CN104891610A - Heterotopic electro-flocculation device and method - Google Patents
Heterotopic electro-flocculation device and method Download PDFInfo
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- CN104891610A CN104891610A CN201510271605.9A CN201510271605A CN104891610A CN 104891610 A CN104891610 A CN 104891610A CN 201510271605 A CN201510271605 A CN 201510271605A CN 104891610 A CN104891610 A CN 104891610A
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Abstract
The invention relates to a heterotopic electro-flocculation device comprising a tank body (1) and at least one pair of electrode plates (2) located inside the tank body (1), wherein the at least one pair of electrode plates (2) are respectively connected with the anode and cathode of a power source; the electrode plate at least connected with the anode of the power source is made of ferrum, aluminum or ferrum-aluminum alloy; and the heterotopic electro-flocculation device is also provided with a gas introducing pipe (5). The invention also relates to a heterotopic electro-flocculation method for realizing heterotopic electro-flocculation on wastewater by using the heterotopic electro-flocculation device, wherein acid gases are introduced to the wastewater through the gas introducing pipe (5). Preferably, the electrode plates in the device disclosed by the invention are hollow electrode plates, and the acid gases are introduced from gas inlets (3) of the hollow electrode plates. The device and method disclosed by the invention can be used for realizing heterotopic flocculation.
Description
Technical field
The invention belongs to sewage treatment equipment and treatment process field.
Background technology
Flocculence is the common methods of process waste water.Conventional chemical flocculation is in waste water, add various flocculation agent, such as polymerize aluminum chloride, poly-ferric chloride, polyaluminum sulfate aluminium chloride ferrum etc., iron ion in these flocculation agents or aluminum ion are all easily hydrolyzed and generate ironic hydroxide or aluminium hydroxide, and there is flocculation sediment along with increasing of its amount, in flocculation sediment process, by to adsorb and volume sweeps effect, by the particulate material in waste water and some adsorbable substance transfer in throw out, play the effect of purifying liquid waste.But chemical flocculation often introduces other negatively charged ion in waste water, such as chlorion or sulfate ion, these ions additionally introduced, finally also need removing, bring the trouble of subsequent disposal.
In recent years, in order to avoid the above-mentioned defect of chemical flocculation, electric flocculence is developed.Its principle is immersed in waste water using iron, aluminium or ferro-aluminium as the anode of electrolyzer, discharges Fe by anodizing
2+and/or Al
3+, Fe
2+be easy to again be oxidized to Fe
3+, they so be hydrolyzed into corresponding oxyhydroxide, occur flocculation sediment.It is except iron ion or aluminum ions source difference, and ultimate principle is identical with chemical flocculation with process.
During electricity flocculence process waste water, often face the difficulty in concrete operations.A difficulty is, in flocculation process, the colloidalmaterial in waste water or organic thick substances or flocs unit easily as silting at the electrode surface, prevent ferrous ion and/or aluminum ion from the further stripping pole plate.Another difficulty is, industrial in order to improve electric flocculation efficiency, usually uses tens of to hundreds of battery lead plates in a flocculation tank side by side, the Fe of stripping simultaneously
2+and/or Al
3+, Fe
2+be easy to again be oxidized to Fe
3+, these metallic cations are hydrolyzed further and flocculate, and because electric flocculation process occurs in electric flocculation reactor inside, a large amount of flocculating settling things is easy to deposit between thickly dotted battery lead plate, causes operating process to interrupt, and has to clear up.For solving the problem, usually adopt mechanical process and ultrasonic method to clear up polar board surface, but such cleaning is wasted time and energy very much, and or electrode surface is damaged, or need extra ultrasonic device is installed, increase cost.
Outside electricity flocculation plant internal electrical throwing out, also there is electrooxidation effect to a certain degree.The mechanism of action of electrochemical oxidation process mainly produces superoxide radical (O2), H by the effect of electrode materials
2o
2, hydroxyl radical free radical (OH) isoreactivity group is oxidized organism in water body.The method only occurs in water, and does not need separately to add catalyzer, avoids secondary pollution.Because its controllability is strong, non-selectivity, the advantages such as mild condition, so have reasonable treatment effect for the organism of bio-refractory.But, usually meet with two problems in actual applications: one is pole plate passivation problem, colloidalmaterial in waste water or organic thick substances or flocculate precipitate easily as silting on negative electrode and anode, negative electrode and anode are stuck with paste, if irregularly cleared up, the contact of battery lead plate and waste water can be had a strong impact on, reduce electrode efficiency.Another is the problem of concentration polarization, that is, superoxide radical (O2), the H of battery lead plate generation
2o
2, hydroxyl radical free radical (OH) isoreactivity group, usually can only work within the scope of distance electrode plate surface number millimeter, and the organism contained in waste body outside this distance range cannot touch these active groups in fact, therefore be also difficult to oxidized, unless they to move near battery lead plate within several millimeters of scopes by diffusion.Pole plate passivation problem and concentration polarization problem all cause electrooxidation decrease in efficiency.
