CN1172774A - Method for degerming by water and processing device used by said method - Google Patents

Method for degerming by water and processing device used by said method Download PDF

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CN1172774A
CN1172774A CN96122055A CN96122055A CN1172774A CN 1172774 A CN1172774 A CN 1172774A CN 96122055 A CN96122055 A CN 96122055A CN 96122055 A CN96122055 A CN 96122055A CN 1172774 A CN1172774 A CN 1172774A
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water
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polyaniline
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negative electrode
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森田健一
大塚茂
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Furong chemical industry co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/46115—Electrolytic cell with membranes or diaphragms

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

The aim of the present invention is to inexpensively and certainly kill a microorganism in water to sterilize water without being accompanied by danger from an aspect of work and generating harmful gas. A plate anode 2 composed of a platinum plated titanium plate, a cathode 1 composed of a platinum plated titanium plate having polyaniline films 3 applied to both main surfaces thereof and a stirrer 5a rotationally driven by a motor 5 are immersed in water 6 housed in a container 7 and a current is supplied across the anode 2 and the cathode 1 while water 6 is stirred by the stirrer 5a. By this constitution, the polyaniline films 3 reduce dissolved oxygen in water 6 to form superoxide which in turn kills a microorganism in water 6. This superoxide also contributes to the reductive reaction of oxygen to reduce once oxidized polyanilin by the reducing current flowing to polyanline capable of again reducing oxygen in water.

Description

Water method for disinfection and the used treatment unit of this method
The present invention relates to a kind of water method for disinfection and the used water treatment device of this method, be particularly related to a kind of such water method for disinfection and the used device of this method, promptly this method and apparatus need not to drop into from the outside materials such as any medicament, do not have operational hazards in addition, and cost that can be lower kills the microorganism in the water really.
People know, be used for killing water such as the hot water of water coolant, common plunge bath of heat exchanger of tap water, factory or buildings of family or office and swimming-pool water, it is harmful microbe method contained in the so-called water, comprise the water ebullient method that makes, Xiang Shuizhong throws method that sterilant such as chlorine, hydrogen peroxide are arranged or electrolytic sterilizing method etc.
Yet above-mentioned existing water method for disinfection has following problems.
Such as, in water boiling method, have following problems, even the essential energy that consumes of water boiling institute is very big, the thermal source that water is heated is managed very complicated in addition.Following situation usually taking place in addition, promptly because of making the water boiling, the water characteristic is changed to some extent, makes water no longer be fit to the application scenario of itself.
Though dropping into the method for chlorine in addition in water is extensive use of as water method for disinfection in the waterpipe, but still has following problems, this problem is: must drop into a large amount of chlorine, residual in the water after the sterilization in addition have ozone, residual chlorine can produce organic chloride (such as three methyl halides) in addition, thereby have the infringement HUMAN HEALTH, cause the danger of environmental pollution.The method that Xiang Shuizhong adds hydrogen peroxide then has following problems, promptly because hydrogen peroxide is easy to decomposition in water, so must drop into relatively large hydrogen peroxide, owing to will carry out fierce oxidizing reaction under high density, hydrogen peroxide is dangerous property when the use onsite moving or in the leaching process in when input in addition.
The electrolytic sterilizing method has following problems, and promptly owing to must use bigger electric energy, its cost is higher like this, if and cut down power consumption and reduce voltage, then the effect of kill microorganisms is bad, in addition, improve voltage if carry out abundant sterilization, then water itself can produce obnoxious flavour because of decomposition.
At above-mentioned situation, the object of the present invention is to provide a kind of water method for disinfection and the used water treatment device of this method, this method and apparatus does not have operational hazards, can not produce obnoxious flavour yet, can really the microorganism in the water be killed with lower cost in addition.
To achieve these goals, water method for disinfection of the present invention may further comprise the steps, anode and its surface and the contacted negative electrode of polyaniline are set in water, between this anode and negative electrode, intermittently or continuously switch on,, microorganism contained in the above-mentioned water is killed simultaneously by reduce the superoxide that above-mentioned oxygen in water generates by polyaniline.That is to say that the inventor finishes water method for disinfection of the present invention because having found following phenomenon, this phenomenon is: if polyaniline is contacted with water, then polyaniline is understood the dissolved oxygen (O in the reductive water 2), and generate superoxide (O with good germicidal action 2 -), the polyaniline because of the temporary transient oxidation of oxygen reduction is able to electrochemical reduction by the reduction current that flows through in the water in addition, thereby is regenerated as the polyaniline that can restore water oxygen.In the water method for disinfection of the invention described above, because of with water in the polyaniline of the temporary transient oxidation of dissolved oxygen reaction the reduction current of negative electrode is able to electrochemical reduction in the water by flowing through, thereby be regenerated as the polyaniline that can restore water oxygen, therefore the process by polyaniline generation superoxide can not stop, even under the bigger situation of the water yield, still can kill the microorganism in the water really.In addition, the needed reduction current density of the polyaniline of oxidation (absolute value) is 0.01～100 μ Acm because the dissolved oxygen in reduction and the water reacts -2So current consumption is less, water itself is decomposed and produce obnoxious flavour do not wish situation.Also have, the nontoxicity of polyaniline own carries out can not producing toxic gas in the oxygen reduction reaction process at polyaniline, also can not follow adventurous situation, thereby can carry out safe operation.
In the method for disinfection of the invention described above, water preferably stirs by agitator, adopt above-mentioned preferred scheme, the water that carries out germicidal treatment is all contacted expeditiously with polyaniline, thereby make the dissolved oxygen in the water be reduced into superoxide expeditiously, contact frequency owing to microorganism in superoxide and the water has increased effectively in addition, thereby can expeditiously the microorganism in the water be killed.
In the water method for disinfection of the invention described above, preferably negative electrode is covered with the cloth shape of polyaniline film, netted or porous plate-like cathodes at least one face on it, and water is flowed by above-mentioned cloth shape, netted or porous plate-like cathodes and polyaniline film, because above-mentioned preferred feature, even under the bigger situation of the water yield of carrying out germicidal treatment, water still can all fully contact with polyaniline, and the dissolved oxygen in the water is reduced into superoxide expeditiously, and then expeditiously the microorganism in the water is killed.
In the water method for disinfection of the invention described above, water is flowed by cloth shape, netted or porous plate-like cathodes and polyaniline film repeatedly, because above-mentioned preferable feature, water can all repeatedly contact with polyaniline, dissolved oxygen in the water can be reduced into superoxide equably, and then basically the microorganism in the water is killed.
In the water method for disinfection of the invention described above, be preferably in the cloth shape, inside and outside two sides netted or the porous plate negative electrode covers polyaniline film, because above-mentioned preferable feature, make water by being located at the polyaniline film on the two sides inside and outside the above-mentioned negative electrode, thereby the water that carries out germicidal treatment is all contacted expeditiously with polyaniline, make the dissolved oxygen in the water be reduced into superoxide within a short period of time, thereby shortened the treatment time of kill microorganisms.
In the water method for disinfection of the invention described above, preferably negative electrode is the cloth shape, netted or porous plate-like cathodes, block cellular structure is pressed and above-mentioned cloth shape, a contacted mode of face netted or the porous plate-like cathodes is provided with, this cellular structure is made by conductive material, its surface attachment has polyaniline, water is by above-mentioned cloth shape, netted or porous plate-like cathodes and cellular structure flow, because above-mentioned preferred feature, even under the bigger situation of the water yield of carrying out germicidal treatment, water still can all fully contact with polyaniline, dissolved oxygen in the water is reduced into superoxide expeditiously, thereby expeditiously the microorganism in the water is killed.
In the water method for disinfection of the invention described above, water is flowed by cloth shape, netted or porous plate-like cathodes and block cellular structure repeatedly, because above-mentioned preferred feature, water can all effectively repeatedly contact with polyaniline, make the dissolved oxygen in the water be reduced into superoxide equably, thereby basically the microorganism in the water is killed.
In the water method for disinfection of the invention described above, the plate-like cathodes that preferably is covered with polyaniline film on plate-shaped anode and its at least one face is oppositely arranged by following mode, this mode is that above-mentioned polyaniline film is towards above-mentioned anode one side, make water by the Clearance Flow between above-mentioned negative electrode and the anode, because above-mentioned preferred feature, water is by above-mentioned plate-like cathodes that is oppositely arranged and the gap between the anode time, can carry out contacting of long period with the polyaniline film that covered on the cathode plane, dissolved oxygen in the water is reduced into superoxide expeditiously, thereby expeditiously the microorganism in the water is killed.
First kind of water treatment device of the present invention comprises the tank of depositing the water that carries out germicidal treatment, immerse the anode that is provided with in the above-mentioned water to small part, its surface attachment has polyaniline film and this polyaniline film to immerse in the above-mentioned water and the negative electrode that is provided with, and the power supply of electric current is provided for above-mentioned anode and negative electrode.Because above-mentioned feature, can carry out water method for disinfection of the present invention in reasonably stability ground, this method can with above-mentioned water in the dissolved oxygen reaction and the polyaniline of oxidation is regenerated as the polyaniline that can restore dissolved oxygen, the while can kill the microorganism in the water.
