KR100380033B1 - Process for preparing pure cupric sulphate from waste cupric chloride - Google Patents

Process for preparing pure cupric sulphate from waste cupric chloride Download PDF

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KR100380033B1
KR100380033B1 KR1020000018399A KR20000018399A KR100380033B1 KR 100380033 B1 KR100380033 B1 KR 100380033B1 KR 1020000018399 A KR1020000018399 A KR 1020000018399A KR 20000018399 A KR20000018399 A KR 20000018399A KR 100380033 B1 KR100380033 B1 KR 100380033B1
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copper sulfate
copper
chloride
hydrochloric acid
cupric
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KR20010088260A (en
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공도영
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서안켐텍 주식회사
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
    • B22D17/20—Accessories: Details
    • B22D17/2015—Means for forcing the molten metal into the die
    • B22D17/203—Injection pistons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
    • B22D17/20—Accessories: Details
    • B22D17/30—Accessories for supplying molten metal, e.g. in rations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
    • B22D17/20—Accessories: Details
    • B22D17/32—Controlling equipment

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

본 발명은 염산 함유 염화동 폐액에 염화동에 대하여 당량비 이상의 진한 황산을 가하고, 감압 증발 농축시킨 후, 생성된 황산동을 알코올 또는 아세톤에 침지하고, 여과하여 얻어진 황산동을 물에 재결정시킴을 특징으로 하는 고순도의 황산동 5수염의 제조방법.The present invention adds concentrated sulfuric acid with an equivalent ratio or more to copper chloride to hydrochloric acid-containing copper chloride, and concentrates by evaporation under reduced pressure. Method for preparing copper sulfate pentahydrate.

Description

염화동 폐액으로부터 고순도 황산동의 제조방법{PROCESS FOR PREPARING PURE CUPRIC SULPHATE FROM WASTE CUPRIC CHLORIDE}Process for producing high purity copper sulfate from copper chloride waste liquid {PROCESS FOR PREPARING PURE CUPRIC SULPHATE FROM WASTE CUPRIC CHLORIDE}

본 발명은 염화동 폐액으로부터 고순도의 황산동을 제조하는 방법에 관한 것이다. 더 상세히는 PCB 기판 제조시에 발생하는 염산 함유 염화동 폐액에 황산을 가하여 황산동을 얻은 후, 이를 알코올로 처리하여 황산동에 함유되어 있는 염소 성분을 제거하여 고순도의 황산동을 제조하는 방법을 제공하는 것이다.The present invention relates to a method for producing high purity copper sulfate from copper chloride waste liquid. More specifically, to provide copper sulfate by adding sulfuric acid to the hydrochloric acid-containing copper chloride waste solution generated in the PCB substrate, and then treated with alcohol to remove the chlorine component contained in copper sulfate to provide a high-purity copper sulfate.

황산동(CuSO4ㆍ5H2O)은 농약, 동염 제조의 원료, 청록계통의 안료, 방부제, 도금용 전해액의 원료 등으로 널리 사용되고 있다. 이러한 황산동의 공업적 제조방법으로서는 공기를 통하면서 동 부스러기를 묽은 염산에 용해시키던가, 또는 동 정련시에 발생하는 전해폐액에 동 부스러기를 넣고, 중화한 후, 증기와 공기를 가하면서 가열하고, 여과한 후, 방냉하여 얻어지는 결정을 분리하여 제조하고 있다. 또한, 실험실적으로는 동을 농황산 또는 황산과 질산의 혼액에 용해하던가, 또는 산화동(Ⅱ)을 묽은 황산에 용해하고, 이를 농축 냉각하여 결정시킴으로서 얻을 수 있다.Copper sulfate (CuSO 4 · 5H 2 O) is widely used as a raw material for the manufacture of pesticides, copper salts, pigments of cyan-based pigments, preservatives, and electrolytic solutions for plating. As an industrial production method of such copper sulfate, the copper waste is dissolved in dilute hydrochloric acid while passing through air, or the copper waste is put into an electrolytic waste solution generated during copper refining, neutralized, heated with steam and air, and filtered. After that, crystals obtained by cooling are separated and manufactured. In the laboratory, it can be obtained by dissolving copper in concentrated sulfuric acid or a mixture of sulfuric acid and nitric acid, or by dissolving copper (II) oxide in dilute sulfuric acid, and concentrating and cooling it.

