic desludging, and applied range; And the adding ultra-sonic generator, effectively destroy various bacteriums and alga cells by ultrasonic wave; Equipment is simple, and has wide range of applications.

Description of drawings

Fig. 1 is the synoptic diagram of diel system;

The white precipitate particle synoptic diagram of Fig. 2 a sea farming electrolysis treatment body;

The fouling synoptic diagram of the cathode surface of the electrolysis treatment system of Fig. 2 b freshwater aquiculture;

The white fouling synoptic diagram of the cathode surface of the self-cleaning sterilizer of water tank that Fig. 2 c high building water tank uses;

Fig. 3 is the curve synoptic diagram that different quality IR absorbs spectrogram;

Fig. 4 is the synoptic diagram of micro-current electrolysis device for sterilizing and removing alga;

Fig. 5 a is the tabular titanium anode construction synoptic diagram of the electrode group of micro-current electroanalysis device;

Fig. 5 b is the tabular titanium cathode construction synoptic diagram of the electrode group of micro-current electroanalysis device;

Fig. 5 c is the flat auxiliary electrode structure synoptic diagram of the electrode group of micro-current electroanalysis device;

Fig. 6 is that the plate electrode group is arranged synoptic diagram in the micro-current electroanalysis device;

Fig. 7 A is a plastic electrode fixing rack structure synoptic diagram;

Fig. 7 B is the synoptic diagram that part is amplified among Fig. 7 A;

Fig. 7 C is the sectional view of B-B among Fig. 7 B;

Fig. 8 is the structure iron of this device middle controller;

Fig. 9 A is a ultrasonic transducer ultrasonic waves transmitted transmission direction synoptic diagram;

Fig. 9 B is the ultrasonic transmission direction synoptic diagram that ultrasound reflectors reflects;

Figure 10 is box micro-current electrolysis device for sterilizing and removing alga synoptic diagram;

Figure 11 be among Fig. 9 A-A to synoptic diagram;

Figure 12 A is 800mm * 500mm titanium anode (structure iron of δ=2.0mm);

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

Figure 12 C is 800mm * 500mm titanium net supporting electrode (structure iron of δ=1.3mm);

Figure 13 is the control principle figure of micro-current electrolysis device for sterilizing and removing alga;

Figure 14 is the electrode arranging structure synoptic diagram of box micro-current electrolysis device for sterilizing and removing alga;

Figure 15 be among Fig. 9 B to synoptic diagram;

Figure 16 is the electrode terminal outlet arrangement architecture synoptic diagram of box micro-current electrolysis device for sterilizing and removing alga enclosed electrode group rubber pad;

Figure 17 is box micro-current electrolysis device for sterilizing and removing alga electrode seal cover board electrode connection synoptic diagram;

Figure 18 A is the front view of connection terminal;

Figure 18 B is the left view of connection terminal;

Figure 19 is a triangular prism arrangement architecture synoptic diagram;

Figure 20 is that box micro-current electrolysis device for sterilizing and removing alga ultra-sonic generator is arranged synoptic diagram;

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

Figure 22 be among Fig. 9 C to synoptic diagram;

Figure 23 A is the ultrasound-enhanced micro-current electroanalysis system architecture synoptic diagram of tubular type micro-current electrolysis device for sterilizing and removing alga;

Figure 23 B is the local enlarged diagram among Figure 23 A;

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

Figure 25 is the plastics flange structural representation of fixing bar-shaped titanium anode, not comprising contact conductor;

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

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

Embodiment

For clearly demonstrating device of the present invention, below in conjunction with accompanying drawing and provide preferred embodiment and describe in detail.

The schematic diagram of the embodiment of the invention can comprise referring to Fig. 4: the electricity that detector detects in the suction culvert is led, and the detected electricity of controller judgement detector is led, and different electricity is led down the ultrasound-enhanced micro-current electroanalysis device of control and worked under corresponding pattern.

Wherein, detector can adopt conductivity sensor or conductivity meter.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.

