CN102491568A - Method for treating wastewater of electrolytic zinc rinsing technology - Google Patents
Method for treating wastewater of electrolytic zinc rinsing technology Download PDFInfo
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- CN102491568A CN102491568A CN2011103805988A CN201110380598A CN102491568A CN 102491568 A CN102491568 A CN 102491568A CN 2011103805988 A CN2011103805988 A CN 2011103805988A CN 201110380598 A CN201110380598 A CN 201110380598A CN 102491568 A CN102491568 A CN 102491568A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for treating wastewater of an electrolytic zinc rinsing technology. The method combines countercurrent rinsing, electrodeposition, and membrane separation: in countercurrent rinsing: subjecting a negative electrode plate used during electrolytic zinc production to a countercurrent rinsing device for rinsing, which specifically comprises: first delivering the negative electrode plate into a first stage countercurrent rinsing trough, i.e. a concentrated water trough, for rinsing in an opposite direction to the water current, then delivering the plate into a last stage trough, i.e. a clear water trough so as to finish the rinsing process; in electrodeposition: leaving the rinsed concentrated water to enter a flat plate electrodeposition device and a three-dimensional electrodeposition device, and recovering metal zinc in wastewater; in membrane separation: subjecting the wastewater from electrodeposition to an ultrafiltration membrane system and a reverse osmosis membrane system in order, leaving the concentrated liquid generated in membrane systems returns to the electrodeposition devices, recovering metal zinc in the membrane concentrated liquid, and leaving membrane effluent to return to the countercurrent rinsing device. By combining countercurrent rinsing, electrodeposition, and membrane separation processes, the method of the invention realizes recycling of wastewater, and basically realizes total recovery and zero discharge of heavy metal pollutants.
Description
Technical field
The present invention relates to a kind of process for treating industrial waste water, specifically, the countercurrent rinsing of the negative plate that relates to use in the electrolytic zinc production process, waste water after the rinsing is carried out galvanic deposit and membrane sepn combination treatment method.
Background technology
Electrolytic process is produced zinc technology in metal-stripping and pole plate cleaning process, can produce a large amount of poaching wastewaters.Contain contents of many kinds of heavy metal ion such as zinc, lead, cadmium in the poaching wastewater.Because its water yield is bigger; Heavy metal (especially zine ion) concentration is higher; If not treated direct discharging; Will cause surrounding environment to seriously influence, wherein contained heavy metal resources also will be wasted simultaneously, and how effectively handling electrolytic zinc rinsing process waste water is the focal issue that industries such as current mining, plating, electrolytic process production zinc are paid close attention to.Efficiently when removing heavy metal ions in wastewater, realize that recovery is the developing direction of heavy metal containing wastewater treatment from now on to waste water recycling with heavy metal.The method of the waste water of conventional process heavy metal comprises: method of chemical treatment, biological treatment, electrochemical treatment method; But during the chemical Treatment heavy metal-containing waste water; Because receive the influence of precipitation agent and envrionment conditions, the precipitator method often go out water concentration and do not reach requirement, need be for further processing; Though it is low that biological treatment has a cost, the advantage of convenient processing, general mikrobe is very little to the tolerance concentration of heavy metal ion, is difficult to the extensive heavy metal wastewater thereby of handling; In Applied Electrochemistry method processing in the past, when heavy metal concentration in the waste water reduces, exist energy consumption big, the problem that treatment effect is relatively poor.
Domestic main employing electrolytic process is carried out the trade effluent of zinc smelting and electroplating enterprise; It is up to standard to adopt traditional heavy metal precipitation art breading heavy metal wastewater thereby to be difficult to, and waste water effluxes the back serious environment pollution, and the recovery is low; Reclaim water quality inferiority; Heavy metal contaminants can't reclaim, and wastes resource, and causes the present situation of secondary pollution easily; The new treatment process heavy metal contaminants of the present invention's exploitation can be realized reclaiming and zero release the novel process that water resources recycles fully fully basically.
Summary of the invention
The objective of the invention is to overcome the weak point that exists in the prior art, and the electrolytic zinc rinsing process method of wastewater treatment of a kind of less investment, high efficiency is provided.
Technical scheme of the present invention is: electrolytic zinc rinsing process method of wastewater treatment, this method are three steps of combined treatment of countercurrent rinsing, galvanic deposit, membrane sepn:
First step: countercurrent rinsing
It is to be composed in series by some tanks that adverse current is cleaned, water inlet in the one-level groove (Rinsing Area) in the end, and from first step groove (dense tank) draining, the cleaning process of water (flow) direction and pole plate is in the opposite direction.The negative plate that uses in the electrolytic zinc production gets into countercurrent rinsing device and carries out rinsing, is introduced into first step countercurrent rinsing groove (dense tank), gets into last step groove (Rinsing Area) at last, accomplishes rinse cycle;
Through countercurrent rinsing, pole plate is along with producer is washed cleaner and cleaner to the battery lead plate that moves, and the Pollutant levels in the rinse water are then increasingly high, and water consumption is few, and cleaning efficiency is high.