그런데, 최근 PCB 기판 제조시에 염산 함유 염화동 폐액이 급격하게 과량으로 발생하여 이를 처리하는 데 커다란 문제로 되고 있다. 이러한 염산 함유 염화동은 제조원에 따라 약간의 차이는 있으나, 대부분 염화동이 200∼300 g/ℓ가 함유되고, 염산이 100∼170 g/ℓ를 함유하고 있다.However, in recent years, a large amount of hydrochloric acid-containing copper chloride wastewater is rapidly generated in manufacturing PCB substrates, which is a great problem in treating this. These hydrochloric acid-containing copper chlorides vary slightly depending on the manufacturer, but most of them contain 200-300 g / l of copper chloride and 100-170 g / l of hydrochloric acid.

종래, 염산 함유 염화동에 진한 황산을 가하여 황산동을 회수하는 방법이 알려져 있다. 그러나, 염산 함유 염화동 폐액에 황산을 첨가하여 증발 농축시킬 때, 염산은 약 2%에서 황산과 공비점을 갖고 있어서 염산을 완전히 제거할 수 없음은 알려져 있다. 따라서, 종래의 방법으로 회수한 황산동에 잔류 염소가 지나치게 높아 이를 산업적으로 재활용하는 것이 곤란하다. 즉, 황산동을 사용하는 대부분의 업계는 염소 잔류량이 대개 30 ppm 이하의 기준으로 하고 있으므로, 이러한 기준에 맞추기 위하여는 얻어진 황산동을 적당한 용매 또는 산에 용해, 증류, 재결정 등을 반복하여야 하나, 이러한 방법에 의해서도 만족할 만한 품질의 황산동을 회수하기 어렵고, 가능하다 하여도 처리비용 및 장치비용이 지나치게 높고, 2차 오염문제가 발생하여 경제적으로 채용될 수 있는 방법이라 할 수 없다.Conventionally, a method of recovering copper sulfate by adding concentrated sulfuric acid to hydrochloric acid-containing copper chloride is known. However, it is known that hydrochloric acid has an azeotropic point with sulfuric acid at about 2%, so that hydrochloric acid cannot be completely removed when sulfuric acid is added to the hydrochloric acid-containing copper chloride waste solution by evaporation. Therefore, the residual chlorine is too high in the copper sulfate recovered by the conventional method, it is difficult to industrially recycle it. In other words, most industries using copper sulfate have a standard of 30 ppm or less of residual chlorine. Therefore, in order to meet these standards, the obtained copper sulfate must be repeatedly dissolved, distilled, and recrystallized in an appropriate solvent or acid. It is difficult to recover copper sulfate of satisfactory quality, and even if it is possible, the treatment cost and the equipment cost are too high, and the secondary pollution problem occurs, and thus it is not a method that can be employed economically.

그러나, 상기와 같이 계속 발생되는 염화동을 재활용하는 획기적인 방법은 제시되지 않고 있으며, 산업계에서는 이러한 문제의 해결이 절실히 요구되고 있다.However, no groundbreaking method for recycling copper chloride, which is continuously generated as described above, has not been proposed, and the industry is urgently required to solve such problems.

본 발명자는 상기 문제점을 해결하기 위하여 예의 연구한 결과, 염화동 폐액에 몰비이상의 진한 황산을 첨가하여 감압 증발 농축시켜 25% 이상의 염산을 회수하고, 얻어진 염산 함유 황산동 슬라임을 알코올 또는 아세톤에 침지시키고, 여과하여 유리 황산 유리 염소 및 유리 염산을 제거하고, 얻어진 황산동을 물에 녹여 결정시켜 순수한 황산동을 얻을 수 있음을 발견하고, 본 발명을 완성하게 되었다.The present inventors have diligently studied to solve the above problems, and as a result, by adding a concentrated sulfuric acid of more than molar ratio to the copper chloride waste solution, it is concentrated under reduced pressure to recover 25% or more of hydrochloric acid, and the obtained hydrochloric acid-containing copper sulfate slime is immersed in alcohol or acetone and filtered. It was found that pure copper sulfate was obtained by removing the free sulfuric acid free chlorine and free hydrochloric acid and dissolving the obtained copper sulfate in water to obtain pure copper sulfate, thereby completing the present invention.

