CN112408670A - Treatment method of electroless copper plating rinsing solution - Google Patents
Treatment method of electroless copper plating rinsing solution Download PDFInfo
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
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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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
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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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- 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 provides a treatment method of electroless copper plating water washing liquid, which comprises the following steps: (1) adjusting the pH value of the electroless copper plating water washing solution to be below 3 by using a pH regulator to obtain an acid solution; (2) treating the acidic solution obtained in the step (1) by using strong acid cation exchange resin until the concentration of copper ions in effluent is 3 mg/L; (3) and (3) regenerating the strong-acid cation exchange resin used in the step (2), and electrolyzing and recovering the obtained regenerated liquid to realize the recovery of copper. The treatment method has no waste liquid discharge, low treatment cost, high treatment speed and high purity of the recovered copper of more than 90wt percent, and can be directly sold as a commodity; therefore, the treatment method not only realizes the treatment of the electroless copper plating washing solution, but also can improve the economic benefit of enterprises.
Description
Technical Field
The invention belongs to the technical field of environmental protection, relates to a method for treating wastewater, and particularly relates to a method for treating electroless copper plating rinsing solution.
Background
The copper plating process has the characteristics of strong universality, wide application range and the like, and is widely applied to industrial production, so that the generated copper plating waste water is greatly increased. The copper plating waste water is mixed waste water containing metal ions and partial organic matters generated in the production process of the copper plating industry, and if the mixed waste water is freely discharged, the mixed waste water can form serious potential risks to the natural ecological environment and human health. The copper plating wastewater contains a large amount of heavy metal ions, shows strong toxicity to animals and plants, is directly discharged into the environment, can not only cause pollution which is difficult to restore to the ecological environment, but also can cause harm to human health through the enrichment function of a food chain.
With the increase of the complexity of the copper plating process and the use of a large amount of refractory organic matters in the copper plating process, the treatment difficulty of copper plating wastewater is gradually increased, and the traditional sewage treatment method is difficult to effectively treat the copper plating wastewater. And the discharge standard of the waste water is continuously improved, and most of the prior copper plating waste water treatment processes can not successfully reach the discharge standard. In the chemical copper plating process, the chemical copper plating rinsing solution generated in the workpiece rinsing process contains heavy metal Cu2+The Cu in the electroless copper plating water washing solution must be treated2+Can be recovered or discharged after being treated.
CN 102162036A discloses a process for enriching copper and nickel from electroplating copper-nickel mixed wastewater, which comprises the following steps: pretreatment: adjusting the pH value of the electroplating copper-nickel mixed wastewater to 4-5 in a neutralization tank, and then discharging the wastewater into a sedimentation tank to ensure that Fe (OH)3Precipitating and separating floc and solid impurities, removing soluble oil and particle impurities, and finally controlling the oxidation-reduction potential of the wastewater to be less than or equal to 30 mV; ion exchange adsorption: the pretreated wastewater enters an ion exchange device, and copper and nickel are adsorbed and enriched by ion exchange resin until the wastewater is saturated; ion exchange regeneration: and communicating the regeneration tank with the ion exchange device, firstly regenerating and recovering copper and nickel by using hydrochloric acid, and then regenerating and recovering the resin activity by using a complexing agent and an organic solvent. However, the method has the problem of copper resource waste in the pretreatment process, and influences the recovery rate of copper.
CN 105502838A discloses a copper plating wastewater water purification system and a water purification method, wherein a resin type particle electrode layer of the copper plating wastewater water purification system is positioned at the top of the water purification system, an anode composed of a titanium net is placed at the top of the resin, a cathode composed of a stainless steel pore plate is placed at the bottom of the resin, the anode and the cathode are respectively connected with an anode and a cathode of an external power supply, an adsorptive biological filter material layer is positioned below the resin type particle electrode layer, and an aeration device and a back washing device are arranged below the adsorptive biological filter material layer. Sewage enters the upper part of the resin type ion electrode layer; aerating resin type ion electrode treatment by an aeration device; microbial treatment and physical filtration; and finally, discharging water. But the treatment capacity of the copper plating wastewater purification system is limited and the energy consumption is higher.
