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Method for recovering copper from acidic etching waste liquid

A technology of acidic etching waste liquid and copper recovery, which is applied in the field of environmental engineering, can solve the problems of value discount, affecting purity, poor appearance, etc., and achieve the effects of inhibiting remelting, improving current efficiency, and reducing etching speed

Active Publication Date: 2014-07-23
GUANGZHOU HONWAY TECH CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] The existing method of direct electrolytic recovery of copper from acidic etching waste liquid is the membrane electrolysis method, because the acidic etching liquid contains a large amount of Cl - (The concentration is between 200g / L-330g / L), which has a strong depolarization effect, making the copper easily obtained in the electrolysis process of the etching waste liquid be powdery or produce serious nodular phenomenon, nodular Copper is easy to block or pierce the diaphragm, causing electrolysis equipment to be paralyzed and affecting production
However, copper powder is easy to peel off to the bottom of the cathode tank, and a special auxiliary system for copper powder removal is required, and copper powder is easily oxidized and discolored, which affects purity, poor appearance, and its value will be greatly reduced

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] The acidic etching waste solution was taken from the acidic etching production line of an electronics factory in Guangdong Province, and the solution was dark green. After analysis, its total copper content is 152.2 g / L, HCl content is 73.5 g / L, Cl - The content is 305.6 g / L. Use this as the anolyte and catholyte, add 1.0% of 50% hydrazine hydrate to the catholyte before electrolysis to make it fully react, and then add 20 mg / L sodium polydithiopropanesulfonate (SPS) and 20mg / L polyvinyl alcohol. Through direct current electrolysis, under stirring conditions (100 r / min), according to the cathode current density of 1000 A / m 2 、600A / m 2 、300A / m 2 Under the conditions of continuous electrolysis for 8 hours, a relatively dense copper block can be obtained.

[0025] The copper block deposited by the cathode has no knots, will not pierce the separator and is easy to peel off and form. The current efficiency of the cathode deposited copper is 91.6%, and the average copper...

Embodiment 2

[0027] The acidic etching waste solution was taken from the acidic etching production line of an electronics factory in Guangdong Province, and the solution was dark green. After analysis, its total copper content is 127.5 g / L, HCl content is 64.6 g / L, Cl - The content is 273.5 g / L. Use this as the anolyte and catholyte, add 0.8% of 50% hydroxylamine to the catholyte before electrolysis to make it fully react, and then add 15 mg / L sodium dimethylformamide sulfonate (TPS) and poly Sodium dithiopropane sulfonate (SPS) composition, polyvinyl alcohol of 15mg / L. Through direct current electrolysis, under stirring conditions (200 r / min), according to the cathode current density of 800 A / m 2 、500A / m 2 、300A / m 2 Under the condition of continuous electrolysis for 7 hours, a relatively dense copper block can be obtained.

[0028] The copper block deposited by the cathode has no knots, will not pierce the separator and is easy to peel off and form. The current efficiency of the cath...

Embodiment 3

[0030] The acidic etching waste solution was taken from the acidic etching production line of an electronics factory in Guangdong Province, and the solution was dark green. After analysis, its total copper content is 108.2 g / L, HCl content is 57.2 g / L, Cl - The content is 266.8 g / L. Use this as the anolyte and catholyte, add 0.5% of 50% hydrazine hydrate to the catholyte before electrolysis to make it react fully, and then add 15 mg / L of 3-mercapto-1-propanesulfonate sodium ( MPS) and 10mg / L polyvinyl alcohol. Through direct current electrolysis, under stirring conditions (150 r / min), according to the cathode current density of 700 A / m 2 、500A / m 2 、200A / m 2 Under the condition of continuous electrolysis for 7 hours, a relatively dense copper block can be obtained.

[0031] The cathode-deposited copper block has no knots, will not pierce the separator and is easy to peel off. The current efficiency of cathode-deposited copper is 92.8%, and the average copper deposition rat...

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Abstract

The invention discloses a method for recovering copper from an acidic etching waste liquid, which comprises the following steps: by using the acidic etching waste liquid emitted by a PCB (printed circuit board) etching process as a catholyte and anolyte, sequentially adding an accelerator, a grain refiner and a leveling agent into the catholyte, and carrying out direct-current electrolysis at the cathode current density of 100-1000A / m<2> for 10-30 hours, thereby obtaining the metal copper in the cathode chamber, wherein the accelerator is an ammonia derivative, the grain refiner is a sulfonic organic sulfide, and the leveling agent is polyvinyl alcohol. The method can be used for directly obtaining a copper block, and the deposited copper block has the advantages of high purity, easy stripping and no branch and can not penetrate through the diaphragm.

Description

technical field [0001] The invention relates to the technical field of environmental engineering, in particular to a method for recovering copper from acidic etching waste liquid. Background technique [0002] Acid etching solution is an etching solution used in the etching process in the production process of printed circuit boards (especially the production of fine lines and the inner layer of multi-layer boards), mainly including HCl / NaCl / CuCl 2 System, HCl / NH 4 Cl / CuCl 2 System, HCl / CuCl 2 system. With the progress of the etching process, the Cu in the etching solution 2+ Concentration decreases continuously, Cu + And the total copper concentration continues to rise, and the etching rate decreases. At this time, it is necessary to discharge the etching waste liquid or perform regeneration. The concentration of copper in the etching waste liquid is very high, between 100 g / L-160 g / L, direct discharge will seriously pollute the environment, if the high value-added c...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C25C1/12C22B7/00C23F1/46
CPCY02P10/20
Inventor 赵国鹏徐海清钟洪胜胡耀红袁国伟陈力格罗慧梅徐金来
Owner GUANGZHOU HONWAY TECH CORP
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