CN111925026A - Treatment process of acidic copper-containing etching waste liquid - Google Patents

Treatment process of acidic copper-containing etching waste liquid Download PDF

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Publication number
CN111925026A
CN111925026A CN202010631968.XA CN202010631968A CN111925026A CN 111925026 A CN111925026 A CN 111925026A CN 202010631968 A CN202010631968 A CN 202010631968A CN 111925026 A CN111925026 A CN 111925026A
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CN
China
Prior art keywords
copper
waste liquid
solution
containing etching
etching waste
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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.)
Pending
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CN202010631968.XA
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Chinese (zh)
Inventor
张建平
邱跃芹
吴芹
万海涛
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Kunshan Zhonghuan Industrial Co ltd
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Kunshan Zhonghuan Industrial Co ltd
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Priority to CN202010631968.XA priority Critical patent/CN111925026A/en
Publication of CN111925026A publication Critical patent/CN111925026A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/001Processes for the treatment of water whereby the filtration technique is of importance
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/06Controlling or monitoring parameters in water treatment pH

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

The invention provides a treatment process of acidic copper-containing etching waste liquid, which comprises the following steps: neutralization process, copper extraction process and blending process. The copper extraction process comprises the steps of placing a solution with the pH value adjusted in an electrolytic cell, and adding a solution with the current density of 200A/m2‑300A/m2Controlling the temperature at 50-60 deg.C for primary electrolysis, and performing secondary electrolysis with current density of 100A/m when the concentration of copper ions in the electrolyte is less than 10g/L2‑200A/m2And the temperature of the secondary electrolysis is 70-80 ℃, and when the solubility of copper ions in the electrolyte is less than 2g/L, the electrolysis process is finished and the electrolyzed simple substance copper and clear liquid are recovered. According to the treatment process of the acidic copper-containing etching waste liquid, provided by the invention, the secondary electrolysis process is adopted, so that copper ions in the electrolyte are converted into the copper simple substance, the energy consumption in the electrolysis process is reduced, the purity of the recovered copper simple substance is higher, and the recovered clear liquid can be repeatedly used, so that the treatment process is green and environment-friendly.

