CN101555081B - Technology for processing and recycling electroplating wastewater containing cyanide and system thereof - Google Patents
Technology for processing and recycling electroplating wastewater containing cyanide and system thereof Download PDFInfo
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- CN101555081B CN101555081B CN2009103016104A CN200910301610A CN101555081B CN 101555081 B CN101555081 B CN 101555081B CN 2009103016104 A CN2009103016104 A CN 2009103016104A CN 200910301610 A CN200910301610 A CN 200910301610A CN 101555081 B CN101555081 B CN 101555081B
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Abstract
The invention relates to a technology for processing and recycling wastewater and a system thereof, in particular to a technology for processing and recycling electroplating wastewater containing cyanide and a system thereof. The processing steps are as follows: a level I reverse osmosis device with high recovery rate is used for separating salt substance from the wastewater containing cyanide; then an electrolysis unit is used for removing cyanide and heavy metal in the reverse osmosis concentrated water; and then a level II reverse osmosis device is used for concentrating the wastewater. Thewastewater containing cyanide is concentrated by 95 to 120 times. By combing the level II reverse osmosis process with the electrolytic process, the technology has the advantages of reducing consumpt ion of chemicals, simplifying operating process and recycling heavy metals of high purity compared with the traditional chemical method.
Description
Technical field
The present invention relates to a kind of waste water treatment process and system thereof, relate in particular to processing and the reuse technology and the system thereof of electroplating cyanic waste water.
Background technology
Plating is one of the current whole world three big contaminated industries.According to incomplete statistics, the annual electroplating wastewater of discharging of national electroplating industry has 40 billion cubic meters approximately, is equivalent to the tap water supply amount of several big and medium-sized cities, the shortage of serious exacerbate water resource.
Generally handle electroplating wastewater at present with following method:
Chemical method: in waste water, add medicament, make wherein toxic substance transform into the throw out that non-toxic substance or toxicity greatly reduce.Chemical method comprises: the neutralization precipitation method, in and coagulant sedimentation, oxidation style, reduction method, barium salt process, ferrite process etc.
Chemical method equipment is simple, invests lessly, uses wider.Need further to handle but often stay mud, and the electroplating wastewater dispersion, mud is difficult for focusing on and utilizing; Chemical method needs the chemical agent of labor, and a large amount of medicaments have increased running cost, increase the weight of business burden; Chemical method can not be recycled the water resources in the electroplating wastewater etc., does not meet the requirement of the cleaner production of country's proposition.
Physico-chemical processes: mainly comprise electrolytic process, ion exchange method and membrane separation process evaporation concentration method etc.
Electrolysis is electric current causes chemical transformation through material a process.Chemical transformation is that material loses the perhaps process of electron gain.Electrolytic process carries out in electrolyzer, and electrolyzer is to be made up of two electrodes of yin, yang that are immersed in respectively in the solution that contains positive and negative ion.Electric current flows to negative potential (negative electrode), and positive ion positively charged in the solution is moved to negative electrode, and combines with electronics, becomes neutral element or molecule; Electronegative negative ion is moved to another electrode (anode), provides electronics, becomes neutral element or molecule.
Cyanide wastewater occupies sizable ratio in electroplating wastewater; Because the toxicity of cyanogen own is very big; Cause cyanide wastewater hazardness strong especially, all to the strictness especially of cyanogen content regulation, cause cyanide wastewater is emphasis and the difficult point of handling in the electroplating wastewater always for environmental regulation and standard.
Chinese patent (application number 200410022037.0) cyanide wastewater treatment process; The cyanide wastewater treatment process of introducing is cyanide wastewater to be sent in the electrolyzer that function positive (being composited by electro-conductive material net, gac and non-conducting material net) is housed carry out electrolysis, and anode is emitted O
2, O
2At gac and Cu
2+Comprehensive absorption and katalysis under, with CN
-Be oxidized to N
2And CO
2And be removed; The galvanic deposit or form precipitation of hydroxide and be removed on negative electrode of heavy metal and precious metal ion.Waste water each item water-quality guideline after the processing reaches discharging standards.But the water quality that obtains is not fine, and energy consumption is than higher, and waste water can not reuse, and treatment effect is not ideal enough.
