CN103243348B - 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
- CN103243348B CN103243348B CN201310161883.XA CN201310161883A CN103243348B CN 103243348 B CN103243348 B CN 103243348B CN 201310161883 A CN201310161883 A CN 201310161883A CN 103243348 B CN103243348 B CN 103243348B
- 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.)
- Active
Links
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
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 electroplating waste water treatment technology field, particularly relate to a kind of method and apparatus that reclaims heavy metal out of electroplating wastewater.
Background technology
Electroplating industry waste water has that the water yield is large, complicated component, environmental pollution are serious, precious metal and the feature such as heavy metal is many, the domestic improvement to such waste water at present, generally adopt general materialization treatment process processing, simultaneously adopt not up to standard be back to accident pool continue process after meeting environmental requirement, discharge.But there is following defect in the method: the one, and in materialization treating processes, need to add a large amount of medicaments, and then produce a large amount of materialized muds, environment is caused to secondary pollution; The 2nd, a large amount of precious metals in electroplating wastewater and heavy metal can not get recycling, and have both caused environmental pollution, have again the shortcoming of waste.For the problems referred to above, people are studied again exploitation, obtain the technique means that ion exchange resin is combined with electrolysis tech, can better process electroplating wastewater, reclaim heavy metal wherein simultaneously, but also there are some defects in these technique means to some extent, because electrolytic process finally can produce concentration polarization, there is selectivity own not high, electrolysis copper purity is out low, and be difficult in flakes, crinosity thorn pin hole, outward appearance is ugly, current efficiency is low, cannot electrolysis low concentration solution etc. shortcoming, and then affect the operation of whole system, due to the restriction of these technology, 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 the little of Practical Project processing.And, in routine techniques, while adopting the processing mode that ion exchange resin treatment and materialization processing combine, conventionally after ion exchange resin treatment process being placed in to materialization treating processes, both can ensure the stability of ion exchange resin, extend its work-ing life, can make again electroplating wastewater obtain sufficient purifying treatment, ensure effluent quality.
Flourish along with Surface Processing Industry, electroplating industry seems particularly important and has the characteristic of high speed development, cause thus the processing of electroplating industry waste water to seem more urgent, supervise people to seek a kind of not only environmental protection and saving but also can make 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 object of the invention is to overcome the defect of prior art, a kind of method that reclaims heavy metal out of electroplating wastewater is provided, the method can be avoided the generation of concentration polarization, and electrolytic process processing and exchanging resin regeneration liquid can be applied in Practical Project.
For achieving the above object, the present invention takes following technical scheme:
A method that reclaims heavy metal out of electroplating wastewater, comprises the following steps:
(1) electroplating wastewater is carried out to ion exchange resin treatment, make heavy metal ion adsorbed on ion exchange resin in electroplating wastewater;
(2) be adsorbed in the heavy metal ion on ion exchange resin with regenerator wash-out, obtain regenerated liquid;
(3) adopt cyclone electrolytic cell technology, controlled circulation flow is 0.4～0.8m/s, voltage 2～4V, current density 50～200A/M
2, electrolytic regeneration liquid at 10-30 DEG C, belongs on negative potential a huge sum of money and separates out.
While adopting aforesaid method to process electroplating wastewater, first pass through ion exchange principle, hydrogen ion on heavy metal cation and ion exchange resin in electroplating wastewater exchanges mutually, hydrogen ion enters solution, and heavy metal cation is adsorbed in stationary phase---be on ion exchange resin, use again subsequently acid regenerator wash-out, allow hydrogen ion in washing and dehydrating integrated machine by heavy metal cation by eluting on stationary phase, adopt subsequently cyclone electrolytic cell, under the condition of solution high-speed rotational, by electrolysis in heavy metal out, complete the object that reclaims heavy metal.Described circular flow is taking the height of regenerated liquid in circulation cyclone electrolytic cell device per second as unit, this parameter value one timing, the absolute value of circular flow is relevant with the sectional area of cyclone electrolytic cell device used, and the little circular flow of sectional area absolute value is little, and greatly circular flow absolute value is large for sectional area.Because heavy metal out of electroplating wastewater ion is relatively simple, general main is copper, nickel, zine ion, and cupric ion has larger potential difference with respect to other metal ion in electroplating wastewater, cupric ion is preferentially separated out at negative electrode, therefore adopt cyclone electrolytic cell technology, avoid the restriction that affected by concentration polarization in traditional electrolytic process, can, by simple cyclone electrolytic cell condition, can electrolysis go out high-quality metal product.
