SU1280036A1 - Method of recovering used copper-ammonia pickle - Google Patents

Abstract

The invention relates to the field of non-ferrous metallurgy and can be used in the regeneration of spent copper-ammonia solutions. The purpose of the invention is to reduce copper losses, reduce the consumption of reagents and reduce environmental pollution. The method of regeneration of spent copper ammonium pickling solutions includes extraction with an organic cation-exchange reagent, washing the organic phase and reextraction of copper with sulphate solutions. After copper extraction with sulfuric acid solutions, the extractant is treated with an ammonia solution obtained after washing the fine copper with the organic phase. Washing i with a copper-rich organic phase is carried out with a solution obtained (L by mixing the extractant treatment solution and the electrolyte spent after electrolysis of copper, to obtain washing solutions with a pH of 5-6, and d-alkylphenol sulfides are used as the organic cation-exchange reagent. 1 hp ff. 00

Description

The invention relates to non-ferrous metallurgy and can be used in the regeneration of spent ammonia-ammonia solutions.

The aim of the invention is to reduce copper losses, reduce reagent consumption and reduce environmental pollution.

Example 1. A well-developed copper-ammonium pickling solution containing 69.9 g / l C and having a pH of 8.62 in the amount of 10 ml / min was contacted with a 0.23 mol / l solution of oktotophore 10 S in kerosene with the addition of 25 vol.% Octanol at a flow rate of 40 ml / mi for 10 min, after phase separation, a regenerated etching solution containing 32.4 g / l Cu was obtained, the degree of copper recovery was 53.6%, and the organic phase containing copper and ammonium were rinsed with a solution (flow rate 13.3 ml / min) obtained by mixing the extractant treatment solution (flow rate 11.3 ml / min) and ref Botan electrolyte (flow rate 2 ml / min), the solution contained 1.7 g / l Cu and had a free acidity of 16 g / l.

After washing, the organic phase, guided by copper sheathing, and the washing solution, having a pH of 5.0 and containing 0.4 g / l C and 50 g / l NH., Were directed to the treatment of the extractant after reextraction. The washed copper organic phase was reextracted with spent electrolyte (flow rate 20 ml / min) containing 27.2 g / l Cu, 153.0 g / l H, S04 and 5.7 g / l NH, and electrolyte was obtained. containing 45.7 g / l Cu and 109.4 g / l H, 2S04, which were sent to electrolysis. The organic phase was treated with an ammonia solution obtained after washing the organic phase with a high purity (flow rate 11.2 mp / min), the resulting aqueous solution was mixed with the spent electrolyte, and the extruder was directed to extracting copper from the spent pickle.

With this implementation of the process, the ammonium concentration in the washing solution and the electrolyte is stabilized; it is equal to 50 and 19 g / l NH, respectively. In this case, the ammonium salts are not precipitated, and there is no need to discard otrabat5

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nlp1 electrolyte, and therefore allow copper loss.

Example 2. A spent copper – ammonia solution containing 73.4 g / l Cu and having a pH of 9.00 in an amount of 10 ml / min was contacted with a 0.23 mol / l octophore 10S solution in kerosene with the addition of 25 vol. 7, octanol at a flow rate of 40 ml / min for 10 minutes, after separation of the phases, a regenerated pickling solution containing 34.0 g / l Cu was obtained, the recovery rate of copper was 53.7%, and the organic phase containing copper and ammonium was directed to washing solution (flow rate of 13.3 ml / min), obtained by mixing the solution of the processing of the extractant (flow rate of 11.3 MP / min) and spent lit (flow rate 2 ml / min), the solution contained 2.2 g / l Cu and had a free acidity of 15.8 g / l After washing, the organic phase was obtained, which was directed to copper reextraction, and the washing solution had a pH of 6.0 and containing 0.3 g / l Cu and 47.7 g / l NH4, directed to the treatment of the extractant after

reextraction. I

The copper-washed organic phase was re-extracted with spent electrolyte (flow rate 20 ml / min) containing 32.7 g / l Cu, 142.2 g / l HjS04 and 18 g / l NH4, yielding an electrolyte containing 56.2 g / l Cu and 146.6 g / l, which were directed to the electrolyte. The organic phase was treated with an ammonia solution obtained after washing with a copper-rich organic phase (flow rate 11.2 MP / min), half of the aqueous solution was mixed with the spent electrolyte, and the extractant was directed to extract copper from the spent pickling solution.

