CN104418408A - Copper-electroplating wastewater treatment method and copper-electroplating wastewater treatment equipment - Google Patents
Copper-electroplating wastewater treatment method and copper-electroplating wastewater treatment equipment Download PDFInfo
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- CN104418408A CN104418408A CN201310391115.3A CN201310391115A CN104418408A CN 104418408 A CN104418408 A CN 104418408A CN 201310391115 A CN201310391115 A CN 201310391115A CN 104418408 A CN104418408 A CN 104418408A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
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- Environmental & Geological Engineering (AREA)
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Abstract
The invention relates to a copper-electroplating wastewater treatment method and copper-electroplating wastewater treatment equipment which are used for recovering metallic copper and water simultaneously; copper-electroplating wastewater contains recovering liquid in a recovering tank and cleaning liquid in a first cleaning tank; the recovering tank is connected with the first cleaning tank; and the first cleaning tank is connected with a second cleaning tank. The copper-electroplating wastewater treatment method disclosed by the invention comprises the following steps: outputting the recovering liquid in the recovering tank into an electro-deposition device to carry out electro-deposition so as to obtain metallic copper, and returning the recovering liquid subjected to electro-deposition into the recovering tank, wherein the balanced concentration range of electro-deposition is 0.5-10 g/L; outputting the cleaning liquid in the first cleaning tank into an ion exchange device to adsorb copper therein, and outputting purified water, for reuse, wherein the copper ion concentration of the cleaning liquid is lower than 0.3 g/L; regenerating the ion exchange device to obtain regenerated eluant; and conveying the regenerated eluant into the electro-deposition device to carry out electro-deposition so as to obtain metallic copper.
Description
Technical field
The present invention relates to wastewater processing technology, especially relate to a kind for the treatment of process and equipment of copper plating wastewater.
Background technology
Acid copper-plating is one of the widest, most important copper plating process in use face, can produce a large amount of copper-containing wastewater in production process, and the main component of waste water is copper sulfate and a small amount of electroplating additive, in acid.
The traditional treatment method of acid copper-plating waste water adopts chemical precipitation method.Cupric ion in waste water is converted into throw out, and after solid-liquid separation, clear water directly discharges, and copper-contained sludge is as dangerous waste disposal.This traditional treatment process, for the purpose of discharged wastewater met the national standard, is not considered copper and Water reuse, not only be have lost resource, and there is the risk of secondary pollution.
Electrodip process is that the reducing metal ions in solution is become the technology of elemental metals by a kind of electrochemical principle that utilizes, and can be applied to the recovery of contained waste liquid.According to electrochemical principle, the current efficiency of galvanic deposit and the quality of product are subject to the impact of many factors, wherein the concentration of metal ion is exactly one of key factor, general concentration is high is conducive to the quality improving current efficiency and electrodeposit metals, if the concentration of contained waste liquid is too low will lose technology and economic feasibility.Therefore, electrodip process is applicable to reclaim copper, but is not suitable for reclaiming the too low copper-containing wastewater of concentration, also cannot reclaim waste water.
Ion exchange technique is the method utilizing reversible chemical reaction purification or the separate substance of carrying out between the ion in liquid phase and solid phase intermediate ion.When being adsorbed on resin containing the cationic waste water of copper other positively charged ion on Zeo-karb cupric ion and ion exchange resin group occurs to exchange, the water of removing cupric ion can be recycled.General ion-exchange is suitable for the waste water (copper content is generally less than 0.3g/L) reclaiming lower concentration, and cupric ion easily leaks when the concentration is too high, and the regeneration period shortens, and lacks practical value.
Therefore, ion exchange method can reclaim waste water, but is not suitable for the copper-containing wastewater reclaiming excessive concentration.
Wish a kind for the treatment of process that simultaneously can realize the copper-containing wastewater of the recovery of metallic copper and water.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind for the treatment of process and equipment of copper plating wastewater, can simultaneously Footwall drift copper and water.
The present invention is that to solve the problems of the technologies described above the technical scheme adopted be the treatment process proposing a kind of copper plating wastewater, this copper plating wastewater comprises the Ethylene recov being positioned at an accumulator tank and the scavenging solution being positioned at one first rinse bath, this accumulator tank is connected with this first rinse bath, this first rinse bath is connected with one second rinse bath, the method comprises the following steps: export this Ethylene recov to an electric deposition device from this accumulator tank and carry out galvanic deposit to obtain metallic copper, and the Ethylene recov through galvanic deposit is returned this accumulator tank, wherein galvanic deposit equilibrium concentration scope is set to 0.5-10g/L; This scavenging solution is exported to an ion exchange unit with absorption copper wherein from this first rinse bath, and output reuse of purifying waste water, wherein the copper ion concentration of this scavenging solution is lower than 0.3g/L; Regenerate to obtain regenerative elution liquid to this ion exchange unit; And this regenerative elution liquid is delivered to this electric deposition device carries out galvanic deposit to obtain metallic copper.
