CN102923827B - Microelectrolysis process for waste water treatment under alkaline condition - Google Patents
Microelectrolysis process for waste water treatment under alkaline condition Download PDFInfo
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Abstract
The invention relates to a microelectrolysis method for waste water treatment under an alkaline condition. The method includes the following processing step: waste water is led into a microelectrolysis reaction tank for microelectrolysis treatment, wherein the potential of hydrogen (PH) value of the waste water is between 8 and 12, the microelectrolysis reaction tank contains an alkaline microelectrode which comprises powder-shaped anode materials and powder-shaped cathode materials, and the powder-shaped anode materials and the powder-shaped cathode materials are arranged on a porous carrier. Compared with an existing microelectrolysis treatment process under an acidic condition, the microelectrolysis process for the waste water treatment under the alkaline condition can be directly used for microelectrolysis treatment of alkaline industrial waste water, the alkaline industrial waste water does not need to be pre-adjusted to acidic waste water, and therefore process is simplified, and cost is saved.
Description
Technical field
The present invention relates to a kind of microelectrolysis processing technique for wastewater treatment; More particularly, the present invention relates to a kind ofly can under alkaline condition, directly process the processing method of alkaline industrial waste water.
Background technology
Micro-electrolysis treatment trade effluent is a kind of emerging green technology, and it utilizes microelectrode to directly act on the various objectionable impuritiess in waste water, makes it be degraded to innoxious substance or makes it be converted into easy degraded and be convenient to the material of subsequent disposal.
Yet the microelectrolysis processing technique of existing bibliographical information is all only under acidic conditions, redox reaction could occur.
For example, Chinese patent application 200410098587.0 discloses a kind of rotary drum type reaction apparatus for waste water treatment by micro-electrolysis and method, it adopts a reaction tank and the rotary drum of horizontal positioned wherein, in rotary drum, there is dividing plate, dividing plate evenly merotomizes rotary drum, iron filings and activated carbon granule that wherein filling mixes, rotary drum is driven by buncher.Rotation by rotary drum makes the micro-electrolysis electric field forming between position between iron filings and gac and iron charcoal that dual displacement occur, and effectively prevents the obstruction caking of iron and carbon bed.In this patent application, adopt iron carbon microelectrode, need to could there is micro-electrolysis reaction in it under acidic conditions, can not directly process alkaline industrial waste water.
For another example, Chinese patent application 201010571686.1 discloses a kind of ultrasonic-assisted ferric-carbon micro-electrolysis waste water treatment method, and it arranges ultrasonic generator in electrolyzer, and packs iron carbon filler formation iron carbon bed electrolysis into.When carrying out wastewater treatment, first in electrolyzer, pack sulphuric acid soln activation 15-25 minutes into, the last 5 minutes unlatching ultrasonic generators that activation is carried out; Secondly, after activation completes, discharge sulphuric acid soln and rinse iron carbon bed electrolysis with tap water, during flushing, also open ultrasonic generator; Finally, then after having rinsed, introduce waste water, open ultrasonic wave rattler simultaneously, carry out iron-carbon micro-electrolysis reaction.Visible, this patent application is also to adopt iron-carbon micro-electrolysis reaction, also can only under acidic conditions, carry out the microelectrolysis processing of waste water.
In addition, Chinese patent application 201010553483.X discloses a kind of dynamic micro-electrolysis wastewater treatment device and water treatment method thereof, its device comprises cylinder reactor, water inlet pipe, inlet pipe, rising pipe, escape pipe, transmission belt, aeration tube and supporting base, cylinder reactor is installed on supporting base, the output shaft of drive-motor is connection for transmission band and cylinder reactor successively, realize the rolling of cylinder reactor, the both sides of cylinder reactor be provided with seal rotary interface and respectively with water inlet pipe, inlet pipe, rising pipe is connected with escape pipe, the outlet of water shoot and aeration tube are all arranged at the inside of cylinder reactor and are connected with seal rotary interface.This patent application adopts iron carbon microelectrode equally, just for iron carbon fixation bed pattern, improves.