In first kind of water treatment device of the invention described above, preferably be provided with the agitator that can stir water, because above-mentioned preferred feature, the water that carries out germicidal treatment contacts with polyaniline expeditiously, make the dissolved oxygen in the water be reduced into superoxide expeditiously, increase the contact frequency of the microorganism in superoxide and the water, thereby improved the efficient of killing of microorganism in the water.
Second kind of water treatment device of the present invention, comprise the electrolyzer assembly parts, these electrolyzer assembly parts are to constitute like this, be formed with on the groove water is introduced first opening in it, with second opening that the water in the groove is discharged outside groove, its at least one face is covered with the cloth shape of polyaniline film, netted or porous plate-like cathodes is located at a side of above-mentioned first opening, the cloth shape, netted or porous plate-shaped anode is located at a side of above-mentioned second opening, water in the above-mentioned first opening lead-ingroove passes through above-mentioned cloth shape, netted or porous plate-like cathodes and polyaniline film, and by above-mentioned cloth shape, netted or porous plate-shaped anode, discharge outside groove from above-mentioned second opening, said apparatus also comprises the power supply that electric current is provided to above-mentioned anode and negative electrode, deposit the tank of the water that carries out germicidal treatment, water is inhaled and sent into the pump of first opening of above-mentioned electrolyzer assembly parts from above-mentioned tank.Because above-mentioned feature, but reasonably stability ground carries out water method for disinfection of the present invention, and this method is by making water by the cloth shape that is covered with polyaniline at least one face, the netted or tabular cathode flow of porous, thereby the microorganism in the water is killed.In addition, because electrolyzer is assembly parts, electrode materials in electrolyzer or polyaniline are through the operating performance variation of for some time, under the situations such as electrode or polyaniline film generation obstruction like this, be easy to this electrolyzer is replaced with new electrolyzer, thereby have good maintainability.
In second kind of water treatment device of the invention described above, water shoot preferably is set, this water shoot is used for the water of discharging from above-mentioned electrolyzer assembly parts is sent in the tank, because above-mentioned preferred feature, but reasonably stability ground carries out water method for disinfection of the present invention, this method can make the water that carries out germicidal treatment easily repeatedly by the electrolyzer assembly parts, above-mentioned like this water can be repeatedly by the cloth shape that is covered with polyaniline film at least one face, the netted or tabular cathode flow of porous, thereby the microorganism in the water is killed.
In second kind of water treatment device of the invention described above, be preferably on the opposite in cloth shape, the netted or porous plate-like cathodes and cover polyaniline film, be covered with the cloth shape of polyaniline film on the one opposite, netted or porous plate-like cathodes is to be provided with like this, even water is successively by being located at the polyaniline film on the above-mentioned opposite in the above-mentioned electrolyzer, because above-mentioned preferred feature, the water that carries out germicidal treatment can contact with polyaniline film expeditiously, dissolved oxygen in the water can be reduced into superoxide at short notice, thereby can shorten the treatment time of kill microorganisms.
The third water treatment device of the present invention, comprise the electrolyzer assembly parts, these electrolyzer assembly parts are to form like this, be formed with second opening that water is introduced first opening in it and the water in the groove is discharged on the groove outside groove, the cloth shape, negative electrode netted or that porous is tabular is located at a side of above-mentioned first opening, the cloth shape, anode netted or that porous is tabular is located at a side of above-mentioned second opening, block cellular structure is by being provided with the contacted mode of above-mentioned negative electrode, this cellular structure is between above-mentioned negative electrode and anode, it is made by conductive material, its surface attachment has polyaniline, the water of sending in the groove from above-mentioned first opening passes through the cloth shape, netted or porous is tabular negative electrode and above-mentioned thicker cellular structure, and by the cloth shape, the anode netted or porous is tabular, discharge outside groove from above-mentioned second opening afterwards, said apparatus also comprises the power supply that electric current is provided to above-mentioned anode and negative electrode, deposit the tank of the water that carries out germicidal treatment, water is inhaled and sent into the pump of first opening part of above-mentioned electrolyzer assembly parts from above-mentioned tank.Because above-mentioned feature, but reasonably stability ground carries out water germicidal treatment method of the present invention, this method makes above-mentioned water circulate by cloth shape, negative electrode and block cellular structure netted or that porous is tabular, this cellular structure is made by electro-conductive material, it is by being provided with the contacted mode of above-mentioned negative electrode, its surface attachment has polyaniline, thereby the microorganism in the water can be killed.Because electrolyzer is assembly parts, electrode materials in electrolyzer or the constituent material in the cellular structure are through operating performance variation after a while, under the situations such as electrode or cellular structure generation obstruction, can at an easy rate this electrolyzer be replaced with new electrolyzer, thereby have good maintainability.
In the third water treatment device of the invention described above, preferably this device is provided with water shoot, second open communication in this water shoot and the electrolyzer assembly parts, thereby will send into the tank from the water that electrolyzer is discharged, because above-mentioned preferred feature, but reasonably stability ground carries out water method for disinfection of the present invention, this method makes the water that carries out germicidal treatment easily repeatedly by the electrolyzer assembly parts, above-mentioned like this water flows by cloth shape, netted or porous plate-like cathodes and block cellular structure repeatedly, thereby the microorganism in the water is killed.
In the third water treatment device of the invention described above, preferably electrolyzer is to be provided with like this, i.e. the cloth shape that the stacked electro-conductive material of multilayer is made between block cellular structure, netted or porous plate-like piece, this cellular structure is between negative electrode and anode, and its surface attachment has polyaniline.In the electrolyzer that is provided with the independent block many shapes cellular structure between negative electrode and anode, if increase the thickness of independent block cellular structure for the contact area that makes polyaniline and water strengthens, then can not make water waltz through cellular structure, in contrast, in the electrolyzer that is provided with by following mode, this mode is the cloth shape that the stacked electro-conductive material of multilayer is made between block cellular structure, netted or porous plate-like piece, this cellular structure surface attachment has polyaniline, what under the situation that each block cellular structure thickness reduces, still can obtain the total thickness of the block many structural parts between negative electrode and anode by the number of plies that increases block cellular structure, like this water often can be smoothly cloth shape by making at the less block cellular structure of each thickness and the electro-conductive material between the block cellular structure, netted or porous plate-like piece, thus make water smoothly by whole electrolyzer.
The 4th kind of water treatment device of the present invention comprises the electrolyzer assembly parts, these electrolyzer assembly parts are to constitute like this, be formed with second opening that water is introduced first opening in it and the water in the groove is discharged on the groove outside groove, be provided with electrode in the above-mentioned groove and be oppositely arranged structural part, this electrode is oppositely arranged on the structure spacing in accordance with regulations and is relatively set with the plate-like cathodes that plate-shaped anode and its at least one face are covered with polyaniline film in the following manner, this mode is that above-mentioned polyaniline is towards above-mentioned anode one side, water in the above-mentioned first opening lead-ingroove is by after being oppositely arranged the plate-like cathodes and the gap between the plate-shaped anode on the structural part at above-mentioned electrode, discharge outside groove from second opening, said apparatus comprises that also anode and negative electrode provide the power supply of electric current, water is inhaled from the tank of depositing the water that carries out germicidal treatment, and send into the pump of first opening part of electrolyzer assembly parts, because above-mentioned feature, but reasonably stability ground carries out water method for disinfection of the present invention, this method can make water by the gap between anode and the plate-like cathodes, the plate-like cathodes that this anode and one face are covered with polyaniline film is oppositely arranged by the mode of above-mentioned polyaniline film towards anode one side, thereby the microorganism in the water can be killed.Because electrolyzer is assembly parts, electrode materials in electrolyzer or polyaniline film can be replaced by this electrolyzer new electrolyzer at an easy rate, thereby have good maintainability under situations such as operating performance variation after a while in addition.
In the 4th kind of water treatment device of the invention described above, preferably the electrolyzer assembly parts are to constitute like this, be to be provided with a plurality of electrodes in it to be oppositely arranged structural part, water is oppositely arranged plate-like cathodes on the structural part and the gap between the anode by laying respectively at above-mentioned a plurality of electrode, because above-mentioned preferable feature, carry out the water and polyaniline lengthening duration of contact of germicidal treatment, thereby the dissolved oxygen in the water is reduced into superoxide expeditiously, has so just improved the efficient of killing of microorganism.
In the first～four kind of water treatment device of the invention described above, strainer preferably is set, this strainer can will not wish to have suspended substance removal near in the water of second opening in the groove of electrolyzer assembly parts, because above-mentioned preferred feature, dust in the water, foreign matter or microorganism remains can be filtered out, thereby can make the water health more that becomes.