In one embodiment of this invention, the step exporting reuse of this being purified waste water comprises: this purified waste water and export this second rinse bath to the part fresh water replacing this second rinse bath supplementary.
In one embodiment of this invention, the step exporting reuse of this being purified waste water comprises: purify waste water this for other matting.
In one embodiment of this invention, this regenerative elution liquid is delivered to the step that this electric deposition device carries out galvanic deposit to comprise: this regenerative elution liquid is added this accumulator tank in batches, and together exports this electric deposition device to this Ethylene recov.
The present invention also proposes a kind for the treatment of facility of copper plating wastewater, this copper plating wastewater comprises the Ethylene recov being positioned at an accumulator tank and the scavenging solution being positioned at one first rinse bath, this accumulator tank is connected with this first rinse bath, this first rinse bath is connected with one second rinse bath, this equipment comprises: electric deposition device, be connected with this accumulator tank, galvanic deposit is carried out to obtain metallic copper for inputting this Ethylene recov, and the Ethylene recov through galvanic deposit is returned this accumulator tank, wherein galvanic deposit equilibrium concentration scope is set to 0.5-10g/L; Ion exchange unit, is connected with this first rinse bath, for inputting this scavenging solution with absorption copper wherein, and output reuse of purifying waste water, wherein the copper ion concentration of this scavenging solution is lower than 0.3g/L; And ion exchange regenerant device, regenerate to obtain regenerative elution liquid to this ion exchange unit, and this regenerative elution liquid is delivered to this electric deposition device carries out galvanic deposit to obtain metallic copper.
In one embodiment of this invention, this ion exchange unit also connects this second rinse bath, and this is purified waste water export to this second rinse bath with replace this second rinse bath supplement part fresh water.
In one embodiment of this invention, this purifies waste water and is supplied to other matting by this ion exchange unit.
In one embodiment of this invention, this ion exchange regenerant device connects this accumulator tank, and this regenerative elution liquid is added this accumulator tank in batches.
The present invention is owing to adopting above technical scheme, when electrodip process is combined with ion exchange method and processes copper plating wastewater by the present invention, give full play to respective advantage, and regenerative elution liquid is carried out galvanic deposit to reclaim copper and waste water further, waste water can be processed fully, improve the rate of recovery.
Accompanying drawing explanation
For above-mentioned purpose of the present invention, feature and advantage can be become apparent, below in conjunction with accompanying drawing, the specific embodiment of the present invention is elaborated, wherein:
Fig. 1 illustrates the structure iron of the treatment facility of the copper-containing wastewater of one embodiment of the invention.
Fig. 2 illustrates the schema of the treatment process of the copper-containing wastewater of one embodiment of the invention.
Embodiment
Embodiments of the invention for acid copper-plating waste water, will describe the treatment technology of copper plating wastewater below.But be appreciated that these embodiments can apply other copper-plating techniques, as tetra-sodium copper facing, cyanide electroplating etc. through suitably changing.Therefore the present invention is not limited to acid copper-plating waste water, but goes for various copper plating wastewater.
Fig. 1 illustrates the structure iron of the treatment facility of the copper-containing wastewater of one embodiment of the invention.First the Production Flow Chart of general acid copper-plating is described with reference to Fig. 1.Electroplating parts from Acid copper bath 11 take out of high density containing copper electrolyte, enter accumulator tank 12 and embathe.Embathe rear plating piece and successively enter the first rinse bath 13 and the second rinse bath 14 cleans, the scavenging solution (for copper-containing wastewater) that the Ethylene recov of accumulator tank 12 brings the first rinse bath 13, first rinse bath 13 into brings the second rinse bath 14 into.For ensureing product cleaning quality, the second rinse bath 14 is by certain flow continuous supplementation fresh water, and the rinse water of the equal water yield from the second rinse bath 14 reverse inflow first rinse bath 13, then can be discharged from the first rinse bath 13, enters Waste Water Treatment.
At this, as long as the water quality of make up water can ensure cleaning quality.Make up water can select tap water or pure water, also can select treated reuse water.