CN 101070206A discloses a chemical copper plating rinsing wastewater treatment process, which comprises the following basic steps: chemical copper plating rinsing wastewater, pH value adjustment, ion exchange, ultrafiltration, reverse osmosis and purified water recycling/concentrated water circulation treatment. The specific process is as follows: adjusting the pH value of the chemical copper plating rinsing wastewater to 3-10, exchanging heavy metal ions in the wastewater with the same type of ions in ion exchange resin through ion exchange resin to recover heavy metal resources in the wastewater, performing ultrafiltration to remove macromolecular impurities contained in the wastewater, performing reverse osmosis treatment, separating unpurified wastewater, conveying the unpurified wastewater back to the beginning rinsing wastewater for cyclic treatment, and recycling purified water. However, the treatment process is complex, needs to be carried out by matching with a membrane system, and is high in cost.
Therefore, it is desirable to provide a simple and easy method for efficiently recovering copper in an electroless copper plating aqueous cleaning solution.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a treatment method of electroless copper plating washing liquid, which can quickly and effectively treat the electroless copper plating washing liquid, can recover copper with the purity of more than 90 wt%, and improves the economic benefit of enterprises.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a treatment method of electroless copper plating water washing liquid, which comprises the following steps:
(1) adjusting the pH value of the electroless copper plating water washing solution to be below 3 by using a pH regulator to obtain an acid solution;
(2) treating the acidic solution obtained in the step (1) by using a strong-acid cation exchange resin to obtain a strong-acid cation exchange resin;
(3) and (3) regenerating the strong-acid cation exchange resin used in the step (2), and electrolyzing and recovering the obtained regenerated liquid to realize the recovery of copper.
The chemical copper plating water washing solution comprises components such as copper sulfate, sodium carbonate, sodium hydroxide, EDTA disodium, conventional stabilizers and the like. In the present invention, the pH of the electroless copper plating aqueous cleaning solution is first adjusted to 3 or less, for example, 0.5, 1, 1.5, 2, 2.5 or 3 by using a pH adjuster, but the pH is not limited to the values listed above, and other values not listed above within the range of values are also applicable. The pH value is adjusted, so that the influence of a complexing agent in the chemical copper plating water washing solution on the subsequent steps is effectively avoided, and the effective adsorption of the strong-acid cation exchange resin on copper ions is ensured.
The strong-acid cation exchange resin is a conventional strong-acid cation exchange resin in the field, and is a cation exchange resin with an exchange group of a sulfonic group. The method adopts the strong-acid cation exchange resin to treat the acidic solution with the pH value less than or equal to 3, and can realize the treatment of Cu2+The effective adsorption of (1).
The end point of the adsorption treatment of the acidic solution by using the strong-acid cation exchange resin is the outlet water Cu2+When the concentration reached 3mg/L, the adsorption saturation of the strongly acidic cation exchange resin was judged at that time.
Preferably, Cu in the electroless copper plating water washing solution2+Is in the range of 10 to 200mg/L, and may be, for example, 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L, 60mg/L, 70mg/L, 80mg/L, 90mg/L, 100mg/L, 110mg/L, 120mg/L, 130mg/L, 140mg/L, 150mg/L, 160mg/L, 170mg/L, 180mg/L, 190mg/L or 200mg/L, but is not limited to the values recited, and other values not recited within the range of values are equally applicable; pH value>10, for example, may be 10.5, 11, 11.5, 12, 12.5, 13, 13.5 or 14, but is not limited to the recited values, other values not otherwise specified within the numerical rangeThe numerical values recited apply equally; COD is 100-200mg/L, and may be, for example, 100mg/L, 110mg/L, 120mg/L, 130mg/L, 140mg/L, 150mg/L, 160mg/L, 170mg/L, 180mg/L, 190mg/L or 200mg/L, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the pH regulator in step (1) is sulfuric acid with a concentration of 40 to 50 wt.%, for example 40 wt.%, 42 wt.%, 45 wt.%, 48 wt.% or 50 wt.%, but not limited to the recited values, and other values not recited in the numerical ranges are equally applicable.