Comprise in the ultrasound-enhanced micro-current electroanalysis device: dc electrolysis power supply, electrolysis electrode group, casing and contact conductor splicing ear, ultra-sonic generator, ultrasound reflectors are formed.

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 ultra-sonic generator.

The electrolysis electrode group can realize the effect of algae removal of sterilizing in the micro-current electroanalysis device, and can add ultra-sonic generator according to practical situation, realizes the fragmentation to bacterium and alga cells.

Mainly comprise in the electrode group of ultrasound-enhanced micro-current electroanalysis device:

(1), titanium anode: to adopt metal titanium or titanium alloy be matrix its surface-coated contain at least a kind of metal Pt, Ir, Ru, Rh, Pd, Os or and oxide compound and the electrode of oxide compound that contains at least a Ta or Ti 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 Fig. 5 a, on terminals, have 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 Fig. 5 b, on terminals, have 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 Fig. 5 c, on terminals, have 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.

Electrode in the electrode group can adopt plate electrode according to the in proper order equidistant arrangement of supporting electrode between negative electrode, anode, forms the electrode group of micro-current electroanalysis system; The electrode group that plate electrode constitutes is arranged referring to Fig. 6, all electrodes all adopt the electrode of dual coating, because the anode cost is higher relatively, can make in the arrangement of last group, mark A place is an anode, and mark C is a negative electrode, and mark B is a supporting electrode, with negative electrode C is outermost, with the space availability ratio of assurance device with reduce cost.

Adopt the plastics locating support, referring to Fig. 7 A, 7B, 7C, Fig. 7 B is the enlarged diagram among Fig. 7 A, and Fig. 7 C is the sectional view of B-B among Fig. 7 B.By the plastics locating support electrode is fixed.

Because the electricity of seawater and freshwater is led difference, therefore, lead by controller by different electricity and to select different electrolysis mode to control electrode work different in the ultrasound-enhanced micro-current electroanalysis device, the synoptic diagram of controller can be referring to Fig. 8, comprise judging unit and electrolysis mode unit, the electrolysis mode unit is divided into seawater electrolysis mode unit, fresh water electrolysis mode unit, the electrolysis mode of falling utmost point unit.

When judgment unit judges goes out the seawater water body of the specific conductivity of detector detection greater than 1500 μ S/cm, trigger the work of seawater electrolysis mode unit, seawater electrolysis mode unit control supporting electrode B does not work, by the electrolytic action between anode A and the negative electrode C, with chlorion, the water molecules electrolysis handled in the water body is the material (ClO-with high oxidation activity, 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;

When judgment unit judges goes out in the fresh water water body of specific conductivity less than 1500 μ S/cm of detector detection, trigger fresh water electrolysis mode cell operation, fresh water electrolysis mode unit control 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, and the operating voltage that can reduce greatly for the electrolysis treatment of the fresh water water body of low conductivity;

In the higher water body of hardness; if supporting electrode B works the long period; surface deposition lime carbonate; the electrolysis mode of falling utmost point unit can be according to number of run; when arriving certain threshold value working time; 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 of falling utmost point unit changes 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, and 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 shows negative electrode fouling certainly in the electrolytic process, electrolytic potential (U1+U2+U3) raise 20% o'clock when electrolysis moved at identical Faradaic current, in identical fresh water water body with employing, adopt the electrolysis mode of falling utmost point scale removal, extremely electrolytic current density is not more than 20mA/cm2, and the electrolysis time of falling the utmost point does not need to get final product greater than 1 hour; And in seawer system, move, need not to adopt the electrolytic descaling of falling the utmost point.

When the electrode group adopted hollow edged electrode, 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 adopted to have no more than 6 plastics flange of uniform brace rod and fixes, to reduce water resistance.

Also can comprise ultra-sonic generator and the ultrasound reflectors that is used to destroy bacterium and alga cells in the device.Ultra-sonic generator comprises housing, transverter, power supply composition, adopt a plurality of ultrasound transducer arrays, in housing, evenly arrange, and 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.