Description

Treatment process of acidic copper-containing etching waste liquid
Technical Field
The invention relates to an acidic copper-containing etching waste liquid, in particular to a treatment process of the acidic copper-containing etching waste liquid, and belongs to the technical field of waste liquid treatment.
Background
The main raw materials of the acidic etching solution comprise ammonium chloride, hydrochloric acid and copper chloride, have strong oxidizing property, and can perform oxidation-reduction reaction with the copper plate and the nickel plate, so that the copper plate and the nickel plate are dissolved, and the copper plate and the nickel plate are etched. The direct discharge of the copper-containing waste liquid can cause serious environmental pollution, and the excessive copper can cause enzyme poisoning in human bodies through the transfer of plants and water into the human bodies, thereby causing the loss of physiological functions of the human bodies. Therefore, the copper-containing etching waste liquid needs to be cleaned timely and effectively.
Disclosure of Invention
The invention aims to provide a treatment process of acidic copper-containing etching waste liquid, which overcomes the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a treatment process of acidic copper-containing etching waste liquid, which comprises the following steps:
(1) providing an alkaline solution with the pH of 8-10, slowly adding the alkaline solution into the acidic copper-containing etching waste liquid, stirring for 1-2 hours at the temperature of 30-40 ℃, adjusting the pH of the acidic copper-containing etching waste liquid to 8-10, and filtering to remove impurities;
(2) the copper extraction process comprises the following steps: putting the solution with the pH value adjusted in the step (1) into an electrolytic cell, and adding the solution with the current density of 200A/m2-300 A/m2Controlling the temperature at 50-60 deg.C for primary electrolysis, and performing secondary electrolysis with current density of 100A/m when the concentration of copper ions in the electrolyte is less than 10g/L2-200 A/m2The temperature of the secondary electrolysis is 70-80 ℃, when the solubility of copper ions in the electrolyte is less than 2g/L, the electrolysis process is finished, and the electrolyzed simple substance copper and clear liquid are recovered;
(3) the blending process comprises the following steps: and (3) adding hydrochloric acid, ammonium chloride and copper ions into the clear liquid recovered in the step (2), adjusting the concentration of the copper ions to be 20-30g/L, and obtaining and using the etching solution when the concentrations of hydrogen ions, ammonium ions and chloride ions in the clear liquid are consistent with the concentration of the etching solution.
Further, NaHCO with the concentration of 0.5-3mol/L is adopted in the step (1)3The alkaline solution adjusts the pH of the acidic copper-containing etching waste solution.
Further, a centrifugal filter is adopted for centrifugal filtration, and the mesh number of the filter cloth is 2000-5000 meshes.
Further, the electrolytic cell in the step (2) is divided into an anode area and a cathode area, and a polymer diaphragm is arranged between the anode area and the cathode area.
Preferably, the cathode of the anode region of the electrolytic cell in the step (2) is made of pure copper, but is not limited thereto.
Preferably, the electrolyte in step (2) includes any one or a combination of two of a sulfuric acid solution and a copper sulfate solution, but is not limited thereto.
Preferably, the anode of the anode region in the step (2) is a titanium plate coated with iridium ruthenium, but is not limited thereto.
Furthermore, the concentration of the chloride ions in the etching solution in the step (3) is 200 g/L-240 g/L.
Further, the concentration of the ammonium ions in the step (3) is 100 g/L-300 g/L.
Furthermore, 1 mol/L-5 mol/L hydrochloric acid is adopted to adjust the acidity of the etching solution in the step (3).
Compared with the prior art, the invention has the advantages that: according to the treatment process of the acidic copper-containing etching waste liquid, provided by the invention, the secondary electrolysis process is adopted, so that copper ions in the electrolyte are converted into the copper simple substance, the energy consumption in the electrolysis process is reduced, the purity of the recovered copper simple substance is higher, and the recovered clear liquid can be repeatedly used, so that the treatment process is green and environment-friendly.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
The embodiment of the invention provides a treatment process of acidic copper-containing etching waste liquid, which comprises the following steps:
(1) providing an alkaline solution with the pH of 8-10, slowly adding the alkaline solution into the acidic copper-containing etching waste liquid, stirring for 1-2 hours at the temperature of 30-40 ℃, adjusting the pH of the acidic copper-containing etching waste liquid to 8-10, and filtering to remove impurities;
(2) the copper extraction process comprises the following steps: putting the solution with the pH value adjusted in the step (1) into an electrolytic cell, and adding the solution with the current density of 200A/m2-300 A/m2Controlling the temperature to be 50-60 ℃ for one-time electrolysis until copper ions in the electrolyteWhen the concentration of (B) is less than 10g/L, secondary electrolysis is carried out, wherein the current density of the secondary electrolysis is 100A/m2-200 A/m2The temperature of the secondary electrolysis is 70-80 ℃, when the solubility of copper ions in the electrolyte is less than 2g/L, the electrolysis process is finished, and the electrolyzed simple substance copper and clear liquid are recovered;
(3) the blending process comprises the following steps: and (3) adding hydrochloric acid, ammonium chloride and copper ions into the clear liquid recovered in the step (2), adjusting the concentration of the copper ions to be 20-30g/L, and obtaining and using the etching solution when the concentrations of hydrogen ions, ammonium ions and chloride ions in the clear liquid are consistent with the concentration of the etching solution.
