CN103243348A - Method and equipment for recovering heavy metal in electroplating wastewater - Google Patents
Method and equipment for recovering heavy metal in electroplating wastewater Download PDFInfo
- Publication number
- CN103243348A CN103243348A CN201310161883XA CN201310161883A CN103243348A CN 103243348 A CN103243348 A CN 103243348A CN 201310161883X A CN201310161883X A CN 201310161883XA CN 201310161883 A CN201310161883 A CN 201310161883A CN 103243348 A CN103243348 A CN 103243348A
- Authority
- CN
- China
- Prior art keywords
- ion exchange
- exchange resin
- heavy metal
- electroplating wastewater
- resin column
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Water Treatment By Electricity Or Magnetism (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention discloses a method and equipment for recovering heavy metal in electroplating wastewater, belonging to the technical field of electroplating wastewater disposal. The method comprises the following steps of: (1) performing ion exchange resin treatment on the electroplating wastewater, and enabling heavy metal ions in the electroplating wastewater to be adsorbed onto the ion exchange ions; (2) eluting the heavy metal ions adsorbed on the ion exchange ions through a regenerant to obtain a regenerated solution; and (3) electrolyzing the regeneration solution by adopting a rotational flow electrolysis technology, and separating out heavy metal on a negative electrode. The equipment comprises a resin exchange treatment unit and an electrolysis recovery treatment unit, wherein the electrolysis recovery treatment unit consists of a rotational flow electrolyzer and a reflux device for controlling the flow velocity of liquid. The concentration polarization can be avoided by introducing the rotational flow electrolysis technology, the simple substance ion finally electrolyzed is smoother and has more selectivity, the low-concentration regenerated solution can be electrolyzed, the electrolysis effect can be ensured, and the exchange resin regenerated solution treated by adopting an electrolysis method can be applied into practical engineering.
Description
Technical field
The present invention relates to the electroplating waste water treatment technology field, particularly relate to a kind of method and apparatus that reclaims heavy metal in the electroplating wastewater.
Background technology
Characteristics such as electroplating industry waste water has that the water yield is big, complicated component, environmental pollution are serious, precious metal and heavy metal are many, domestic improvement to such waste water at present, generally adopt general materialization treatment process to handle, adopt the accident pool that is back to not up to standard to continue to handle and after satisfying environmental requirement, discharge simultaneously.But there is following defective in this method: the one, and in the materialization treating processes, need to add a large amount of medicaments, and then produce a large amount of materialized muds, environment is caused secondary pollution; The 2nd, a large amount of precious metals in the electroplating wastewater and heavy metal can not get recycling, and have both caused environmental pollution, and the shortcoming of waste is arranged again.At the problems referred to above, people research and develop again, obtain technique means that ion exchange resin is combined with electrolysis tech, can better handle electroplating wastewater, reclaim heavy metal wherein simultaneously, but also there are some defectives to some extent in these technique means, because electrolytic process finally can produce concentration polarization, it is not high to have selectivity own, and the copper purity that electrolysis is come out is low, and is difficult in flakes, crinosity thorn pin hole, outward appearance is ugly, and current efficiency is low, can't the electrolysis low concentration solution etc. shortcoming, and then influence the operation of whole system, because these technology limitation cause electrolytic process processing and exchanging resin regeneration liquid also to rest on laboratory stage or lab scale, the pilot scale stage, be applied to that actual engineering handles then seldom.And, in routine techniques, when adopting ion exchange resin treatment and materialization to handle the processing mode that combines, usually the ion exchange resin treatment process is placed after the materialization treating processes, both can guarantee the stability of ion exchange resin, prolong its work-ing life, can make electroplating wastewater obtain sufficient purifying treatment again, ensure effluent quality.
Flourish along with the surface treatment industry, electroplating industry seems particularly important and has the characteristic of high speed development, cause the processing of electroplating industry waste water to seem more urgent thus, supervise people to seek a kind of not only environmental protection and saving but also can make the electroplating wastewater qualified discharge or reach the electroplating effluent treatment method of reuse water influent quality requirement.
Summary of the invention
Based on this, the objective of the invention is to overcome the defective of prior art, a kind of method that reclaims heavy metal in the electroplating wastewater is provided, this method can be avoided the generation of concentration polarization, and electrolytic process processing and exchanging resin regeneration liquid can be applied in the actual engineering.
For achieving the above object, the present invention takes following technical scheme:
A kind of method that reclaims heavy metal in the electroplating wastewater may further comprise the steps:
(1) electroplating wastewater is carried out ion exchange resin treatment, make heavy metal ion adsorbed on ion exchange resin in the electroplating wastewater;
(2) be adsorbed in heavy metal ion on the ion exchange resin with the regenerator wash-out, obtain regenerated liquid;
(3) adopt the eddy flow electrolysis tech, the control circular flow is 0.4～0.8m/s, voltage 2～4V, current density 50～200A/M
2, 10-30 ℃ of following electrolytic regeneration liquid belongs on the negative potential huge sum of money and separates out.