Summary of the invention
The present invention provides mainly that a kind of reuse is effective, and energy consumption is low, has realized zero release, effectively removes cyanogen class and the electroplating cyanic waste water of other various objectionable impuritiess in the electroplating cyanic waste water; It is bad to solve existing in prior technology reuse effect, and energy consumption is big, the dissatisfactory technical problem of water treatment effect.
Above-mentioned technical problem of the present invention mainly is able to solve through following technical proposals: a kind of processing of electroplating cyanic waste water and reuse technology, and it comprises the following step: pre-treatment is carried out with electroplating cyanic waste water in (1), removes the mechanical impurity in the waste water; (2) handle through first-stage reverse osmosis through pretreated filtered water, cyanogen class material and heavy metal class saliferous material thereof are removed, produce water and be recycled to the reuse water tank; (3) will pass through the dense water process two-pass reverse osmosis processing that contains cyanogen class and heavy metal class that first-stage reverse osmosis is handled, and produce water and be recycled to the reuse water tank; The liquid concentrator that contains cyanogen class and heavy metal class that (4) will pass through after two-pass reverse osmosis is handled carries out electrolysis treatment; The electrolysis of cyanogen class material is to discharge behind carbonic acid gas and the nitrogen; The heavy metal reduction is reclaimed heavy metal at electrolytic negative electrode, in the dense water tank before return of waste water is handled to two-pass reverse osmosis.
This technology is handled the back through first-stage reverse osmosis and has been obtained the technology pure water on the one hand, can be used as the use water of technology, dense on the other hand water through behind the two-pass reverse osmosis for electrolysis provides liquid concentrator, thereby improved electrolytic efficiency.Under the effect of liquid concentrator electric current in electrolyzer, cyanogen class (CN
-) have negative electricity, shift to anode, and lose electronics, the oxidized N that resolves into
2And CO
2Thereby be discharged Deng gas, and then reduce the content of prussiate in the cyanide wastewater, the heavy metal ion in the waste water is (like Cu
2+, Ag
1 +, Zn
2+Deng) have positive electricity, shift to negative electrode and obtain electronics, become metal simple-substance; In addition cyanogen class material depositing the electroconductibility that has strengthened electrolysis wastewater, make current efficiency improve, and strengthen electrolyzer counterweight metal recovery rate; Reach the purpose that reduces pollutent in the waste water through above electrolyzer, electrowinning process has not only reclaimed the heavy metal in the waste water, and has reached the purpose of broken cyanide.Above-mentioned technology is at first removed big impurity through pre-treatment; Obtain liquid concentrator through two-pass reverse osmosis then; So that the better effect of performance cyanogen class in electrowinning process; Improve electrolyzing rate to improve the treatment effect of waste water, reached the target of " zero release ", simultaneously the waste water after the electrolysis is got back to the two-pass reverse osmosis operation concentrated electrolysis treatment that circulates again.
As preferably, described pre-treatment is carried out micro-filtration or ultrafiltration for adopting microfiltration membrane or ultra-filtration membrane.Electroplating wastewater contains trace impurity, adopts accurate filter to carry out pre-treatment and can prevent the obstruction of reverse osmosis membrane effectively with the big Impurity removal in the waste water, prolong the cleaning interval, thereby convenient back operation is handled further to waste water.
As preferably, described two-pass reverse osmosis has concentrated 95～120 times with electroplating cyanic waste water, and the dense water of first-stage reverse osmosis has been concentrated 8～12 times.Two-pass reverse osmosis further concentrates dense water, increases the cyanogen class concentration of the inside, thereby strengthens the electrolyzing rate of back one one-step electrolysis operation, improves the effect of wastewater treatment.
Corresponding system comprises the wastewater collection pond with the treatment process of above-mentioned electroplating wastewater; It comprises the wastewater collection pond; The wastewater collection pond is connecting pretreatment unit, and pretreatment unit is connecting the first-stage reverse osmosis device, and the water purification mouth of first-stage reverse osmosis device is connecting the reuse water tank; The concentrated water spout of first-stage reverse osmosis device is connecting the water-in and the two-pass reverse osmosis device of first-stage reverse osmosis device respectively through pipeline; The concentrated water spout of two-pass reverse osmosis device is connecting electrolyzer, and the water purification mouth of two-pass reverse osmosis device is connecting the wastewater collection pond, and electrolyzer is through the water-in of pipe connection to the two-pass reverse osmosis device.The said system compact construction, floor space is little, the waste water recovery that can circulate, the two-pass reverse osmosis device further concentrates dense water, thereby improves electrolytic efficiency, makes that waste water reclamation efficient is higher.Return of waste water circular treatment behind the electrolytic tank electrolysis reclaims, and has effectively removed the objectionable impurities in the waste water.The mounting or dismounting of this cover system are convenient, can the repeated multiple times utilization.First-stage reverse osmosis is the high-recovery reverse osmosis unit; Through increasing the reverse osmosis membrane surface velocity; Reduce the risk of reverse osmosis membrane surface concentration polarization, and most of dense water that refluxes, thereby cyanide wastewater has been concentrated 8-12 doubly; And the recovery pure water, first-stage reverse osmosis device water comprehensive utilization ratio is at 75%-95%.