With this implementation of the process, the ammonium concentration in the washing solution and the electrolyte stabilizes, it is 47.7 and 18 g / l NH4, respectively. In this case, ammonium salts are not precipitated and there is no need to dump the electrolyte, and therefore prevent the loss of copper.

When regeneration of spent copper-ammonia pickling solutions is carried out by a known method, ammonium accumulates in 6 liters of electrolyte in 40 hours of operation

to a maximum concentration of 20 g / l and the electrolyte must be completely replaced, thus the loss of copper with electrolyte is 30 g / l (6 l 180 g). At the same time, over 40 hours of work, 899.2 g of copper is extracted from the spent pickling solution at a flow rate of 10 ml / min, i.e. when changing the electrolyte, 20% of the extracted copper is lost.

When regeneration is carried out according to a known method, with a feed rate of the pickling solution equal to .1 O m / s with the organic phase after the crafting, as a result of capture with a microemulsion, 2.5 g / h 50 is transferred into the regenerated pickling solution.

When additional washing is introduced in the proposed method after re-extraction, a qualitative analysis of the regenerated pickling solution with barium chloride shows the absence of SO ions in it.

When conducting a washing with a copper-rich organic phase with a solution, — obtained by mixing the solution of the treatment of the extractant and the spent electrolyte to obtain washing solutions with a pH of 6;

is washed out of the organic phase and subsequently accumulated in the electrolyte. When the extractant treatment solution and the spent electrolyte are mixed to obtain washing solutions with pH 5 together with ammonia, copper is leached from the organic phase, which leads to its loss with waste solutions.

Thus, the use of the proposed method of regeneration of copper-ammonia pickling solutions avoids the discharge of electrolyte.

Compiled by D. Krivoshey Editor K. Voloshchuk Tekhred L. Oleinik Proofreader A. Obruchar

Order 7024/25 Circulation 567 Subscription

VNIIPI USSR State Committee

for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5

Production and printing company, Uzhgorod, st. Design, And

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by preventing the accumulation of ammonium ion and thereby reducing copper losses by 20% and preventing contamination of the electrolyte with ammonium ions, and the etching solution with sulfate ions. This makes it possible to significantly reduce the consumption of reagents for etching printed circuit boards due to the turnover of spent pickling solutions, use them for a longer time and prevent environmental pollution by eliminating the discharge of both pickling solutions and electrolyte.

Claims (2)