In the ultrasonic transmission process that ultra-sonic generator produces, referring to Fig. 9 A, Fig. 9 B, though disperse function is arranged, if but run into and the vertical plane of working direction, to have 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 changes hyperacoustic reflection direction, strengthen the cleanup action of counter electrode, alleviate scale formation; 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 materials such as plastics, metal titanium, titanium alloy, stainless steel, carbon steel or copper alloy, and the corrosion of material is member the best with metal titanium, titanium alloy, plastics when moving for anti-locking system.

Ultrasound reflector can be triangular prism or semicylinder, a cylinder of triangular prism is connected with casing, and parallel with electrode, a rib of triangular prism is vertical with the transmission direction of ultra-sonic generator 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 ultra-sonic generator 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 conical structure.

The structure iron of employing plate electrode can be referring to Figure 10 in this device, box ultrasound-enhanced micro-current electrolysis device for sterilizing and removing alga connects water-in flange 1, in inlet channel, be provided with induction type conductivity sensor 2, have board-like electrode group 4 in the box-type shell 5 of this device, be provided with the plastic electrode fixed support 3 of fixing board-like electrode in the board-like electrode group 4; Connect water-output flange 6 on the box-type shell 5, and outlet pipeline is provided with chlorine residue electrode 7 and chlorine residue transmitter; Ultrasound reflectors 9 is installed in the device, the board-like electrode group 4 outer electrode group sealing rubber pads 10 that are equipped with, be fixed on the box-type shell 5 by cover plate 15, and it is fixing by fastening piece 11, titanium anode 12, negative electrode 13, titanium net supporting electrode 14 are installed on the plastic electrode fixed support 3, one end of device is equipped with ultra-sonic generator housing 16, ultrasonic transducer 17 is installed in the housing 16, be connected with sealing rubber pad 18 between ultra-sonic generator housing 16 and the casing, and fixing by ultra-sonic generator cover plate 19.

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

U-PVC (polyvinyl chloride) plate that device adopts thickness to be preferably 15mm is made.Inner preferred neat is of a size of the box-type shell 5 of 1580mm * 600mm * 515mm, the external diameter of water inlet joint flange 2 and water outlet joint flange 6 is preferably 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, as shown in figure 11, Figure 11 be among Fig. 9 A to synoptic diagram.

Board-like electrode group 4 is preferred to adopt the titanium anode 12 of long 800mm, wide by 500, thickness δ 2.5mm surface-coated Ir, Rh oxide compound and TiO2; Preferred long 800mm, wide by 500, thickness δ 2.5mm, core are that the electrode of oxide compound of metal titanium surface-coated Ta, Ti is as negative electrode 13; Preferred long 800mm, wide 500mm, thickness δ 1.3mm, core are 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 12 A to Figure 12 C.

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 Fig. 7 and Figure 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 the location is installed, 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, Figure 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, electrode terminal, metal sheeting 30, hollow holding bolt 31 constitute connection terminal, shown in Figure 18 A, Figure 18 B.