In the first～four kind of water treatment device of the present invention, preferably the electrolyzer assembly parts are communicated with strainer, do not wish to have suspended substance removal in the water that this strainer can be discharged second opening from the electrolyzer assembly parts, because above-mentioned feature, dust in the water, foreign matter or microorganism remains can be filtered out, thereby can make water become limpider.
As mentioned above, the inventor has found following phenomenon, if promptly polyaniline contacts with water, and the dissolved oxygen (O in the polyaniline meeting reductive water 2), and generation has the superoxide of good germicidal action, polyaniline because of the temporary transient oxidation of the reduction reaction of oxygen carries out electrochemical reduction by the reduction current that flows through electrode in the water in addition, thereby be regenerated as and reduce the polyaniline of water oxygen once more, the inventor has finished water method for disinfection of the present invention thus, this method steps comprises: in water with electrode (negative electrode) by being provided with the contacted mode of polyaniline, make the reduction current of reducible polyaniline flow through electroplax (negative electrode), generate superoxide by polyaniline reduction of dissolved oxygen simultaneously.In the water method for disinfection of the invention described above, polyaniline and dissolved oxygen reaction in water, and the reduction reaction principle that goes up polyaniline at electrode (negative electrode) is as shown in Figure 1.N among the figure represents the natural integer of the multiplicity (polymerization degree) as polymerized unit, x represents to constitute the natural integer of bimolecular body (a) of aniline of the reduced form structure of polymerized unit, and y represents to constitute the quantity of bimolecular body (b) of the oxidized form structure aniline of polymerized unit.
That is to say the dissolved oxygen (O in the water 2) be reduced to superoxide (O by contacting with polyaniline 2 -).Like this, though be positioned at and impel dissolved oxygen (O 2) the bimolecular body (a) of aniline of reduced form structure of polymerized unit in the reductive polyaniline become the bimolecular body (b) of temporary transient oxidized form structure aniline, but owing to flow through the effect of the reduction current of electrode (negative electrode), it can reduce and return reduced form structure (a), therefore, by making reduction current flow through electrode (negative electrode), polyaniline remains on oxygen reduction (O 2) state (state of bimolecular body that contains the aniline of reduced form structure), and can carry out semi-permanent water germicidal treatment in fact.
Polyaniline used in the present invention is at least a complex body that contains in the represented polyaniline of following chemical structural formula 1～4.
[changing 1]
Figure A9612205500111
[changing 2] Chemical structural formula 3 Chemical structural formula 4
Figure A9612205500122
In above-mentioned chemical structure, A is negative ions such as sulfuric acid, perchloric acid, trifluoroacetic acid, boron trifluoride, polyacrylic acid, polystyrene acid, cresol sulfonic acid, camphorsulfonic acid, n is the integer in 2～5000, be the best with the integer in 10～1000 wherein, x and y are for satisfying the number of x+y=1 and 0≤Y≤0.5 two condition simultaneously.
The alleged water of the present invention is the water in the waterpipe, underground water, and process water etc., such as sweet water, the water coolant in the heat exchanger, the water of usefulness such as various cleaning waters, swimming-pool water, bath pool water.
In the present invention, the microorganism in the water to be killed is bacterium, bacterium, thread fungus, intestinal bacteria, yeast, mycetozoan, unicellular algae, protozoon, virus etc.
In the present invention, as negative electrode and anode, employed electrode is by carbon materials, and conductive materials such as precious metals such as titanium, platinized titanium, platinum, ferrite are made, its be shaped as laminar, tabular, cloth shape, netted, porous is tabular, porous block etc.Under the state of the use electrode that makes water (processed water) by its inside, this electrode can adopt the cloth shape, netted, porous is tabular and shape such as porous block.Carbon materials in the best above-mentioned electrode materials has electroconductibility, and nontoxicity can not produce ion or oxyhydroxide, and cost is lower in addition, to the metal non-corrosiveness.
In the present invention, preferably polyaniline contacts with whole cathode surface as much as possible, here, generally is to adopt known overlay technique such as electrolysis coincidence method on the whole surface of negative electrode, and the whole surface attachment that promptly constitutes the electrode materials of negative electrode forms polyaniline film.Polyaniline also can adopt at negative electrode supporting member surface attachment polyaniline in addition with contacting of negative electrode in addition, and makes this supporting member and the contacted form of negative electrode.
Adhere to the occasion that forms polyaniline film at cathode surface, though the weight ratio of polyaniline and negative electrode (polyaniline: negative electrode) needn't specifically limit, generally in 0.001: 1～0.3: 1 scope.In addition, though the thickness of polyaniline film will approach as far as possible, if it is but thin excessively, the absolute magnitude of polyaniline can be because of reducing formed amount of peroxides very little, if blocked up might the impeded electrode surface current flow, thereby reduce the regeneration efficiency of polyaniline, cost of manufacture is increased.Here, the thickness of best polyaniline film is in the scope of 0.1～10 μ m.
Under following occasion, promptly adopt the supporting member surface attachment polyaniline beyond negative electrode, thereby make the contacted form of this supporting member and negative electrode realize contacting of polyaniline and negative electrode, preferably this supporting member is that conductive material is made, and has certain thickness block cellular structure simultaneously.Like this, owing to adopted and had certain thickness block vesicular structure, water not only contacts with the polyaniline that adheres on the outmost surface, but also with the wall that surrounds a plurality of internal holes, be that the polyaniline that adheres on the inner surface contacts, thereby improved the formation efficiency of superoxide, in addition owing to have conductivity, the reduction current that flows through negative electrode also can flow through supporting member, with the contacted polyaniline of negative electrode and be positioned at the lip-deep polyaniline of supporting member and all regenerative response can take place, improved the regeneration efficiency of polyaniline thus like this.Above-mentioned conductive material is made the felt formula pad that block cellular structure can adopt carbon fibre to make, or the block solid forming spare of making by carbon materials with a plurality of continuous holes etc.Be the occasion that block porous surface that conductive material is made adheres to polyaniline, though preferably polyaniline is as far as possible by not losing the very thin whole surface that is attached to above-mentioned conductive material equably of its porous mode, if but above-mentioned polyaniline thickness is thin excessively, then because the minimizing of polyaniline absolute magnitude, thereby formed amount of peroxides might reduce, if above-mentioned in addition polyaniline film is blocked up, then cost of manufacture increases, the mobile of electric current can reduce in addition, because of the space stenosis between the porous solid forming spare, the mobile of water hindered.Therefore, the thickness of polyaniline film is generally in the scope of 0.1～10 μ m.In addition, though the weight ratio of polyaniline and block cellular structure (polyaniline: cellular structure) needn't specifically limit, it is preferably in 0.001: 1～0.3: 1 scope in.
In the present invention, the mobile electric current should be and reduces polyaniline reaction (regenerative response) necessary alap electric current on cathode stabilization ground between anode and negative electrode, and current density (absolute value) is 0.01～100 μ Acm -2If satisfy above-mentioned condition, can not take place to produce obnoxious flavour, thereby can stablize the reduction reaction (regenerative response) of carrying out polyaniline because of the electrolytic reaction of water itself.
The water germicidal treatment generally adopts the method for following manner batch processing, this mode is: put the water of capable germicidal treatment into having certain volumetrical groove internal memory, anode and its surface and the contacted negative electrode of polyaniline are set in the water in depositing in above-mentioned groove, between above-mentioned anode and negative electrode, switch on.Under this occasion, all contact with polyaniline expeditiously in order to make the water of depositing in the groove, preferably adopt agitator that water is stirred.
Above-mentioned treatment process though promptly have certain volumetrical water to carry out the performance, relevant as the kind of the microorganism of sterilization object etc. of the method for germicidal treatment in batch and agitator to it, if increase the water that carries out germicidal treatment, then may strengthen the treatment time.Thus, under the processing occasion bigger to the water yield, preferably use following method, this method adopts following electrolyzer assembly parts, be provided with water inlet and outlet, in groove, be provided with electrode (negative electrode and anode) and press the polyaniline that is provided with the negative electrode way of contact, make the water that carries out germicidal treatment by electrolyzer assembly parts inside when between negative electrode and anode, switching on, thereby the dissolved oxygen in the water is contacted with polyaniline.Under this occasion, though sterilization effect and polyaniline in the electrolyzer assembly parts and dissolved oxygen to contact effect relevant, for further improve sterilization effect, preferably make carry out germicidal treatment water by electrolyzer assembly parts inside.But the groove in the above-mentioned electrolyzer assembly parts is preferably by life-time service, and the material with electrical insulation capability is made, and it generally adopts synthetic resins to make.Though be located at negative electrode and generally spacing setting in accordance with regulations of anode in the groove in addition, but also between is provided with barrier film and is short-circuited to prevent two electrodes.Above-mentioned barrier film can adopt such as woven fiber glass, has the mesh that the synthetic resins of electrical insulation capability is made, and has porous-film that the synthetic resins of electrical insulation capability makes etc.In addition, if near electrolyzer assembly parts inner outlet place strainer is being set, can make the water health more that becomes so that the dead bones of the body of microorganism that produced in contained dust, foreign matter or the electrolyzer in water etc. filter out.In addition, even electrolyzer assembly parts and strainer are not monolithic moldings, then when using the electrolyzer assembly parts, still can obtain identical effect by strainer is communicated with the outlet of electrolyzer assembly parts.