00 o The invention relates to non-ferrous metallurgy and can be used in the regeneration of spent copper-ammonia solutions. The aim of the invention is to reduce copper losses, reduce reagent consumption and reduce environmental pollution. Example 1. A refined copper ammonium pickling solution containing 69.9 g / l C and having a pH of 8.62 in an amount of 10 ml / min was contacted with 0.23 mol / l octophore 10 S solution in kerosene with the addition of 25 vol% octanol at After a phase separation, a regenerated etching solution containing 32.4 g / l Cu was obtained, the recovery rate of copper was 53.6%, and the organic phase containing copper and ammonium was directed to washing with a solution (flow rate 13.3 ml / min) obtained by mixing the extractant treatment solution (flow rate 11.3 ml / min) and discharging tannogo electrolyte (flow rate 2 ml / min), the solution contained 1.7 g / l Cu and had a free acidity of 16 g / l. After washing, the organic phase, guided by copper sheathing, and the washing solution, having a pH of 5.0 and containing 0.4 g / l Cu and 50 g / l NH., Were obtained, sent to the extractant after re-extraction. The washed copper organic phase was reextracted with spent electrolyte (flow rate 20 ml / min) containing 27.2 g / l Cu, 153.0 g / l H, S04 and 5.7 g / l NH, and an electrolyte containing 45 was obtained. , 7 g / l Cu and 109.4 g / l H, 2S04, which were sent for electrolysis. The organic phase was treated with an ammonia solution obtained after washing the organic phase with copper (consumption 11.2 mp / min), the resulting aqueous solution was mixed with the spent electrolyte, and the extractant was sent for copper extraction from the spent pickling solution. With such an implementation of the process, the concentration of ammonium in the washing solution and electrolyte is stabilized; it is equal to 50 and 19 g / l NH, respectively. In this case, the ammonium salts are not precipitated and there is no need to dump the electrolyte from the electrolyte, and therefore to prevent the loss of copper. Example 2. A spent ammonium ammonia solution containing 73.4 g / l Cu and having a pH of 9.00 in an amount of 10 ml / min was contacted with a 0.23 mol / l octofor 10S solution in kerosene with the addition of 25 vol 7, octanol at a flow rate of 40 ml / min for 10 minutes, after separation of the phases, a regenerated pickling solution containing 34.0 g / l Cu was obtained, the recovery rate of copper was 53.7%, and the organic phase containing copper and ammonium was directed to washing with a solution ( flow rate of 13.3 ml / min), obtained by mixing the solution of the processing of the extractant (flow rate of 11.3 MP / min) and spent electrical Ita (flow rate 2 ml / min), the solution contained 2.2 g / l C and had a free acidity of 15.8 g / l. After washing, the organic phase was obtained, which was directed to copper reextraction, and the washing solution had a 1st pH of 6.0 and containing 0.3 g / l Cu and 47.7 g / l NH4, which is directed to the processing of the extractant after re-extraction. I The washed organic copper phase was reextracted with spent electrolyte (flow rate 20 ml / min) containing 32.7 g / l Cu, 142.2 g / l HjS04 and 18 g / l NH4, thus obtaining an electrolyte containing 56.2 g / l C and 146.6 g / l, which were directed to the electrolyte. The organic phase was treated with an ammonia solution obtained after washing with a copper-rich organic phase (flow rate 11.2 MP / min), half of the aqueous solution was mixed with the spent electrolyte, and the extractant was directed to extract copper from the spent pickling solution. With this implementation of the process, the ammonium concentration in the washing solution and the electrolyte stabilizes, it is 47.7 and 18 g / l NH4, respectively. In this case, ammonium salts are not precipitated and there is no need to dump the electrolyte, and therefore prevent the loss of copper. When regeneration of spent copper ammonia pickling solutions is carried out by a known method in 6 liters of electrolyte for 40 hours of operation of the installation ammonium accumulates to a maximum concentration of 20 g / l and the electrolyte must be completely replaced, thus copper loss with electrolyte is 30 g / l (6 l 180 g). At the same time, over 40 hours of work, 899.2 g of copper is extracted from the spent pickling solution at a flow rate of 10 ml / min, i.e. when changing the electrolyte, 20% of the recovered copper is lost. When regeneration is carried out according to a known method, the feed rate of the pickling solution is equal to .1 O mp / s with the organic phase after the crafting, as a result of the capture with a microemulsion, 2.5 g / h 50 is transferred into the regenerated pickling solution. With the introduction of additional washing in the proposed method after re-extraction, a qualitative analysis of the regenerated pickling solution with barium chloride shows the absence of SO ions in it. When conducting a washing with a copper-rich organic phase with a solution, - obtained by mixing the treatment solution of the extractant and the spent electrolyte to obtain washing solutions with a pH of 6, ammonia is slightly washed away from the organic phase and is subsequently accumulated in the electrolyte. When the extractant treatment solution and the spent electrolyte are mixed to obtain washing solutions with pH 5 together with ammonia, copper is leached from the organic phase, which leads to its loss with waste solutions. Thus, the use of the proposed method of regenerating copper ammonium pickling solutions avoids electrolyte discharge by preventing the accumulation of ammonium ion and thereby reducing copper loss by 20% and preventing electrolyte contamination by ammonium ions, and the pickling solution by sulfation ions. This makes it possible to significantly reduce the consumption of reagents for etching printed circuit boards due to the turnover of spent pickling solutions, use them for a longer time and prevent environmental pollution by eliminating the discharge of both pickling solutions and electrolyte. 1. Method for regeneration of spent copper-ammonium pickling solutions by extraction with an organic cation-exchange reagent, washing the copper-rich organic phase, copper extraction with sulfuric acid solutions and its electrolytic separation, characterized in that, in order to reduce copper losses, reduce reagent consumption and reduce the charge. after stripping, the extractant is treated with an ammonia solution obtained after washing the organic phase with a saturated copper, and myvku saturated copper organic phase is carried out with a solution obtained offset extractant treatment solution and spent electrolyte to obtain a leaching solution having a pH of 5-6. 2. A method according to claim 1, characterized in that p-alkylphenol disulfides are used as an organic cation exchange reagent.