Electrode in the board-like electrode group 4 is connected with linear constant current direct supply, and as shown in figure 13, linear constant current power supply output terminal i, iii, v are cathode output end, and ii, iv are cathode output end; Negative electrode 13 is connected with output terminal ii, the iii of linear constant current direct supply respectively by connection terminal 28, supporting electrode 14 is connected with output terminal iv, the v of linear constant current direct supply respectively by connection terminal 29, output terminal i, iii, the v of linear constant current direct supply 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), controller is connected i, the ii output terminal of linear constant current direct supply; When the electrolysis of fresh water system moves (specific conductivity is less than 1500 μ S/cm), controller is connected i, iii, the iv output terminal of linear constant current direct supply; During the scale removal of falling utmost point operation, controller is connected ii, the v output terminal of linear constant current direct supply; 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 welded on the box-type shell 5, referring to Fig. 9, Figure 19 according to the direction arrangement parallel with electrode; With 10 TYH-50-25 type power 50W, the ultrasonic transducer 17 of operating frequency 25KHz, with the AB glue bond is on the Cr18Ni9Ti stainless steel ultra-sonic generator housing 16 of 2mm at thickness, uniform distribution, referring to Fig. 9, Figure 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 is connected with the input terminus of controller, and the output terminal of controller is connected with the power supply of ultra-sonic generator 21, linear DC constant current power supply, and it is the 0-30V/800A linear power supply that linear constant current direct supply adopts model specification; Instruction by controller detects chlorine residue in the specific conductivity of influent quality, the draining water quality, and each electrolysis cells is according to the specific conductivity decision electrolysis mode of being surveyed, according to chlorine residue size adjustment Faradaic current, voltage in the controller; Voltage, the current signal of linear constant current direct supply are transferred to controller, and whether the decision of the electrolysis mode of falling utmost point unit needs to carry out down the utmost point in the controller; Controller can also be selected ultrasonic transducer 17 work of respective sets number according to predetermined electric power, controls with the power to ultra-sonic generator.

The top device of describing board-like electrode group in detail, the micro-current electrolysis device for sterilizing and removing alga of detailed description tubular pole group below.

Shown in Figure 23 A, the tubular type 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, ultrasound reflectors, conductivity transmitter, ultra-sonic generator power supply, linear constant current direct supply, controller, ultra-sonic generator 33, flanged (FLGD) threeway 34, fixing bar-shaped titanium anode plastics flange 35-1,35-2, fixedly 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 is in the same place with bolted with the electrode group by plastic three-way 34, the middle sealing rubber pad 40 that adds with ultrasound reflectors 41, and the installation of sealing rubber pad 40 can be referring to Figure 23 B.Ultrasound reflector 41 be shaped as taper shape, circular cone top towards ultra-sonic generator.Hollow edged electrode can be by circular arrangement, and at this moment, each ultrasonic transducer is also by circular arrangement, and with the center of circle of hollow edged electrode be concentric.

Water inlet joint flange 1 can be connected with inlet channel, outlet conduit respectively with holding bolt with water outlet joint flange 6.Flange 35-1,35-2 is used for fixing bar-shaped titanium anode 39, referring to Figure 23 A, Figure 23 B, Figure 24, Figure 25, for reducing water resistance, the plastics flange of fixed electorde adopts the uniform brace rod of the no more than six roots of sensation, flange 35-1, the thickness of 35-2 is generally and is not less than 12mm, the flange 35-1 that has contact conductor 50, central position along one root brace rod is drilled with the fixedly through hole of circular groove of the through electrode of Φ 3.5～Φ 5.0mm, fixedly the degree of depth of circular 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, gap between electrode and the plastics flange 35-1 circular groove is sealed with the waterproof insulation glue bond, its the other end is chimeric with the fixedly circular 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 A, Figure 23 B, Figure 26, Figure 27, for reducing water resistance, the plastics flange of same fixed electorde adopts the uniform brace rod of the no more than six roots of sensation, thickness of flange is not less than 12mm, the diameter of the annulus of support electrode is between the interior diameter Φ-2mm～outside diameter Φ+2mm of perforated tubular supporting electrode, offering 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 diameter of phi 3.5～Φ 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, v connects, then the gap between electrode and the 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, be connected with output terminal ii, the iii of dc constant flowing power as the sleeve cathode 38 of the water route body lead terminal 42 by the band copper backing, perforated tubular negative electrode 37 and sleeve cathode 38 are coaxial with bar-shaped titanium anode 39.

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

Controller and the power supply of detector, ultra-sonic generator, mode of connection, master mode between the linear constant current direct supply are identical with embodiment 1, repeat no more herein.

