CN104891610B - Heterotopic electro-flocculation device and method - Google Patents
Heterotopic electro-flocculation device and method Download PDFInfo
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- CN104891610B CN104891610B CN201510271605.9A CN201510271605A CN104891610B CN 104891610 B CN104891610 B CN 104891610B CN 201510271605 A CN201510271605 A CN 201510271605A CN 104891610 B CN104891610 B CN 104891610B
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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 handling process field.
Background technology
Flocculence is the common methods for processing waste water.Conventional chemical flocculation is that various flocculant are added in waste water,
Such as aluminium polychlorid, poly-ferric chloride, polyaluminum sulfate aluminium chloride ferrum etc., the iron ion or aluminium ion in these flocculant holds
Facile hydrolysiss generate hydrated ferric oxide. or aluminium hydroxide, and flocculation sediment occurs with increasing for its amount, in flocculation sediment process
In, by absorption and the volume effect of sweeping, the particulate material in waste water and some adsorbable materials are transferred in flocculate, play
The effect of purification waste water.But chemical flocculation often introduces other aniones, such as chloride ion or sulfate ion in waste water,
These ions for additionally introducing, are finally also required to remove, and bring the trouble of subsequent treatment.
In recent years, in order to avoid the drawbacks described above of chemical flocculation, electric flocculation method is developed.Its principle be by ferrum, aluminum or
Ferroaluminium as electrolyzer anode and be immersed in waste water, Fe is discharged by anodizing2+And/or Al3+, Fe2+Again
It is easily oxidized into Fe3+, they are further hydrolyzed into corresponding hydroxide, and flocculation sediment occurs.It is except iron ion or aluminum
The source of ion is different outer, and ultimate principle and process are identical with chemical flocculation.
When electric flocculation method processes waste water, the difficulty in concrete operations is often faced.One difficulty is, in flocculation process, gives up
Colloidal substance or organic thick substances or floccule body in water easily as siltation at the electrode surface, prevent it is ferrous from
The further dissolution of son and/or aluminium ion from pole plate.Another difficulty is that, industrially in order to improve electric flocculation efficiency, usually
Side by side using tens of to hundreds of battery lead plates in a flocculation tank, while dissolution Fe2+And/or Al3+, Fe2+It is easy to again by oxygen
Chemical conversion Fe3+, these metal cations are further hydrolyzed and flocculated, because electric flocculation process occurs in electric flocculation reactor
Portion, substantial amounts of flocculating sedimentation thing is easy to deposit between thickly dotted battery lead plate, causes operating process to interrupt, it has to
Cleared up.To solve the above problems, generally polar board surface is cleared up using Mechanical Method and ultrasonic method, but such cleaning
It is very time-consuming laborious, or and electrode surface is damaged, or needing to install extra ultrasonic device, increase cost.
The electric flocculation effect of electric flocculation device inside is outer, and a certain degree of electroxidation effect also occurs.Electrochemical oxidation process
The mechanism of action mainly produces superoxide radical (O2), H by the effect of electrode material2O2, hydroxyl radical free radical (OH) etc. it is living
Property group to aoxidize water body in Organic substance.The method is only occurred in water, and is not required to separately add catalyst, avoids secondary dirt
Dye.Due to its controllability by force, the advantages of non-selectivity, mild condition, so comparing for the Organic substance of bio-refractory has
Good treatment effect.But, two problems are frequently suffered from actual applications：One is pole plate passivation problem, the glue in waste water
Body material or organic thick substances or flocculate precipitate have pasted negative electrode and sun easily as siltation on negative electrode and anode
Pole, if irregularly cleaning, can have a strong impact on contact of the battery lead plate with waste water, reduces electrode efficiency.Another is concentration polarization
Problem, i.e. battery lead plate produce superoxide radical (O2), H2O2, hydroxyl radical free radical (OH) isoreactivity group, generally only
Can working in the range of electrode plate surface several millimeters, and the Organic substance contained in waste body outside this distance range its
In fact these active groups cannot be touched, therefore also be difficult to be oxidized, unless they move to electrode by diffusion
Plate is nearby within the scope of several millimeters.Pole plate passivation problem and concentration polarization problem result in the decline of electroxidation efficiency.