In above-mentioned any method, the residence time of water in groove, though the actual contact time that is water and polyaniline is wanted suitably according to the purposes of handling back water, the pending water yield and the size of treatment unit or shape wait to determine, but it is generally 5～600 seconds scope, if the above-mentioned time in above-mentioned scope, then can kill microorganism under the situation that does not reduce processing efficiency fully.
Below, describe content of the present invention in detail with embodiment.
Fig. 1 is polyaniline and the dissolved oxygen reaction in the water, and the reaction principle explanatory view of going up the polyaniline reduction reaction at electrode (negative electrode);
Fig. 2 is the section of structure of the embodiment of the invention 1 employed water treatment device;
Fig. 3 is the section of structure of the embodiment of the invention 2 employed water treatment device;
Fig. 4 is the section of structure of the embodiment of the invention 3 employed water treatment device;
Fig. 5 is the section of structure of the embodiment of the invention 4 employed water treatment device;
Fig. 6 is the structure skeleton view of the embodiment of the invention 5 employed water treatment device;
Fig. 7 is the section of structure of the embodiment of the invention 5 employed water treatment device.
Embodiment 1
With reference to water treatment device shown in Figure 2.In the drawings, label 90 is a water treatment device, it comprises cathode assembly and the anode assemblies of being located in the container 7 that polyethylene makes, this cathode assembly comprises negative electrode 1, the two sides of this negative electrode 1 is attached with polyaniline film 3, this negative electrode 1 is made by the titanium plate that is coated with platinum, above-mentioned anode assemblies comprises anode 2, the surface of this anode 2 is covered with woven fiber glass 4, above-mentioned anode 2 is made by the titanium plate that is coated with platinum equally, above-mentioned cathode assembly and anode assemblies spacing are in accordance with regulations sling, thereby by agitator (agitating vane) 5a that drives rotation by motor 5 water 6 are stirred.In addition, negative electrode 1 and anode 2 link to each other with not shown direct supply respectively, are used for reducing the reduction current of polyaniline thereby can produce at negative electrode.Here, the volume of the container 7 that polyethylene is made is 2 liters, and the titanium board size that is coated with platinum is 5cm * 10cm, and the thickness of polyaniline film 3 is 2 μ m.
Prepare pending former water, this former water adds weight percent in salt solution be that 0.2% factory's discharge waters that contain a large amount of general bacteriums are made, and this salt solution adds weight percent in distilled water be that 0.9% salt is made.Add the pending former water 6 of 1000cc in the container 7 of above-mentioned water treatment device 90,5a stirs it with agitator (agitating vane).When handling beginning, energising between negative electrode 1 and anode 2 when promptly adding pending former water 6, here set the electric current that flows through negative electrode 1 for-(current density is-30.0 μ Acm to 3.0mA -2).
In required time above-mentioned pending former water 6 is taken a sample at every turn, sampling water is carried out agar cultivate, measure and cultivate bacterial count contained in the water of back (colony's number: individual/number).Above-mentioned culture condition is 36 ℃, 24 hours.The result is as shown in table 1 below for this culture experiment.In table 1, also listed not the comparative example 1 of the above-mentioned culture experiment that its electrode is switched in addition, not to the result of the comparative example 2 of its electrodes polyaniline and the above-mentioned culture experiment of its electrode not being switched on.
Table 1
Embodiment 1 Comparative example 1 Comparative example 2
Electrifying electrodes Have Do not have Do not have
Polyaniline Have Have Do not have
Handle the elapsed time 0 minute ???1800 ???1800 ????1800
30 minutes ????5 ????8 ????1800
1 hour ????3 ????5 ????1800
3 hours ????0 ????1 ????2200
5 hours ????0 ????0 ????2300
24 hours ????0 ????2500 ????3800
27 hours ????0 ????2500 ????3900
48 hours ????0 ????3700 ????5600
50 hours ????0 ????3700 ????5600
Can confirm the sterilization effect of polyaniline according to above-mentioned test-results, can know if adhere to (contact has) polyaniline and also switch at negative electrode, then general bacterium has been killed basically through 1 hour processing, is killed fully in 3 hours, and its sterilization effect is sustainable more than 48 hours in addition.For cold occasion, through still having sterilization effect in 5 hours, but as surpass 24 hours and then lose sterilization effect.Hence one can see that, if no power, through the activity of a few hours polyaniline, the hydrogen reduction that is about in the water becomes the ability of superoxide to disappear, and as crossing energising, its activity is renewable.
Embodiment 2
With reference to water treatment device shown in Figure 3.In Fig. 3, label 100 is a water treatment device, the treatment trough 18 that this device is made by the polyethylene that holds treating water (carrying out the water of germicidal treatment) 16, electrolyzer assembly parts 100a, pump 15 and flexible pipe 52 constitute, the treating water 16 that said pump 15 will be contained in the treatment trough 18 upwards siphons away by flexible pipe 51a, send among the inlet 17a of electrolyzer assembly parts 100a by flexible pipe 51b simultaneously, above-mentioned flexible pipe 52 is communicated with the outlet 17b of electrolyzer assembly parts 100a, and the treating water 16 that will discharge from electrolyzer assembly parts 100a is sent in the treatment trough 18.
Electrolyzer assembly parts 100a constitutes like this, promptly in the cylindrical groove of making by acrylic resin 17 that is provided with inlet 17a and outlet 17b, side at inlet 17a is provided with negative electrode 11, this negative electrode is clamped by polyvinyl chloride porous plate 50 about in the of 11, negative electrode 11 has the carbon fiber sheet of polyaniline film 13 to constitute by its surface attachment, the side of outlet 17b in groove 17 is provided with the anode 12 that carbon fiber sheet constitutes, be provided with woven fiber glass 14 below it, being clamped by the polyvinyl chloride porous plate up and down of anode 12 is being provided with strainer 19 near outlet 17b one side in addition.Here, the area sum of inside and outside two faces of the negative electrode of being made by carbon fiber sheet 11 is 47.5cm2, and the thickness of the polychloroethylene film 13 that above-mentioned each face is accompanying is 3 μ m.The outer edge surface of polyvinyl chloride porous plate 50 contacts with the inner-wall surface of groove 17 and fixes in addition, and negative electrode 11, woven fiber glass 14 and anode 12 remain on prescribed position thus.In addition, strainer 19 is by wire netting and filter paper is stacked constitutes, and is fixed in the inner-wall surface of groove 17.Have, negative electrode 11 links to each other with the not shown direct supply that is positioned at groove 17 outsides with anode 12 again.
In above-mentioned water treatment device 100, be loaded on treating water 16 in the treatment trough 18 by pump 15 from groove 18 by the flexible pipe 51a sucking-off that makes progress, relend and help pump 15 to enter among the inlet 17a of electrolyzer assembly parts 100a by flexible pipe 51b, after passing through electrolyzer assembly parts 100a inside, discharge outside groove from the outlet 17b of electrolyzer assembly parts 100a, return once more in the treatment trough 18 by flexible pipe 52 then.That is to say that treating water 16 produces circulation by electrolyzer assembly parts 100a repeatedly by pump 15, the dissolved oxygen in the treating water 16 contacts with polyaniline repeatedly, thereby the dissolved oxygen in the treating water 16 all contacts with polyaniline (polyaniline film 13).In addition, building blocks such as the negative electrode 11 in electrolyzer assembly parts 100a, anode 12 and polyaniline film 13 are through after a while handling property variation, when negative electrode 11, anode 12 or polyaniline film 13 take place to stop up, these electrolyzer assembly parts can be replaced with new electrolyzer assembly parts.
Adopt above-mentioned water treatment device 100, inject the pending former water of 1500cc to treatment trough 18, this former water is that to add weight percent in distilled water be in the salt solution made of 0.9% salt, add weight percent and be 0.2% the factory's discharge water that contains a large amount of general bacteriums and form the flow velocity circulation that above-mentioned pending former water is divided with 2000cc/.In the energising between negative electrode 11 and anode 12 simultaneously of beginning round-robin, suppose the electric current that flows through the negative electrode 11 that carbon fiber sheet makes for-(current density is-63.2 μ Acm to 3.0mA -2).
In required time the water after the processing of discharging from flexible pipe 52 is taken a sample at every turn, the treating water of taking a sample is carried out agar cultivate, measure cultivating bacterial count contained in the aftertreatment water (colony's number: individual/as to count).In addition, after handling beginning during, add weight percent once more and be 0.2% aforementioned factory discharge water, handle continuously through 49 hours.Its culture condition is 36 ℃, 24 hours.The culture experiment result is as shown in table 2 below.