In an embodiment, while adopting cyclone electrolytic cell, controlled circulation flow is 0.4～0.6m/s, voltage 2～3V, current density 100～200A/M therein
2, temperature is 15～25 DEG C.
In an embodiment, described ion exchange resin is the special polymeric adsorbent of copper therein.As what the Dow Chemical Company produced, copper is had to the Hydrogen resin cation (R.C.) of special adsorptive power.General resin is difficult to cupric ion to separate, and in final regenerated liquid, copper ion concentration is only 10g/L left and right, and adopts the special polymeric adsorbent of this copper, can make in regenerated liquid concentration of metal ions higher, reach 40g/L left and right, make current efficiency higher, can be recovered to purity and exceed 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 feature of long service life.
In an embodiment, described regenerator is sulphuric acid soln therein.The routine that is chosen as of its concentration is selected, and is controlled at 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 while having avoided electrolysis produces, and the tail washings acidity producing after electrolysis is high.And in the time that recovery metal is copper, the copper sulfate producing after regenerator is processed is blue, can judge regeneration terminal by color, rationally use regenerator to regenerate, saving dosing.
In an embodiment, also comprise the step of the electroplating wastewater through ion exchange resin treatment being carried out to materialization processing therein.After the process that electroplating wastewater combines through ion exchange resin and materialization processing is processed, the heavy metal content≤0.3mg/L in water outlet, can reach emission request, also can be back to electroplating system, solve electroplating wastewater, the particularly difficult difficult problem up to standard of acid copper waste water, and realize decrement discharge target.Complete materialization treating processes can effectively ensure that water outlet reaches reuse water water inlet and requires or can reach discharging standards.
The present invention also provides a kind of equipment that adopts the method for above-mentioned recovery heavy metal out of electroplating wastewater to reclaim heavy metal out of electroplating wastewater, comprise the resins exchange processing unit and the electrolytic recovery processing unit that connect successively by pipeline, on described pipeline, be in series with and promote the mobile lift pump of waste water; Described electrolytic recovery processing unit is cyclone electrolytic cell unit, and this cyclone electrolytic cell unit comprises cyclone electrolytic cell device and controls the reflux of flow rate of liquid.
By reflux, regenerated liquid is circulated, form tangential force, reduce 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, ensure electrolysis effectiveness, electrolytic process processing and exchanging resin regeneration liquid can be applied in Practical Project.Described reflux both can be installed on cyclone electrolytic cell device inside, formed internal reflux, can be installed on again cyclone electrolytic cell device outside, and formed and reflux between outside vessel.Described reflux is mainly made up of reflux pump and under meter, can control and produce constant flow velocity, ensures that cyclone electrolytic cell carries out under a stable environment.
In an embodiment, described resins exchange processing unit comprises the wastewater collecting basin, guard column, ion exchange resin column, the regenerating unit that connect successively therein; Described regenerating unit comprises the regenerator Scatula, the regenerative pump that connect successively, and described regenerative pump is connected with ion exchange resin water side.The water side of described ion exchange resin column is also 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 ensures resin is constant, can also judge 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 object of water quality homogeneous.This guard column can be held back suspended matter and macrobead colloid, prevents from stopping up resin hole, ensures resins exchange effect, thereby reaches the object of protection resin.Resin regeneration adopts counter-current regeneration, is conducive to ensure effluent quality.Described guard column and ion exchange resin column are all provided with backwashing system, prevent suspended substance occluding device, cause that pressure reduction increases phenomenon.