The present invention innovatively develops a kind of dystopy flocculation electric flocculation device and dystopy electro-flucculation process, can solve the problem that above-mentioned
Realistic problem.
The content of the invention
A first aspect of the present invention provides a kind of dystopy and flocculates electric flocculation device, and it includes cell body, in the cell body
At least one pair of battery lead plate in portion, at least one pair of battery lead plate connects respectively the positive pole and negative pole of power supply, wherein at least connection power supply
The material of the battery lead plate of positive pole is ferrum, aluminum or ferroaluminium, wherein dystopy flocculation electric flocculation device is also passed through with gas
Pipe.
In the present invention, the battery lead plate can be solid battery lead plate, or hollow electrode plate.
In a preferred embodiment of the invention, the battery lead plate be hollow electrode plate, on the hollow electrode plate have with
The gas access of its connects with the internal cavities, on each side wall of the hollow electrode plate several cinclides are respectively provided with, and cinclides is level
Hole or angling hole.
In a preferred embodiment of the invention, the multipair hollow electrode plate is spaced from each other a distance and is arranged side by side,
And the cinclides on the side wall of adjacent hollow battery lead plate is arranged with being staggered each other.
In a preferred embodiment of the invention, the gas inlet pipe is arranged on cell body.When using the hollow electricity
During pole plate, it is also possible to using the gas access as the gas inlet pipe.
A second aspect of the present invention provides a kind of dystopy electro-flucculation process, and the method is come using dystopy flocculation electric flocculation device
Implement, the dystopy flocculation electric flocculation includes cell body, at least one pair of battery lead plate inside the cell body, at least one pair of electrode
Plate connects respectively the positive pole and negative pole of power supply, and the material of the battery lead plate of wherein at least connection positive source is that ferrum, aluminum or ferrum aluminum are closed
Gold, wherein dystopy flocculation electric flocculation device also has gas inlet pipe；In operating process, via the gas inlet pipe to treating
Process and sour gas is passed through in waste water, the sour gas is selected from carbon dioxide, sulfur dioxide or combustion tail gas.
A third aspect of the present invention also provides a kind of dystopy electro-flucculation process, and the method uses dystopy flocculation electric flocculation device
To implement, the dystopy flocculation electric flocculation includes cell body, at least one pair of battery lead plate inside the cell body, at least one pair of electricity
Pole plate connects respectively the positive pole and negative pole of power supply, and the material of the battery lead plate of wherein at least connection positive source is ferrum, aluminum or ferrum aluminum
Alloy, wherein the battery lead plate is hollow electrode plate, has the gas access with its connects with the internal cavities on the hollow electrode plate,
Several cinclides are respectively provided with each side wall of the hollow electrode plate, cinclides is lateral aperture or angling hole；In operating process, successively
Sour gas, the sour gas are passed through in pending waste water via the gas access, the internal cavities and the cinclides
Selected from carbon dioxide, sulfur dioxide or combustion tail gas.
In a preferred embodiment of the invention, the useless of the dystopy flocculation electric flocculation device will be left in other container
The pH value of water is raised, there is flocculating sedimentation.
In specific embodiments of the present invention, the diameter of the cinclides can as needed be adjusted by technical staff
It is whole, for example can be 0.05mm-0.5mm, it is therefore preferable to 0.05mm-0.2mm, more preferably 0.1mm.
In a preferred embodiment of the invention, the cinclides on the side wall of adjacent hollow battery lead plate is staggered each other arrangement.This
It can be that horizontal level is staggered, vertical position is staggered to plant the arrangement that is staggered, or the two has concurrently.
In embodiments of the invention, in described at least one pair of battery lead plate, the battery lead plate being at least connected with positive source
For solubility battery lead plate, for example its material can be aluminum, ferrum or ferroaluminium, and the battery lead plate being connected with power cathode can be
Inert electrode plate, such as its material can be graphite or titanium or the inertia material of other not dissolutions.Preferably, it is described at least one pair of
The material of battery lead plate is both selected from aluminum, ferrum or ferroaluminium, and realizes positive-negative electrode plate by periodically exchanging both positive and negative polarity
It is uniform to consume.