As preferably, described pretreatment unit is micro-filtration, ultrafiltration or accurate filter.As more preferably, described pretreatment unit accurate filter.
As preferably, be provided with intermediate water tank between described pretreatment unit and the first-stage reverse osmosis device, intermediate water tank is connected on the first-stage reverse osmosis device through security personnel's strainer and HPP.The precision of security personnel's strainer is 5 μ m.Intermediate water tank is used to collect the filtered water of pretreatment unit, reduces the energy consumption of device.
As preferably, be provided with dense water tank between described first-stage reverse osmosis device and the two-pass reverse osmosis device, dense water tank is connected on the two-pass reverse osmosis device through security personnel's strainer and HPP.Dense water tank is used to collect the dense water of first-stage reverse osmosis device, and security personnel protect filter and gone out the particulate matter in the dense water simultaneously.
As preferably, described reverse osmosis membrane adopts alkali-proof polyamide reverse osmose membrane.It is the rolled film of polyimide that described reverse osmosis membrane adopts material, can anti-PH＞10, and the rolled film treatment effect is good, and is simple in structure.
Therefore; The processing of electroplating cyanic waste water of the present invention has following advantage with reuse technology and system thereof: the first-stage reverse osmosis device with high-recovery separates the salts substances in the cyanide wastewater; Again with cyanogen class in the electrolyzer removal reverse osmosis concentrated water and heavy metal etc.; Concentrate waste water with the two-pass reverse osmosis device again, cyanide wastewater is concentrated 95-120 doubly; The combined process of two-pass reverse osmosis operation and electrowinning process makes technology of the present invention compare with the traditional chemical method, has reduced the consumption of chemical, has simplified operating process, can reclaim highly purified heavy metal; In technology of the present invention, the cyanogen class and the heavy metal that can't pass reverse osmosis membrane all are back to dense water tank, and the electrolytic action of process electrolyzer, and electroplating wastewater is in constantly degraded circulation, and the water yield does not have loss, has reached the target of " zero release "; The present invention simultaneously has compact construction, and structural manufacturing process is simple relatively, can effectively remove cyanogen class and other various objectionable impuritiess in the electroplating cyanic waste water, the corresponding waste water of reuse, and this cover system dismounting, easy to assembly can repeated multiple times be used.
Description of drawings:
Fig. 1 is the processing of electroplating cyanic waste water of the present invention and the synoptic diagram of reuse technology.
Fig. 2 is the processing of electroplating cyanic waste water of the present invention and the synoptic diagram of reclaiming system.
Embodiment:
Pass through embodiment below, and combine accompanying drawing, do further bright specifically technical scheme of the present invention.
Embodiment:
As shown in Figure 1, a kind of processing of electroplating cyanic waste water and reuse technology, it comprises the following step: the pre-treatment of ultrafiltration is carried out with electroplating cyanic waste water in (1), removes impurity bigger in the waste water; (2) handle through first-stage reverse osmosis through pretreated filtered water, cyanogen class material and heavy metal class saliferous material thereof can not pass through reverse osmosis membrane, are trapped within the dense water, produce the water recovery and use for producing; (3) will pass through the dense water process of the first-stage reverse osmosis that contains cyanogen class and the heavy metal class two-pass reverse osmosis processing that first-stage reverse osmosis is handled, two-pass reverse osmosis has concentrated 8-12 doubly with the dense water of first-stage reverse osmosis, produces water and reclaims for the production use; The liquid concentrator that contains cyanogen class and heavy metal class that (4) will pass through after two-pass reverse osmosis is handled carries out electrolysis treatment, under the effect of liquid concentrator electric current in electrolyzer, and cyanogen class (CN
-) have negative electricity, shift to anode, and lose electronics, the oxidized N that resolves into
2And CO
2Thereby be discharged Deng gas, and then reduce the content of prussiate in the cyanide wastewater, the heavy metal ion in the waste water is (like Cu
2+, Ag
1+, Zn
2+Deng) have positive electricity, shift to negative electrode and obtain electronics, become metal simple-substance; In addition cyanogen class material depositing the electroconductibility that has strengthened electrolysis wastewater, make current efficiency improve, and strengthen electrolyzer counterweight metal recovery rate; Again concentrated electrolysis treatment circulates in the dense water tank before return of waste water is handled to two-pass reverse osmosis.