But many in trade effluent is alkaline waste water, thereby when micro-electrolysis treatment, need acid adding in waste water in advance, regulate its pH value to acid, after micro-electrolysis, with alkaline matters such as lime, regulate back alkalescence again, so that subsequent disposal.This makes treatment scheme obviously elongated, and cost significantly increases.At present, industry there is no a kind of micro-electrolysis treatment method that can directly process alkaline industrial waste water.
Therefore, industry can be under alkaline condition be directly processed the microelectrolysis processing technique of alkaline industrial waste water in the urgent need to a kind of, while making wastewater treatment without the pH value that repeatedly regulates waste water, thereby shorten treatment scheme, and reduce costs.
Summary of the invention
The object of this invention is to provide a kind of microelectrolysis processing technique that can process waste water under alkaline condition, a kind of micro-electrolysis process method that can directly process alkaline industrial waste water is particularly provided, alkaline waste water can directly be processed and without regulating its pH value.
For realizing object of the present invention, the inventor is through a large amount of research, design a kind of can be in the method for microelectrolysis processing waste water under alkaline condition, the method comprises following treatment step: pH value is introduced to micro-electrolysis reaction pond for the waste water of 8-12 and carry out microelectrolysis processing; Wherein, alkaline microelectrode is housed in micro-electrolysis reaction pond, this alkalescence microelectrode comprises powdery anode material and the powdery cathode material being carried on porous carrier.
The method of the invention described above can directly be processed alkaline industrial waste water, and the experiment proved that it has good treatment effect.
In alkaline micro-electrolysis treatment method of the present invention, alkalescence microelectrode can be contained in by filter cloth and make and be evenly equipped with on it 50～300 object holes to guarantee in the anti-corrosion mesh bag of ventilative water permeability, and packed alkaline microelectrode can be placed on the set support barrier in bottom, micro-electrolysis reaction pond.Like this, can prevent the deposition of microelectrode, thereby improve the efficiency of micro-electrolysis reaction and the work-ing life of microelectrode material, and be beneficial to the replacing of microelectrode material.
In alkaline micro-electrolysis treatment method of the present invention, any flocculation agent that flocculation sediment can adopt in Industrial Wastewater Treatment to be commonly used, such as polyacrylamide flocculation agent, ferrous salt flocculation agent (as ferrous sulfate), inorganic polymer flocculant (as bodied ferric sulfate), composite flocculation agent etc.
In fact, method of the present invention also can be for the processing of non-alkaline waste water, for example, and for the treatment of acid or neutral trade effluent, now, before introducing the present invention's alkalescence micro-electrolysis reaction pond, acid or neutral trade effluent also to carry out following treatment step:
(a) waste water is homogenized processing;
(b) waste water homogenizing after processing is introduced to equalizing tank and the pH value of waste water is adjusted to 8-12.
In addition, method of the present invention when directly processing alkaline industrial waste water, also can be first to the alkaline industrial waste water processing that homogenizes.The treatment step homogenizing is very important for industrial treatment waste water, because its composition fluctuation of the waste water that different times produces may be larger, particularly in the situation that Industrial processes have fluctuation, and the fluctuation of waste water composition produces larger impact compared with senior general to microelectrode, thereby affect its processing to toxicant (nitrifier and denitrifying bacteria are had to inhibiting material), and then have influence on the treatment effect of follow-up biochemical treatment system and oxidation pond, cause wastewater treatment not up to standard.
Further, method of the present invention can also comprise the step of the waste water introducing flocculation sedimentation tank after microelectrolysis processing being carried out to flocculation sediment.Wherein, at waste water, after carrying out flocculation sediment, flocculation sedimentation tank can also comprise following treatment step:
(c) the pH value of waste water after flocculation sediment is adjusted to 8-9;
(d) clear liquid that is 8-9 by pH value enters biochemical treatment system and is further processed.