Therein in an 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 ion exchange resin column B water intake end, and be all connected by pipeline between ion exchange resin column B water side and ion exchange resin column A water intake end, on this pipeline, be equipped with switching valve; The water intake end of described ion exchange resin column A and ion exchange resin column B is all 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, coordinate the open and close of valve, the ion exchange resin column of regenerate can be connected in series to do not regenerate after, reach better ion-exchange effect.And due to two post series connection, and 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 in an embodiment, described cyclone electrolytic cell unit also comprises regenerated liquid receiving tank and the circulation of elecrolyte groove of controlling the current stabilizer of electric current, connection successively, described regenerated liquid receiving tank connects resin switch processing unit, and described circulation of elecrolyte groove is also interconnection by two circulation of elecrolyte pipelines with cyclone electrolytic cell device; Described circulation of elecrolyte groove is also connected by tail washings circulation tube with resins exchange unit; Described cyclone electrolytic cell device shell is made up of insulating material, and anode is made of titanium, and negative electrode is made up of stainless steel.After cyclone electrolytic cell completes, electrolysis tail washings directly enters resins exchange unit by tail washings circulation tube, for regenerating resin.Shell uses insulating material, has ensured the security of operation, and anode uses titanium rod, be not easy to corrosion, increased work-ing life on the one hand, can also make on the other hand tail washings not contaminated, without other secondary pollutant, can be directly used in regenerating resin, reach the object of tail washings recycle.Negative electrode uses stainless steel polar plate, is conducive to coming off and having advantages of cheap of copper sheet.
Therein in an embodiment, this equipment also comprises by pipeline and is connected in the physicochemical treatment unit after resins exchange processing unit.After materialization treating processes is put in to ion-exchange, intractability is little, easily stably reaching standard, and mud is low containing heavy metal amount, can not cause the wasting of resources, and mud is processed few a lot than the direct materialization of electroplating wastewater.Complete materialization treating processes can effectively ensure that water outlet reaches reuse water water inlet and requires or can reach discharging standards.
In an embodiment, described physicochemical treatment unit comprises the resin water outlet water collecting basin, pH regulator pond, reserved oxidation pond, coagulation basin, flocculation basin, settling tank and the clean water basin that connect successively therein; Described settling tank bottom is ramped shaped, and the lowest part of this ramped shaped bottom is provided with spoil disposal pipeline.Because resin adopts acid regeneration, after regeneration, the in the initial stage of that to go out acidity of water high, makes the resin water outlet of different times at this mixed equilibrium by resin water outlet water collecting basin, and pH value tends towards stability, and ensures that the later stage adjusts pH simply stable; So this resin water outlet water collecting basin has the effect of stabilizing water quality.Poor when effluent quality, while having part complex compound to precipitate, start reserved oxidation pond, drop into oxygenant, allow complex compound oxidation precipitation, effluent quality is ensured.
Compared with prior art, the present invention has following beneficial effect:
The method of recovery heavy metal out of electroplating wastewater of the present invention, by having adopted cyclone electrolytic cell technology, can, under rotational flow at a high speed, produce tangential force, thereby mixing solutions be avoided concentration polarization, also make final electrolysis elemental metals out more smooth, and have more selectivity, the regenerated liquid of energy electrolysis lower concentration, is about to process below 1g/L containing the heavy metal concentration in heavy metal solution, ensure electrolysis effectiveness, electrolytic process processing and exchanging resin regeneration liquid can be applied in Practical Project.
And the method is because the resin regeneration agent adopting is sulfuric acid, and anode uses the reasons such as titanium rod, makes the tail washings after electrolysis can be directly used in regeneration, has reduced investment and the management of equipment.The method is a technology turning waste into wealth, and can create profit, and be applicable in Practical Project, 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 recovery heavy metal out of electroplating wastewater of the present invention, by the application of cyclone electrolytic cell unit, reduces concentration polarization effect, for electrolysis provides good environment, electrolytic process processing and exchanging resin regeneration liquid can be applied in Practical Project.And the electrolysis tail washings in electrolytic recovery processing unit is not contaminated, can be directly used in regenerating resin, reaches the object of tail washings recycle.
Simultaneously the exchange column in resins exchange processing unit adopts switching mode to connect, the resin column of regenerate can be connected in series to do not regenerate after, effluent quality is guaranteed.