In a preferred embodiment of the invention, directly waste water and sour gas can also be jointly passed through into the hollow electricity
In the gas access of pole plate, and it flow in the cell body via the internal cavities and cinclides of hollow electrode plate jointly.
As a example by being passed through CO2 in pending waste water, the course of work of the concrete apparatus and method for introducing the present invention is as follows：
In conventional electric flocculation reactor, when using solubility electrode such as iron electrode, aluminium electrode or ferroaluminium electrode
When, it is electrolysed dissolution Fe2+And/or Al3+, wherein Fe2+Fe is easily oxidized into again3+.Inventor is through the observation to long term accumulation
Data find after being studied, in the range of wastewater pH=6.5-7.5, Al3+Significant flocculating sedimentation reaction can occur, pH is low
When 6.5, Al3+Although also there are partial hydrolysiss, obvious flocculating sedimentation will not occur, estimate now Al3+Hydrolyzate be
Partial hydrolysate, i.e., with Al (OH)2+Or Al (OH)2 +In the form of, the physical aspect of these partial hydrolysates is more
It is relative stable suspersion " colloid " rather than " flocculate precipitate ", when only to pH being higher than 6.5, just has substantial amounts of Al (OH)3
Form and produce obvious flocculation sediment.When pH is higher than 7.5, due to for amphoteric hydroxide, Al (OH)3Can dissolve on the contrary,
Can not recur to the effect of flocculating sedimentation.Inventor also passes through research and finds, in the range of pH=3.5-6.5, Fe2+With
Fe3+Can hydrolyze, belong to partial hydrolysiss, and though have precipitate to produce precipitate in waste water in suspended state, Bu Hui great
Amount precipitation.Until when pH is higher than 6.5, Fe2+And Fe3+The hydrolysis of notable ratio can just occur and significant precipitation is produced, it is high to pH
When 8.5, Fe2+And Fe3+Meeting complete hydrolysis are simultaneously precipitated completely.
Inventor is based on above-mentioned data results, creatively proposes and is passed through sour gas regulation pH value of waste water with reality
The technical scheme of existing dystopy flocculation.By taking CO2 as an example, CO2 is passed through to saturation, its pH is 5.6 or so under normal pressure in water；In pressurization
Lower to be passed through CO2 in water, its pH even can as little as 3.7.Therefore, it is passed through after CO2, effectively can completely avoids Al3+Occur
PH scopes 6.5-7.5 of notable flocculating sedimentation, in aluminium electrode used in electric flocculation device, it is possible to realize the dissolution from electrode
Al3+, in electric flocculation device under conditions of pH is for 5.6, the Al3+Only there are partial hydrolysiss, but flocculation sediment does not occur, wait to give up
Water flows out and enters into after the electric flocculation device in a relatively spacious container, then (for example reducing pressure or heating up makes by heightening pH value
CO2 is escaped, or incorporation neutrality material for example mixes calcium carbonate granule or mixes another strand of alkaline waste water, etc.), make Al3+
Generation complete hydrolysis and flocculation sediment.Hereby it is achieved that dystopy flocculation.In the same manner, in iron electrode used in electric flocculation device, although
It is passed through CO2 to be not enough to the pH regulator of waste water to 5.6 to prevent Fe completely2+And Fe3+Hydrolysis, but be at least avoided that they occur
Significantly the hydrolysis of ratio and flocculation sediment, also partly alleviate the flocculation sediment inside electric flocculation device.Treat that waste water flows out the electricity
During a relatively spacious container is entered into after flocculator, then by heightening pH value (for example reduce pressure or heating up escape CO2, or
Person mixes neutrality material and for example mixes calcium carbonate granule or mix another strand of alkaline waste water, etc.), make Fe2+And Fe3+Occur
Complete hydrolysis and flocculation sediment.Thus, dystopy flocculation is realized at least in part.In the same manner, the ferrum aluminum used in electric flocculation device is closed
During meter electrode, dystopy flocculation also can be at least in part realized.