It is the 0-30V/800A linear power supply that linear constant current direct supply in this device adopts model specification; With thickness is that 1.5mm, mesh (width between centers) are the titanium bar of the titanium net of 3.0mm * 6.0mm with wide 10mm, thick 1.5mm, be welded near (Φ=60mm, long 1030mm) POROUS TITANIUM pipe, 120 ℃ of processing of heating 3 hours and reducing to room temperature according to 1～2 ℃/min rate of temperature fall in air, make its coated with uniform TiO2, as perforated tubular supporting electrode 37; With titanium pipe (Φ=108mm, δ=6.5mm, long 1000mm), use the same method handle after, as negative electrode 38, with the bar-shaped titanium anode 39 (Φ=20mm, long 1060mm) of surface-coated Pt, Ir oxide compound, the ultra-sonic generator of power 40W disposes as main body, can realize handling the water body sterilization algae removing that flow is 30M3/hr.

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

Test and working conditions:

(1), the 50M3 stainless steel water tank, the test water body is a tap water, water-quality guideline is referring to table 1;

The experiment tap water quality:

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

Table 1

(2), the seawater-culture pond water body, area 0.8km2, duration of test (32 days) seawater quality index sees Table 2;

The test seawater quality

Table 2

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

Test fresh water water quality

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

Table 3

The result calculates:

Result's measuring method, with reference to GB15979, adopt each 1.00ml of water sample that handles front and back through 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.

Test-results:

(1), tap water water body test:

A, the processing power that adopts board-like electrode is the box micro-current electrolysis device for sterilizing and removing alga of 300M3/hr, tap water with 50M3 carries out sterile test, the water body water pump is handled according to the flow volume delivery access to plant of 250M3/hr, by each operation of 3 kinds of current densities, titanium anode 12 and former negative electrode 13 are all as electrolytic anode, with supporting electrode 14 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 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 the different current density conditions

Current density mA/cm2	Intestinal bacteria	Streptococcus aureus	Bacillus subtilus	Operating voltage (V)
					1.0	99.2	93.7	92.3	3.6
8.0	100	100	99.9	8.3
					16.0	100	100	100	13

Table 4

B, adopting processing power is the tubular type micro-current electrolysis device for sterilizing and removing alga of 30M3/hr, tap water with 50M3 carries out sterile test, same with the flow volume delivery access to plant processing of water pump according to 30M3/hr, by each operation (because anode diameter difference of 3 kinds of current densities, can't accurate description electrolysis operating mode with current density, with total current 35A, 18A, 7A describes more definite, the approximate current density of respective tube anode 38 is 5.0mA/cm2 respectively, 2.5mA/cm2,1.0mA/cm2), 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 the different current density conditions

The current density mA/cm2 of tube anode 38 correspondences	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
					5.0	100	100	100	15.8

Table 5

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

Adopting processing power is the box micro-current electrolysis device for sterilizing and removing alga of 300M3/hr, the water body water pump is handled according to the flow enhancement feeder of 300M3/hr, with titanium anode 12 and negative electrode 13 work, supporting electrode is not worked, the employing current density is 16mA/cm2, running voltage is 6.4V, 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), with chlorophyll supposition in contrast former water chlorophyll and the water body for the treatment of water after 24 hours killing action to algae, the results are shown in table 6, suppressed algae grows effectively in the device operational process.

Seawater-culture pond sterilization algae removal effect (current density is 16.0mA/cm2)

Date

Total aerobic count (cfu/g)

Chlorophyll reduces (%)

	Former water	Treating water
				The 1st day	1.9×10 5	5	93.2
The 30th day	5.2×10 3	6	90.0

Table 6

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 the conclusion of CaCO3.

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

Adopting processing power is the box micro-current electrolysis device for sterilizing and removing alga of 300M3/hr, the water body water pump is handled according to the flow enhancement feeder of 300M3/hr, titanium anode 12 and former negative electrode 13 are all as electrolytic anode, with supporting electrode 14 as negative electrode, the employing current density is 10mA/cm2, running voltage is 9.6V, 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 (Totalaerobic count), with chlorophyll supposition in contrast former water chlorophyll and the water body for the treatment of water after 24 hours killing action to 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 12.2V gradually, is 8mA/cm2 with the current density, and 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 9.6V, until the 30th day, running voltage reverts to 12V.