Generally, the partially recycled liquid in accumulator tank 12 returns Acid copper bath 11, with the vaporization losses of supplementary plating solution.Because pickling copper facing is cold galvanising, steam output is less, the amount returning the Ethylene recov of Acid copper bath 11 is limited, the total amount that cupric ion brings accumulator tank 12 into from Acid copper bath 11 is greater than the total amount returning Acid copper bath 11 from accumulator tank 12, so the copper ion concentration of accumulator tank 12 Ethylene recov is continuous ascendant trend.When the amount of makeup water of follow-up second rinse bath 14 is constant, the copper ion concentration in the first rinse bath 13 and the second rinse tank 14 increases with the rising of Ethylene recov concentration.The electroplating quality (acid copper-plating is generally intermediate deposit) of later process can be affected when copper ion concentration is too high, and increase wastewater treatment load can be caused to increase from the waste water copper ion concentration that the first rinse bath 13 is discharged.If the method at this moment by directly changing Ethylene recov in accumulator tank 12 reduces concentration, then often raise and reach tens, even the contained waste liquid of tens grams will enter Waste Water Treatment, not only affect water treatment effect, and waste a large amount of copper resources.
The treatment facility of the copper-containing wastewater of one embodiment of the invention comprises electric deposition device 21, ion exchange unit 22 and ion exchange regenerant device 23.Electric deposition device 21 implements electrodeposition process, makes cupric ion be reduced into metallic copper at its negative electrode.Containing ion exchange resin in ion exchange unit 22, can degree of depth absorbing copper ion, waste water is purified.Ion exchange resin needs to regenerate in ion exchange regenerant device 23, returns in ion exchange unit 22 and continues to use.
Electric deposition device 21, ion exchange unit 22 and ion exchange regenerant device 23 are all ripe equipment, no longer launch to describe to its concrete structure at this.
In one embodiment, electric deposition device 21 connects aforesaid accumulator tank 12.Ion exchange unit 22 connects aforesaid first rinse bath 13 and the second rinse bath 14.Ion exchange regenerant device 23 connects aforesaid accumulator tank 12.
Fig. 2 illustrates the schema of the treatment process of the copper-containing wastewater of one embodiment of the invention.Referring now to Fig. 1 and Fig. 2, treatment process of the present invention is described.
In step 31, export Ethylene recov to electric deposition device 21 from accumulator tank 12 and carry out galvanic deposit to obtain metallic copper, and the Ethylene recov through galvanic deposit is returned accumulator tank 12.
Specifically, the Ethylene recov of the cupric in accumulator tank 12 can be extracted out by recycle pump by electric deposition device 21, returns accumulator tank 12 after galvanic deposit.In circulation electrodeposition process, cupric ion obtains electronics at negative electrode, is reduced to laminated metal copper.When the speed that electrodepositing speed and the Acid copper bath 11 of copper brings accumulator tank 12 into is identical, in accumulator tank 12, the cupric ion of Ethylene recov reaches equilibrium concentration, the copper ion concentration of the first rinse bath 3 and the second rinse bath 4 also tends towards stability, and is conducive to ensureing rear road electroplating work procedure quality and alleviating wastewater treatment load.
In this step 31, galvanic deposit equilibrium concentration controls more lowly more be conducive to electroplating quality and wastewater treatment, but can reduce the quality of current efficiency and acid copper when galvanic deposit equilibrium concentration is too low.In order to avoid the appearance of this situation, need the rational sedimentation equilibrium concentration range of setting one, the galvanic deposit equilibrium concentration scope of the present embodiment is set to 0.5-10g/L.
Step 32, exports scavenging solution to ion exchange unit 22 with absorption copper wherein from the first rinse bath 13, and output reuse of purifying waste water.At this, in the first rinse bath 13, the copper ion concentration of scavenging solution is usually less than 0.3g/L, within the reasonable range of application of ion exchange technique.
The scavenging solution of copper ions is after ion exchange unit 22, and the cupric ion of more than 99% can be adsorbed.
In one embodiment, purify waste water and can be back to the second rinse bath 14 direct reuse, such reusing can reduce the magnitude of recruitment of the fresh water to the second rinse bath 14.
In another embodiment, purifying waste water also can reuse indirectly, such as by the effluent reuse of ion exchange unit 22 in the relatively low matting of water quality requirement.In this embodiment, ion exchange unit 22 does not need to be connected with the second rinse bath 14.
Step 33, in ion exchange regenerant device 23, regenerates to obtain regenerative elution liquid to the ion exchange resin of ion exchange unit 22.
The necessary regenerating resin when ion exchange resin is saturated, to recover its absorption property.Can regenerator regeneration of sulfuric acid ion exchange resin be used, obtain copper sulfate regenerative elution liquid.In copper sulfate regenerative elution liquid, copper ion concentration generally can reach 20-50g/L.After regeneration, the absorption property of ion exchange resin recovers, and can be put into ion exchange unit 22 and reuse.