Table 2
Handle the elapsed time Embodiment 2
0 minute (stoste) ????1600
30 minutes ??????3
1 hour ??????0
5 hours ??????0
24 hours ??????0
48 hours ??????0
[adding bacterium (discharge water) through 49 hours again]
After adding again Add stoste again ????2100
1 hour ??????0
3 hours ??????0
24 hours ??????0
According to above test-results as can be known, if adopt this electrolyzer assembly parts, its major surfaces that these electrolyzer assembly parts are oppositely arranged by the internal surface at groove is attached with the anode that negative electrode that the cloth shape electrode of polyaniline forms and cloth shape electrode form and constitutes, and when this negative electrode and anode carry out suitable energising, make water pass through electrolyzer repeatedly with suitable flow velocity, then the general bacterium in the water was handled through 30 minutes and is killed basically, in 1 hour, be killed fully, above-mentioned sterilization effect can be continued more than 48 hours, even and interpolation bacterium, the activity of polyaniline can not disappear yet, thereby can carry out semi-permanent germicidal treatment to water.In addition, know that also the water sample of sampling aftertreatment water is less at the dust or the foreign matter of later stage appearance, and the strainer of being located in the electrolyzer assembly parts has the effect that can remove the seston of not wanting in the treating water.
Embodiment 3
With reference to water treatment device shown in Figure 4.In Fig. 4, represent same or analogous parts with label identical among Fig. 3, label 200 is a water treatment device, replaces the electrolyzer assembly parts 100a in the employed water treatment device 100 in the foregoing description 2 with electrolyzer assembly parts 200a in this device.
Electrolyzer assembly parts 200a comprises the negative electrode 11 that carbon fiber sheet forms, be provided with successively on it and on carbon fibre pad surface, adhere to the block cellular structure 33 that the polyaniline laminated film is made, the anode 12 that woven fiber glass 14 and carbon fiber sheet form, upper and lower clamping at above-mentioned molding has polyvinyl chloride porous plate 50, and the negative electrode 11 that is positioned at groove 17 is fixed in the side of inlet 17a.Here, the carbon fibre pad that constitutes block cellular structure 33 is 1.65 by proportion, and diameter is that the carbon fibre of 18 μ m forms, and pad weight is 7 grams, the thickness of the polyaniline film of carbon fibre pad surface attachment is 3 μ m, and the thickness of block cellular structure 33 is 70mm.In addition, negative electrode 11 links to each other with the not shown direct supply that is positioned at groove 17 outsides with anode 12.
In addition, the operational process of the operational process of this water treatment device 200 and aforementioned water treatment device 100 is basic identical.That is to say that treating water 16 circulates by electrolyzer assembly parts 200a repeatedly by pump 15, the dissolved oxygen in the treating water 16 contacts with polyaniline in the cellular structure 33 repeatedly.In addition, to above-mentioned water treatment device 200, even the structure units such as negative electrode 11, anode 12 and block cellular structure 33 in the electrolyzer assembly parts 200a are through after a while and degradation, when negative electrode 11, anode 12 or block cellular structure 33 take place to stop up, also these electrolyzer assembly parts can be replaced with new electrolyzer assembly parts.
Adopt above-mentioned water treatment device 200, inject the pending former water of 1500cc to handling tank 18, this pending former water adds weight percent in distilled water be that to add weight percent in the salt solution made of 0.9% salt be that 0.2% the factory's discharge water that contains a large amount of general bacteriums is made, and the flow velocity that divides with 2000cc/ flows above-mentioned pending former water cycle.Energising between negative electrode 11 and anode 12 in circulation beginning, the electric current that flows through negative electrode 11 be decided to be-and (current density that flows through the carbon fibre pad electric current in the block cellular structure 33 is-0.53 μ Acm to 5.0mA -2).
Once more in required time, from the treating water that flexible pipe 52 is discharged, take a sample, the sampling treating water is carried out agar cultivate, measure and cultivate bacterial count contained in the water of back (colony's number: individual/number).This culture condition is 36 ℃, 24 hours.The culture experiment result is as shown in table 3 below.In addition, in table 3, also listed not the counter electrode energising and carry out with the comparative example 3 of above-mentioned same culture experiment and do not adhere to polyaniline at negative electrode, and not counter electrode energising and carry out result with the comparative example 4 of above-mentioned same culture experiment.
Table 3
Embodiment 3 Comparative example 3 Comparative example 4
Electrifying electrodes Have Do not have Do not have
Polyaniline Have Have Do not have
Handle the elapsed time 0 minute ???2300 ????2300 ????2300
30 minutes ????10 ?????23 ????2300
1 hour ????6 ?????13 ????2300
5 hours ????0 ?????5 ????2800
24 hours ????0 ????2700 ????4800
27 hours ????0 ????2700 ????4800
48 hours ????0 ????4100 ????5600
50 hours ????0 ????4100 ????5600
According to above test-results as can be known, adopt following electrolyzer assembly parts, these electrolyzer assembly parts are that the anode that the negative electrode in groove cloth shape electrode made and cloth shape electrode are made is oppositely arranged, the carbon fibre pad that is attached with polyaniline between them on the filling surface forms, if between negative electrode and anode, carry out in the suitable energising, make water repeatedly by the electrolyzer assembly parts with suitable flow velocity, general bacterium in the water is killed basically through 1 hour processing, killed fully with interior at 5 hours, this sterilization effect is sustainable more than 48 hours.In addition, also know, through still having sterilization effect in 5 hours, if but through more than 24 hours then can lose sterilization effect for the no power occasion.Hence one can see that, even in following occasion, be that negative electrode itself does not adhere to polyaniline, its surface attachment of making at conductive material has the block cellular structure of polyaniline to contact with negative electrode, then owing to the electric current that flows through negative electrode also can flow in the conductive material of cellular structure, the activity that has temporarily lost active polyaniline on the cellular structure surface also can be regenerated.
Embodiment 4
With reference to water treatment device shown in Figure 5.In Fig. 5, represent same or analogous parts with Fig. 3,4 identical labels, label 300 is a water treatment device, in this device is to replace electrolyzer assembly parts 100a in the previous embodiment 2 employed water treatment device 100 with electrolyzer assembly parts 300a.
Electrolyzer assembly parts 300a comprises the negative electrode 11 that carbon fiber sheet is made, the overlapping in order block cellular structure 33a that is placed with its carbon fibre pad surface attachment polyaniline laminated film on it, carbon fiber sheet 53, the block cellular structure 33b of its carbon fibre pad surface attachment polyaniline laminated film, carbon fiber sheet 53, the block cellular structure 33c of its carbon fibre pad surface attachment polyaniline laminated film, the anode 12 that woven fiber glass 14 and carbon fiber sheet form, both sides up and down at this laminated piece are clamped by polyvinyl chloride porous plate 50, and the negative electrode 11 that is positioned at groove 17 is fixed in the side of inlet 17a.Here, each block cellular structure 33a～33c makes like this, be 1.65 at proportion promptly, diameter is that weight that the carbon fibre of 18 μ m is made is that the surface attachment thickness of the carbon fibre pads of 2 grams is the polyaniline film of 3 μ m, and the thickness of each cellular structure is 20mm.In addition, negative electrode 11 links to each other with the not shown direct supply that is positioned at groove 17 outsides with anode 12.
The operational process of the water treatment device 100 of the operational process of above-mentioned water treatment device 300 and previous embodiment 2 is basic identical.That is to say that repeatedly by electrolyzer assembly parts 300a, the dissolved oxygen in the treating water 16 contacts with polyaniline (polyaniline film) in the cellular structure 33 treating water 16 repeatedly by pump 15.For this water treatment device 300, even when the negative electrode 11 among the electrolyzer assembly parts 300a, anode 12, carbon fiber sheet 53 anodes 12, carbon fiber sheet 53 or block cellular structure 33a～33c takes place to stop up, also replaceable new electrolyzer assembly parts.
Adopt above-mentioned water treatment device 300, inject the pending former water of 1500cc to handling tank 18, this pending former water adds weight percent in distilled water be that to add weight percent in the salt solution made of 0.9% salt be that 0.2% factory's discharge waters that contain a large amount of general bacteriums are made, and the flow velocity that divides with 2000cc/ flows above-mentioned pending former water cycle.Energising between negative electrode 11 and anode 12 in circulation beginning, the electric current of negative electrode 11 be decided to be-and (current density that flows through electric current in the carbon fibre pad among block cellular structure 33a～33c is-0.62 μ A-cm to 5.0mA -2).In required time to taking a sample the water after the processing of discharging, the treating water of taking a sample is carried out agar cultivate at every turn, measure bacterial count contained in the cultivation aftertreatment water (colony's number: individual/number) from flexible pipe 52.After handling beginning, be 0.2% aforementioned factory discharge water in addition, handle continuously through adding weight percent in 49 hours once more.Culture condition is 36 ℃, 24 hours.The culture experiment result is as shown in table 4 below.