Brief description of the drawings
Fig. 1 is the each integral part connection diagram that reclaims the equipment of heavy metal out of electroplating wastewater described in embodiment 1;
Fig. 2 is equipment intermediate ion exchange resin column A and B and the regenerating unit connection diagram that reclaims heavy metal out of electroplating wastewater described in embodiment 1.
Wherein: 1. wastewater collecting basin; 2. waste water lifting 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. cyclone electrolytic cell device; 11. resin water outlet water collecting basins; 12. physical reaction inlet water lifting pumps; 13.pH equalizing tank I; 14. reserved oxidation ponds; 15.pH equalizing tank II; 16. coagulation basins; 17. flocculation basins; 18. settling tanks; 19. clean water basin; 20. spoil disposal pipelines; 21. circulation of elecrolyte pipelines; 22. qualified discharges; 23. sludge thickeners; 24. plate-and-frame filter press; The outer processing of 25. filter cake committees; 26. regeneration Scatulas; 27. regeneration ponds; 28. tail washings lift pumps; 29. regenerative agent lift pumps; 30. regeneration water pumps; 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 out of electroplating wastewater, comprise the resins exchange processing unit and the electrolytic recovery processing unit that connect successively by pipeline, and be connected in resins exchange processing unit physicochemical treatment unit afterwards by pipeline, on described pipeline, be in series with and promote the mobile lift pump of waste water.
Described resins exchange processing unit comprise successively the wastewater collecting basin 1 that connects, waste water lifting pump 2, guard column 3, two adopt each other ion exchange resin column A4 that switching mode connects and ion exchange resin column B5, regenerating unit.The water side of described ion exchange resin column is also 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 ion exchange resin column B5 water intake end, and be all connected by pipeline between ion exchange resin column B5 water side and ion exchange resin column A4 water intake end, on this pipeline, be equipped with switching valve, 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 is all 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, be 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, then water intaking valve D water inlet, enters ion exchange column B, the mode of outlet valve C water outlet; Also can adopt water intaking valve D water inlet, switching valve E water outlet, then enters ion exchange column A, the mode of outlet valve F water outlet; By above-mentioned switching mode, the ion exchange resin column of having regenerated can be connected in series to not regeneration after, reach better ion-exchange effect.Described regenerating unit comprises the regenerator Scatula 26, the regenerative agent lift pump 29 that connect successively, also comprises the regeneration pond 27 that connects 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, on this pipeline, be respectively equipped with regenerator water intaking valve G and regenerator water intaking valve H, and the water intake end of ion exchange resin column A4 and ion exchange resin column B5 is also respectively equipped with regenerated liquid outlet valve I and regenerated liquid outlet valve J, this regenerated liquid outlet valve I is all connected with the regenerated liquid receiving tank 6 in cyclone electrolytic cell unit with regenerated liquid outlet valve J.In the time that ion exchange resin column B5 regenerates, can intake by water intaking valve A, outlet valve F water outlet; When ion exchange column Resin A 4 is regenerated, can intake by water intaking valve D, outlet valve C water outlet, realizes switching and ensureing 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 from outlet valve I or outlet valve J out.
Described electrolytic recovery processing unit is cyclone electrolytic cell unit, and this cyclone electrolytic cell unit comprises cyclone electrolytic cell device 10, controls the reflux of flow rate of liquid and the current stabilizer of control electric current.Described reflux is mainly made up of reflux pump (being electrolytic solution reflux pump 9 in this example) and under meter.Described cyclone electrolytic cell unit also comprises the regenerated liquid receiving tank 6, regenerated liquid lift pump 7 and the circulation of elecrolyte groove 8 that connect 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 cyclone electrolytic cell device, and described reflux pump and under meter are located on this circulation line; Described circulation of elecrolyte groove 8 is also connected by tail washings circulation tube with the regenerator Scatula 26 in resins exchange unit, and this pipeline is provided with tail washings lift pump 28; Described cyclone electrolytic cell device 10 shells are made up of insulating material, and anode is made of titanium, and negative electrode is made up of stainless steel.