Employed series water trough number is generally 4-10, is preferably 4-8, is preferably 6-8 especially, and those skilled in the art can adjust according to corresponding particular case;
Second step: galvanic deposit
Dense water after the rinsing gets into equalizing tank, regulates its water yield and flow velocity, gets into flat electric deposition device, three-dimensional electric deposition device more successively, reclaims metallic zinc in the waste water;
Galvanic deposit refers to flat electric deposition device and three-dimensional electric deposition device;
Regulating pondage and flow velocity will confirm that in this experiment, the water yield after the adjusting is 5m according to concrete experimental requirements
3, flow velocity is 1m
3/ h.
Third step: membrane sepn
Waste water after the galvanic deposit; Get into ultrafiltration membrane system, reverse osmosis membrane system successively; Waste water is through the two-stage film separating system, and promptly ultrafiltration membrane system and reverse osmosis membrane system gained liquid concentrator are back to galvanic deposit equalizing tank before; Pass through flat electric deposition device, three-dimensional electric deposition device then, the metallic zinc in the reclamation film liquid concentrator.The water outlet of ultrafiltration membrane system gets into reverse osmosis membrane system and further handles, the last step groove (Rinsing Area) of reverse osmosis membrane system effluent recycling in the countercurrent rinsing device;
Membrane sepn refers to that ultrafiltration membrane system separates with reverse osmosis membrane system;
And have only 1 mouth through the waste water recycling water outlet after galvanic deposit and the film system handles, from reverse osmosis system;
Metallic zinc retrieve to come from two parts, a part is the electrodeposition process that derives from waste water behind the countercurrent rinsing, recovery be the metallic zinc of waste water behind the countercurrent rinsing; A part derives from the waste water after the galvanic deposit in addition, is back to the electrodeposition process behind the electric deposition device through the liquid concentrator that produces behind ultrafiltration membrane system, the reverse osmosis membrane system, recovery be the metallic zinc in the liquid concentrator that the film system produces in this combination treatment method.
The processing condition of following each parts of stated and function:
Countercurrent rinsing is through cleaning the number of times control countercurrent rinsing water outlet Zn of pole plate
2+Concentration is about 3000mg/L;
Equalizing tank: be used for retaining, regulate its water yield and flow velocity, stationary flow; Regulating pondage and flow velocity will confirm that in this experiment, the water yield after the adjusting is 5m according to concrete experimental requirements
3, flow velocity is 1m
3/ h.
The Zn of flat electric deposition device
2+Minimum concentration reduce and to reach 800mg/L;
Flat electric deposition device commonly used comprises: like the electrolyzer that is used for electrochemical process that CN1930325 announces, and the diaphragm electrolyzer with metal anodes that CN1995461 announces.
The condition of said three-dimensional electrodeposition process zinc-containing water is: electrode materials is selected graphite anode/stainless steel cathode counter-electrodes for use; Bath voltage and electrolysis time need to confirm according to the concentration of zine ion in the waste water and hydraulic detention time; Bath voltage is 4.0V-8.0V generally speaking, and electrolysis time is 60min-90min; Three-dimensional galvanic deposit is granular or other fragmental working electrode material of filling between the conventional two-dimensional electrolytic tank electrode, and makes the granular electrode material surface of filling charged, becomes a new utmost point (the 3rd utmost point), in working electrode material surface energy generation electrochemical reaction; Zn after three-dimensional electric deposition device is handled
2+Minimum concentration be lower than 80mg/L, the clearance of zine ion reaches more than 90%;
Three-dimensional electric deposition device commonly used comprises: the 3 D electrode reactor of announcing like CN101186361 and utilize the 3 D electrode reactor in its method of handling chlorobenzene waste water, the 3 D electrode reactor in a kind of 3 D electrode reactor that CN101514040 announces and the application in organic wastewater with difficult degradation thereby is handled thereof.
Ultrafiltration membrane system is to remove materials such as suspended substance, colloid in the water; Water quality reaches the feed water by reverse osmosis requirement and (is mainly SDI (alluvial index)＜3.0; Turbidity is less than 0.10); Average removal efficient at ultra-filtration and separation process zine ion is 60%～70%, adds 15mg/L Seignette salt PST, and the removal efficient of zine ion reaches 99%;
Ultrafiltration membrane system commonly used such as the Millipore ultrafiltration system (the small-sized cross-flow ultrafiltration of labscale TFF system, Congent-M ultrafiltration system, Pellicon ultrafiltration system) of U.S. Millipore Corp.,
1500 pressure type ultrafiltration membrane system that GE company produces,
CP pressure type ultrafiltration system of SIEMENS company.