In the same manner, when the gases such as sulfur dioxide, combustion tail gas (such as flue gas) are passed through in waste water, also can realize it is identical or
Similar dystopy flocculating effect.
When hollow electrode plate used in electric flocculation device, it is passed through the gas access of the hollow electrode plate as the gas
Pipe equally can also realize same or similar dystopy flocculating effect being passed through sour gas.
Beneficial effects of the present invention are as follows：
1st, dystopy flocculation：As described above, the present invention in electric flocculation device by setting up gas inlet pipe and to pending
Sour gas is passed through in waste water, can realize that dystopy is flocculated so that flocculate flocculation sediment is in the relatively empty of electric flocculation device downstream
In spacious independent container, it is to avoid flocculate is deposited on battery lead plate or is deposited on inside electric flocculation device, and then it is multiple to alleviate structure
Miscellaneous electric flocculation device cleaning burden.
2nd, electrode efficiency is improved：The hollow electrode plate used in electric flocculation device and lead to from the gas access of the hollow electrode plate
When entering sour gas, the gas being passed through is successively via the gas access, the internal cavities of the hollow electrode plate and the wall
Hole is entered in pending waste water, moreover it is possible to play souring, prevents polar board surface alluvial dirt.When the sour gas being passed through
For high pressure when, because the cinclides on the relative two sides of two blocks of hollow electrode plates relative to each other is staggered setting, therefore from wall
The burs such as the battery lead plate of the air scour offside that hole high speed sprays, the sludge on removing offside electrode plate surface, prevent pole
Plate is passivated and because the current efficiency that pole plate passivation is caused declines；This high-speed jet is acted on also between adjacent electrode plates
Waste water plays stirring action, and promotion waste body is exchanged with the waste water of electrode wall surfaces, thus slows down concentration polarization problem.
When the sour gas being passed through is low pressure, escaping gas may be not enough to jet to offside battery lead plate from cinclides, but escape
The fluid for going out can wash away the battery lead plate sludge of itself along the floating of itself electrode wooden partition, it is this it is autologous wash away by way of
Prevent pole plate passivation.Either gases at high pressure or low-pressure gas, because with the presence of certain pressure, preventing pending
Waste water is from the internal cavities that the cinclides enters the hollow electrode plate, it is to avoid pollutant are in hollow electrode intralaminar part cavity
Deposition.Eliminate pole plate passivation and mitigate concentration polarization, no matter for electric flocculation or electroxidation, be all advantageous for improving electrode
Efficiency.
3rd, safety is improved：Also inevitably there are some electrolysis liberation of hydrogen oxygen evolution reaction, i.e. electrolysis waters on battery lead plate
Reaction, the hydrogen and oxygen of precipitation run up to finite concentration in electric flocculation reactor and have explosion danger, i.e., so-called " hydrogen
It is quick-fried ".By being passed through CO2 in waste water, part CO2 of the dissolubility beyond CO2 in waste water can exist with gas phase, can
Effectively to dilute above-mentioned hydrogen and oxygen, it is to avoid hydrogen occurs quick-fried.
Description of the drawings
Fig. 1 is the structural representation of the dystopy flocculation electric flocculation device of the present invention.
Fig. 2 is that the structure of the hollow electrode plate in the dystopy flocculation electric flocculation device of the employing hollow electrode plate of the present invention is shown
It is intended to.
Fig. 3 is that the hollow porous pole plate shown in Fig. 2 cuts view that is rear and looking along direction shown in arrow open along M-M lines.
Fig. 4 is that the hollow porous pole plate shown in Fig. 2 cuts view that is rear and looking along direction shown in arrow open along N-N lines.
Fig. 5 is that the hollow porous pole plate shown in Fig. 2 cuts view that is rear and looking along direction shown in arrow open along K-K lines,
Which show respectively horizontal cinclides and incline each independent cinclides arrangement of two kinds of cinclides.
Fig. 6 is the schematic diagram of the dystopy flocculation electric flocculation device of the employing hollow electrode plate of the present invention, wherein schematically
Show that 8 hollow porous pole plates are placed side by side, wherein the setting that is staggered between adjacent cinclides.