Described physicochemical treatment unit comprises the resin water outlet water collecting basin 11, physical reaction inlet water lifting pumps 12, pH regulator pond I13, reserved 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
The method that the equipment of the recovery heavy metal out of electroplating wastewater of employing embodiment 1 reclaims heavy metal out of electroplating wastewater is as follows:
First making copper ion concentration is that the electroplating industry acid copper waste water of 200-300mg/L enters wastewater collecting basin 1; stop 6 hours; can play the effect of stabilizing water quality; then put forward positive delivery to guard column 3 through waste water lifting pump 2; in this guard column 3, fill inert plastic (plastic floating ball); for holding back suspended matter and the part colloidalmaterial of waste water, object is to reduce suspended substance to enter ion exchange resin column, improves ion exchange resin column operation stability.Enter again ion exchange resin column A4 and the ion exchange resin column B5 of series connection, what this ion exchange resin column adopted that Tao Shi develops has the Ambersep M64 resin of special absorption to copper, exchange column tank body is that diameter is 3000mm, be highly the cylindrical of 4000mm, pack 10 cubes of resins into, process flow velocity and keep 90m
3/ h.Two ion exchange resin columns adopt switching mode operation, and waste water is first by the ion exchange resin column of not regenerated, then the ion exchange resin column of getting well by regeneration, ensures effluent quality.
Entered in resin water outlet water collecting basin 11 and mixed by the electroplating wastewater of ion exchange resin column, stop 1h, make water quality more stable, then entering useful volume by physical reaction inlet water lifting pumps 12 is 40m
3, be equipped with in the pH regulator pond I13 of macropore aeration head bottom, regulates pH with sodium hydroxide, stops 27min.Selecting to regulate the reason of pH with sodium hydroxide is its good water solubility, is difficult for separating out in solution, and as adopted calcium hydroxide to regulate pH, its solubleness is lower, may in reuse process, produce the problem of stopping up miscellaneous equipment.Entering useful volume is 135m again
3, bottom is equipped with in the reserved oxidation pond 14 of macropore aeration head and is stopped 1.5h, and then entering useful volume is 40m
3, be equipped with in the pH regulator pond II15 of macropore aeration head bottom, regulates pH with sodium hydroxide, stops 27min.Then entering useful volume is 40m
3, be equipped with in the coagulation basin 16 of macropore aeration head bottom, adds PAC(polymerize aluminum chloride) and as coagulating agent, now aeration mainly plays the effect of composite waste, stops 27min.Entering useful volume is 40m again
3, macropore aeration head is equipped with in bottom, and be equipped with stirrer flocculation basin 17 in stop 27min, now aeration rate is little, mainly with stirrer stir, flco is not broken up.Then entering effect volume is 180m again
3, (useful volume is 90m to be divided into gravitational settling district
3) and (useful volume is 90m in tube settling district
3) settling tank 18 in stop 2h.It is 135m that clear water after precipitation enters useful volume
3, the clean water basin 19 that macropore aeration head is equipped with in bottom, return adjust pH as required, and stop therein 1.5h.Final maybe can enter reuse in 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%.The mud wherein obtaining through precipitation is discharged by spoil disposal pipeline 20, enters in sludge thickener 23, after plate-and-frame filter press 24 press filtrations, forms filter cake, and filter cake committee is outer processes 25.
In the time judging that by conductivity meter and pH meter or color ion exchange resin column need to be regenerated, adopt row's regeneration in 5% sulfuric acid adverse current, with electronic grout flow meter or spinner-type flowmeter control regeneration velocity be 2BV/h, regeneration consumes the 1.5-2BV that 5% sulfuric acid is resin, and the lower concentration regenerated liquid of generation is used for applying mechanically regeneration and uses.