Said in the reverse osmosis isolation process, the working pressure of use is controlled at 0.7～1.0MPa, Zn in the water outlet
2+Concentration is reduced to 0.1-0.5mg/L, and the average removal efficient of zine ion is 90%, goes out water power and leads and be reduced to 50 μ S/cm; 25 ℃～35 ℃ of waste water working temperatures, reverse osmosis membrane technology producing water ratio is 60%～70%, average rejection is produced water water quality and is superior to the industrial circulating water water quality standard 92%～95%, can be back to industrial cycle water system or water quality requirement high use water spot;
YMRO-0.25-500 reverse osmosis water treatment system, Beijing that reverse osmosis membrane system commonly used such as Dongguan City benefit people water treatment Science and Technology Ltd. produce are opened and can be found the 2T/H single-stage reverse osmosis equipment that source environment project ltd generates.
Waste water after the above-mentioned processing; Carry out ultrafiltration membrane treatment technology earlier, carry out reverse osmosis membrane separation again, to guarantee the water outlet effect of r-o-; And the required energy of saving reverse osmosis equipment; Fully heavy metal in the concentrating spent liquor makes the concentration of metal ions in the liquid concentrator obtain bigger raising, is applicable to galvanic deposit recovery heavy metal;
The two-stage membrane separation process produces 30%～40% liquid concentrator; Gets into the equalizing tank reuse again through circulation, reclaim metallic zinc, the Rinsing Area of effluent reuse in the countercurrent rinsing device;, and realize that heavy metal contaminants can be realized reclaiming fully and zero release basically in the whole device.
The present invention compared with prior art has following advantage:
First; Use countercurrent rinsing device that the negative plate that uses in the electrolytic zinc production process is carried out rinsing; Along with producer is washed cleaner and cleaner to the battery lead plate that moves, the Pollutant levels in the rinse water are then increasingly high, and water consumption is few; Cleaning efficiency is high, and helps the reuse of waste water and the recovery of heavy metal ion.
Second; Utilize galvanic deposit earlier to zinc ion content higher countercurrent rinsing water outlet carry out the recovery of metallic zinc, waste water is through the processing of film, fully heavy metal in the concentrating spent liquor then; Make the concentration of metal ions in the liquid concentrator obtain bigger raising; Combine with electro-deposition techniques, be highly suitable for the electrolytic recovery heavy metal, be easy to realize circulating Reuse of Waste Water.Combine electro-deposition techniques and membrane separation treating process, give full play to the advantage of galvanic deposit and membrane separation technique, solved the problem of electrochemical reduction processing mode existence in the past.
The 3rd, the purification of waste water reuse of heavy metal containing wastewater treatment and heavy metal reclaim simultaneously and accomplish, and have realized the benign cycle of producing and handling.
The 4th, to the waste water of different concns and composition corresponding treatment process mode is proposed, for the appropriate design of device and the optimization of operating process provide theoretical direction.
Waste water after this art breading of the present invention all is back in the countercurrent rinsing device; Replenish the required water yield in the countercurrent rinsing device; Produce processing back return of waste water from waste water, formed a water cycle, running cost is low; Whole technology has only the discharge reuse outlet of a clear water, and heavy metal contaminants can be realized reclaiming fully and zero release basically.
Advantage according to countercurrent rinsing, galvanic deposit and membrane separation technique; Can reach minimum working cost and optimal separating efficiency, when realizing the qualified discharge of water, heavy metal resources in the efficient recovery waste water; In efficient recovery waste water, in the heavy metal, realize recycling of water.
Description of drawings
Fig. 1 is an electrolytic zinc rinsing process waste water zero emission treatment process method flow diagram of the present invention
Embodiment
Enumerate 1 embodiment below,, the present invention is further specified, but the present invention is not only limited to this embodiment in conjunction with accompanying drawing.