The present invention develops a kind of dystopy innovatively and to flocculate electric flocculator and dystopy electro-flucculation process, can solve above-mentioned realistic problem.
Summary of the invention
A first aspect of the present invention provides a kind of dystopy to flocculate electric flocculation plant, it comprises cell body (1), is positioned at inner at least one pair of battery lead plate (2) of described cell body (1), this at least one pair of battery lead plate (2) connects positive pole and the negative pole of power supply respectively, the material wherein at least connecting the battery lead plate of positive source is iron, aluminium or ferro-aluminium, and the wherein said dystopy electric flocculation plant that flocculates also has gas inlet pipe (5).
In the present invention, described battery lead plate can be solid battery lead plate, also can be hollow electrode plate.
In a preferred embodiment of the invention, described battery lead plate (2) is hollow electrode plate, this hollow electrode plate has the gas inlet (3) be communicated with its internal cavities, each sidewall of this hollow electrode plate all has several cinclides (4), cinclides (4) is lateral aperture or angling hole.
In a preferred embodiment of the invention, multipair described hollow electrode plate is spaced from each other a distance and is arranged side by side, and the cinclides (4) on the sidewall of adjacent hollow battery lead plate is arranged with being staggered each other.
In a preferred embodiment of the invention, described gas inlet pipe (5) is arranged on cell body (1).When using described hollow electrode plate, also can using described gas inlet (3) as described gas inlet pipe (5).
A second aspect of the present invention provides a kind of dystopy electro-flucculation process, the method uses the dystopy electric flocculation plant that flocculates to implement, the flocculation of this dystopy flocculation electricity comprises cell body (1), is positioned at inner at least one pair of battery lead plate (2) of described cell body (1), this at least one pair of battery lead plate (2) connects positive pole and the negative pole of power supply respectively, the material wherein at least connecting the battery lead plate of positive source is iron, aluminium or ferro-aluminium, and the wherein said dystopy electric flocculation plant that flocculates also has gas inlet pipe (5); In operating process, in pending waste water, pass into sour gas via this gas inlet pipe (5), described sour gas is selected from carbonic acid gas, sulfurous gas or combustion tail gas.
A third aspect of the present invention also provides a kind of dystopy electro-flucculation process, the method uses the dystopy electric flocculation plant that flocculates to implement, the flocculation of this dystopy flocculation electricity comprises cell body (1), be positioned at least one pair of battery lead plate (2) that described cell body (1) is inner, this at least one pair of battery lead plate (2) connects positive pole and the negative pole of power supply respectively, the material wherein at least connecting the battery lead plate of positive source is iron, aluminium or ferro-aluminium, wherein said battery lead plate (2) is hollow electrode plate, this hollow electrode plate has the gas inlet (3) be communicated with its internal cavities, each sidewall of this hollow electrode plate all have several cinclides (4), cinclides (4) is lateral aperture or angling hole, in operating process, in pending waste water, pass into sour gas via this gas inlet (3), described internal cavities and described cinclides (4) successively, described sour gas is selected from carbonic acid gas, sulfurous gas or combustion tail gas.
In a preferred embodiment of the invention, in other container by leave described dystopy flocculate electric flocculator waste water pH value raise, there is flocculating settling.
In specific embodiment of the invention scheme, the diameter of described cinclides 4 can be adjusted as required by technician, and can be such as 0.05mm-0.5mm, be preferably 0.05mm-0.2mm, be more preferably 0.1mm.
In a preferred embodiment of the invention, the cinclides (4) on the sidewall of adjacent hollow battery lead plate is staggered layout each other.This layout that is staggered can be that level attitude is staggered, vertical position is staggered, or the two has concurrently.
In embodiments of the invention, in at least one pair of battery lead plate described, the battery lead plate be at least connected with positive source is solubility battery lead plate, such as its material can be aluminium, iron or ferro-aluminium, and the battery lead plate be connected with power cathode can be noble electrode plate, such as its material can be the inertia material of graphite or titanium or other not stripping.Preferably, the material of at least one pair of battery lead plate described is all selected from aluminium, iron or ferro-aluminium, and realizes the even consumption of positive-negative electrode plate by periodically exchanging positive and negative electrode.