Regenerated liquid after wash-out enters in 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 lower concentration regenerated liquid, use for applying mechanically regeneration.The applicable regenerated liquid of concentration is promoted and is entered in circulation of elecrolyte groove 8 by regenerated liquid lift pump 7, due to the effect of electrolytic solution reflux pump 9, make regenerated liquid pass through circulation of elecrolyte pipeline 21 and form closed return-flow system in cyclone electrolytic cell device 10 and circulation of elecrolyte groove 8, ensure liquid high-speed circulating always in cyclone electrolytic cell device 10, form tangential force, electrolysis goes out smooth copper sheet.When cyclone electrolytic cell, control flow is 0.4m/s, voltage 2.4V, current density 100A/M
2, electrolysis at 15 DEG C, the copper purity that final electrolysis obtains is more than 99%.And the tail washings that electrolysis finishes to produce is again for regenerating resin, reach the object of tail washings recycle.
Embodiment 3
The equipment of the recovery heavy metal out of electroplating wastewater of employing embodiment 1 reclaims the method for heavy metal out of electroplating wastewater, be different from embodiment 2:
(1) when ion exchange resin column is regenerated, row's regeneration in the sulfuric acid adverse current of employing 10%.
(2), when cyclone electrolytic cell, control flow is 0.6m/s, voltage 4V, current density 200A/M
2, electrolysis at 25 DEG C.
Embodiment 4 electroplating wastewater processing results
The water sample that extracts each stage in above-described embodiment 2 and 3 treatment schemees, detects wherein content of copper ion, specific conductivity and pH value, the results are shown in following table 1.
Water sample information slip of each stage of table 1. electroplating wastewater processing.
From result in above-mentioned table 1, after treatment, the content of copper ion in electroplating wastewater significantly reduces, and reaches " electroplating industry pollution discharge standard " requirement.
Embodiment 5 ion exchange resin absorbing copper ion effect tests
According to the method in embodiment 2, by electroplating wastewater different resins processing, adopt the method regenerating resin in embodiment 2, detect the copper ion concentration in regenerated liquid, result is as following table 2.
Table 2. different resins carries out after ion-exchange, copper ion concentration information slip in regenerated liquid.
From result in above-mentioned table 2, adopt the special polymeric adsorbent of copper in embodiment 2 to process after electroplating wastewater, in its regenerated liquid, copper ion concentration is far above other resins, for the effect of postorder cyclone electrolytic cell provides guarantee.
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 the scope of the claims of the present invention.It 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 (3)
1. reclaim a method for heavy metal out of electroplating wastewater, it is characterized in that comprising the following steps:
(1) electroplating wastewater is carried out to ion exchange resin treatment, make heavy metal ion adsorbed on ion exchange resin in electroplating wastewater;
(2) be adsorbed in the heavy metal ion on ion exchange resin with regenerator wash-out, obtain regenerated liquid;
(3) adopt cyclone electrolytic cell technology, control, controls flow is 0.4m/s, voltage 2.4V, and current density 100A/M2, electrolysis at 15 DEG C, makes to belong on negative potential and separate out with much money; Described ion exchange resin is the special polymeric adsorbent of copper; Described regenerator is sulphuric acid soln, and concentration is 5%～10%;
Also comprise the step of the electroplating wastewater through ion exchange resin treatment being carried out to materialization processing;
Wherein, the method that reclaims heavy metal out of electroplating wastewater adopts the equipment that reclaims heavy metal in electroplating wastewater, described equipment comprises the resins exchange processing unit and the electrolytic recovery processing unit that connect successively by pipeline, is in series with and promotes the mobile lift pump of waste water on described pipeline; Described electrolytic recovery processing unit is cyclone electrolytic cell unit, and this cyclone electrolytic cell unit comprises cyclone electrolytic cell device and controls the reflux of flow rate of liquid;
Described resins exchange processing unit comprises the wastewater collecting basin, guard column, ion exchange resin column, the regenerating unit that connect successively; Described regenerating unit comprises the regenerator Scatula, the regenerative pump that connect successively, and described regenerative pump is connected with ion exchange resin water side;
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 ion exchange resin column B water intake end, and be all connected by pipeline between ion exchange resin column B water side and ion exchange resin column A water intake end, on this pipeline, be equipped with switching valve; The water intake end of described ion exchange resin column A and ion exchange resin column B is all 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.