When adopting aforesaid method to handle electroplating wastewater, at first pass through ion exchange principle, heavy metal cation in the electroplating wastewater and the hydrogen ion on the ion exchange resin exchange mutually, hydrogen ion enters solution, and heavy metal cation is adsorbed in stationary phase---be on the ion exchange resin, use acid regenerator wash-out subsequently again, allow hydrogen ion in the washing and dehydrating integrated machine with heavy metal cation by eluting on the stationary phase, adopt the eddy flow electrolysis subsequently, under the condition of solution high-speed rotational, electrolysis in the heavy metal is come out, finish the purpose that reclaims heavy metal.Described circular flow is unit with the height of regenerated liquid in the per second circulation eddy flow electrolyzer, this parameter value one regularly, the absolute value of circular flow is relevant with the sectional area of used eddy flow electrolyzer, and the little then circular flow of sectional area absolute value is little, and greatly then the circular flow absolute value is big for sectional area.Because heavy metal ion is simpler relatively in the electroplating wastewater, general main is copper, nickel, zine ion, and cupric ion has bigger potential difference with respect to other metal ion in the electroplating wastewater, cupric ion is preferentially separated out at negative electrode, therefore adopt the eddy flow electrolysis tech, avoid the restriction that influenced by concentration polarization in traditional electrolytic process, can pass through simple eddy flow electrolytic condition, can electrolysis go out high-quality metal product.
Among embodiment, when adopting the eddy flow electrolysis, the control circular flow is 0.4～0.6m/s, voltage 2～3V, current density 100～200A/M therein
2, temperature is 15～25 ℃.
Among embodiment, described ion exchange resin is the special polymeric adsorbent of copper therein.The Hydrogen resin cation (R.C.) of producing as the Dow Chemical Company that copper is had special adsorptive power.General resin is difficult to cupric ion is separated, and copper ion concentration only is about 10g/L in the final regenerated liquid, and adopts the special polymeric adsorbent of this copper, can make in the regenerated liquid concentration of metal ions higher, reach about 40g/L, make current efficiency higher, can be recovered to purity and surpass 95% electrolytic metal simple substance.And this ion exchange resin is not easy to pollute, and the life-span can reach 3～5 years, has the characteristics of long service life.
Among embodiment, described regenerator is sulphuric acid soln therein.The routine that is chosen as of its concentration is selected, and control gets final product 5%～10%.Adopt regeneration of sulfuric acid and without regeneration of hydrochloric acid, produce vitriol, the gas that anode produces is oxygen, corrosive effect is little, also can not cause secondary pollution, the problem that produces the etching apparatus of poisonous chlorine and follow-up appearance when having avoided electrolysis produces, and the tail washings acidity height that produces after the electrolysis.And when the recovery metal was copper, the copper sulfate that produces after regenerator is handled was blue, can judge the terminal point of regenerating by color, rationally use regenerator to regenerate, and saved dosing.
Among embodiment, also comprise the electroplating wastewater through ion exchange resin treatment is carried out the step that materialization is handled therein.Electroplating wastewater is after ion exchange resin and materialization are handled the process that combines and handled, and the heavy metal content≤0.3mg/L in the water outlet can reach emission request, also can be back to electroplating system, solved electroplating wastewater, the particularly difficult difficult problem up to standard of acid copper waste water, and realization decrement discharge target.Complete materialization treating processes can guarantee effectively that water outlet reaches reuse water water inlet requirement or can reach discharging standards.
The present invention also provides a kind of method that adopts heavy metal in the above-mentioned recovery electroplating wastewater to reclaim the equipment of heavy metal in the electroplating wastewater, comprise the resins exchange processing unit and the electrolytic recovery processing unit that connect successively by pipeline, be in series with the lift pump that promotes that waste water flows on the described pipeline; Described electrolytic recovery processing unit is the eddy flow electrolysis cells, and this eddy flow electrolysis cells comprises the reflux of eddy flow electrolyzer and control flow rate of liquid.
By reflux regenerated liquid is circulated, form tangential force, reduce the concentration polarization effect, for electrolysis provides good environment, electrolysis goes out smooth metal simple-substance, and has more selectivity, the regenerated liquid of energy electrolysis lower concentration, guaranteed electrolysis effectiveness, electrolytic process processing and exchanging resin regeneration liquid can be applied in the actual engineering.Described reflux both can be installed on eddy flow electrolyzer inside, formed internal reflux, can be installed on eddy flow electrolyzer outside again, and formed backflow between the outside vessel.Described reflux mainly is made up of reflux pump and under meter, can control to produce constant flow velocity, and the electrolysis of assurance eddy flow is carried out under a stable environment.
Among embodiment, described resins exchange processing unit comprises wastewater collecting basin, guard column, ion exchange resin column, the regenerating unit that connects successively therein; Described regenerating unit comprises regenerator Scatula, the regenerative pump that connects successively, and described regenerative pump is connected with the ion exchange resin water side.The water side of described ion exchange resin column also is provided with resin and catches gripper, conductivity meter and pH meter, resin is caught gripper can prevent that resin runs off, the total amount that guarantees resin is constant, can also judge the resins exchange situation according to conductivity meter and pH meter, rationally uses regenerator to regenerate.The electroplating wastewater that wastewater collecting basin can make different time sections discharge mixes therein, reaches the purpose of water quality homogeneous.This guard column can be held back suspended matter and macrobead colloid, prevents from stopping up the resin hole, ensures the resins exchange effect, thereby reaches the purpose of protection resin.Counter-current regeneration is adopted in resin regeneration, is conducive to guarantee effluent quality.Described guard column and ion exchange resin column all are provided with the backwash system, prevent the suspended substance occluding device, cause that pressure reduction increases phenomenon.