Further, NaHCO with the concentration of 0.5-3mol/L is adopted in the step (1)3The alkaline solution adjusts the pH of the acidic copper-containing etching waste solution.
Further, a centrifugal filter is adopted for centrifugal filtration, and the mesh number of the filter cloth is 2000-5000 meshes.
Further, the electrolytic cell in the step (2) is divided into an anode area and a cathode area, and a polymer diaphragm is arranged between the anode area and the cathode area.
Preferably, the cathode of the anode region of the electrolytic cell in the step (2) is made of pure copper, but is not limited thereto.
Preferably, the electrolyte in step (2) includes any one or a combination of two of a sulfuric acid solution and a copper sulfate solution, but is not limited thereto.
Preferably, the anode of the anode region in the step (2) is a titanium plate coated with iridium ruthenium, but is not limited thereto.
Furthermore, the concentration of the chloride ions in the etching solution in the step (3) is 200 g/L-240 g/L.
Further, the concentration of the ammonium ions in the step (3) is 100 g/L-300 g/L.
Furthermore, 1 mol/L-5 mol/L hydrochloric acid is adopted to adjust the acidity of the etching solution in the step (3).
According to the treatment process of the acidic copper-containing etching waste liquid, provided by the invention, the secondary electrolysis process is adopted, so that copper ions in the electrolyte are converted into the copper simple substance, the energy consumption in the electrolysis process is reduced, the purity of the recovered copper simple substance is higher, and the recovered clear liquid can be repeatedly used, so that the treatment process is green and environment-friendly.
The technical solution of the present invention is further explained below with reference to several examples.
Example 1
(1) Providing NaHCO with pH 93Slowly adding the solution into the acidic copper-containing etching waste liquid, stirring for 1h at the temperature of 35 ℃, adjusting the pH value of the acidic copper-containing etching waste liquid to 8, and filtering to remove impurities;
(2) the copper extraction process comprises the following steps: putting the solution with the pH value adjusted in the step (1) into an electrolytic cell, and adding the solution with the current density of 200A/m2Performing primary electrolysis at 50 deg.C, and performing secondary electrolysis with current density of 100A/m when the concentration of copper ions in the electrolyte is less than 10g/L2The temperature of secondary electrolysis is 80 ℃, when the solubility of copper ions in the electrolyte is less than 2g/L, the electrolysis process is finished, and the electrolyzed simple substance copper and clear liquid are recovered;
(3) the blending process comprises the following steps: and (3) adding hydrochloric acid, ammonium chloride and copper ions into the clear liquid recovered in the step (2), adjusting the concentration of the copper ions to be 30g/L, and obtaining and using the etching solution when the concentrations of hydrogen ions, ammonium ions and chloride ions in the clear liquid are consistent with the concentration of the etching solution.
Example 2
(1) Providing NaHCO at pH 103Slowly adding the solution into the acidic copper-containing etching waste liquid, stirring for 1h at the temperature of 30 ℃, adjusting the pH value of the acidic copper-containing etching waste liquid to 9, and filtering to remove impurities;
(2) the copper extraction process comprises the following steps: putting the solution with the pH value adjusted in the step (1) into an electrolytic cell, and adding the solution with the current density of 250A/m2Performing primary electrolysis at 60 deg.C, and performing secondary electrolysis with current density of 200A/m when the concentration of copper ions in the electrolyte is less than 10g/L2The temperature of secondary electrolysis is 80 ℃, when the solubility of copper ions in the electrolyte is less than 2g/L, the electrolysis process is finished, and the electrolyzed simple substance copper and clear liquid are recovered;
(3) the blending process comprises the following steps: and (3) adding hydrochloric acid, ammonium chloride and copper ions into the clear liquid recovered in the step (2), adjusting the concentration of the copper ions to be 20g/L, and obtaining and using the etching solution when the concentrations of hydrogen ions, ammonium ions and chloride ions in the clear liquid are consistent with the concentration of the etching solution.
Example 3
(1) Providing NaHCO at pH 103Slowly adding the solution into the acidic copper-containing etching waste liquid, stirring for 1h at the temperature of 30 ℃, adjusting the pH value of the acidic copper-containing etching waste liquid to 9, and filtering to remove impurities;
(2) the copper extraction process comprises the following steps: putting the solution with the pH value adjusted in the step (1) into an electrolytic cell, and adding the solution with the current density of 300A/m2Performing primary electrolysis at 60 deg.C, and performing secondary electrolysis with current density of 150A/m when the concentration of copper ions in the electrolyte is less than 10g/L2The temperature of secondary electrolysis is 75 ℃, when the solubility of copper ions in the electrolyte is less than 2g/L, the electrolysis process is finished, and the electrolyzed simple substance copper and clear liquid are recovered;
(3) the blending process comprises the following steps: and (3) adding hydrochloric acid, ammonium chloride and copper ions into the clear liquid recovered in the step (2), adjusting the concentration of the copper ions to be 25g/L, and obtaining and using the etching solution when the concentrations of hydrogen ions, ammonium ions and chloride ions in the clear liquid are consistent with the concentration of the etching solution.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (10)