In one embodiment, the whole ion exchange column being filled with ion exchange resin can be pulled down from ion exchange unit 22, be installed in ion exchange regenerant device 23 and regenerate.Again ion exchange column is reinstalled ion exchange unit 22 after regeneration.
Step 34, is delivered to electric deposition device 21 and carries out galvanic deposit to obtain metallic copper by regenerative elution liquid.
Because the copper ion concentration of regenerative elution liquid is very high, and main component is identical with Ethylene recov, is all copper sulfate, is very suitable for the application of galvanic deposit recovery technology, utilizes electric deposition device 21 pairs of regenerative elution liquid to recycle in the present embodiment.
In one embodiment, regenerative elution liquid can add accumulator tank 12 in batches, together enters into electric deposition device 21 carry out galvanic deposit recovery with Ethylene recov.The amount that elutriant adds in batches can to return the amount of Acid copper bath 11 roughly the same with Ethylene recov.
Can find out, although independent copper plating wastewater treatment process is unsatisfactory, when being combined with ion exchange method by electrodip process, respective advantage can be played, waste water can be processed fully.Especially, regenerative elution liquid is carried out galvanic deposit to reclaim copper and waste water further, improve the rate of recovery.Typically, the ratio that copper reclaims can reach about 99%, and the ratio of waste water recycling can also reach about 70%.
The technique effect of the embodiment of the present invention is described with the example of example below.
The basic parameter of acid copper-plating production process is as follows:
Bath concentration: the copper ion concentration of acid copper-plating tank liquor is 50g/L;
Solution drag-out: the plating solution being attached to plated item surface in electroplating process brings accumulator tank 12 with plating piece from Acid copper bath 11 with the amount of 5L/h, the Ethylene recov of accumulator tank 12 brings the first rinse bath 13 into the amount of 5L/h equally, wherein h representative hour;
Plating solution cupric ion takes speed out of: the speed that cupric ion brings accumulator tank into from Acid copper bath 11 is 250g/h;
Plating solution cupric ion takes speed=50g/L × 5L/h=250g/h out of
Equilibrium concentration: setting galvanic deposit equilibrium concentration is cupric ion 5g/L;
Ethylene recov cupric ion takes speed out of: Ethylene recov is with the equilibrium concentration of 5g/L, and the drag-out of 5L/h enters the first rinse bath 13, and the speed of taking out of of cupric ion is 25g/h;
Ethylene recov cupric ion takes speed=5g/L × 5L/h=25g/h out of
Galvanic deposit current density: setting galvanic deposit current density is 0.5A/dm
2;
Rate of water make-up: the rate of water make-up of the second rinse bath 14 is 1000L/h.
Operating performance is as follows:
Galvanic deposit recovery rate: electric deposition device 21 recovery stratiform per hour copper is about 250g under these conditions, with plating solution cupric ion to take speed out of substantially identical;
The galvanic deposit rate of recovery: the copper recovery of electric deposition device 21 is 90%;
The galvanic deposit rate of recovery=(50g/L-5g/L) ÷ 50g/L × 100%;
The ion-exchange rate of recovery: water outlet copper ion concentration is reduced to 1mg/L(0.001g/L after ion exchange unit 22 adsorbs) below, the rate of recovery of copper is 96%;
The ion-exchange rate of recovery=(5g/L × 5L/h-0.001g/L × 1000L/h) ÷ (5g/L × 5L/h) × 100%;
The total yield of copper reaches 99.6%(galvanic deposit and ion exchange unit combines)
Total yield=(50g/L × 5L/h-0.001g/L × 1000L/h) ÷ (50g/L × 5L/h) × 100%
Water-saving rate: the copper-containing wastewater of the first rinse bath 13 is after ion exchange unit 22 processes, content of copper ion is reduced to below 1mg/L, and return the second rinse bath 14 Substitute For Partial make up water, the magnitude of recruitment of fresh water is by original 1000L/h, reduce to 300L/h, water-saving rate is 70%.
Regenerate with regenerator sulfuric acid when the resin in ion exchange unit 22 is saturated, sulfuric acid concentration is 5%, regeneration obtains the regenerative elution liquid of copper ion concentration 35g/L, regenerative elution liquid returns when Acid copper bath 11 supplements plating solution vaporization losses at Ethylene recov and adds accumulator tank 12, and add-on is consistent with Ethylene recov back amount.Because the regenerative elution liquid total amount produced within a regeneration period is less than the total amount of plating solution vaporization losses, so regenerative elution liquid can all add accumulator tank 12.Add the regenerative elution liquid of accumulator tank 12 and Ethylene recov to combine together and carry out galvanic deposit recovery simultaneously, obtain laminated metal copper.