Therein among embodiment, described ion exchange resin column is two, be respectively ion exchange resin column A and ion exchange resin column B, between this ion exchange resin column A water side and the ion exchange resin column B water intake end, and all be connected by pipeline between ion exchange resin column B water side and the ion exchange resin column A water intake end, be equipped with switching valve on this pipeline; The water intake end of described ion exchange resin column A and ion exchange resin column B all is connected with guard column, and water intake end and the water side of ion exchange resin column A and ion exchange resin column B are equipped with valve.Adopt above-mentioned mode of connection, cooperate the open and close of valve, can be connected in series to the not back of regeneration by the ion exchange resin column that regeneration is good, reach better ion-exchange effect.And because the series connection of two posts, and the resin effect is identical, and when a resin column fault, another also can normally move, and has avoided the impact of waste water to physicochemical treatment unit.
Therein among embodiment, described eddy flow electrolysis cells also comprises the current stabilizer of controlling electric current, regenerated liquid receiving tank and the circulation of elecrolyte groove that connects successively, described regenerated liquid receiving tank connects the resin switch processing unit, and described circulation of elecrolyte groove is also interconnection by two circulation of elecrolyte pipelines with the eddy flow electrolyzer; Described circulation of elecrolyte groove also is connected by the tail washings circulation tube with the resins exchange unit; Described eddy flow electrolyzer shell is made by insulating material, and anode is made of titanium, and negative electrode is made by stainless steel.After the eddy flow electrolysis was finished, the electrolysis tail washings directly entered the resins exchange unit by the tail washings circulation tube, was used for regenerating resin.Shell uses insulating material, has guaranteed the security of operation, and anode uses the titanium rod, be not easy to corrosion, increased work-ing life on the one hand, can also make tail washings not contaminated on the other hand, do not have other secondary pollutant, can be directly used in regenerating resin, reach the purpose of tail washings recycle.Negative electrode uses stainless steel polar plate, is conducive to coming off and having cheap advantage of copper sheet.
Among embodiment, this equipment also comprises by the physicochemical treatment unit of pipe connection after the resins exchange processing unit therein.The materialization treating processes is put in after the ion-exchange, and intractability is little, stably reaching standard easily, and it is low that mud contains the heavy metal amount, can not cause the wasting of resources, and mud is handled than the direct materialization of electroplating wastewater and lack a lot.Complete materialization treating processes can guarantee effectively that water outlet reaches reuse water water inlet requirement or can reach discharging standards.
Therein among embodiment, described physicochemical treatment unit comprises the resin water outlet water collecting basin, the pH regulator pond that connect successively, reserves oxidation pond, coagulation basin, flocculation basin, settling tank and clean water basin; Described settling tank bottom is ramped shaped, and the lowest part of this ramped shaped bottom is provided with the spoil disposal pipeline.Because resin adopts acid regeneration, the initial stage goes out the acidity of water height after the regeneration, and the resin water outlet that makes different times by resin water outlet water collecting basin is at this mixed equilibrium, and pH value tends towards stability, and guarantees that the later stage transfers pH simply stable; So this resin water outlet water collecting basin has the effect of stabilizing water quality.Relatively poor when effluent quality, when having the part complex compound to precipitate, start to reserve oxidation pond, drop into oxygenant, allow the complex compound oxidation precipitation, effluent quality is guaranteed.
Compared with prior art, the present invention has following beneficial effect:
The method of heavy metal in the recovery electroplating wastewater of the present invention, by having adopted the eddy flow electrolysis tech, can under rotational flow at a high speed, produce tangential force, thereby mixing solutions have been avoided concentration polarization, the elemental metals that final electrolysis is come out is more smooth, and have more selectivity, the regenerated liquid of energy electrolysis lower concentration, the heavy metal concentration that is about to contain in the heavy metal solution is handled below the 1g/L, guaranteed electrolysis effectiveness, electrolytic process processing and exchanging resin regeneration liquid can be applied in the actual engineering.
And this method is because the resin regeneration agent of adopting is sulfuric acid, and anode uses reasons such as titanium rod, makes that the tail washings after the electrolysis can be directly used in regeneration, has reduced investment and the management of equipment.This method is a technology that turns waste into wealth, and can create profit, and be applicable in the actual engineering, is conducive to its implementation in electroplating wastewater processing, has started new situation for the processing of electroplating wastewater, further promotes the development of electroplating waste water treatment technology.
The equipment of heavy metal in the recovery electroplating wastewater of the present invention by the application of eddy flow electrolysis cells, reduces the concentration polarization effect, for electrolysis provides good environment, electrolytic process processing and exchanging resin regeneration liquid can be applied in the actual engineering.And the electrolysis tail washings in the electrolytic recovery processing unit is not contaminated, can be directly used in regenerating resin, reaches the purpose of tail washings recycle.
Exchange column in the resins exchange processing unit adopts switching mode to connect simultaneously, can be connected in series to the not back of regeneration by the resin column that regeneration is good, and effluent quality is guaranteed.
Description of drawings
Fig. 1 is each integral part connection diagram of the equipment of heavy metal in the embodiment 1 described recovery electroplating wastewater;
Fig. 2 is equipment intermediate ion exchange resin column A and B and the regenerating unit connection diagram of heavy metal in the embodiment 1 described recovery electroplating wastewater.