The sulfuric acid used in the invention is 40-50 wt% sulfuric acid, not only can be chemically pure sulfuric acid, but also can be industrial sulfuric acid, thereby greatly reducing the cost for adjusting the pH value.
Preferably, after adjusting the pH value to 3 or less in step (1), the mixture is allowed to stand for 10 to 30min, such as 10min, 15min, 20min, 25min or 30min, but not limited to the values listed, and other values not listed in the numerical range are also applicable.
According to the invention, the pH value is adjusted and then the chemical copper plating rinsing solution is kept stand, so that the complexing agent (such as EDTA disodium) in the chemical copper plating rinsing solution is fully hydrolyzed, and the influence of the complexing agent on resin adsorption is effectively avoided.
Preferably, the step (2) of treating the acidic solution obtained in the step (1) with a strong acid cation exchange resin comprises the following specific steps: the acidic liquid flows through an ion exchange column, and the ion exchange column is filled with a strong-acid cation exchange resin.
Preferably, the ion exchange column has an aspect ratio of (2-4):1, for example 2:1, 2.5:1, 3:1, 3.5:1 or 4:1, but not limited to the values recited, and other values not recited within the range of values are equally applicable.
Preferably, the acid stream is passed through the ion exchange column at a flow rate of 5 to 15 column volumes/hour, for example 5 column volumes/hour, 8 column volumes/hour, 10 column volumes/hour, 12 column volumes/hour or 15 column volumes/hour, but not limited to the values recited, and other values not recited within the range of values are equally applicable.
Preferably, the regeneration in step (3) comprises the following specific steps: the washing liquid washes the ion exchange column to realize the regeneration of the ion exchange column.
Preferably, the washing liquid is sulfuric acid with a concentration of 3-8 wt%; the concentration of sulfuric acid is 3 to 8% by weight, and can be, for example, 3%, 4%, 5%, 6%, 7% or 8% by weight, but is not limited to the values listed, and other values not listed in the numerical ranges are equally applicable.
The sulfuric acid can be chemically pure sulfuric acid or industrial sulfuric acid which is obtained by dilution.
Preferably, the washing solution is used in an amount of 3 to 5 times the volume of the ion exchange column, for example, 3 times, 3.5 times, 4 times, 4.5 times, or 5 times, but not limited to the recited values, and other values not recited within the numerical range are also applicable.
Preferably, the electrolysis conditions in step (3) are as follows: current density of 100-400A/m2The temperature is 15-30 ℃, the anode is a titanium electrode, and the cathode is a stainless steel electrode.
The current density during the electrolysis is 100-400A/m2For example, it may be 100A/m2、150A/m2、200A/m2、250A/m2、300A/m2、350A/m2Or 400A/m2But are not limited to the recited values, and other values within the numerical range not recited are equally applicable.
The temperature in the electrolysis of the present invention is 15 to 30 ℃ and may be, for example, 15 ℃, 18 ℃, 20 ℃, 21 ℃, 24 ℃, 25 ℃, 27 ℃, 28 ℃ or 30 ℃, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the solution after the regenerated liquid obtained by the electrolysis recovery in the step (3) is reused for washing the ion exchange column after the sulfuric acid concentration is adjusted to be 3-8 wt%.