Table 4
Handle the elapsed time Embodiment 2
0 minute (stoste) ??????600
30 minutes ????????3
1 hour ????????0
5 hours ????????0
24 hours ????????0
48 hours ????????0
[adding bacterium (discharge water) through 49 hours again]
After adding again Be added into stoste again ?????1100
1 hour ????????5
3 hours ????????0
24 hours ????????0
According to above result as can be known, if adopt following electricity to touch the groove assembly parts, these electrolyzer assembly parts are to constitute like this, promptly the anode made of negative electrode of in groove cloth shape electrode being made and cloth shape electrode is oppositely arranged, filling replaces that its surface attachment of overlapping placement has the carbon fibre pad of polyaniline and carbon fiber sheet and the multilayer body that forms between them, and when anticathode and anode are suitably switched on, make water repeatedly by the electrolyzer assembly parts with suitable flow velocity, then the general bacterium in the water is killed basically through 30 minutes processing, be killed fully through 1 hour, know also that in addition sterilization effect can keep 48 hours.In addition, even add bacterium again, the adding property of polyaniline can not disappear, and can carry out semi-permanent water germicidal treatment.Have, 3 results compare with previous embodiment again, and treating water 16 current intelligences in the electrolyzer assembly parts in the present embodiment are good, and germicidal treatment efficient improves.
Embodiment 5
With reference to water treatment device shown in Figure 6.This Fig. 6 is a skeleton view.In the drawings, identical with Fig. 5 label is represented same or analogous parts.Label 400 is a water treatment device, the treatment trough 18 that this device is made by the polyethylene that holds treating water (carrying out the water of germicidal treatment) 16, electrolyzer assembly parts 400a, the scupper hose 65 that pump 15 and electrolyzer assembly parts 400a outlet 60b are communicated with constitutes, this pump 15 will be loaded on the treating water 16 in the treatment trough 18 by flexible pipe 51a to be inhaled, and this treating water 16 is sent to the inlet 60a of electrolyzer assembly parts 400a by flexible pipe 51b.
Electrolyzer assembly parts 400a constitutes like this, it comprises square plastic containers (120 * a 70 * 8mm, internal capacity 23ml) 60, in the one opposite flank bigger to area, near the diagonal angle, form inlet 60a and outlet 60b with mutual maintenance maximum spacing ground, centre in this container 60 is provided with cathode assembly (below be called negative electrode 61), it is that to cover polyaniline on two faces of negative electrode of constituting of the plate electrode that forms plating platinum on the titanium mainboard film formed, the both sides of this plate electrode are provided with electrode and are oppositely arranged structural part 70, these structural part 70 relative plate electrodes 61 are the anode 62a that constitutes of spacing plate electrode that platinum plating on the titanium mainboard is formed in accordance with regulations, 62b is oppositely arranged, negative electrode 61 and anode 62a, the 62b direct supply 63 outer with being positioned at plastic containers is communicated with.Here, the cathode surface area of platinum plating plate electrode formation is 84cm 2(12 * 7), the polyaniline film that outer within it two sides forms forms by electrolysis overlay technique [a coincidence coulomb number (Coulombnumber): 3.2 coulombs], and the thickness of this film is 2.7 μ m.
Fig. 7 is the top plan view of electrolyzer assembly parts 400a, as shown in the figure, anode 62a, among the 62b along the end 62c of its vertical side (right side among the figure), other end beyond the 62d is connected with container 60 inwalls, and negative electrode 61 is connected with container 60 inwalls along other end beyond the end 61c of the opposite side (left side among the figure) of its longitudinal direction, makes water 16 at the polyaniline film 61a from two faces of inlet 60a and negative electrode 61,61b contacts, and forms simultaneously towards outlet 60b flow passage 64.
In above-mentioned water treatment device 400, treating water 16 in the treatment trough 18 are sent in the electrolyzer assembly parts 400a by pump 15, and the dissolved oxygen in the treating water is oppositely arranged flow passage 64 that structure 70 forms by electrode and contacts repeatedly with polyaniline film on 61 two faces of negative electrode.
Adopt above-mentioned water treatment device 400, make negative electrode 61 have-(making negative electrode 61 that current density be arranged is-17.8 μ Acm when the electric current of 0.3mA flows through -2Electric current when flowing through), the flow velocity that divides with 30ml/ makes normal saline solution pass through electrolyzer assembly parts 400a inside.The amount of contained hydrogen peroxide is 5ppm in the effusive normal saline solution, has confirmed owing to contact with polyaniline, can generate superoxide (this is based on the principle that generates hydrogen peroxide by homogenizing reaction not from superoxide) in water effectively.In addition, biological salt solution interfacial tension was 70.6dyne/cm before it enters electrolyzer, but after electrolyzer flows out, corresponding value is 54.2dyne/cm.Can in water, generate superoxide effectively even like this, still confirm.
Here, identical with previous embodiment, if adopt following pending former water, this pending former water is that to add weight percent in distilled water be in the salt solution made of 0.9% salt, adding weight percent again is that the 0.2% factory's discharge water that contains general in a large number bacterium is made, and pending former water is carried out germicidal treatment by following mode, this mode is that the flow velocity that pending former water is divided with 30cc/ flows into electrolyzer assembly parts 400a, and the result who is drawn is basic identical with previous embodiment 1～4.In addition here, treating water 16 is not circulated, but can make the treating water 16 of discharging return treatment trough 18 yet, and make the treating water circulation from scupper hose 65.
Though in above any embodiment, maintenance between negative electrode and the anode is switched on continuously, but this not necessarily, also can switch on discontinuously, after energising for some time, when polyaniline can not oxygen reduction, when promptly the bimolecular body of the aniline in the polyaniline reduced form structure does not exist fully, can switch on once more and carry out intermittently power-on.
As mentioned above, if adopt water method for disinfection of the present invention, anode and surface attachment are set in water the contacted negative electrode of polyaniline is arranged, between this anode and negative electrode, intermittently or continuously switch on, the superoxide that generates by the dissolved oxygen in the above-mentioned polyaniline reductive water simultaneously, and the microorganism that is contained in the above-mentioned water is killed, so just need not medicament, and only adopt small voltage just can carry out germicidal treatment expeditiously water.Therefore, the present invention has following effect, promptly can not produce fully and transport, extracts, takes care of etc. relevant safety problem with medicament, or cause environmental pollution problems, can adopt less energy and lower cost that water is carried out germicidal treatment in addition, and very useful water method for disinfection can be provided.
In the water method for disinfection of the invention described above, promptly stir water owing to can be in the preferred state of following institute by means of agitator, thereby produce following effect, even carrying out the water of germicidal treatment contacts with polyaniline expeditiously, make the dissolved oxygen in the water be reduced into superoxide expeditiously, also can effectively improve the contact frequency of microorganism in superoxide and the water in addition, thereby improve germ-killing efficiency.
In the water method for disinfection of the invention described above, because can be in following preferred condition is that negative electrode is the cloth shape, its at least one face is covered with the cloth shape of polyaniline, netted or porous plate-like cathodes, water is flowed by above-mentioned cloth shape, netted or porous plate-like cathodes and polyaniline film, thereby can produce following effect, even carrying out the water of germicidal treatment all fully contacts with polyaniline, base is under the very big situation of the water yield of carrying out germicidal treatment, dissolved oxygen in the water still can be reduced into the change thing expeditiously, and expeditiously the microorganism in the water was killed.
In the water method for disinfection of the invention described above, owing to can be in following preferred condition, even water flows by cloth shape, netted or porous plate-like cathodes and polyaniline film repeatedly, thereby produced following effect, even water all repeatedly fully contacts with polyaniline, make the dissolved oxygen in the water be reduced into superoxide equably, even under the very big situation of the water yield of carrying out germicidal treatment, still can reach the effect that the microorganism in the water is killed basically.
In the water method for disinfection of the invention described above, owing to can be in following preferred condition, promptly on the inside and outside two sides of cloth shape, netted or porous plate-like cathodes, be covered with polyaniline, thereby can obtain following effect, even water is by being located at the polyaniline film on two sides inside and outside the negative electrode, the water that carries out germicidal treatment so all contacts with polyaniline expeditiously, makes the dissolved oxygen in the water be reduced into superoxide in the short period of time, and then shortens the time of microorganism being carried out germicidal treatment.
Making in the water method for disinfection of the invention described above, owing to can be in following preferred condition, be that negative electrode is the cloth shape, netted or porous is tabular, block cellular structure is pressed and above-mentioned cloth shape, a contacted mode of face netted or the porous plate-like cathodes is provided with, this structural part is made of conductive material, its surface attachment has polyaniline, make water pass through above-mentioned cloth shape, netted or porous plate-like cathodes and cellular structure and flow, thereby can obtain following effect, the water that promptly carries out germicidal treatment all fully contacts with polyaniline, dissolved oxygen in the water is reduced into superoxide equably, even under the very big situation of the water yield of carrying out germicidal treatment, still can expeditiously the microorganism in the water be killed.