Above-mentioned biochemical treatment system can, for any suitable a kind of in existing biochemical processing, be generally anaerobic-aerobic method.For example, biochemical treatment system can be sbr reactor pond (sequencing batch reactor reaction tank).
If adopt sbr reactor pond, preferably after processing, sbr reactor pond also comprises following treatment step:
(e) waste water of discharging from sbr reactor pond is introduced to oxidation pond and carry out catalytic oxidation, wherein, in oxidation pond He in sbr reactor pond, all can add starch as carbon source.
No matter be in sbr reactor pond, or in oxidation pond, the object that adds starch is to increase carbon source, with guarantee biochemical treatment smoothly, steadily carry out.
The method of the invention described above can also combine with other waste water treatment process, forms the waste water treatment process of combination, to reach special treatment effect, or for the treatment of the trade effluent under special occasions or specific occasion.
For example, the method for the invention described above can combine with adopting the acid microelectrolysis processing technique of acid microelectrode.In this combination process, except utilizing alkaline microelectrode to carry out microelectrolysis processing waste water under alkaline condition, before this or afterwards, also be included under the acidic conditions that pH is 3-5 and utilize iron carbon microelectrode to process waste water, to realize single acid microelectrolysis processing or the alkaline microelectrolysis processing treatment effect that is beyond one's reach.
In the present invention, the anode material of the alkaline microelectrode adopting in alkaline micro-electrolysis reaction pond can be zinc powder, and cathode material can be Manganse Dioxide, and porous carrier can be haydite.Preferably, the particle diameter of Manganse Dioxide is 20～120 orders, more preferably 60～100 orders are as 80 orders, and the particle diameter of zinc powder is 20～160 orders, more preferably 60～120 orders are as 80～100 orders, and the particle diameter of haydite is 1～10mm, be preferably 3～8mm; And by weight, the ratio of zinc powder, Manganse Dioxide and haydite is 0.5～1.5:0.5～1.5:0.2～1.0, preferred ratio is 1.0～1.5:1.0～1.5:0.2～1.0.
In the present invention, can, by changing the weight ratio of alkaline microelectrode component Manganse Dioxide, zinc powder, haydite, reach the best effect to Different Alkali wastewater microelectrolysis processing.
In the present invention, the porous carrier adopting in alkaline microelectrode is preferably the carrier that proportion is less than water, so that when processing waste water, it can produce the power of lifting upwards, prevents that anode material and cathode material are too deposited on the bottom in micro-electrolysis reaction pond etc.This power of lifting making progress contributes to improve the efficiency of microelectrolysis processing.In addition, carrier adopts porous material, contributes to the distribution of anode material and cathode material, thereby contributes to form numerous galvanic cells, also and then contribute to improve the efficiency of microelectrolysis processing.
Because haydite also has light weight, the feature such as acidproof, alkaline-resisting, and be conveniently easy to get, with low cost, particularly the good alkaline-resisting ability of haydite, makes it especially be suitable as the carrier of the alkaline microelectrode of processing alkaline waste water.The haydite using is not particularly limited, and on market, general commercial haydite all can be used as the carrier of neutral and alkali microelectrode of the present invention, but generally selects proportion lower than the haydite of water.
When preparation microelectrode of the present invention, can adopt various known particle loaded methods, the cathode material of the anode material of powdery and powdery is carried on porous carrier.Wherein, the simplest method is that the cathode material of the anode material of powdery, powdery and porous carrier are mixed 10～60 minutes under 25 ℃～100 ℃ conditions in mixer.
For the waste water of light pollution, for example the light sanitary wastewater polluting can obtain the directly standard of discharge after the micro-electrolysis process of alkalescence of the present invention is processed, but the treatment time obviously shortens than common biochemical treatment system; For the waste water of heavily contaminated, can adopt the micro-electrolysis process of alkalescence of the present invention and biochemical treatment system to carry out combination treatment, to realize the qualified discharge of waste water, because the micro-electrolysis process of alkalescence of the present invention can make to be difficult to the pollution substance generation micro-electrolysis reaction of degraded.