Wherein: 1. wastewater collecting basin; 2. waste water lift pump; 3. guard column; 4. ion exchange resin column A; 5. ion exchange resin column B; 6. regenerated liquid receiving tank; 7. regenerated liquid lift pump; 8. circulation of elecrolyte groove; 9. electrolytic solution reflux pump; 10. eddy flow electrolyzer; 11. resin water outlet water collecting basin; 12. physical reaction inlet water lifting pumps; 13.pH equalizing tank I; 14. reservation oxidation pond; 15.pH equalizing tank II; 16. coagulation basin; 17. flocculation basin; 18. settling tank; 19. clean water basin; 20. spoil disposal pipeline; 21. circulation of elecrolyte pipeline; 22. qualified discharge; 23. sludge thickener; 24. plate-and-frame filter press; Handle 25. filter cake committee is outer; 26. regeneration Scatula; 27. regeneration pond; 28. tail washings lift pump; 29. regenerative agent lift pump; 30. regeneration water pump; A. ion exchange resin column A water intaking valve; B. switching valve; C. ion exchange resin column B outlet valve; D. ion exchange resin column B water intaking valve; E. switching valve; F. ion exchange resin column A outlet valve; G. regenerator water intaking valve; H. regenerator water intaking valve; I. regenerated liquid outlet valve, J. regenerated liquid outlet valve.
Embodiment
Describe the present invention in detail below in conjunction with the drawings and specific embodiments.
Embodiment 1
As shown in Figure 1, a kind of equipment that reclaims heavy metal in the electroplating wastewater, comprise the resins exchange processing unit and the electrolytic recovery processing unit that connect successively by pipeline, and by the physicochemical treatment unit of pipe connection after the resins exchange processing unit, be in series with the lift pump that promotes that waste water flows on the described pipeline.
Comprise described resins exchange the processing unit successively wastewater collecting basin 1 that connects, waste water lift pump 2, guard column 3, two adopt ion exchange resin column A4 that switching mode connects and ion exchange resin column B5, regenerating unit each other.The water side of described ion exchange resin column also is provided with resin and catches gripper, conductivity meter and pH meter.As shown in Figure 2; between described ion exchange resin column A4 water side and the ion exchange resin column B5 water intake end; and all be connected by pipeline between ion exchange resin column B5 water side and the ion exchange resin column A4 water intake end; be equipped with switching valve on this pipeline; be respectively switching valve B and switching valve E; and the water intake end of ion exchange resin column A4 and ion exchange resin column B5 all is connected with guard column; water intake end and the water side of ion exchange resin column A4 and ion exchange resin column B5 are equipped with valve, are respectively ion exchange resin column A water intaking valve A; ion exchange resin column B water intaking valve D; ion exchange resin column A outlet valve F; ion exchange resin column B outlet valve C.In actual applications, can adopt water intaking valve A water inlet, switching valve B water outlet, water intaking valve D water inlet then enters ion exchange column B, the mode of outlet valve C water outlet; Also can adopt water intaking valve D water inlet, ion exchange column A is advanced in switching valve E water outlet then, the mode of outlet valve F water outlet; By above-mentioned switching mode, can be connected in series to the not back of regeneration by the ion exchange resin column that regeneration is good, reach better ion-exchange effect.Described regenerating unit comprises regenerator Scatula 26, the regenerative agent lift pump 29 that connects successively, also comprises the regeneration pond 27 that connects the ion exchange resin column water side by regeneration water pump 30.Described regeneration water pump 30 is connected by pipeline with the water side of ion exchange resin column B5 with ion exchange resin column A4 respectively, be respectively equipped with regenerator water intaking valve G and regenerator water intaking valve H on this pipeline, and the water intake end of ion exchange resin column A4 and ion exchange resin column B5 also is respectively equipped with regenerated liquid outlet valve I and regenerated liquid outlet valve J, and this regenerated liquid outlet valve I and regenerated liquid outlet valve J all are connected with regenerated liquid receiving tank 6 in the eddy flow electrolysis cells.When ion exchange resin column B5 regenerates, can intake outlet valve F water outlet by water intaking valve A; During 4 regeneration of ion exchange column Resin A, can intake by water intaking valve D, outlet valve C water outlet realizes switching also assurance and moves continuously.Regenerative agent can enter ion exchange column Resin A 4 or ion exchange resin column B5 from water intaking valve G or water intaking valve H, and regenerated liquid comes out from outlet valve I or outlet valve J.
Described electrolytic recovery processing unit is the eddy flow electrolysis cells, and this eddy flow electrolysis cells comprises the reflux of eddy flow electrolyzer 10, control flow rate of liquid and the current stabilizer of control electric current.Described reflux mainly is made up of reflux pump (being electrolytic solution reflux pump 9 in this example) and under meter.Described eddy flow electrolysis cells also comprises regenerated liquid receiving tank 6, regenerated liquid lift pump 7 and the circulation of elecrolyte groove 8 that connects successively, described regenerated liquid receiving tank 6 connects ion exchange resin column, described circulation of elecrolyte groove 8 is also interconnection by two circulation of elecrolyte pipelines 21 with the eddy flow electrolyzer, and described reflux pump and under meter are located on this circulation line; Described circulation of elecrolyte groove 8 also with the resins exchange unit in regenerator Scatula 26 be connected by the tail washings circulation tube, this pipeline is provided with tail washings lift pump 28; Described eddy flow electrolyzer 10 shells are made by insulating material, and anode is made of titanium, and negative electrode is made by stainless steel.
Described physicochemical treatment unit comprises resin water outlet water collecting basin 11, physical reaction inlet water lifting pumps 12, pH regulator pond I13, reservation oxidation pond 14, pH regulator pond II15, coagulation basin 16, flocculation basin 17, settling tank 18 and the clean water basin 19 that connect successively; Described settling tank 18 bottoms are ramped shaped, and the lowest part of this ramped shaped bottom is provided with spoil disposal pipeline 20.