The technical indicator of the waste water of the above-mentioned processing of process reaches:
Water use efficiency:＞99%
The heavy metal recovery:＞98%
The heavy metal purity that reclaims:＞95%
Reuse water cost: 2-4 unit/ton
Reuse water specific conductivity:＜20 μ s/cm
Reuse water heavy metal content:＜0.1ppm
Through embodiment, can realize the zero release of electroplating wastewater, and reclaim the heavy metal more than 98% in the waste water that system operation is easy.
As shown in Figure 2, corresponding to the processing and the reclaiming system of the electroplating cyanic waste water of aforesaid operations technology, comprise the wastewater collection pond 1 that after undue matter is collected, enters by plating shop waste water; Mainly comprise cyanogen class and heavy metal contaminants in the electroplating cyanic waste water; Wastewater collection pond 1 is connected on the ultra-filtration equipment 3 through topping-up pump 2, removes impurity bigger in the waste water etc., and ultra-filtration equipment 3 is connected to intermediate water tank 4; Intermediate water tank 4 is connected on the first-stage reverse osmosis device 7 with HPP 6 through security personnel's strainer 5; Cyanogen class material and other heavy metal class saliferous materials can not see through reverse osmosis membrane, thereby are trapped within dense water side, are discharged by concentrated water spout; The dense water of a part is discharged into dense water tank 8 by outlet, and another part concentrate recirculation is recycled to HPP 6 front ends of first-stage reverse osmosis device 7 front ends.Water moleculess etc. can see through reverse osmosis membrane, and collect in the water purification side, flow to reuse water tank 9 from the water purification mouth, and reuse water tank 9 is directly connected to the water of productive use system; Dense water tank 8 is connected to two-pass reverse osmosis device 10 through security personnel's strainer 5 with HPP 6; Two-pass reverse osmosis device 10 dense water end (W.E.)s are connected electrolyzer 11 and wastewater collection pond 1 respectively with the clear water end; Through the inspissated of two-pass reverse osmosis device 10, heavy metal ion content is concentrated to about 100 times in the electroplating wastewater, and electrolyzer 11 is electrolyzed to produce free of contamination materials such as carbonic acid gas and nitrogen with cyanogen class material; With reduction such as heavy metal at electrolytic negative electrode; Thereby the content of cyanogen class and heavy metal in the reduction waste water reclaims the heavy metal in the electroplating wastewater, and the discharge of wastewater after the electrolysis is to the recovery that circulates of dense water tank 8.
Utilize electrolytic again technology behind technology of the present invention, the reverse osmosis process now respectively, also have, utilize these three kinds of technologies to handle electroplating cyanic waste water respectively and handle, draw down column data through test through electrolytic again technology after the two-pass reverse osmosis technology:
(like Cu2+, Zn2+) be example, the electrolytic power consumption and the heavy metal rate of recovery the results are shown in Table 1 with bivalent metal ion.
Table 1
| Electrolytic power consumption (kwh/m3 waste water) divalence is an example | The heavy metal recovery | |
| Technology of the present invention (contain cyanogen and electroplate water) | 0.43 | ＞97％ |
| 1 grade of RO+ electrolysis (contain cyanogen and electroplate water) | 0.52 | ＞90％ |
| 2 grades of RO+ electrolysis (non-cyanogen plating water) | 0.45 | ＞95％ |
Electrolytic power consumption is with respect to total wastewater flow rate.