Compare with the acid microelectrolysis processing technique of existing iron carbon microelectrode, can under alkaline condition, there is redox reaction in method of the present invention, directly apply to the microelectrolysis processing of alkaline industrial waste water, trade effluent is without acidifying in advance, simplified flow process, reduced cost, the treatment effect of some waste water has been better than to acid microelectrolysis processing technique.
Below in conjunction with the drawings and specific embodiments, the present invention is described further; But be appreciated that these concrete embodiments are just for the present invention is described, rather than limitation of the present invention.Those of ordinary skill in the art completely can be under enlightenment of the present invention; the specific embodiment of the present invention is improved; or some technical characterictic is equal to replacement, but these technical schemes after improving or replacing still belong to protection scope of the present invention.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of micro-electrolysis combined technology one embodiment of the present invention;
Fig. 2 is the process flow sheet of another embodiment of micro-electrolysis combined technology of the present invention.
Embodiment
The preparation of embodiment 1 alkaline microelectrode
Get respectively: granularity is 60 orders, 80 orders, the commercially available Manganse Dioxide of 100 object (content >=20% of Manganse Dioxide); Granularity is 60 orders, 80 orders, the commercially available zinc powder of 120 object (zinc content >=60%); With particle diameter be the commercially available haydite of 3mm, 8mm.Above three kinds of materials, respectively according to the ratio of weight part 0.5:0.5:0.2,1:1:0.5 and 1.5:1.5:1.0, are mixed 10～60 minutes under 25 ℃～100 ℃ conditions in mixer, obtain the microelectrode for the treatment of alkaline waste water of the present invention.
The alkaline microelectrolysis processing of embodiment 2
The alkaline microelectrode (80 order Manganse Dioxide, 80 order zinc powders, 3mm haydite are in the ratio of 1:1:0.5) of embodiment 1 preparation is contained in by filter cloth and makes and be evenly equipped with on it 50～300 object holes to guarantee in the anti-corrosion mesh bag of ventilative water permeability.On the inwall of waste water water reservoir that is provided with intake-outlet, be coated with alkaline-resisting anti-corrosive coating layer, in the bottom in pond, be provided with the barrier that supports packed microelectrode, at Chi Dishang, be provided with aeration pipe network.
Alkaline waste water from printing and dyeing mill (PH=11～12) is passed in the above-mentioned the present invention's of being equipped with the waste water water reservoir of alkaline microelectrode.By following technical process, process:
A: alkaline waste water → alkaline micro-electrolysis → SBR processing → water outlet
As a comparison, disclosed iron carbon microelectrode in Chinese patent ZL 20091003893.1 is also contained in by filter cloth and makes and be evenly equipped with on it 50～300 object holes to guarantee in the anti-corrosion mesh bag of ventilative water permeability.In the waste water water reservoir with above-mentioned same structure, by following technical process, process the alkaline waste water from printing and dyeing mill:
B: alkaline waste water → acidifying → acid micro-electrolysis (iron carbon microelectrode) → SBR processing → water outlet.
Table 1 has below provided the treatment effect contrast of this dyeing waste water after alkaline microelectrode is processed and after the processing of acid microelectrode respectively:
Table 1
| Index | COD | Colourity |
| Former water (alkaline waste water) | 1802.14 | 1000 |
| After alkalescence microelectrode is processed | 758.51 | 60 |
| After acid microelectrode is processed | 1196.12 | 100 |
The alkaline microelectrolysis processing of embodiment 3
According to mode same in embodiment 2, to processing and the processing of acid microelectrode through alkaline microelectrode respectively from certain surface active agent wastewater (PH=9), the treatment effect of this surface active agent wastewater is listed in table 2 kind:
Table 2
| Index | COD | Colourity |
| Former water | 1060.86 | 80 |
| After alkalescence microelectrode is processed | 550.32 | 20 |
| After acid microelectrode is processed | 607.34 | 20 |
From the data of table 1 and table 2, can see, method of the present invention can directly be processed alkaline industrial waste water under alkaline condition, and without acidifying in advance, thereby simplified flow process, reduced cost, and the treatment effect of some waste water has also been better than to the treatment process of acid micro-electrolysis.