In a preferred embodiment of the invention, can also directly waste water and sour gas be passed in the gas inlet of described hollow electrode plate jointly, and the common internal cavities via hollow electrode plate and cinclides flow in described cell body.
To pass into CO2 in pending waste water, the working process specifically introducing equipment of the present invention and method is as follows:
In the electric flocculation reactor of routine, when using solubility electrode such as iron electrode, aluminium electrode or ferro-aluminium electrode, electrolysis stripping Fe
2+and/or Al
3+, wherein Fe
2+be easy to again be oxidized to Fe
3+.Contriver finds after studying the observed data of long term accumulation, in the scope of wastewater pH=6.5-7.5, and Al
3+can occur significant flocculating settling reaction, pH lower than 6.5 time, Al
3+although also have partial hydrolysis, obvious flocculating settling can not be there is, estimate now Al
3+hydrolysate be partial hydrolysate, namely with Al (OH)
2+or Al (OH)
2 +form exist, the physical aspect of these partial hydrolysates is relatively stable suspension " colloid " but not " flocculate precipitate " more, only have to pH higher than 6.5 time, just have a large amount of Al (OH)
3formed and produce obvious flocculation sediment.When pH higher than 7.5 time, owing to being amphoteric hydroxide, Al (OH)
3can dissolve on the contrary, the effect of the flocculating settling that can not recur.Contriver finds through research equally, in the scope of pH=3.5-6.5, and Fe
2+and Fe
3+can be hydrolyzed, all belong to partial hydrolysis, and though have throw out to produce throw out in waste water in suspended state, can not precipitate in a large number.Until pH higher than 6.5 time, Fe
2+and Fe
3+just can there is the hydrolysis of remarkable ratio and produce significant precipitation, to pH higher than 8.5 time, Fe
2+and Fe
3+can complete hydrolysis also precipitate completely.
Contriver, based on above-mentioned data results, creatively proposes the technical scheme passing into sour gas and regulate waste water ph to flocculate to realize dystopy.For CO2, in water, pass into CO2 under normal pressure to saturated, its pH is about 5.6; In water, pass into CO2 under elevated pressure, its pH even can be low to moderate 3.7.Therefore, after passing into CO2, effectively Al can be avoided completely
3+there is the pH scope 6.5-7.5 of remarkable flocculating settling, when using aluminium electrode in electric flocculator, just can realize stripping Al from electrode
3+, be under the condition of 5.6 at pH in electric flocculator, this Al
3+only generating portion hydrolysis; but there is not flocculation sediment; flow out until waste water and after this electric flocculator, to enter into a relatively spacious container; by heightening pH value, (such as decompression or intensification make CO2 overflow again; or mix neutrality material such as mix calcium carbonate granule or mix another strand of alkaline waste water; etc.), make Al
3+there is complete hydrolysis and flocculation sediment.Thus, dystopy flocculation is achieved.In like manner, when using iron electrode in electric flocculator, the pH regulator to 5.6 of waste water is not enough to stop Fe completely although pass into CO2
2+and Fe
3+hydrolysis, but at least can avoid them that hydrolysis and the flocculation sediment of remarkable ratio occur, also part alleviates the flocculation sediment in electric flocculator inside.Flow out until waste water and after this electric flocculator, to enter into a relatively spacious container; by heightening pH value, (such as decompression or intensification make CO2 overflow again; or mix neutrality material such as mix calcium carbonate granule or mix another strand of alkaline waste water, etc.), make Fe
2+and Fe
3+there is complete hydrolysis and flocculation sediment.Thus, dystopy flocculation is achieved at least in part.In like manner, when using iron aluminium aggregated electrode in electric flocculator, also can achieve dystopy flocculation at least in part.
In like manner, when passing into the gas such as sulfurous gas, combustion tail gas (such as stack gas) in waste water, same or similar dystopy flocculating effect can also be realized.
When using hollow electrode plate in electric flocculator, the gas inlet 3 of this hollow electrode plate being passed into sour gas as described gas inlet pipe 5, equally also can realize same or similar dystopy flocculating effect.
Beneficial effect of the present invention is as follows:
1, dystopy flocculation: as mentioned above, the present invention by setting up gas inlet pipe and pass into sour gas in pending waste water in electric flocculation plant, dystopy flocculation can be realized, make throw out flocculation sediment in the relatively spacious independent container in electric flocculator downstream, avoid throw out to be deposited on battery lead plate or be deposited on electric flocculator inside, and then alleviating baroque electric flocculator cleaning burden.