Embodiment 2
It is as follows to adopt the equipment of heavy metal in the recovery electroplating wastewater of embodiment 1 to reclaim in the electroplating wastewater method of heavy metal:
At first making copper ion concentration is that the electroplating industry acid copper waste water of 200-300mg/L enters wastewater collecting basin 1; stopped 6 hours; can play the effect of stabilizing water quality; put forward positive delivery to guard column 3 through waste water lift pump 2 then; adorn inert plastic (plastics ball float) in this guard column 3; be used for holding back suspended matter and the part colloidalmaterial of waste water, purpose is to reduce suspended substance to enter ion exchange resin column, improves the ion exchange resin column operation stability.Enter ion exchange resin column A4 and the ion exchange resin column B5 of series connection again, what this ion exchange resin column adopted that Tao Shi develops has the Ambersep M64 resin of special absorption to copper, the exchange column tank body is that diameter is 3000mm, highly be the cylindrical of 4000mm, the 10 cubes of resins of packing into are handled flow velocity and are kept 90m
3/ h.Two ion exchange resin columns adopt the switching mode operation, and waste water passes through the not good ion exchange resin column of regeneration earlier, by regeneration ion exchange resin column well, guarantees effluent quality again.
Electroplating wastewater by ion exchange resin column enters mixing in the resin water outlet water collecting basin 11, stops 1h, makes water quality more stable, and entering useful volume by physical reaction inlet water lifting pumps 12 then is 40m
3, be equipped with among the pH regulator pond I13 of macropore aeration head the bottom, regulates pH with sodium hydroxide, stops 27min.The reason that selection is regulated pH with sodium hydroxide is its good water solubility, is difficult for separating out in solution, regulates pH as adopting calcium hydroxide, and its solubleness is lower, may produce the problem of stopping up miscellaneous equipment in the reuse process.Entering useful volume again is 135m
3, the bottom is equipped with in the reservation oxidation pond 14 of macropore aeration head and is stopped 1.5h, and then entering useful volume is 40m
3, be equipped with among the pH regulator pond II15 of macropore aeration head the bottom, regulates pH with sodium hydroxide, stops 27min.Entering useful volume then is 40m
3, be equipped with in the coagulation basin 16 of macropore aeration head the bottom, adds the PAC(polymerize aluminum chloride) and as coagulating agent, this moment, aeration mainly played the effect of composite waste, stopped 27min.Entering useful volume again is 40m
3, the macropore aeration head is equipped with in the bottom, and be equipped with stirrer flocculation basin 17 in stop 27min, this moment, aeration rate was little, mainly stirred with stirrer, and flco is not broken up.Then entering again and imitating volume is 180m
3, (useful volume is 90m to be divided into the gravitational settling district
3) and (useful volume is 90m in the tube settling district
3) settling tank 18 in stop 2h.Entering useful volume through the clear water of post precipitation is 135m
3, the clean water basin 19 that the macropore aeration head is equipped with in the bottom return adjust pH as required, and stop 1.5h therein.Final maybe can enter reuse in the intermediate water reuse system through the clear water of handling well the qualified discharge 22 that meets the demands, reclamation rate is higher than 60%.Wherein the mud that obtains through precipitation is discharged by spoil disposal pipeline 20, enters in the sludge thickener 23, forms filter cake after plate-and-frame filter press 24 press filtrations, and filter cake committee is outer to handle 25.
When judging that by conductivity meter and pH meter or color ion exchange resin column need be regenerated, adopt row's regeneration in the 5% sulfuric acid adverse current, controlling regeneration velocity with electronic grout flow meter or spinner-type flowmeter is 2BV/h, it is the 1.5-2BV of resin that regeneration consumes 5% sulfuric acid, and the lower concentration regenerated liquid of generation is used for applying mechanically regeneration to be used.
Regenerated liquid behind the wash-out enters in the regenerated liquid receiving tank 6, and the volume of this regenerated liquid receiving tank is 20m
3, guarantee to load the electrolytic solution of twice regeneration, as required, can also be provided with another regenerated liquid receiving tank, mainly collect the lower concentration regenerated liquid, be used for applying mechanically regeneration and use.The regenerated liquid that concentration is fit to is promoted by regenerated liquid lift pump 7 and enters in the circulation of elecrolyte groove 8, because the effect of electrolytic solution reflux pump 9, make regenerated liquid pass through circulation of elecrolyte pipeline 21 and in eddy flow electrolyzer 10 and circulation of elecrolyte groove 8, form closed return-flow system, guarantee liquid circulation at a high speed always in the eddy flow electrolyzer 10, form tangential force, electrolysis goes out smooth copper sheet.During the eddy flow electrolysis, the control flow is 0.4m/s, voltage 2.4V, current density 100A/M
2, 15 ℃ of following electrolysis, the copper purity that final electrolysis obtains is more than 99%.And the tail washings that electrolysis finishes to produce is used for regenerating resin again, reaches the purpose of tail washings recycle.
Embodiment 3
Adopt the equipment of heavy metal in the recovery electroplating wastewater of embodiment 1 to reclaim the method for heavy metal in the electroplating wastewater, and embodiment 2 different being:
When (1) ion exchange resin column is regenerated, row's regeneration in the sulfuric acid adverse current of employing 10%.
(2) during the eddy flow electrolysis, the control flow is 0.6m/s, voltage 4V, current density 200A/M
2, 25 ℃ of following electrolysis.
Extract the water sample in each stage in above-described embodiment 2 and 3 treatment schemees, detect wherein content of copper ion, specific conductivity and pH value, the results are shown in following table 1.