As a preferable technical solution of the treatment method of the present invention, the treatment method comprises the steps of:
(1) adjusting the pH value of electroless copper plating water washing liquid to be below 3 by using sulfuric acid with the concentration of 40-50 wt%, and standing for 10-30min to obtain acid liquid; cu in the electroless copper plating water washing solution2+The content of (B) is 10-200mg/L, pH value>10, COD is 100-200 mg/L;
(2) acid solution flows through an ion exchange column at the speed of 5-15 times of column volume/hour until the concentration of copper ions in effluent is 3mg/L, and strong acid cation exchange resin is filled in the ion exchange column; the height-diameter ratio of the ion exchange column is (2-4) 1;
(3) washing the ion exchange column by using a washing solution with the volume 3-5 times of that of the ion exchange column to realize the regeneration of the ion exchange column, wherein the washing solution is sulfuric acid with the concentration of 3-8 wt%; electrolyzing and recovering the obtained regenerated liquid to realize the recovery of copper, wherein the electrolysis conditions are as follows: current density of 100-400A/m2The temperature is 15-30 ℃, the anode is a titanium electrode, and the cathode is a stainless steel electrode; regulating the sulfuric acid concentration of the solution after electrolyzing and recycling the obtained regenerated liquid to be 3-8 wt% and then recycling the solution for washing the ion exchange column.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
(1) the treatment method has no waste liquid discharge, low treatment cost and high treatment speed, and the purity of the recovered copper is more than 90wt percent and can be directly sold as a commodity; therefore, the treatment method not only realizes the treatment of the electroless copper plating washing solution, but also can improve the economic benefit of enterprises;
(2) the pH regulator can select industrial sulfuric acid with higher concentration, and reduces the treatment cost of the chemical copper plating water washing solution.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a treatment method of electroless copper plating water washing liquid, which comprises the following steps:
(1) adjusting electroless copper plating water by using sulfuric acid with concentration of 45 wt%Standing the washing solution for 20min after the pH value of the washing solution reaches 2 to obtain an acid solution; the electroless copper plating water washing solution is electroless copper plating water washing solution of Huaian certain electronic factory, and Cu in the electroless copper plating water washing solution is measured2+Has a content of 120mg/L and a pH value>10, COD is 150 mg/L;
(2) acid solution flows through an ion exchange column at a speed of 10 times of column volume/hour until the concentration of copper ions in effluent is 3mg/L, and 001 × 7(732) type strong-acid cation exchange resin is filled in the ion exchange column; the height-diameter ratio of the ion exchange column is 3: 1; when the ion exchange column is not saturated, the concentration of copper ions in stable effluent is 0.2 mg/L;
(3) washing the ion exchange column by using a washing solution with the volume 4 times that of the ion exchange column to realize the regeneration of the ion exchange column and obtain a regeneration solution with the copper ion concentration of 13g/L, wherein the washing solution is sulfuric acid with the concentration of 5 wt%; electrolyzing and recovering the obtained regenerated liquid to realize the recovery of copper, wherein the electrolysis conditions are as follows: current density 250A/m2The temperature is 20 ℃, the anode is a titanium electrode, and the cathode is a stainless steel electrode; the concentration of copper ions in the solution after the obtained regeneration liquid is recycled through electrolysis is 2g/L, and the concentration of sulfuric acid is adjusted to 5 wt% and then the sulfuric acid is reused for washing an ion exchange column.
The purity of the copper finally obtained by electrolysis in the embodiment is 94.5 wt%, and the copper can be directly sold as a product; in addition, in the embodiment, the electrolyzed solution is recycled for eluting the ion exchange column, so that the discharge of wastewater is avoided, the high recovery rate of Cu can be realized, and the economic benefit of enterprises is improved.
Example 2
The embodiment provides a treatment method of electroless copper plating water washing liquid, which comprises the following steps:
(1) adjusting the pH value of electroless copper plating water washing liquid to 1 by using sulfuric acid with the concentration of 50 wt%, and standing for 30min to obtain acid liquid; the electroless copper plating water washing solution is electroless copper plating water washing solution of Huaian certain electronic factory, and Cu in the electroless copper plating water washing solution is measured2+Has a content of 70mg/L and a pH value>10, COD is 120 mg/L;
(2) acid solution flows through an ion exchange column at the speed of 12 times of column volume/hour until the concentration of copper ions in effluent is 3mg/L, and 001 x 4(734) type strong acid cation exchange resin is filled in the ion exchange column; the height-diameter ratio of the ion exchange column is 2.5: 1; when the ion exchange column is not saturated, the concentration of copper ions in stable effluent is 0.15 mg/L;
(3) washing the ion exchange column by using a washing solution with the volume 3.5 times of that of the ion exchange column to realize the regeneration of the ion exchange column and obtain a regenerated solution with the copper ion concentration of 12.8g/L, wherein the washing solution is sulfuric acid with the concentration of 7 wt%; electrolyzing and recovering the obtained regenerated liquid to realize the recovery of copper, wherein the electrolysis conditions are as follows: the current density is 180A/m2The temperature is 25 ℃, the anode is a titanium electrode, and the cathode is a stainless steel electrode; the copper ion concentration in the solution after the obtained regeneration liquid is recycled through electrolysis is 1.9g/L, and the sulfuric acid concentration is adjusted to 7 wt% and then is reused for washing the ion exchange column.