본 발명은 염산을 함유하는 염화동 폐액을 당량비 이상의 진한 황산으로 반응시켜 황산동을 얻고, 이를 증발 농축, 바람직하기로는 감압하에서 증발 농축하여 염산을 구축한다. 이 때, 구축된 염산은 별도의 공지의 장치를 이용하여 회수할 수 있으며, 이 공정에서 감압은 약 400∼550 mmHg 정도가 바람직하며, 또한 이 때의 반응기 내부의 온도는 80∼100℃로 유지하는 것이 바람직하다. 또한, 이 반응은 교반하지 않아도 진행되나, 반응 열전도 등을 고려하여 교반하는 것이 바람직하다.In the present invention, copper chloride effluent containing hydrochloric acid is reacted with concentrated sulfuric acid or more in equivalent ratio to obtain copper sulfate, which is concentrated by evaporation, preferably under reduced pressure to build hydrochloric acid. At this time, the constructed hydrochloric acid can be recovered by using a separate known device. In this process, the reduced pressure is preferably about 400 to 550 mmHg, and the temperature inside the reactor at this time is maintained at 80 to 100 ° C. It is desirable to. In addition, although this reaction proceeds without stirring, it is preferable to agitate in consideration of reaction heat conduction and the like.

상기에서 얻어진 소량의 염산이 함유된 황산동 슬라임을 에탄올, 메탄올과 같은 알코올 또는 아세톤에 침지시킨다. 이 공정에서 황산동에 함유된 염산, 염소 성분 등은 알코올 또는 아세톤으로 이행된다. 이를 여과하여 황산동을 회수하고, 얻어진 황산동을 물에 재결정시켜 황산동 5수염을 얻는다. 여기서 사용되는 알코올로서는 메탄올이 바람직하며, 메탄올은 80% 이상의 것이 바람직하고 아세톤은 95%이상의 것이 바람직하다. 80%이하의 메탄올이나 아세톤을 사용하면, 황산동 5수염이 메탄올 또는 아세톤 수용액에 용해되어 염산과 함께 이행되므로 용매추출의 의미가 없게 된다. 회수된 메탄올 또는 아세톤액은 재증류하거나, 본 발명자의 선출원인 특허출원 제 99-3390호의 방법에 의해 메탄올중의 수분을 제거하여 다음 공정에 사용하여도 좋다.Copper sulfate slime containing a small amount of hydrochloric acid obtained above is immersed in an alcohol such as ethanol, methanol or acetone. In this process, the hydrochloric acid, chlorine component, and the like contained in copper sulfate are transferred to alcohol or acetone. This is filtered to recover copper sulfate, and the obtained copper sulfate is recrystallized in water to obtain a copper sulfate pentachloride. As an alcohol used here, methanol is preferable, methanol is preferably 80% or more, and acetone is preferably 95% or more. When 80% or less of methanol or acetone is used, the copper sulfate pentachloride is dissolved in methanol or acetone aqueous solution and is transferred together with hydrochloric acid, so that solvent extraction is not meaningful. The recovered methanol or acetone solution may be distilled again, or may be used in the next step by removing water in methanol by the method of Patent Application No. 99-3390, which is a prior application of the present inventors.

이하 실시예를 들어 본 발명은 더 구체적으로 설명한다. 그러나, 이들 실시예가 본 발명의 범위를 한정하는 것은 아니다.The present invention will be described in more detail with reference to the following examples. However, these examples do not limit the scope of the present invention.

실시예 1Example 1

염산 함유 염화동 폐액(염화동 함유량: 268 g/ℓ, 염산 함유량 134 g/ℓ) 1000 g에 98% 황산 215 g을 가하고, 반응기의 내온 95℃ 및 내압을 500 mmHg에서 교반하면서 40분간 반응시켰다. 농축된 잔류물에 85% 메탄올 400cc로 추출하고, 얻어진 황산동을 물에 결정화시켜 487.9 g의 황산동 5수염을 얻었다. 이를 분석하여 본 바, 황산동 5수염에 함유된 염소이온은 10 ppm 이었다.215 g of 98% sulfuric acid was added to 1000 g of hydrochloric acid-containing copper chloride waste liquid (copper chloride content: 268 g / L, hydrochloric acid content 134 g / L), and the reaction was allowed to react for 40 minutes while stirring the reactor's internal temperature at 95 ° C and internal pressure at 500 mmHg. The concentrated residue was extracted with 400cc of 85% methanol, and the obtained copper sulfate was crystallized in water to obtain 487.9 g of copper sulfate pentachloride. As a result of analysis, the chloride ion contained in copper sulfate pentachloride was 10 ppm.