1. The process for treating the acidic copper-containing etching waste liquid is characterized by comprising the following steps of:
(1) providing an alkaline solution with the pH of 8-10, slowly adding the alkaline solution into the acidic copper-containing etching waste liquid, stirring for 1-2 hours at the temperature of 30-40 ℃, adjusting the pH of the acidic copper-containing etching waste liquid to 8-10, and filtering to remove impurities;
(2) the copper extraction process comprises the following steps: putting the solution with the pH value adjusted in the step (1) into electrolysisAdding into the cell at a current density of 200A/m2-300A/m2Controlling the temperature at 50-60 deg.C for primary electrolysis, and performing secondary electrolysis with current density of 100A/m when the concentration of copper ions in the electrolyte is less than 10g/L2-200A/m2The temperature of the secondary electrolysis is 70-80 ℃, when the solubility of copper ions in the electrolyte is less than 2g/L, the electrolysis process is finished, and the electrolyzed simple substance copper and clear liquid are recovered;
(3) the blending process comprises the following steps: and (3) adding hydrochloric acid, ammonium chloride and copper ions into the clear liquid recovered in the step (2), adjusting the concentration of the copper ions to be 20-30g/L, and obtaining and using the etching solution when the concentrations of hydrogen ions, ammonium ions and chloride ions in the clear liquid are consistent with the concentration of the etching solution.
2. The process for treating an acidic copper-containing etching waste liquid according to claim 1, wherein the process comprises the following steps: NaHCO with the concentration of 0.5-3mol/L is adopted in the step (1)3The alkaline solution adjusts the pH of the acidic copper-containing etching waste solution.
3. The process for treating an acidic copper-containing etching waste liquid according to claim 1, wherein the process comprises the following steps: centrifugal filtration is carried out by adopting a centrifugal filter, and the mesh number of the filter cloth is 2000 meshes to 5000 meshes.
4. The process for treating an acidic copper-containing etching waste liquid according to claim 1, wherein the process comprises the following steps: the electrolytic cell in the step (2) is divided into an anode area and a cathode area, and a polymer diaphragm is arranged between the anode area and the cathode area.
5. The process for treating an acidic copper-containing etching waste liquid according to claim 1, wherein the process comprises the following steps: and (3) the cathode of the anode area of the electrolytic cell in the step (2) is made of pure copper.
6. The process for treating an acidic copper-containing etching waste liquid according to claim 1, wherein the process comprises the following steps: the electrolyte in the step (2) comprises any one or combination of two of a sulfuric acid solution and a copper sulfate solution.
7. The process according to claim 1, wherein the acidic copper-containing etching solution comprises: and (3) the anode of the anode region in the step (2) is a titanium plate coated with iridium ruthenium.
8. The process for treating an acidic copper-containing etching waste liquid according to claim 1, wherein the process comprises the following steps: the concentration of the chloride ions in the etching solution in the step (3) is 200 g/L-240 g/L.
9. The process for treating an acidic copper-containing etching waste liquid according to claim 1, wherein the process comprises the following steps: the concentration of the ammonium ions in the step (3) is 100 g/L-300 g/L.
10. The process for treating an acidic copper-containing etching waste liquid according to claim 1, wherein the process comprises the following steps: and (3) adjusting the acidity of the etching solution by using 1-5 mol/L hydrochloric acid.
CN202010631968.XA 2020-07-03 2020-07-03 Treatment process of acidic copper-containing etching waste liquid Pending CN111925026A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4051001A (en) * 1974-08-26 1977-09-27 Hitachi, Ltd. Process for regenerating etching solution
JP2010059521A (en) * 2008-09-05 2010-03-18 Ebara Engineering Service Co Ltd Method and apparatus for removing and recovering copper from copper-containing acidic waste liquid
CN102303917A (en) * 2011-08-25 2012-01-04 石祥阁 Method for mixed treatment of waste liquid from acid etching and micro etching of printed circuit boards
CN107662988A (en) * 2016-07-30 2018-02-06 湖北永绍科技股份有限公司 A kind of processing method of acidic etching waste liquid
CN110453225A (en) * 2019-08-29 2019-11-15 深圳市祺鑫天正环保科技有限公司 The processing method of acidic etching waste liquid

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4051001A (en) * 1974-08-26 1977-09-27 Hitachi, Ltd. Process for regenerating etching solution
JP2010059521A (en) * 2008-09-05 2010-03-18 Ebara Engineering Service Co Ltd Method and apparatus for removing and recovering copper from copper-containing acidic waste liquid
CN102303917A (en) * 2011-08-25 2012-01-04 石祥阁 Method for mixed treatment of waste liquid from acid etching and micro etching of printed circuit boards
CN107662988A (en) * 2016-07-30 2018-02-06 湖北永绍科技股份有限公司 A kind of processing method of acidic etching waste liquid
CN110453225A (en) * 2019-08-29 2019-11-15 深圳市祺鑫天正环保科技有限公司 The processing method of acidic etching waste liquid

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
余继燮等编: "《重金属冶金学》", 30 September 1981, 冶金工业出版社 *

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Application publication date: 20201113