The purity of the copper finally obtained by electrolysis in the embodiment is 94.8 wt%, and the copper can be directly sold as a product; in addition, in the embodiment, the electrolyzed solution is recycled for eluting the ion exchange column, so that the discharge of wastewater is avoided, the high recovery rate of Cu can be realized, and the economic benefit of enterprises is improved.
Example 3
The embodiment provides a treatment method of electroless copper plating water washing liquid, which comprises the following steps:
(1) adjusting the pH value of the electroless copper plating water washing solution to 3 by using sulfuric acid with the concentration of 40 wt%, and standing for 10min to obtain an acid solution; the electroless copper plating water washing solution is electroless copper plating water washing solution of Huaian certain electronic factory, and Cu in the electroless copper plating water washing solution is measured2+Has a content of 100mg/L and a pH value>10, COD is 180 mg/L;
(2) acid solution flows through an ion exchange column at a speed of 8 times of column volume/hour until the concentration of copper ions in effluent is 3mg/L, and D001 type strong acid cation exchange resin is filled in the ion exchange column; the height-diameter ratio of the ion exchange column is 3.5: 1; when the ion exchange column is not saturated, the concentration of copper ions in stable effluent is 0.18 mg/L;
(3) washing the ion exchange column by using a washing solution with the volume 4.5 times of that of the ion exchange column to realize the regeneration of the ion exchange column and obtain a regenerated solution with the copper ion concentration of 12.5g/L, wherein the washing solution is sulfuric acid with the concentration of 4 wt%; the regenerated liquid obtained by electrolysis is recovered to realize the recovery of copperThe electrolysis conditions are as follows: current density 350A/m2The temperature is 18 ℃, the anode is a titanium electrode, and the cathode is a stainless steel electrode; the copper ion concentration in the solution after the obtained regeneration liquid is recycled through electrolysis is 1.8g/L, and the sulfuric acid concentration is adjusted to 4 wt% and then is reused for washing the ion exchange column.
The purity of the copper finally obtained by electrolysis in the embodiment is 94.6 wt%, and the copper can be directly sold as a product; in addition, in the embodiment, the electrolyzed solution is recycled for eluting the ion exchange column, so that the discharge of wastewater is avoided, the high recovery rate of Cu can be realized, and the economic benefit of enterprises is improved.
Example 4
The embodiment provides a treatment method of electroless copper plating water washing liquid, which comprises the following steps:
(1) adjusting the pH value of the electroless copper plating water washing solution to 1.5 by using sulfuric acid with the concentration of 48 wt%, and standing for 25min to obtain an acid solution; the electroless copper plating water washing solution is electroless copper plating water washing solution of Huaian certain electronic factory, and Cu in the electroless copper plating water washing solution is measured2+Has a content of 200mg/L and a pH value>10, COD is 200 mg/L;
(2) acid solution flows through an ion exchange column at the speed of 5 times of column volume/hour until the concentration of copper ions in effluent is 3mg/L, and 001 × 7(732) type strong-acid cation exchange resin is filled in the ion exchange column; the height-diameter ratio of the ion exchange column is 4: 1; when the ion exchange column is not saturated, the concentration of copper ions in stable effluent is 0.23 mg/L;
(3) washing the ion exchange column by using a washing solution with the volume 3 times that of the ion exchange column to realize the regeneration of the ion exchange column and obtain a regeneration solution with the copper ion concentration of 13.3g/L, wherein the washing solution is sulfuric acid with the concentration of 8 wt%; electrolyzing and recovering the obtained regenerated liquid to realize the recovery of copper, wherein the electrolysis conditions are as follows: current density 100A/m2The temperature is 30 ℃, the anode is a titanium electrode, and the cathode is a stainless steel electrode; the copper ion concentration in the solution after the obtained regeneration liquid is recycled through electrolysis is 2.2g/L, and the sulfuric acid concentration is adjusted to 8 wt% and then is reused for washing the ion exchange column.