Claims (6)
1. the processing of an electroplating cyanic waste water and reuse technology, it is characterized in that: it comprises the following step: the pre-treatment of ultrafiltration is carried out with electroplating cyanic waste water in (1), removes impurity bigger in the waste water; (2) handle through first-stage reverse osmosis through pretreated filtered water, cyanogen class material and heavy metal class saliferous material thereof are trapped within the dense water, produce the water recovery and use for producing; (3) will pass through the dense water process two-pass reverse osmosis processing that contains cyanogen class and heavy metal class that first-stage reverse osmosis is handled, the dense water of first-stage reverse osmosis concentrated 8-12 doubly, and produce water and reclaim for the production use; The liquid concentrator that contains cyanogen class and heavy metal class that (4) will pass through after two-pass reverse osmosis is handled carries out electrolysis treatment; The electrolysis of cyanogen class material is to discharge behind carbonic acid gas and the nitrogen; The heavy metal reduction is reclaimed heavy metal at electrolytic negative electrode, and concentrated electrolysis treatment again circulates in the dense water tank before return of waste water is handled to two-pass reverse osmosis.
2. the corresponding system of the processing of electroplating cyanic waste water according to claim 1 and reuse technology; It is characterized in that: it comprises the wastewater collection pond; The wastewater collection pond is connecting pretreatment unit, and pretreatment unit is connecting the first-stage reverse osmosis device, and the water purification mouth of first-stage reverse osmosis device is connecting the reuse water tank; The concentrated water spout of first-stage reverse osmosis device is connecting the water-in and the two-pass reverse osmosis device of first-stage reverse osmosis device respectively through pipeline; The concentrated water spout of two-pass reverse osmosis device is connecting electrolyzer, and the water purification mouth of two-pass reverse osmosis device is connecting the wastewater collection pond, and electrolyzer is through the water-in of pipe connection to the two-pass reverse osmosis device.
3. the corresponding system of the processing of electroplating cyanic waste water according to claim 2 and reuse technology, it is characterized in that: described pretreatment unit is micro-filtration, ultrafiltration or accurate filter.
4. according to the processing and the corresponding system of reuse technology of claim 2 or 3 described electroplating cyanic waste waters; It is characterized in that: be provided with intermediate water tank between described pretreatment unit and the first-stage reverse osmosis device, intermediate water tank is connected on the first-stage reverse osmosis device through security personnel's strainer and HPP.
5. according to the processing and the corresponding system of reuse technology of claim 2 or 3 described electroplating cyanic waste waters; It is characterized in that: be provided with dense water tank between described first-stage reverse osmosis device and the two-pass reverse osmosis device, dense water tank is connected on the two-pass reverse osmosis device through security personnel's strainer and HPP.
6. according to the processing and the corresponding system of reuse technology of claim 2 or 3 described electroplating cyanic waste waters, it is characterized in that: described reverse osmosis membrane adopts alkali-proof polyamide reverse osmose membrane.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830592B (en) * | 2010-05-11 | 2014-01-15 | 吴志文 | Nickel-containing washing waste water recycling treatment system |
| CN102092878B (en) * | 2010-12-08 | 2013-04-24 | 湖州森蓝环境工程有限公司 | Treatment method of heavy metal organic industrial waste water |
| CN102502994B (en) * | 2011-11-09 | 2014-07-16 | 北京纬纶华业环保科技股份有限公司 | Method and system for treating cyanide-containing wastewater at low concentration |
| CN102583862B (en) * | 2012-02-22 | 2015-07-01 | 北京纬纶华业环保科技股份有限公司 | Method and system for treating saline wastewater to zero discharge and recycling |
| CN104230113B (en) * | 2014-09-23 | 2016-03-02 | 扬州佳境环境科技股份有限公司 | A kind of electroplating and complexing waste water zero discharge treatment process |
| CN107151042A (en) * | 2016-03-02 | 2017-09-12 | 上海丰信环保科技有限公司 | Anti-pollution reverse-osmosis system |
| CN105671317B (en) * | 2016-03-24 | 2018-10-12 | 中山品高电子材料有限公司 | A kind of plating noble metal recovery system |
| CN111517556A (en) * | 2020-05-14 | 2020-08-11 | 逸辰环保科技(厦门)有限公司 | Electroplating wastewater treatment process and system |
| CN111908678A (en) * | 2020-07-02 | 2020-11-10 | 逸辰环保科技(厦门)有限公司 | Process and system for guaranteeing safe discharge of electroplating wastewater |
| CN112723616A (en) * | 2020-12-14 | 2021-04-30 | 九江德福科技股份有限公司 | Wastewater recycling method |
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