Each stage water sample information slip of table 1. electroplating wastewater processing.
By result in the above-mentioned table 1 as can be known, after treatment, the content of copper ion in the electroplating wastewater significantly reduces, and reaches " electroplating industry pollution discharge standard " requirement.
According to the method among the embodiment 2, electroplating wastewater is handled with different resins, adopt the method regenerating resin among the embodiment 2, detect the copper ion concentration in the regenerated liquid, result such as following table 2.
After table 2. different resins carries out ion-exchange, copper ion concentration information slip in the regenerated liquid.
By result in the above-mentioned table 2 as can be known, adopt the special polymeric adsorbent of copper among the embodiment 2 to handle electroplating wastewater after, copper ion concentration is far above other resins, for the effect of postorder eddy flow electrolysis provides guarantee in its regenerated liquid.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. method that reclaims heavy metal in the electroplating wastewater is characterized in that may further comprise the steps:
(1) electroplating wastewater is carried out ion exchange resin treatment, make heavy metal ion adsorbed on ion exchange resin in the electroplating wastewater;
(2) be adsorbed in heavy metal ion on the ion exchange resin with the regenerator wash-out, obtain regenerated liquid;
(3) adopt the eddy flow electrolysis tech, the control circular flow is 0.4～0.8m/s, voltage 2～4V, current density 50～200A/M
2, 10-30 ℃ of following electrolytic regeneration liquid belongs on the negative potential huge sum of money and separates out.
2. the method for heavy metal in the recovery electroplating wastewater according to claim 1 is characterized in that, when adopting the eddy flow electrolysis, the control circular flow is 0.4～0.6m/s, voltage 2～3V, current density 100～200A/M
2, temperature is 15～25 ℃.
3. the method for heavy metal in the recovery electroplating wastewater according to claim 1 is characterized in that, described ion exchange resin is the special polymeric adsorbent of copper.
4. the method for heavy metal in the recovery electroplating wastewater according to claim 1 is characterized in that described regenerator is sulphuric acid soln.
5. according to the method for heavy metal in each described recovery electroplating wastewater of claim 1-4, it is characterized in that, also comprise the electroplating wastewater through ion exchange resin treatment is carried out the step that materialization is handled.
6. the method for heavy metal reclaims the equipment of heavy metal in the electroplating wastewater in the recovery electroplating wastewater that adopts claim 1, comprise the resins exchange processing unit and the electrolytic recovery processing unit that connect successively by pipeline, be in series with the lift pump that promotes that waste water flows on the described pipeline; It is characterized in that: described electrolytic recovery processing unit is the eddy flow electrolysis cells, and this eddy flow electrolysis cells comprises the reflux of eddy flow electrolyzer and control flow rate of liquid.
7. the equipment of heavy metal in the recovery electroplating wastewater according to claim 6 is characterized in that: described resins exchange processing unit comprises wastewater collecting basin, guard column, ion exchange resin column, the regenerating unit that connects successively; Described regenerating unit comprises regenerator Scatula, the regenerative pump that connects successively, and described regenerative pump is connected with the ion exchange resin water side.
8. the equipment of heavy metal in the recovery electroplating wastewater according to claim 7, it is characterized in that: described ion exchange resin column is two, be respectively ion exchange resin column A and ion exchange resin column B, between this ion exchange resin column A water side and the ion exchange resin column B water intake end, and all be connected by pipeline between ion exchange resin column B water side and the ion exchange resin column A water intake end, be equipped with switching valve on this pipeline; The water intake end of described ion exchange resin column A and ion exchange resin column B all is connected with guard column, and water intake end and the water side of ion exchange resin column A and ion exchange resin column B are equipped with valve.
9. the equipment of heavy metal in the recovery electroplating wastewater according to claim 6, it is characterized in that: described eddy flow electrolysis cells also comprises the current stabilizer of controlling electric current, regenerated liquid receiving tank and the circulation of elecrolyte groove that connects successively, described regenerated liquid receiving tank connects the resin switch processing unit, and described circulation of elecrolyte groove is also interconnection by two circulation of elecrolyte pipelines with the eddy flow electrolyzer; Described circulation of elecrolyte groove also is connected by the tail washings circulation tube with the resins exchange unit; Described eddy flow electrolyzer shell is made by insulating material, and anode is made of titanium, and negative electrode is made by stainless steel.