실시예 2Example 2

실시예 1에서 메탄올 600cc로 추출한 것 이외에는 실시예 1과 동일하게 조작하였다.The same operation as in Example 1 was conducted except that the extract was extracted with 600 cc of methanol in Example 1.

그 결과, 얻어진 황산동 5수염에 함유된 염소이온은 4 ppm 이었다.As a result, the chloride ion contained in the obtained copper sulfate pentahydrate was 4 ppm.

실시예 3Example 3

실시예 1에서 메탄올 400cc씩 2회 추출한 것 이외에는 실시예 1과 동일하게 조작하였다.The same operation as in Example 1 was carried out except that 400 cc of methanol was extracted twice in Example 1.

그 결과, 얻어진 황산동 5수염에 함유된 염소이온은 0.5 ppm 이었다.As a result, the chloride ion contained in the obtained copper sulfate pentahydrate was 0.5 ppm.

실시예 4Example 4

실시예 1에서 메탄올대신에 95% 아세톤 400cc씩을 사용하여2회 추출한 것 이외에는 실시예 1과 동일하게 조작하였다.The same operation as in Example 1 was carried out except that the extraction was carried out twice using 400cc of 95% acetone instead of methanol in Example 1.

그 결과, 얻어진 황산동 5수염에 함유된 염소이온은 0.05 ppm 이었다.As a result, the chloride ion contained in the obtained copper sulfate pentahydrate was 0.05 ppm.

상술한 바와 같이, 본 발명은 다량으로 발생하는 염산함유 염화동을 황산과 반응시켜 황산동을 얻은 후, 이를 알코올 또는 아세톤으로 추출하여 유리산 및 유리 염소가 없는 고순도의 황산동을 얻을 수 있다. 이러한 본 발명의 방법에 의하여 전자부품업체에서 발생하는 염화동을 처리하여 고가의 황산동 5수염을 제조함으로서 경제적으로 유익할 뿐 아니라, 환경오염을 방지하는 유용한 발명이다.As described above, the present invention can be obtained by reacting a large amount of copper chloride containing hydrochloric acid with sulfuric acid to obtain copper sulfate, and then extracted with alcohol or acetone to obtain a high purity copper sulfate free of free acid and free chlorine. By the method of the present invention by treating the copper chloride generated in the electronic parts manufacturers to produce expensive copper sulfate pentachloride is not only economically beneficial, it is a useful invention to prevent environmental pollution.

Claims (5)

염산 함유 염화동 폐액에 염화동에 대하여 당량비 이상의 진한 황산을 가하고, 감압 증발 농축시켜 황산동 5수염을 제조하는 방법에 있어서,In a method of producing copper sulfate pentachloride by adding concentrated sulfuric acid having an equivalent ratio or higher to copper chloride to copper chloride-containing copper chloride waste liquid, and evaporating under reduced pressure, 생성된 황산동을 80%이상의 메탄올 또는 95%이상의 아세톤에 침지하고, 여과하여 얻어진 황산동을 물에 재결정시킴을 특징으로 하는 염소 잔류량이 10ppm이하의 고순도 황산동 5수염의 제조방법.A method for producing a high-purity copper sulfate pentachloride having a residual amount of chlorine of 10 ppm or less, wherein the produced copper sulfate is immersed in 80% or more methanol or 95% or more acetone, and the copper sulfate obtained by filtration is recrystallized in water. 삭제delete 삭제delete 삭제delete 삭제delete
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KR100504235B1 (en) * 2002-10-14 2005-07-27 서안켐텍 주식회사 Process for preparing mono hydrate copper chloride soln.

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KR100620112B1 (en) * 2004-11-04 2006-09-12 이재철 The making method of watery copper sulphate and making device
CN115044769B (en) * 2021-05-31 2023-10-27 阮氏化工（常熟）有限公司 Combined production line and production method of stripping solution and copper nitrate, copper sulfate and tin crystal

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