Reference implication is as follows in figure：
1- cell bodies；2- battery lead plates；3- gas accesses；4- cinclides；5- gas inlet pipes.
Specific embodiment
With reference to embodiments the present invention is described in further details with accompanying drawing, embodiment is only limitted to the explanation present invention,
Rather than limitation of the invention.
Embodiment 1
Waste water, the solid electrode plate are processed using the dystopy flocculation electric flocculation device of the employing solid electrode plate shown in Fig. 1
For ferroaluminium pole plate, number is 150, and the DC voltage applied between each pair pole plate is for about 1.5V.And from positioned at cell body bottom
Gas inlet pipe be passed through normal pressure CO2 gases, the pH of waste water is adjusted to into 5.8 or so.Observation in experiment finds, in the electricity wadding
In solidifying device, only there is little flocculation phenomenon, be embodied in waste water and only slightly become cloudy, but substantially do not precipitate.To leave
The waste water of the electric flocculation device is passed through in another container, wherein being found in the appearance with lifting pH value containing a large amount of calcium carbonate granules
There are a large amount of flocculation sediment phenomenons in device.
Embodiment 2
Waste water is processed using the dystopy flocculation electric flocculation device of the employing hollow electrode plate shown in Fig. 6, pole plate is the conjunction of ferrum aluminum
Golden pole plate, number is 150, and the DC voltage applied between each pair pole plate is for about 1.5V.Lead to from the gas access of hollow pole plate
Enter normal pressure CO2, and successively the internal cavities and cinclides of the hollow pole plates of Jing are passed through in pending waste water.The pH of waste water is adjusted to
5.8 left and right.Observation in experiment finds in the electric flocculation device, little flocculation phenomenon only occurs, and is embodied in waste water and only slightly becomes
Muddiness, but substantially do not precipitate.The waste water for leaving the electric flocculation device is passed through in another container, wherein containing some carbon
To lift pH value, in this embodiment a large amount of flocculation sediment phenomenons in discovery to sour calcium granule there are.It is additionally observed that in experiment, due to CO2
The souring of air-flow, electrode plate surface almost without dirt alluvial phenomenon, maintains its surface cleaning.
From above-mentioned experiment, apparatus and method of the present invention, can successfully realize that dystopy is flocculated.And when using hollow
During battery lead plate, can be washed away with the offside because of the sour gas being passed through or autologous souring, effectively eliminate pole plate passivation
Phenomenon, and concentration polarization phenomenon is alleviated significantly.Therefore, the dissolution efficiency of battery lead plate is greatly improved.
Claims (6)
1. a kind of dystopy is flocculated electric flocculation device, including cell body (1), positioned at least one pair of internal battery lead plate of the cell body (1)
(2), at least one pair of battery lead plate (2) connects respectively the positive pole and negative pole of power supply, and wherein at least connects the battery lead plate of positive source
Material be ferrum, aluminum or ferroaluminium, wherein dystopy flocculation electric flocculation device also has gas inlet pipe (5)；Its feature
It is that the battery lead plate (2) is hollow electrode plate, there is the gas access with its connects with the internal cavities on the hollow electrode plate
(3), several cinclides (4) are respectively provided with each side wall of the hollow electrode plate, cinclides (4) is lateral aperture or angling hole；With institute
Gas access (3) is stated as the gas inlet pipe (5)；In operating process, successively via gas access (3), the inside
Cavity and the cinclides (4) are passed through sour gas in pending waste water, and the sour gas is selected from carbon dioxide, sulfur dioxide
Or combustion tail gas；The pH value for leaving the waste water of the dystopy flocculation electric flocculation device is raised in other container, to occur
Flocculating sedimentation.
2. dystopy according to claim 1 is flocculated electric flocculation device, it is characterised in that the multipair hollow electrode plate is each other
Keep at a certain distance away and be arranged side by side, and the cinclides (4) on the side wall of adjacent hollow battery lead plate is arranged with being staggered each other.
3. dystopy according to claim 1 is flocculated electric flocculation device, it is characterised in that the gas inlet pipe (5) is arranged
On cell body (1).