10. the equipment of heavy metal in the recovery electroplating wastewater according to claim 6, it is characterized in that: this equipment also comprises by the physicochemical treatment unit of pipe connection after the resins exchange processing unit.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310161883.XA CN103243348B (en) | 2013-05-03 | 2013-05-03 | Method and equipment for recovering heavy metal in electroplating wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310161883.XA CN103243348B (en) | 2013-05-03 | 2013-05-03 | Method and equipment for recovering heavy metal in electroplating wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103243348A true CN103243348A (en) | 2013-08-14 |
| CN103243348B CN103243348B (en) | 2014-09-17 |
Family
ID=48923220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310161883.XA Active CN103243348B (en) | 2013-05-03 | 2013-05-03 | Method and equipment for recovering heavy metal in electroplating wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103243348B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833167A (en) * | 2014-03-13 | 2014-06-04 | 黄运富 | Chromic acid wastewater treatment method and system |
| CN104108818A (en) * | 2014-08-05 | 2014-10-22 | 浙江科菲科技股份有限公司 | Heavy metal-containing wastewater treatment method by virtue of ion exchange and cyclone electrolysis technologies |
| CN104418408A (en) * | 2013-08-30 | 2015-03-18 | 上海轻工业研究所有限公司 | Copper-electroplating wastewater treatment method and copper-electroplating wastewater treatment equipment |
| CN104775035A (en) * | 2015-04-30 | 2015-07-15 | 江苏地一环保科技有限公司 | Electrolytic treatment technology for low-copper electroplating wastewater |
| WO2015165234A1 (en) * | 2014-04-30 | 2015-11-05 | 南京大学 | Method for decontamination treatment and utilization as resource of ion exchange resin desorption solution |
| CN110980876A (en) * | 2019-11-21 | 2020-04-10 | 武汉百富环保工程有限公司 | Treatment process for recovering copper and recycling chromium from passivation solution |
| CN113388866A (en) * | 2021-06-25 | 2021-09-14 | 定颖电子(黄石)有限公司 | Combined recovery system and method for palladium-containing waste liquid of circuit board |
| CN113698031A (en) * | 2021-08-10 | 2021-11-26 | 广西贵港市蓝月亮水处理环保科技有限公司 | Method and equipment for recovering precious metals from comprehensive wastewater |
| CN115465979A (en) * | 2022-10-08 | 2022-12-13 | 青岛理工大学 | Rotational flow electrolysis-ion exchange coupling system and method for deeply removing and recovering heavy metal ions in water body |
| CN115537816A (en) * | 2022-10-08 | 2022-12-30 | 青岛理工大学 | Rotational flow electrolysis system and method for regeneration of acidic copper chloride etchant and copper recovery |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3875639A1 (en) * | 2020-03-04 | 2021-09-08 | AT & S Austria Technologie & Systemtechnik Aktiengesellschaft | Method for manufacturing printed circuit boards and / or substrates within a valuable material circuit |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1403385A (en) * | 2001-09-03 | 2003-03-19 | 陈正书 | Double-recovering circulation method for cyanic electroplating effluent and heavy metal-containing electroplating effluent |
| CN101041483A (en) * | 2007-02-16 | 2007-09-26 | 曹喜平 | Industrial wastewater treatment method and system |
| CN101580957A (en) * | 2009-06-05 | 2009-11-18 | 东莞庞思化工机械有限公司 | Method and device for purifying and recycling chromium electroplating solution and waste solution thereof |
| US20100163491A1 (en) * | 2008-12-03 | 2010-07-01 | Rainer Bauder | System and method for wastewater treatment |
| CN101787547A (en) * | 2010-02-09 | 2010-07-28 | 中南大学 | Method for recovering valuable metals from waste printed circuit board |
| CN101974689A (en) * | 2010-09-26 | 2011-02-16 | 金川集团有限公司 | Method for processing material containing copper |
| CN102295321A (en) * | 2011-09-06 | 2011-12-28 | 冯云香 | Method for treating acid copper-containing waste liquor of printed-circuit board and producing electrolytic copper |
-
2013
- 2013-05-03 CN CN201310161883.XA patent/CN103243348B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1403385A (en) * | 2001-09-03 | 2003-03-19 | 陈正书 | Double-recovering circulation method for cyanic electroplating effluent and heavy metal-containing electroplating effluent |
| CN101041483A (en) * | 2007-02-16 | 2007-09-26 | 曹喜平 | Industrial wastewater treatment method and system |
| US20100163491A1 (en) * | 2008-12-03 | 2010-07-01 | Rainer Bauder | System and method for wastewater treatment |
| CN101580957A (en) * | 2009-06-05 | 2009-11-18 | 东莞庞思化工机械有限公司 | Method and device for purifying and recycling chromium electroplating solution and waste solution thereof |
| CN101787547A (en) * | 2010-02-09 | 2010-07-28 | 中南大学 | Method for recovering valuable metals from waste printed circuit board |
| CN101974689A (en) * | 2010-09-26 | 2011-02-16 | 金川集团有限公司 | Method for processing material containing copper |
| CN102295321A (en) * | 2011-09-06 | 2011-12-28 | 冯云香 | Method for treating acid copper-containing waste liquor of printed-circuit board and producing electrolytic copper |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104418408A (en) * | 2013-08-30 | 2015-03-18 | 上海轻工业研究所有限公司 | Copper-electroplating wastewater treatment method and copper-electroplating wastewater treatment equipment |
| CN103833167A (en) * | 2014-03-13 | 2014-06-04 | 黄运富 | Chromic acid wastewater treatment method and system |
| CN103833167B (en) * | 2014-03-13 | 2016-06-08 | 黄运富 | Chromic acid method of wastewater treatment and treatment system |
| WO2015165234A1 (en) * | 2014-04-30 | 2015-11-05 | 南京大学 | Method for decontamination treatment and utilization as resource of ion exchange resin desorption solution |
| CN104108818A (en) * | 2014-08-05 | 2014-10-22 | 浙江科菲科技股份有限公司 | Heavy metal-containing wastewater treatment method by virtue of ion exchange and cyclone electrolysis technologies |