2, electrode efficiency improves: when using hollow electrode plate in electric flocculator and pass into sour gas from the gas inlet (3) of this hollow electrode plate, the gas passed into enters into pending waste water via the internal cavities of described gas inlet, described hollow electrode plate and described cinclides successively, can also souring be played, prevent polar board surface alluvial dirt.When the sour gas passed into is high pressure, because the cinclides on the relative two sides of two blocks of hollow electrode plates respect to one another is staggered setting, therefore from the battery lead plate of the air scour offside of cinclides high speed ejection, remove the burs such as the mud on offside electrode plate surface, prevent pole plate passivation and the current efficiency that causes due to pole plate passivation declines; This high-speed jet effect also plays stirring action to the waste water between adjacent electrode plates, promotes the exchange of the waste water of waste body and battery lead plate wall surface, slows down concentration polarization problem thus.When the sour gas passed into is low pressure, from cinclides 4, escaping gas may be not enough to jet on offside battery lead plate, but the fluid of effusion can wash away the mud of this battery lead plate self along the floating of self electrode wooden partition, prevents pole plate passivation by this autologous mode of washing away.No matter be high pressure gas or low-pressure gas, because there being certain pressure to exist, all can preventing pending waste water from entering in the internal cavities of described hollow electrode plate from described cinclides, avoiding the deposition of pollutent in hollow electrode intralamellar part cavity.Eliminate pole plate passivation and alleviate concentration polarization, no matter for electricity flocculation or electrooxidation, being all conducive to improving electrode efficiency.
3, security improves: battery lead plate also inevitably occurs for some electrolysis liberation of hydrogen oxygen evolution reaction, i.e. reactions of brine electrolysis, and the hydrogen of precipitation and oxygen run up to finite concentration and has explosion hazard in electric flocculation reactor, i.e. so-called " hydrogen is quick-fried ".By passing into CO2 in waste water, the part CO2 exceeding the solubleness of CO2 in waste water can exist with gas phase, can effectively dilute above-mentioned hydrogen and oxygen, avoids that hydrogen occurs quick-fried.
Accompanying drawing explanation
Fig. 1 is that dystopy of the present invention is flocculated the structural representation of electric flocculation plant.
Fig. 2 is that the dystopy of employing hollow electrode plate of the present invention is flocculated the structural representation of the hollow electrode plate in electric flocculation plant.
Fig. 3 is after the hollow porous pole plate shown in Fig. 2 is cut open along M-M line and the view of looking along direction shown in arrow.
Fig. 4 is after the hollow porous pole plate shown in Fig. 2 is cut open along N-N line and the view of looking along direction shown in arrow.
Fig. 5 is after the hollow porous pole plate shown in Fig. 2 is cut open along K-K line and the view of looking along direction shown in arrow, which show respectively horizontal cinclides and the respective independently cinclides decoration form of inclination cinclides two kinds.
Fig. 6 is that the dystopy of employing hollow electrode plate of the present invention is flocculated the schematic diagram of electric flocculation plant, and which schematically illustrates 8 hollow porous pole plates placed side by side, be staggered between wherein adjacent cinclides setting.
In figure, Reference numeral implication is as follows:
1-cell body; 2-battery lead plate; 3-gas inlet; 4-cinclides; 5-gas inlet pipe.
Embodiment
Be described in further details the present invention below in conjunction with embodiment and accompanying drawing, embodiment is only limitted to the present invention is described, but not limitation of the invention.
Embodiment 1
Adopt the dystopy of the employing solid electrode plate shown in Fig. 1 to flocculate electric flocculation plant process waste water, this solid electrode plate is ferro-aluminium pole plate, and number is 150, and the volts DS applied between often pair of pole plate is about 1.5V.And pass into normal pressure CO2 gas from the gas inlet pipe be positioned at bottom cell body 1, the pH of waste water is adjusted to about 5.8.In experiment, observation finds, in this electric flocculation plant, little flocculation phenomenon only occurs, and is embodied in waste water and only slightly becomes muddy, but substantially do not precipitate.The waste water leaving this electric flocculation plant is passed in another container, wherein contain a large amount of calcium carbonate granule to promote pH value, find a large amount of flocculation sediment phenomenon occurs in this embodiment.