4. dystopy according to claim 1 is flocculated electric flocculation device, wherein the cell body (1) and the hollow electrode plate are removed
Outside fluid inlet and outlet, its entirety is closed.
5. a kind of dystopy electro-flucculation process, it is characterised in that it flocculates electric flocculation device using dystopy to implement, dystopy flocculation
Electric flocculation device is including cell body (1), positioned at least one pair of internal battery lead plate (2) of the cell body (1), at least one pair of battery lead plate
(2) positive pole and negative pole of power supply are connected respectively, the material of the battery lead plate of wherein at least connection positive source is that ferrum, aluminum or ferrum aluminum are closed
Gold, wherein the battery lead plate (2) is hollow electrode plate, has the gas access with its connects with the internal cavities on the hollow electrode plate
(3), several cinclides (4) are respectively provided with each side wall of the hollow electrode plate, cinclides (4) is lateral aperture or angling hole；Operation
During, it is passed through acidity in pending waste water via the gas access (3), the internal cavities and the cinclides (4) successively
Gas, the sour gas is selected from carbon dioxide, sulfur dioxide or combustion tail gas；The dystopy will be left in other container
The pH value of the waste water of flocculation electric flocculation device is raised, there is flocculating sedimentation.
6. dystopy electro-flucculation process according to claim 5, wherein by being passed through the sour gas by the pH of pending waste water
Adjust to less than 5.6.
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| CN105347582B (en) * | 2015-11-26 | 2017-08-25 | 北京科技大学 | A kind of device and method of iron-carbon micro-electrolysis degrading alkaline organic wastewater |
| CN107055889A (en) * | 2017-07-03 | 2017-08-18 | 辽宁科技学院 | A kind of marine culture wastewater efficient electrolysis denitrification dephosphorization apparatus and method |
| CN108502988A (en) * | 2018-04-24 | 2018-09-07 | 浙江奇彩环境科技股份有限公司 | A kind of electrolytic method for improving treatment of Organic Wastewater effect |
| CN110228876A (en) * | 2019-06-13 | 2019-09-13 | 北京朗新明环保科技有限公司南京分公司 | A kind of coal-contained wastewater processing system and its method |
| CN112759146A (en) * | 2019-10-21 | 2021-05-07 | 中国石油天然气集团有限公司 | Method and device for enhanced demulsification and oil removal of crude oil electric desalting wastewater |
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| JP2000176455A (en) * | 1998-12-16 | 2000-06-27 | Sanyo Electric Co Ltd | Treatment device and method for phosphate ion- containing water |
| CN2500670Y (en) * | 2001-08-09 | 2002-07-17 | 张启德 | Electrocoagulation equipment of sewage processing system |
| JP4159455B2 (en) * | 2003-11-27 | 2008-10-01 | 株式会社西日本流体技研 | Water recovery system by electrochemical method |
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| CN201437512U (en) * | 2009-05-06 | 2010-04-14 | 云南银发绿色环保产业股份有限公司 | High-voltage pulse electric flocculation sewage treatment plant |
| CN101811757B (en) * | 2010-04-26 | 2013-11-06 | 中国科学院过程工程研究所 | Air-assisted electro-coagulation algae water separation device and using method thereof |
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| CN203048643U (en) * | 2012-11-28 | 2013-07-10 | 北京京润新技术发展有限责任公司 | Catalyzed oxidation inertness electrode plate, compound electrode and device for processing high-COD (Chemical Oxygen Demand) sewage |
| US20140246375A1 (en) * | 2013-03-03 | 2014-09-04 | Hamed Gharibi | Electrochemical-based reactor for the removal of free cyanides and iron cyanide from industrial wastewater |
| CN104370350B (en) * | 2013-08-15 | 2016-08-10 | 中国石油天然气股份有限公司 | A kind of electrochemical appliance processed for water and method |
| CN103910416A (en) * | 2014-04-08 | 2014-07-09 | 山东金昊三扬环保机械股份有限公司 | Electric flocculation air floatation machine with aeration device |
| CN203878007U (en) * | 2014-05-22 | 2014-10-15 | 盛发环保科技（厦门）有限公司 | Power plant desulfurization wastewater treatment device |
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