The purity of the copper finally obtained by electrolysis in the embodiment is 95.2 wt%, and the copper can be directly sold as a product; in addition, in the embodiment, the electrolyzed solution is recycled for eluting the ion exchange column, so that the discharge of wastewater is avoided, the high recovery rate of Cu can be realized, and the economic benefit of enterprises is improved.
Example 5
The embodiment provides a treatment method of electroless copper plating water washing liquid, which comprises the following steps:
(1) adjusting the pH value of the electroless copper plating water washing solution to 2.5 by using sulfuric acid with the concentration of 42 wt%, and standing for 15min to obtain an acid solution; the electroless copper plating water washing solution is electroless copper plating water washing solution of Huaian certain electronic factory, and Cu in the electroless copper plating water washing solution is measured2+Has a content of 10mg/L and a pH value>10, COD is 100 mg/L;
(2) acid solution flows through an ion exchange column at the speed of 15 times of column volume/hour until the concentration of copper ions in effluent is 3mg/L, and 001 × 7(732) type strong-acid cation exchange resin is filled in the ion exchange column; the height-diameter ratio of the ion exchange column is 2: 1; when the ion exchange column is not saturated, the concentration of copper ions in stable effluent is 0.21 mg/L;
(3) washing the ion exchange column by using a washing solution with the volume 5 times that of the ion exchange column to realize the regeneration of the ion exchange column and obtain a regeneration solution with the copper ion concentration of 13.2g/L, wherein the washing solution is sulfuric acid with the concentration of 3 wt%; electrolyzing and recovering the obtained regenerated liquid to realize the recovery of copper, wherein the electrolysis conditions are as follows: current density 400A/m2The temperature is 10 ℃, the anode is a titanium electrode, and the cathode is a stainless steel electrode; the concentration of copper ions in the solution after the obtained regeneration liquid is recycled through electrolysis is 1.7g/L, and the concentration of sulfuric acid is adjusted to 3 wt% and then the sulfuric acid is reused for washing an ion exchange column.
The purity of the copper finally obtained by electrolysis in the embodiment is 94.9 wt%, and the copper can be directly sold as a product; in addition, in the embodiment, the electrolyzed solution is recycled for eluting the ion exchange column, so that the discharge of wastewater is avoided, the high recovery rate of Cu can be realized, and the economic benefit of enterprises is improved.
Example 6
This example provides a method of treating an electroless copper plating aqueous rinse, which was the same as in example 1 except that the sulfuric acid in step (1) was replaced with concentrated hydrochloric acid.
Hydrochloric acid is used for adjusting pH, so that copper salt in the obtained regenerated liquid is copper chloride, and when the regenerated liquid containing the copper chloride is electrolyzed, toxic gas such as chlorine gas and the like can be generated, and the electrode can be corroded, so that the long-term stable use of an electrolysis system is not facilitated.
Example 7
This example provides a method of treating an electroless copper plating aqueous cleaning solution, which is the same as that of example 1 except that the cleaning solution in step (3) is sulfuric acid having a concentration of 2 wt%.
Due to insufficient hydrogen ion concentration in the washing solution, sufficient elution of the ion exchange column cannot be achieved.
If the purpose of elution is needed, more washing liquid is needed for elution, which not only increases the consumption of the washing liquid, but also reduces the copper concentration in the regenerated liquid and the electrolytic efficiency.
Example 8
This example provides a method of treating an electroless copper plating aqueous cleaning solution, which is the same as that of example 1 except that the cleaning solution in step (3) is sulfuric acid having a concentration of 10 wt%.
The concentration of hydrogen ions in the washing solution is too high, which can not improve the elution effect of the ion exchange column, and can cause the increase of the elution cost, and is not beneficial to the cleaning of the ion exchange column.
Comparative example 1
This comparative example provides a treatment method of an electroless copper plating water washing solution, which is the same as in example 1 except that sulfuric acid having a concentration of 45% by weight was used in step (1) to adjust the pH of the electroless copper plating water washing solution to 3.5.
Due to the fact that the pH value is high, the complexing agent in the chemical copper plating washing solution influences the adsorption of the step (2) on copper ions, and stable water outlet cannot be achieved when the ion exchange column is not saturated.