Embodiment 4 combined treatment process
According to the technical process shown in Fig. 1, Pharmaceutical Fermentation Wastewater is processed: the waste water that homogenizes after grid or filter screen filtering by particle in waste water and suspended substance, in equalizing tank, use H
2sO
4regulate PH=3～5, enter acid micro-electrolysis reactor <1>, the structure of this acidity micro-electrolysis reactor can be the disclosed structure of Chinese patent ZL 201110050540.7, the acid microelectrode using under its built-in acidic conditions, iron carbon microelectrode as disclosed in China Patent No. ZL 20091003893.1; Through acid micro-electrolysis reaction, after 30～240 minutes, enter in flocculation sedimentation tank <1>, add liming to regulate PH=8～12 and flocculation agent (as FeSO
4deng) precipitation; Clear liquid enters alkaline micro-electrolysis reactor <2>, the structure of this alkalescence micro-electrolysis reactor is with above-mentioned acid micro-electrolysis reactor <1>, but its inwall changes tool alkali prevention coating, the prepared alkaline microelectrode of the present invention of applying under built-in alkaline condition; Through alkaline micro-electrolysis reaction, after 30～240 minutes, enter flocculation sedimentation tank <2>, add flocculation agent (as FeSO
4deng), regulate PH=8～9, staticly settle rear clear liquid to enter after follow-up biochemical treatment system processing water outlet discharge or reuse.Follow-up biochemical processing method is the suitable a kind of of existing biochemical processing, is generally anaerobic-aerobic method.
Wherein, the processing condition that the present embodiment adopts and treatment effect (before biochemical treatment system processing) are in Table 3:
Table 3
Embodiment 5 combined treatment process
According to the technical process shown in Fig. 2, cowboy's pulp waste water is processed: the waste water that homogenizes after grid or filter screen filtering by particle in waste water and suspended substance, in equalizing tank, regulate PH=8～12, enter alkaline micro-electrolysis reactor <1>, the structure of this alkalescence micro-electrolysis reactor can be disclosed structure in Chinese ZL 201110050540.7, the prepared alkaline microelectrode of the present invention of applying under alkaline condition; Through alkaline micro-electrolysis reaction, after 30～240 minutes, enter in flocculation sedimentation tank <1>, add flocculation agent (as FeSO
4) regulate PH=8～9 to precipitate; Clear liquid H
2sO
4regulate PH=3～5, enter acid micro-electrolysis reactor <2>, this acidity micro-electrolysis reactor structure is with above-mentioned alkaline micro-electrolysis reactor <1>, but its inwall changes tool anti-acid coat, the acid microelectrode of applying under built-in acidic conditions, iron carbon microelectrode as disclosed in China Patent No. ZL 20091003893.1; Through acid micro-electrolysis reaction, after 30～240 minutes, enter flocculation sedimentation tank <2>, add lime and regulate PH=8～9, staticly settle rear clear liquid and enter after follow-up biochemical treatment system processing, water outlet discharge or reuse.Follow-up biochemical processing method is the suitable a kind of of existing biochemical processing, is generally anaerobic-aerobic method, as sbr reactor pond.
Wherein, the processing condition that the present embodiment adopts and treatment effect (before biochemical treatment system processing) are in Table 4:
Table 4
Claims (11)
1. a method for microelectrolysis processing waste water under alkaline condition, the method comprises following treatment step: the waste water that is 8-12 by pH value is introduced micro-electrolysis reaction pond and carried out microelectrolysis processing;
Wherein, in described micro-electrolysis reaction pond, alkaline microelectrode is housed, this alkalescence microelectrode comprises powdery anode material and the powdery cathode material being carried on porous carrier; Wherein, the anode material of described alkaline microelectrode is zinc powder, and cathode material is Manganse Dioxide.