2. the method for recovery heavy metal out of electroplating wastewater according to claim 1, it is characterized in that: described cyclone electrolytic cell unit also comprises regenerated liquid receiving tank and the circulation of elecrolyte groove of controlling the current stabilizer of electric current, connection successively, described regenerated liquid receiving tank connects resin switch processing unit, and described circulation of elecrolyte groove is also interconnection by two circulation of elecrolyte pipelines with cyclone electrolytic cell device; Described circulation of elecrolyte groove is also connected by tail washings circulation tube with resins exchange unit; Described cyclone electrolytic cell device shell is made up of insulating material, and anode is made of titanium, and negative electrode is made up of stainless steel.
3. the method for recovery heavy metal out of electroplating wastewater according to claim 1, is characterized in that: described equipment also comprises by pipeline and is connected in the physicochemical treatment unit after 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 CN103243348A (en) | 2013-08-14 |
| CN103243348B true 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 (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 |
Families Citing this family (10)
| 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 |
| CN103833167B (en) * | 2014-03-13 | 2016-06-08 | 黄运富 | Chromic acid method of wastewater treatment and treatment system |
| CN103936112A (en) * | 2014-04-30 | 2014-07-23 | 南京大学 | Harmless treating and recycling method for ion exchange resin desorption solution |
| 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 |
| CN113388866B (en) * | 2021-06-25 | 2022-09-13 | 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 |
| 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 |
| 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 |
Citations (6)
| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI428290B (en) * | 2008-12-03 | 2014-03-01 | Rainer Bauder | Systems and methods for wastewater treatment |
-
2013
- 2013-05-03 CN CN201310161883.XA patent/CN103243348B/en active Active
Patent Citations (6)
| 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 |
| 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 (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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103243348A (en) | 2013-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103243348B (en) | Method and equipment for recovering heavy metal in electroplating wastewater | |
| 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 | |
| CN101648757B (en) | Recycling processing method for stainless steel processing process wastewater grading precipitation | |
| CN104944646B (en) | Wastewater advanced treatment method coupling membrane and electricity | |
| CN100482594C (en) | Electrodeionization water-purifying device and method for recovering cation and anion without scaling | |
| CN204727706U (en) | A kind of film electrical coupling system of Sewage advanced treatment | |
| CN103539283B (en) | Comprehensive treatment method for removing Sb and Bi impurities in Cu electrolyte | |
| CN104478140A (en) | Non-ferrous smelting waste acid purification treatment method | |
| CN104313584A (en) | Method and system for electrolyzing copper-containing etching liquid to obtain copper plate and regenerating and recycling etching liquid | |
| CN101838065B (en) | Method for recycling hexavalent chromium in electrolytic manganese production tail end wastewater | |
| WO2020228638A1 (en) | Method for efficiently regenerating resin by using electrolytic salt solution | |
| CN105565533A (en) | Zero-discharge on-line treatment process for preparing deionized water from copper sulphate electroplating waste water | |
| CN103693773A (en) | Chromium-containing waste water reuse treatment method | |
| CN110422948A (en) | Copper sulphate Sewage treatment metallic copper treatment process is electroplated | |
| CN102560499A (en) | Device for recycling printed circuit board acidic etching solution | |
| CN101935126A (en) | Combined treatment method for electro-deposition and membrane separation of zinc-containing heavy metal waste water | |
| CN103951017A (en) | Method for treating cyanogen-containing copper-containing electroplating wastewater by electrolysis and recycling copper | |
| CN203602414U (en) | System for recovering silvering wastewater and silver | |
| CN203270048U (en) | Equipment for recycling heavy metal in electroplating wastewater | |
| CN112159005A (en) | Treatment process and treatment system for aluminum processing anode waste liquid | |
| CN104030500A (en) | Process and equipment for removing nickel ions from wastewater of aluminum profile | |
| CN104108818B (en) | A kind of method using ion-exchange and cyclone electrolytic cell technical finesse heavy metal wastewater thereby | |
| CN105731696B (en) | Silicon carbide pickling waste water reclaiming treatment process | |
| CN201762103U (en) | Separating system for inorganic acid and inorganic acid salt in waste acid |
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 |
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. |
|
| CP02 | Change in the address of a patent holder |