Embodiment 2
Adopt the dystopy of the employing hollow electrode plate shown in Fig. 6 to flocculate electric flocculation plant process waste water, pole plate is ferro-aluminium pole plate, and number is 150, and the volts DS applied between often pair of pole plate is about 1.5V.Pass into normal pressure CO2 from the gas inlet 3 of hollow pole plate, and pass in pending waste water through the internal cavities of hollow pole plate and cinclides successively.The pH of waste water is adjusted to about 5.8.In experiment, observation finds, in this electric flocculation plant, little flocculation phenomenon only occurs, and is embodied in waste water and only slightly becomes muddy, but substantially do not precipitate.The waste water leaving this electric flocculation plant is passed in another container, wherein contain some calcium carbonate granules to promote pH value, find a large amount of flocculation sediment phenomenon occurs in this embodiment.Also observe in experiment, due to the souring of CO2 air-flow, electrode plate surface does not almost have dirt alluvial phenomenon, maintains its surface cleaning.
From above-mentioned experiment, apparatus and method of the present invention, successfully can realize dystopy flocculation.And when adopting hollow electrode plate, can also wash away or autologous souring because of the offside of the sour gas passed into, effectively eliminating pole plate passivation phenomenon, and greatly alleviate concentration polarization phenomenon.Therefore, the dissolution efficiency of battery lead plate is promoted greatly.
Claims (10)
1. a dystopy is flocculated electric flocculation plant, it is characterized in that, it comprises cell body (1), is positioned at inner at least one pair of battery lead plate (2) of described cell body (1), this at least one pair of battery lead plate (2) connects positive pole and the negative pole of power supply respectively, the material wherein at least connecting the battery lead plate of positive source is iron, aluminium or ferro-aluminium, and the wherein said dystopy electric flocculation plant that flocculates also has gas inlet pipe (5).
2. dystopy according to claim 1 is flocculated electric flocculation plant, it is characterized in that, described battery lead plate (2) is hollow electrode plate, this hollow electrode plate has the gas inlet (3) be communicated with its internal cavities, each sidewall of this hollow electrode plate all has several cinclides (4), cinclides (4) is lateral aperture or angling hole.
3. dystopy according to claim 2 is flocculated electric flocculation plant, and it is characterized in that, multipair described hollow electrode plate is spaced from each other a distance and is arranged side by side, and the cinclides (4) on the sidewall of adjacent hollow battery lead plate is arranged with being staggered each other.
4. dystopy according to claim 1 is flocculated electric flocculation plant, and it is characterized in that, described gas inlet pipe (5) is arranged on cell body (1).
5. dystopy according to claim 2 is flocculated electric flocculation plant, it is characterized in that, using described gas inlet (3) as described gas inlet pipe (5).
6. dystopy according to claim 2 is flocculated electric flocculation plant, and wherein said cell body 1 and described hollow electrode plate are except fluid inlet and outlet, and its entirety is airtight.
7. a dystopy electro-flucculation process, it is characterized in that, it uses dystopy electric flocculation plant that flocculates to implement, the flocculation of this dystopy flocculation electricity comprises cell body (1), is positioned at inner at least one pair of battery lead plate (2) of described cell body (1), this at least one pair of battery lead plate (2) connects positive pole and the negative pole of power supply respectively, the material wherein at least connecting the battery lead plate of positive source is iron, aluminium or ferro-aluminium, and the wherein said dystopy electric flocculation plant that flocculates also has gas inlet pipe (5); In operating process, in pending waste water, pass into sour gas via this gas inlet pipe (5), described sour gas is selected from carbonic acid gas, sulfurous gas or combustion tail gas.
8. a dystopy electro-flucculation process, it is characterized in that, it uses dystopy electric flocculation plant that flocculates to implement, the flocculation of this dystopy flocculation electricity comprises cell body (1), be positioned at least one pair of battery lead plate (2) that described cell body (1) is inner, this at least one pair of battery lead plate (2) connects positive pole and the negative pole of power supply respectively, the material wherein at least connecting the battery lead plate of positive source is iron, aluminium or ferro-aluminium, wherein said battery lead plate (2) is hollow electrode plate, this hollow electrode plate has the gas inlet (3) be communicated with its internal cavities, each sidewall of this hollow electrode plate all have several cinclides (4), cinclides (4) is lateral aperture or angling hole, in operating process, in pending waste water, pass into sour gas via this gas inlet (3), described internal cavities and described cinclides (4) successively, described sour gas is selected from carbonic acid gas, sulfurous gas or combustion tail gas.
9. according to the dystopy electro-flucculation process of claim 7 or 8, wherein by passing into described sour gas by below the pH regulator to 5.6 of pending waste water.
10. according to the dystopy electro-flucculation process of claim 7 or 8, wherein in other container by leave described dystopy flocculate electric flocculator waste water pH value raise, there is flocculating settling.
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