Although the present invention describes with reference to current specific embodiment, but those of ordinary skill in the art will be appreciated that, above embodiment is only used to the present invention is described, change or the replacement of various equivalence also can be made when not departing from spirit of the present invention, therefore, as long as all will drop in the scope of claims of the application the change of above-described embodiment, modification in spirit of the present invention.
Claims (8)
1. the treatment process of a copper plating wastewater, this copper plating wastewater comprises the Ethylene recov being positioned at an accumulator tank and the scavenging solution being positioned at one first rinse bath, this accumulator tank is connected with this first rinse bath, and this first rinse bath is connected with one second rinse bath, and the method comprises the following steps:
Export this Ethylene recov to an electric deposition device from this accumulator tank and carry out galvanic deposit to obtain metallic copper, and the Ethylene recov through galvanic deposit is returned this accumulator tank, wherein galvanic deposit equilibrium concentration scope is set to 0.5-10g/L;
This scavenging solution is exported to an ion exchange unit with absorption copper wherein from this first rinse bath, and output reuse of purifying waste water, wherein the copper ion concentration of this scavenging solution is lower than 0.3g/L;
Regenerate to obtain regenerative elution liquid to this ion exchange unit; And
This regenerative elution liquid is delivered to this electric deposition device and carries out galvanic deposit to obtain metallic copper.
2. the method for claim 1, is characterized in that, the step exporting reuse of this being purified waste water comprises: this purified waste water and export this second rinse bath to the part fresh water replacing this second rinse bath supplementary.
3. the method for claim 1, is characterized in that, the step exporting reuse of this being purified waste water comprises: purify waste water this for other matting.
4. the method for claim 1, is characterized in that, this regenerative elution liquid is delivered to the step that this electric deposition device carries out galvanic deposit and comprises: this regenerative elution liquid is added this accumulator tank in batches, and together exports this electric deposition device to this Ethylene recov.
5. a treatment facility for copper plating wastewater, this copper plating wastewater comprises the Ethylene recov being positioned at an accumulator tank and the scavenging solution being positioned at one first rinse bath, and this accumulator tank is connected with this first rinse bath, and this first rinse bath is connected with one second rinse bath, and this equipment comprises:
Electric deposition device, is connected with this accumulator tank, and carry out galvanic deposit to obtain metallic copper for inputting this Ethylene recov, and the Ethylene recov through galvanic deposit is returned this accumulator tank, wherein galvanic deposit equilibrium concentration scope is set to 0.5-10g/L;
Ion exchange unit, is connected with this first rinse bath, for inputting this scavenging solution with absorption copper wherein, and output reuse of purifying waste water, wherein the copper ion concentration of this scavenging solution is lower than 0.3g/L; And
Ion exchange regenerant device, regenerates to obtain regenerative elution liquid to this ion exchange unit, and this regenerative elution liquid is delivered to this electric deposition device carries out galvanic deposit to obtain metallic copper.
6. equipment as claimed in claim 5, it is characterized in that, this ion exchange unit also connects this second rinse bath, and this is purified waste water and export the part fresh water that this second rinse bath supplements to replace this second rinse bath to.
7. equipment as claimed in claim 5, it is characterized in that, this purifies waste water and is supplied to other matting by this ion exchange unit.
8. equipment as claimed in claim 5, it is characterized in that, this ion exchange regenerant device connects this accumulator tank, and this regenerative elution liquid is added this accumulator tank in batches.
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| CN108360056A (en) * | 2018-03-27 | 2018-08-03 | 台州市宏民环保科技有限公司 | A kind of electro-coppering is water-saving and the method for copper recycling |
| CN108396365A (en) * | 2018-03-27 | 2018-08-14 | 台州市宏民环保科技有限公司 | A kind of electronickelling is water-saving and the method for nickel recycling |
| CN109913914A (en) * | 2019-02-19 | 2019-06-21 | 厦门建霖健康家居股份有限公司 | The control method of copper ion concentration in a kind of cyanide-free copper electroplating solution |
| CN112408670A (en) * | 2020-12-09 | 2021-02-26 | 淮安中顺环保科技有限公司 | Treatment method of electroless copper plating rinsing solution |
| CN112941581A (en) * | 2021-01-27 | 2021-06-11 | 河海大学 | Method for treating concrete by using copper plating wastewater |
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