2. the method for claim 1, wherein described alkaline microelectrode is contained in by filter cloth and makes and be evenly equipped with on it 50～300 object holes to guarantee in the anti-corrosion mesh bag of ventilative water permeability.
3. the method for claim 1, wherein described method also comprised following treatment step before waste water is introduced micro-electrolysis reaction pond:
(a) waste water is homogenized processing;
(b) waste water homogenizing after processing is introduced to equalizing tank and the pH value of waste water is adjusted to 8-12.
4. the method as described in one of claim 1-3, wherein, described method also comprises:
Waste water after microelectrolysis processing is introduced to flocculation sedimentation tank and carry out flocculation sediment.
5. method as claimed in claim 4 wherein, also comprises following treatment step after flocculation sedimentation tank carries out flocculation sediment at waste water:
(c) the pH value of waste water after flocculation sediment is adjusted to 8-9;
(d) clear liquid that is 8-9 by pH value enters biochemical treatment system and processes.
6. method as claimed in claim 5, wherein, described biochemical treatment system is sbr reactor pond (sequencing batch reactor reaction tank).
7. method as claimed in claim 6, wherein, described method also comprises following treatment step after process in sbr reactor pond:
(e) waste water of discharging from sbr reactor pond is introduced to oxidation pond and carry out catalytic oxidation, wherein, in oxidation pond He in sbr reactor pond, all add starch as carbon source.
8. the method for claim 1, wherein under alkaline condition, utilize before or after alkaline microelectrode carries out microelectrolysis processing to waste water, be also included in the step of utilizing iron carbon microelectrode to process waste water under the acidic conditions that pH is 3-5.
9. the method for claim 1, wherein the porous carrier of described alkaline microelectrode is haydite.
10. method as claimed in claim 9, wherein, the particle diameter of described Manganse Dioxide is 20～120 orders, and the particle diameter of described zinc powder is 20～160 orders, and the particle diameter of described haydite is 1～10mm; And by weight, the ratio of zinc powder, Manganse Dioxide and haydite is 0.5～1.5:0.5～1.5:0.2～1.0.
11. methods as claimed in claim 10, wherein, the particle diameter of described Manganse Dioxide is 60～100 orders, and the particle diameter of described zinc powder is 60～120 orders, and the particle diameter of described haydite is 3～8mm; And by weight, the ratio of zinc powder, Manganse Dioxide and haydite is 1.0～1.5:1.0～1.5:0.2～1.0.
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| CN102452707A (en) * | 2010-11-03 | 2012-05-16 | 赵强 | Micro-electrolysis metallic packing |
| CN102583659A (en) * | 2012-01-18 | 2012-07-18 | 山东大学 | Granular anti-hardening acid-base dual-purpose ternary micro-electrolysis filler and preparation method thereof |
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| CN102452707A (en) * | 2010-11-03 | 2012-05-16 | 赵强 | Micro-electrolysis metallic packing |
| CN102276091A (en) * | 2011-06-10 | 2011-12-14 | 南京科盛环保科技有限公司 | Method for pretreating printing and dyeing wastewater with micro-electrolytic fluidized bed technique |
| CN102583659A (en) * | 2012-01-18 | 2012-07-18 | 山东大学 | Granular anti-hardening acid-base dual-purpose ternary micro-electrolysis filler and preparation method thereof |
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Address after: 511517 District 7, hi tech Industrial Development Zone, Guangdong, Qingyuan Patentee after: The prompt chemical industry company limited that manufactures of Guangdong spirit Address before: 7 No. 511517, hi tech Industrial Development Zone, Guangdong, Qingyuan Patentee before: Qingyuan City Lingjie Manufacture Chemical Co., Ltd. |