In the water method for disinfection of the invention described above, owing to can be in following preferred condition, be that water is repeatedly by cloth shape, netted or porous plate-like cathodes and block cellular structure, thereby can obtain following effect, be that whole water repeatedly fully contact with polyaniline, dissolved oxygen in the water is reduced into superoxide equably, even under the very big situation of the water yield of carrying out germicidal treatment, still the microorganism in the water can be killed basically.
In the water method for disinfection of the invention described above, owing to can be in following preferred condition, be that the plate-like cathodes that is covered with polyaniline film on plate-shaped anode and its at least one face is oppositely arranged by following mode, this mode is that polyaniline film is towards anode one side, water passes through from the gap between above-mentioned negative electrode and the anode, thereby can obtain following effect, promptly at water during by the plate-like cathodes that is oppositely arranged and the gap between the anode, water carries out being in contact with one another of long period with the polyaniline film that covers on cathode plane, dissolved oxygen in the water is reduced into superoxide expeditiously, thereby can expeditiously the microorganism in the water be killed.
According to first kind of water treatment device of the present invention, because this device comprises the tank that holds the water that carries out germicidal treatment, at least a portion anode immerses in the above-mentioned water, its surface attachment has polyaniline film and this polyaniline film to immerse negative electrode in the above-mentioned water, the power supply of electric current is provided to above-mentioned anode and negative electrode, thereby can obtain following effect, can carry out water method for disinfection of the present invention in reasonably stability ground.Aforesaid method can with above-mentioned water in dissolved oxygen reaction and the polyaniline of oxidation is regenerated as the polyaniline that can restore dissolved oxygen, simultaneously the microorganism in the water is killed.
In first kind of water treatment device of the invention described above, owing to can be in following preferred condition, the agitator that water is stirred promptly is set, thereby can obtain following effect, even carrying out the water of germicidal treatment contacts with polyaniline expeditiously, dissolved oxygen in the water is reduced into superoxide expeditiously, can also increase the contact frequency of microorganism in superoxide and the water in addition, and then improves the efficient of killing kill microorganism in the water.
According to second kind of water treatment device of the present invention, comprise the electrolyzer assembly parts, these electrolyzer assembly parts are to constitute like this, promptly on groove, be formed with second opening that water is entered first opening in it and the water in the groove is discharged outside groove, be covered with the cloth shape of polyaniline film at least one face, negative electrode netted or that porous is tabular is located at a side of above-mentioned first opening, the cloth shape, anode netted or that porous is tabular is located at a side of above-mentioned second opening, thereby make the water that enters in the groove from above-mentioned first opening pass through above-mentioned cloth shape, netted or porous is tabular negative electrode and polyaniline film, and by above-mentioned cloth shape, the anode netted or porous is tabular, and outside the above-mentioned second opening drain tank, said apparatus comprises that also anode and negative electrode provide galvanic direct supply, deposit the tank of the water that carries out germicidal treatment, water is inhaled and is sent into the pump of first opening of electrolyzer from this tank, thereby can obtain following effect, water method for disinfection reasonably stability of the present invention ground is carried out, this method makes water be covered with the cloth shape of polyaniline by its at least one face, the cathode flow netted or porous is tabular, thus the microorganism in the water is killed.In addition in the following cases, promptly electrode materials in the electrolyzer assembly parts or polyaniline, are easy to these electrolyzer assembly parts are replaced with new electrolyzer assembly parts when electrode or polyaniline film take place to stop up through degradation after a while.
In second kind of water treatment device of the invention described above, owing to can be in following preferred condition, promptly be provided with water shoot, second open communication in this water shoot and the electrolyzer assembly parts, thereby the water of discharging from these electrolyzer assembly parts can be entered in the tank, can obtain following effect like this, the water that promptly carries out germicidal treatment is easily repeatedly by the electrolyzer assembly parts, water method for disinfection reasonably stability of the present invention ground is carried out, this method makes water be covered with the cloth shape of polyaniline repeatedly by its at least one face, the cathode flow netted or porous is tabular, thus the microorganism in the water is killed.
In second kind of water treatment device of the invention described above, owing to can be in following preferred condition, it is the cloth shape, inside and outside two faces netted or the porous plate-like cathodes are covered with polyaniline film, these outer within it two faces are covered with the cloth shape of polyaniline film, negative electrode netted or that porous is tabular is to be provided with like this, be that water is successively by the polyaniline film of being located at above-mentioned inside and outside two faces in the above-mentioned electrolyzer, thereby can obtain following effect, the water that promptly carries out germicidal treatment contacts with polyaniline expeditiously, dissolved oxygen in the water is reduced into superoxide at short notice, thereby has shortened the treatment time of kill microorganisms.
According to the third water treatment device of the present invention, because this device comprises the electrolyzer assembly parts, these electrolyzer assembly parts are to constitute like this, be to be formed with first opening of in it, introducing water on the groove, with second opening that the water in the groove is discharged outside groove, the cloth shape, negative electrode netted or that porous is tabular is located at a side of above-mentioned first opening, the cloth shape, anode netted or that porous is tabular is located at a side of above-mentioned second opening, block cellular structure is to be provided with the contacted mode of above-mentioned negative electrode, this structural part is between above-mentioned negative electrode and anode, it is made by conductive material, its surface attachment has polyaniline, water in the above-mentioned first opening lead-ingroove passes through above-mentioned cloth shape, the negative electrode netted or porous is tabular, the cellular structure bigger with above-mentioned thickness, and by the cloth shape, the anode netted or porous is tabular, discharge outside groove from above-mentioned second opening afterwards, said apparatus also comprises to above-mentioned anode and negative electrode provides galvanic direct supply, deposit the tank of the water that carries out germicidal treatment, water is inhaled from this tank, and be transported to the pump of first opening in the electrolyzer, thereby can obtain following effect, water method for disinfection reasonably stability of the present invention ground is carried out, this method makes above-mentioned water by the cloth shape, negative electrode and block cellular structure netted or that porous is tabular flow, thereby the microorganism in the water is killed, above-mentioned block cellular structure is provided with in a contacted mode of face with negative electrode, it is made by conductive material, its surface attachment has polyaniline, in addition in the following cases, promptly electrode materials in the electrolyzer assembly parts or the constituent material in the cellular structure are through after a while operating performance variation, during situations such as electrode or cellular structure generation obstruction, can easily these electrolyzer assembly parts be replaced with new electrolyzer assembly parts.
In the third water treatment device of the present invention, owing to can be in following preferred condition, promptly be provided with water shoot, second open communication of this water shoot and electrolyzer assembly parts, thereby the water of discharging from above-mentioned electrolyzer assembly parts can be introduced above-mentioned tank, can obtain following effect like this, even the water that carries out germicidal treatment is easily repeatedly by the electrolyzer assembly parts, water method for disinfection reasonably stability of the present invention ground is carried out, this method can make water repeatedly by the cloth shape, negative electrode and block cellular structure netted or that porous is tabular flow, thereby the microorganism in the water is killed, above-mentioned cellular structure is provided with in a contacted mode of face with negative electrode, made by conductive material, its surface attachment has polyaniline.
In the third water treatment device of the invention described above, owing to can be in following preferred condition, be that electrolyzer is to be provided with like this, its surface attachment between negative electrode and anode has the block cellular structure of polyaniline, the overlapping cloth shape of making by conductive material that is provided with of multilayer between it, the tabular assembly of netted or porous, thereby can obtain following effect, even promptly under the less situation of each block cellular structure thickness, still can obtain the total thickness of the block cellular structure between negative electrode and anode by the stacked number of plies that increases block cellular structure, even under the bigger situation of the thickness of the block cellular structure between negative electrode and the anode, water is the cloth shape by making at the conductive material that has between the block cellular structure of less thickness smoothly still generally, the tabular assembly of netted or porous, thereby smoothly by whole electrolyzer.
According to the 4th kind of water treatment device of the present invention, this device comprises the electrolyzer assembly parts, these electrolyzer assembly parts are to constitute like this, be to be formed with first opening that water is entered its mouthful on the groove, with second opening that the water in the groove is discharged outside groove, be provided with electrode in this groove and be oppositely arranged structural part, it is relatively set with the plate-like cathodes that is coated with polyaniline film on plate-shaped anode and its at least one face by following mode with prescribed distance, this mode is that above-mentioned polyaniline film is towards above-mentioned anode one side, water in the above-mentioned first opening lead-ingroove is by after being oppositely arranged the plate-like cathodes and the gap between the plate-shaped anode on the structural part at electrode, discharge outside groove with second opening, said apparatus also comprises makes the direct supply of switching between above-mentioned anode and the negative electrode, from the tank of depositing the water that carries out germicidal treatment with above-mentioned suction waterborne, and enter the pump of first opening of above-mentioned electrolyzer, thereby can obtain following effect, water method for disinfection reasonably stability of the present invention ground is carried out, this method can make above-mentioned water be covered with gap between the plate-like cathodes of polyaniline by plate-shaped anode and one face, above-mentioned anode and negative electrode are provided with by the mode of polyaniline towards anode one side, thereby the microorganism in the water is killed, when the electrode materials in the electrolyzer assembly parts or polyaniline film during, can at an easy rate these electrolyzer assembly parts be replaced with new electrolyzer assembly parts in addition through after a while operating performance variation.