| CN104108818B (en) * | 2014-08-05 | 2016-01-27 | 浙江科菲科技股份有限公司 | A kind of method using ion-exchange and cyclone electrolytic cell technical finesse heavy metal wastewater thereby |
| CN104775035A (en) * | 2015-04-30 | 2015-07-15 | 江苏地一环保科技有限公司 | Electrolytic treatment technology for low-copper electroplating wastewater |
| CN110980876A (en) * | 2019-11-21 | 2020-04-10 | 武汉百富环保工程有限公司 | Treatment process for recovering copper and recycling chromium from passivation solution |
| CN113388866A (en) * | 2021-06-25 | 2021-09-14 | 定颖电子(黄石)有限公司 | Combined recovery system and method for palladium-containing waste liquid of circuit board |
| CN113698031A (en) * | 2021-08-10 | 2021-11-26 | 广西贵港市蓝月亮水处理环保科技有限公司 | Method and equipment for recovering precious metals from comprehensive wastewater |
| CN115465979A (en) * | 2022-10-08 | 2022-12-13 | 青岛理工大学 | Rotational flow electrolysis-ion exchange coupling system and method for deeply removing and recovering heavy metal ions in water body |
| CN115537816A (en) * | 2022-10-08 | 2022-12-30 | 青岛理工大学 | Rotational flow electrolysis system and method for regeneration of acidic copper chloride etchant and copper recovery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103243348B (en) | 2014-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103243348B (en) | Method and equipment for recovering heavy metal in electroplating wastewater | |
| CN101648757B (en) | Recycling processing method for stainless steel processing process wastewater grading precipitation | |
| CN102603097B (en) | Advanced treatment and recycling process for wastewater containing heavy metal ions | |
| CN101648759B (en) | Recycling processing method for wastewater produced by processing stainless steel | |
| CN100482594C (en) | Electrodeionization water-purifying device and method for recovering cation and anion without scaling | |
| CN103539283B (en) | Comprehensive treatment method for removing Sb and Bi impurities in Cu electrolyte | |
| CN103539294B (en) | Reclaim the method for silver-plated waste water and silver | |
| CN104478140A (en) | Non-ferrous smelting waste acid purification treatment method | |
| CN105858987A (en) | Recycling treatment process for recovering pure water and pure nickel from electro-nickelling rinsing wastewater | |
| CN104355365A (en) | Chromium-containing wastewater treatment method capable of realizing zero emission of pollutants | |
| CN103693773A (en) | Chromium-containing waste water reuse treatment method | |
| CN110422948A (en) | Copper sulphate Sewage treatment metallic copper treatment process is electroplated | |
| CN101935126A (en) | Combined treatment method for electro-deposition and membrane separation of zinc-containing heavy metal waste water | |
| CN101708908B (en) | Novel method for treating electroplating chromium-containing wastewater and recovering metal ions | |
| CN201021439Y (en) | An antiscaling electric ion removal and cleaning device and recycling negative ion and positive ion | |
| CN203602414U (en) | System for recovering silvering wastewater and silver | |
| CN101549920A (en) | Method for recovering nickel salts in nickel-electroplating waste water | |
| CN203270048U (en) | Equipment for recycling heavy metal in electroplating wastewater | |
| CN112159005A (en) | Treatment process and treatment system for aluminum processing anode waste liquid | |
| CN104108818B (en) | A kind of method using ion-exchange and cyclone electrolytic cell technical finesse heavy metal wastewater thereby | |
| CN201762103U (en) | Separating system for inorganic acid and inorganic acid salt in waste acid | |
| CN106116029B (en) | A kind of processing system of industrial wastewater | |
| CN105731696B (en) | Silicon carbide pickling waste water reclaiming treatment process | |
| CN213924392U (en) | Recovery processing device of nickeliferous waste liquid | |
| CN103787467A (en) | Equipment and process for treating nickel-cobalt wastewater in hydrometallurgy industry through electrolytic method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: GUANGDONG NEW DAYU ENVIRONMENTAL TECHNOLOGY CO., L Free format text: FORMER NAME: GUANGDONG XINDAYU ENVIRONMENTAL ENGINEERING CO., LTD. |
|
| CP03 | Change of name, title or address |
Address after: 510000 Guangdong City, Luogang District Science City, science Avenue, No. 182, C2 District, floor third, annex building, unit 310 Patentee after: GUANGDONG XINDAYU ENVIRONMENTAL PROTECTION TECHNOLOGY CO., LTD. Address before: 510660, Luogang District District, Guangdong hi tech Industrial Development Zone, science Avenue, No. 182, C2 District, third storey, annex 310, building, Guangzhou Patentee before: Guangdong Xindayu Environmental Engineering Co., Ltd. |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160510 Address after: 510000 Guangdong City, Luogang District Science City, science Avenue, No. 182, C2 District, floor third, annex building, unit 310 Patentee after: GUANGDONG XINDAYU ENVIRONMENTAL PROTECTION TECHNOLOGY CO., LTD. Patentee after: Zhongshan Mingyu sewage treatment Co., Ltd. Address before: 510000 Guangdong City, Luogang District Science City, science Avenue, No. 182, C2 District, floor third, annex building, unit 310 Patentee before: GUANGDONG XINDAYU ENVIRONMENTAL PROTECTION TECHNOLOGY CO., LTD. |
|
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 510000 Guangdong science and Technology Development Zone, Guangzhou City, Department of science and Technology Department, No. two street, room 17, room 101 Co-patentee after: Zhongshan Mingyu sewage treatment Co., Ltd. Patentee after: GUANGDONG XINDAYU ENVIRONMENTAL PROTECTION TECHNOLOGY CO., LTD. Address before: 510000 Guangdong City, Luogang District Science City, science Avenue, No. 182, C2 District, floor third, annex building, unit 310 Co-patentee before: Zhongshan Mingyu sewage treatment Co., Ltd. Patentee before: GUANGDONG XINDAYU ENVIRONMENTAL PROTECTION TECHNOLOGY CO., LTD. |