Embodiment 1
The inventive method step adopts the process combination of countercurrent rinsing-flat electric deposition device-three-dimensional electric deposition device-ultrafiltration membrane system-reverse osmosis membrane system, and concrete technical process is following:
First step: countercurrent rinsing
It is to be composed in series by four tanks that adverse current is cleaned, water inlet in the one-level groove (Rinsing Area) in the end, and from first step groove (dense tank) draining, the cleaning process of water (flow) direction and pole plate is in the opposite direction.The negative plate that uses in the electrolytic zinc production gets into countercurrent rinsing device and carries out rinsing, is introduced into first step countercurrent rinsing groove (dense tank), gets into last step groove (Rinsing Area) at last, accomplishes rinse cycle, countercurrent rinsing water outlet Zn
2+Concentration is about 3000mg/L;
Second step: galvanic deposit
Dense water after the rinsing gets into equalizing tank, regulates its water yield and flow velocity, gets into flat electric deposition device, three-dimensional electric deposition device again, reclaims metallic zinc in the waste water, Zn in the waste water after the galvanic deposit
2+Concentration is about 100mg/L;
Third step: membrane sepn
The waste water that galvanic deposit is come out, temperature are controlled at 20 ℃～35 ℃, get into ultrafiltration membrane system; Add 15mg/L Seignette salt PST, materials such as the suspended substance in the removal water, colloid, the removal efficient of zine ion reaches 99%; Get into reverse osmosis membrane system again, Zn in the reverse osmosis membrane system water outlet
2+Concentration is 0.1-0.5mg/L; The film separating system effluent recycling is in countercurrent rinsing device, and waste water is back to galvanic deposit equalizing tank before through two-stage film separating system gained liquid concentrator; Pass through flat electric deposition device, three-dimensional electric deposition device then, the metallic zinc in the reclamation film liquid concentrator.
And waste water recycling has only 1 mouth, from reverse osmosis system.Heavy metal contaminants can be realized reclaiming fully and zero release basically, and the waste water after the processing all is back in the countercurrent rinsing device, forms a water cycle.
Claims (3)
1. electrolytic zinc rinsing process method of wastewater treatment is characterized in that this method comprises three steps of combined treatment of countercurrent rinsing, galvanic deposit, membrane sepn:
First step: countercurrent rinsing
Countercurrent rinsing is to be composed in series by some tanks, water inlet in the one-level groove (that is, Rinsing Area) in the end, and from first step groove (that is, dense tank) draining, the cleaning process of water (flow) direction and pole plate is in the opposite direction.The negative plate that uses in the electrolytic zinc production technique gets in the countercurrent rinsing device and carries out rinsing, is introduced into first step countercurrent rinsing groove (that is, dense tank), gets into the last step groove (that is, Rinsing Area) of countercurrent rinsing groove at last, accomplishes the rinse cycle of pole plate.
Second step: galvanic deposit
Dense water after the rinsing gets into equalizing tank, regulates its water yield and flow velocity, gets into flat electric deposition device, three-dimensional electric deposition device again, reclaims metallic zinc in the waste water;
Third step: membrane sepn
Waste water after the galvanic deposit; Get into ultrafiltration membrane system, reverse osmosis membrane system successively; Waste water is back to galvanic deposit equalizing tank before through two-stage film separating system gained liquid concentrator, passes through flat electric deposition device, three-dimensional electric deposition device then; Metallic zinc in the reclamation film liquid concentrator, the film separating system effluent recycling is in countercurrent rinsing device;
Membrane sepn refers to that ultrafiltration membrane system separates with reverse osmosis membrane system;
And the waste water recycling water outlet has only 1 mouth, from reverse osmosis system;
Metallic zinc retrieve to come from two parts, a part is the electrodeposition process that derives from waste water behind the countercurrent rinsing, recovery be the metallic zinc in the waste water behind the countercurrent rinsing; A part derives from the waste water after the galvanic deposit in addition, is back to the electrodeposition process behind the electric deposition device through the liquid concentrator that produces behind ultrafiltration membrane system, the reverse osmosis membrane system, recovery be the metallic zinc in the liquid concentrator that the film system produces in this combination treatment method.
2. electrolytic zinc rinsing process method of wastewater treatment as claimed in claim 1; It is characterized in that: the operational condition of said three-dimensional galvanic deposit is: electrode materials is selected graphite anode/stainless steel cathode counter-electrodes for use; Bath voltage is 4.0V-8.0V, and electrolysis time is 60min-90min.
3. electrolytic zinc rinsing process method of wastewater treatment as claimed in claim 1 is characterized in that: said in the reverse osmosis isolation process, the working pressure of use is controlled at 0.7～1.0MPa, Zn in the water outlet
2+Concentration is 0.1-0.5mg/L, and the average removal efficient of zine ion is 90%.
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| CN103014782A (en) * | 2012-12-27 | 2013-04-03 | 云南云铜锌业股份有限公司 | Magnesium removal method in zinc electrolysis process |
| CN103663803A (en) * | 2012-09-17 | 2014-03-26 | 武汉环材科技有限公司 | Efficient electro-deposited heavy metal cleaning system |
| CN106673285A (en) * | 2016-11-29 | 2017-05-17 | 环境保护部华南环境科学研究所 | Resource recycling method for gold-containing electroplating wastewater |
| CN111018203A (en) * | 2019-12-27 | 2020-04-17 | 肇庆学院 | Nickel-containing heavy metal wastewater resource recovery device |
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Application publication date: 20120613 |