Freshwater aquiculture pond sterilization algae removal effect (current density is 10.0mA/cm2)

Table 7

Device among the present invention can obviously draw the sterilizing and algae-removing effect of apparatus of the present invention by above-mentioned test, and can be applied to sterilization algae removing in seawater or the fresh water simultaneously, and can realize automatic desludging, and applied range; And the adding ultra-sonic generator, effectively destroy various bacteriums and alga cells by ultrasonic wave; Equipment is simple, and has wide range of applications.For the device of being set forth among each embodiment of the present invention, within the spirit and principles in the present invention all, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1, a kind of micro-current electrolysis device for sterilizing and removing alga, it is characterized in that, comprise: the detector that is installed in induction solution conductivity value on the inlet channel of casing, the interior order according to group inner anode, supporting electrode, negative electrode of described casing is installed the electrode group more than at least one group, controller is judged the size of described electric conductivity value, control electrode in the described casing polarity, and circuit connect;

Comprise in the described controller:

Judging unit is used to judge the size of described electric conductivity value, and triggers corresponding seawater electrolysis mode unit, fresh water electrolysis mode unit, the electrolysis mode of falling utmost point cell operation according to judged result;

Described seawater electrolysis mode unit, after being used for receiving triggering, the circuit of the described anode of conducting, negative electrode connects, and the circuit that disconnects supporting electrode connects;

Described fresh water electrolysis mode unit after being used for receive triggering, changes the polarity of described negative electrode into anode, changes the polarity of described supporting electrode into negative electrode, and the circuit that conducting do not change the polar anode, change polar anode, negative electrode connects;

The described mode unit of falling the utmost point, after the number of run, working time that is used for judgment means surpasses setting threshold, change the polarity of described supporting electrode into anode, conducting changes the polar anode, does not change the circuit connection of polar negative electrode, disconnects not changing the connection of polar anodic circuit.

2, device according to claim 1 is characterized in that, the electrode shape in the described electrode group is pellet electrode or hollow edged electrode.

3, device according to claim 2 is characterized in that, also comprises:

Be installed in ultra-sonic generator, and the ultrasound reflector of described tank ends, comprise at least more than one ultrasonic transducer in the described ultra-sonic generator, the position of described electrode group is between described ultra-sonic generator and ultrasound reflector.

4, device according to claim 3 is characterized in that,

When described electrode shape is sheet, described ultrasound reflector be shaped as triangular prism shaped or circular arc, prismatical seamed edge or circular arc protrude towards the direction of ultra-sonic generator;

When described electrode shape is tubulose, described ultrasound reflector be shaped as taper shape, circular cone top towards ultra-sonic generator.

5, device according to claim 4 is characterized in that, when described electrode shape was tubulose, described each electrode, each ultrasonic transducer were the circular arrangement in the same center of circle.

6, device according to claim 1 is characterized in that, described detector is specific conductivity induction type conductivity sensor or conductivity transmitter.

7, device according to claim 1, it is characterized in that, described titanium anode is to be matrix with a kind of of metal titanium or titanium alloy at least, contain in metal Pt, Ir, Ru, Rh, Pd or Os and the oxide compound thereof at least a and contain the coated electrode (DSA) of the oxide compound of Ta at least or Ti in its surface-coated.

8, device according to claim 1 is characterized in that, described supporting electrode and negative electrode are to be matrix with a kind of of metal titanium or titanium alloy at least, at the electrode member of the oxide compound of at least a Ta of its surface-coated or Ti.

9, device according to claim 1 is characterized in that, the material of described ultrasound reflectors comprises a kind of material members of plastics, metal titanium, titanium alloy, stainless steel, carbon steel or copper alloy at least.

10, device according to claim 1 is characterized in that, also comprises:

Be installed in the potentiometer that is used for detecting solution cl content after the electrolysis on the described casing outlet conduit or chlorine residue electrode, and chlorine residue transmitter;

Described each electrolysis cells is regulated electrolytic electric current, magnitude of voltage according to described cl content value.

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