In conclusion, the treatment method has no waste liquid discharge, low treatment cost, high treatment speed and high purity of the recovered copper of more than 90wt percent, and can be directly sold as a commodity; therefore, the treatment method not only realizes the treatment of the electroless copper plating washing solution, but also can improve the economic benefit of enterprises; the pH regulator can select industrial sulfuric acid with higher concentration, and reduces the treatment cost of the chemical copper plating water washing solution.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The treatment method of the electroless copper plating rinsing solution is characterized by comprising the following steps:
(1) adjusting the pH value of the electroless copper plating water washing solution to be below 3 by using a pH regulator to obtain an acid solution;
(2) treating the acidic solution obtained in the step (1) by using a strong-acid cation exchange resin until the strong-acid cation exchange resin is saturated in adsorption;
(3) and (3) regenerating the strong-acid cation exchange resin used in the step (2), and electrolyzing and recovering the obtained regenerated liquid to realize the recovery of copper.
2. The treatment method as set forth in claim 1, wherein Cu in the electroless copper plating water washing solution2+The content of (B) is 10-200mg/L, pH value>10, COD is 100-200 mg/L.
3. The treatment method according to claim 1 or 2, wherein the pH adjusting agent of step (1) is sulfuric acid having a concentration of 40 to 50 wt%;
preferably, after the pH value is adjusted to be below 3 in the step (1), standing is carried out for 10-30 min.
4. The treatment method according to any one of claims 1 to 3, wherein the step (2) of treating the acidic solution obtained in the step (1) with a strong acid cation exchange resin comprises the following specific steps: the acidic liquid flows through an ion exchange column, and the ion exchange column is filled with a strong-acid cation exchange resin.
5. The process according to claim 4, wherein the ion exchange column has an aspect ratio of (2-4) 1;
preferably, the acid liquid flows through the ion exchange column at an over-flow rate of 5 to 15 column volumes per hour.
6. The treatment process according to any one of claims 1 to 5, wherein the specific steps of the regeneration of step (3) are: the washing liquid washes the ion exchange column to realize the regeneration of the ion exchange column.
7. The treatment process according to claim 6, wherein the washing liquid is sulfuric acid having a concentration of 3 to 8 wt%;
preferably, the amount of the washing solution is 3 to 5 times the volume of the ion exchange column.
8. The process according to any one of claims 1 to 7, wherein the conditions of the electrolysis of step (3) are: current density of 100-400A/m2The temperature is 15-30 ℃, the anode is a titanium electrode, and the cathode is a stainless steel electrode.
9. The process according to any one of claims 1 to 8, wherein the solution after recovering the regenerated liquid by electrolysis in step (3) is returned to the washing ion exchange column after adjusting the sulfuric acid concentration to 3 to 8% by weight.
10. The process according to any one of claims 1 to 8, characterized in that it comprises the following steps:
(1) adjusting the pH value of electroless copper plating water washing liquid to be below 3 by using sulfuric acid with the concentration of 40-50 wt%, and standing for 10-30min to obtain acid liquid; cu in the electroless copper plating water washing solution2+The content of (B) is 10-200mg/L, pH value>10, COD is 100-200 mg/L;
(2) acid solution flows through an ion exchange column at the speed of 5-15 times of column volume/hour until the concentration of copper ions in effluent is 3mg/L, and strong acid cation exchange resin is filled in the ion exchange column; the height-diameter ratio of the ion exchange column is (2-4) 1;
(3) washing the ion exchange column by using a washing solution with the volume 3-5 times of that of the ion exchange column to realize the regeneration of the ion exchange column, wherein the washing solution is sulfuric acid with the concentration of 3-8 wt%; electrolyzing and recovering the obtained regenerated liquid to realize the recovery of copper, wherein the electrolysis conditions are as follows: current density of 100-400A/m2The temperature is 15-30 ℃, the anode is a titanium electrode, and the cathode is a stainless steel electrode; regulating the sulfuric acid concentration of the solution after electrolyzing and recycling the obtained regenerated liquid to be 3-8 wt% and then recycling the solution for washing the ion exchange column.
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