In the 4th kind of water treatment device of the invention described above, owing to can be in following preferred condition, be that the electrolyzer assembly parts are to constitute like this, be provided with a plurality of electrodes in it and be oppositely arranged structural part, water can be oppositely arranged plate-shaped anode on the structural part and the gap between the plate-like cathodes by laying respectively at a plurality of electrodes, thereby can obtain following effect, the duration of contact of promptly carrying out the water of germicidal treatment and polyaniline is longer, make the dissolved oxygen in the water be reduced into superoxide expeditiously, thereby can improve the efficient of killing of microorganism.
In the first～four kind of water treatment device of the invention described above, owing to can be in following preferred condition, promptly be provided with strainer, this strainer can be with the undesirable suspended substance removal in the close second opening water in the groove in the electrolyzer assembly parts, thereby can obtain following effect, promptly in water germicidal treatment process, the dust in the water, foreign matter or microorganism remains can be filtered out, thereby can make water become limpider.
In the first～four kind of water treatment device of the invention described above, owing to can be in following preferred condition, being the electrolyzer assembly parts is communicated with the strainer of undesirable suspended substance removal the water of discharging from this groove second opening, thereby can obtain following effect, promptly in water germicidal treatment process, the dust in the water, foreign matter or microorganism remains can be filtered out, thereby make water become limpider.

Claims (20)

1. water method for disinfection, this method may further comprise the steps, anode and its surface and the contacted negative electrode of polyaniline are set in water, between this anode and negative electrode intermittently or energising continuously, simultaneously by polyaniline reduce in the above-mentioned water dissolved oxygen and the superoxide that generates kills microorganism contained in the above-mentioned water.
2. method according to claim 1 is characterized in that by agitator water being stirred.
3. method according to claim 1 is characterized in that above-mentioned negative electrode is cloth shape, the netted or porous plate-like cathodes that one face is covered with polyaniline film, and water is flowed by above-mentioned cloth shape, netted or porous plate-like cathodes and polyaniline film.
4. method according to claim 3 is characterized in that making water to flow by cloth shape, netted or porous plate-like cathodes and polyaniline film repeatedly.
5. method according to claim 3 is characterized in that cloth shape, the inside and outside two sides of netted or porous plate-like cathodes are covered with polyaniline film.
6. method according to claim 1, it is characterized in that above-mentioned negative electrode is cloth shape, netted or porous plate-like cathodes, by block cellular structure being set with above-mentioned cloth shape, netted or contacted mode of face of porous plate-like cathodes, it is made by conductive material, its surface attachment has polyaniline, and water flows by above-mentioned cloth shape, netted or porous plate-like cathodes and block cellular structure.
7. method according to claim 6 is characterized in that making water to flow by cloth shape, netted or porous plate-like cathodes and block cellular structure repeatedly.
8. method according to claim 1, it is characterized in that the plate-like cathodes that is covered with polyaniline film on plate-shaped anode and its at least one face is oppositely arranged by following mode, this mode be above-mentioned polyaniline film towards above-mentioned anode one side, make water pass through gap between above-mentioned negative electrode and the anode.
9. dedicated water treatment unit of method according to claim 1, it comprises the tank of depositing the water that carries out germicidal treatment, immerse the anode that is provided with in the above-mentioned water to small part, its surface attachment has polyaniline film and this polyaniline film to immerse the negative electrode that is provided with in the above-mentioned water, and the power supply of electric current is provided to above-mentioned anode and negative electrode.
10. device according to claim 8 is characterized in that it is provided with the agitator that can stir water.
11. dedicated water treatment unit of method according to claim 1, it is characterized in that this device comprises the electrolyzer assembly parts, this electrolyzer assembling is to constitute like this, be formed with second opening that water is introduced first opening in it and the water in the groove is discharged on the groove outside groove, its at least one face is covered with the cloth shape of polyaniline film, netted or porous plate negative electrode is located at a side of above-mentioned first opening, the cloth shape, netted or porous plate-shaped anode is located at a side of above-mentioned second opening, water in the above-mentioned first opening lead-ingroove passes through above-mentioned cloth shape, netted or porous plate-like cathodes and polyaniline film, and by above-mentioned cloth shape netted or porous plate-shaped anode and outside groove, discharging from above-mentioned second opening, said apparatus also comprises the power supply that electric current is provided to above-mentioned anode and negative electrode, deposit the tank of the water that carries out germicidal treatment, water is inhaled from above-mentioned tank, and sent into the pump of first opening part of above-mentioned electrolyzer assembly parts.
12. device according to claim 11 is characterized in that it is provided with water shoot, second open communication in this water shoot and the electrolyzer assembly parts, thus will enter tank from the water that above-mentioned electrolyzer assembly parts are discharged.
13. according to claim 11 or 12 described devices, it is characterized in that being covered with polyaniline film on cloth shape, inside and outside two sides netted or the porous plate-like cathodes, above-mentioned inside and outside two sides is covered with the cloth shape of polyaniline film, netted or porous plate-like cathodes is provided with by following mode, and this mode is that water is successively by the polyaniline film of being located at above-mentioned inside and outside two sides in the above-mentioned electrolyzer assembly parts.
14. dedicated water treatment unit of method according to claim 1, it is characterized in that this device comprises the electrolyzer assembly parts, these electrolyzer assembly parts are to constitute like this, be formed with second opening that water is introduced first opening in it and the water in the groove is discharged on the groove outside groove, the cloth shape, netted or porous plate-like cathodes is located at a side of above-mentioned first opening, the cloth shape, netted or porous plate-shaped anode is located at a side of above-mentioned second opening, block cellular structure is by being provided with the contacted mode of above-mentioned negative electrode, this cellular structure is between above-mentioned anode and negative electrode, it is made by conductive material, its surface attachment has polyaniline, the water of sending in the groove from above-mentioned first opening passes through the cloth shape, netted or porous plate-like cathodes and above-mentioned cellular structure, and by the cloth shape, netted or porous plate-shaped anode, discharge outside groove from above-mentioned second opening afterwards, said apparatus also comprises the power supply that electric current is provided to above-mentioned anode and negative electrode, deposit the tank of the water that carries out germicidal treatment, water is inhaled from above-mentioned tank, and sent into the pump of first opening part of above-mentioned electrolyzer assembly parts.
15. device according to claim 14 is characterized in that it is provided with water shoot, second open communication in this water shoot and the electrolyzer assembly parts, thus will enter in the tank from the water that above-mentioned electrolyzer assembly parts are discharged.
16. according to claim 14 or 15 described devices, it is characterized in that electrolyzer is to be provided with like this, i.e. the cloth shape that the stacked conductive material of multilayer is made between block cellular structure, netted or porous plate-like piece, this cellular structure is between negative electrode and anode, and its surface attachment has polyaniline.
17. dedicated water treatment unit of method according to claim 1, it is characterized in that this device comprises the electrolyzer assembly parts, these electrolyzer assembly parts are to constitute like this, be formed with second opening that water is introduced first opening in it and the water in the groove is discharged on the groove outside groove, be provided with electrode in the above-mentioned groove and be oppositely arranged structural part, this electrode is oppositely arranged on the structural part with prescribed distance and is relatively set with the plate-like cathodes that plate-shaped anode and its at least one face are covered with polyaniline film by following mode, this mode is that above-mentioned polyaniline is towards above-mentioned anode one side, water in the above-mentioned first opening lead-ingroove is by after being oppositely arranged the plate-like cathodes and the gap between the plate-shaped anode on the structural part at above-mentioned electrode, discharge outside groove from first opening, said apparatus comprises that also anode and negative electrode provide the power supply of electric current, water is inhaled and sent into the pump of first opening part of electrolyzer assembly parts from the tank of depositing the water that carries out germicidal treatment.
18. device according to claim 17, it is characterized in that the electrolyzer assembly parts are to constitute like this, be to be provided with a plurality of electrodes in it to be oppositely arranged structural part, water is oppositely arranged plate-like cathodes on the structural part and the gap between the plate-shaped anode by laying respectively at electrode.
19. according to the described device of arbitrary claim in the claim 9～18, it is characterized in that it is provided with strainer, this strainer can be with the undesirable suspended substance removal in the close water of second opening in the groove of electrolyzer assembly parts.
20. according to the described device of arbitrary claim in the claim 9～18, it is characterized in that the electrolyzer assembly parts are communicated with strainer, this strainer will be from the undesirable suspended substance removal the water that electrolyzer assembly parts second opening is discharged.
CN96122055A 1996-08-07 1996-09-09 Method for degerming by water and processing device used by said method Pending CN1172774A (en)

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JP20824396 1996-08-07
JP208243/96 1996-08-07

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