KR100352378B1 - Process for simultaneously preparing cupric sulfate and zinc chloride - Google Patents

Process for simultaneously preparing cupric sulfate and zinc chloride Download PDF

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KR100352378B1
KR100352378B1 KR1020000011877A KR20000011877A KR100352378B1 KR 100352378 B1 KR100352378 B1 KR 100352378B1 KR 1020000011877 A KR1020000011877 A KR 1020000011877A KR 20000011877 A KR20000011877 A KR 20000011877A KR 100352378 B1 KR100352378 B1 KR 100352378B1
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zinc
chloride
copper
sulfate
zinc chloride
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KR1020000011877A
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KR20010087975A (en
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김수태
공도영
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서안켐텍 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/10—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/04—Halides
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing

Abstract

본 발명은 기판 염화동 폐액에 함유된 염산을 아연재(ZnO)로 중화시킨 후, 황산아연을 첨가하여 염화동과 복분해시키고, 생성된 염화아연과 황산동을 알코올로 처리하여 염화아연과 황산동을 분리함을 특징으로 하는 염화아연 및 황산동의 동시 제조방법을 개시한다.The present invention neutralizes the hydrochloric acid contained in the substrate copper chloride waste solution with zinc (ZnO), and then adds zinc sulfate to metathesis with copper chloride, and the resulting zinc chloride and copper sulfate are treated with alcohol to separate zinc chloride and copper sulfate. Disclosed is a simultaneous production method of zinc chloride and copper sulfate.

Description

염화동으로부터 황산동 및 염화아연의 동시 제조방법 {PROCESS FOR SIMULTANEOUSLY PREPARING CUPRIC SULFATE AND ZINC CHLORIDE}Method for simultaneously producing copper sulfate and zinc chloride from copper chloride {PROCESS FOR SIMULTANEOUSLY PREPARING CUPRIC SULFATE AND ZINC CHLORIDE}

본 발명은 염화동으로부터 황산동 및 염화아연을 동시 제조하는 방법에 관한 것이다. 더 상세히는 PCB 기판에서 발생하는 염산을 함유하는 염화동을 아연재(ZnO)로 중화시키고, 여기에 황산아연을 첨가하여 염화동과 복분해시키고, 생성된 염화아연과 황산동을 알코올로 처리하여 염화아연과 황산동을 회수함을 특징으로 하는 염화아연 및 황산동의 동시 제조방법에 관한 것이다.The present invention relates to a process for the simultaneous production of copper sulfate and zinc chloride from copper chloride. More specifically, the copper chloride containing hydrochloric acid generated from the PCB substrate is neutralized with zinc (ZnO), and zinc sulfate is added to metathesis with copper chloride, and the resulting zinc chloride and copper sulfate are treated with alcohol to produce zinc chloride and copper sulfate. It relates to a simultaneous production method of zinc chloride and copper sulfate, characterized in that to recover.

근년, 전자산업의 발달로 인하여 전자회로기판 부식용 폐액인 염화동 액체가 대량으로 발생하고 있다.In recent years, due to the development of the electronic industry, a large amount of copper chloride liquid, which is a waste liquid for electronic circuit board corrosion, is generated.

이러한 염화동 액체는 염화동의 함량이 약 15∼20%, 염산이 약 10∼12% 기타 불순물을 함유하는 액체로서, 지금까지 이 폐액을 재활용하여 시안화동(CuCN), 동 분말 등의 제품으로 하는 방안이 강구되어 왔다. 그러나, 기판 부식용 폐액의 발생량이 급증하여 종래의 방법으로 시안화동을 제조하여 판매하는 것은 판매시장이 부족하여 폐액을 처리할 수 없고, 그대로 폐기하는 것은 토양이나 하수를 오염시키기 때문에 산업계에서는 이러한 염화동 폐액의 처리에 고심하고 있다.The copper chloride liquid is a liquid containing about 15 to 20% of copper chloride and about 10 to 12% of hydrochloric acid. Thus, this waste solution is recycled to produce products such as copper cyanide (CuCN) and copper powder. This has been taken. However, the production of copper cyanide by the conventional method is rapidly increasing due to the rapid increase in the amount of waste liquid for substrate corrosion, and the industrial waste is insufficient to treat the waste liquid. We are troubled with disposal of waste liquid.

종래, 상기 상황을 해결하기 위하여 염화동 폐액을 당량비의 황산을 첨가하여 교반하면서, 가열 농축하여 염산을 제거하고, 황산동을 회수하여 여러 차례 재결정하여 황산동 5수화물을 제조하였다. 그러나, 이러한 방법은 발생하는 염산을 회수하기 위한 콘덴서 등의 장치가 부식되므로 이를 방지하기 위하여 고가의 장비를 사용할 수 밖에 없고, 고순도의 염산을 얻을 수 없으며, 이러한 회수된 저순도의 염산의 판매가 문제로 되어 본 사업인 황산동의 제조에 큰 어려움을 가져왔다. 더욱이 제조한 황산동의 잔존 염소 규격이 30 ppm 이하로 되어 있어, 이러한 규격을 맞도록 하기 위하여 재결정 등을 반복하는 것은 제조원가를 상승시켜 제품 경쟁력이 약하다.Conventionally, in order to solve the above situation, the copper chloride waste liquid was heated and concentrated while adding and stirring sulfuric acid in an equivalent ratio, to remove hydrochloric acid, and copper sulfate was recovered and recrystallized several times to prepare copper sulfate pentahydrate. However, in such a method, since equipment such as a condenser to recover generated hydrochloric acid is corroded, it is necessary to use expensive equipment to prevent this, high purity hydrochloric acid cannot be obtained, and the sale of the recovered low purity hydrochloric acid is a problem. This has brought great difficulties in the manufacture of copper sulfate. In addition, the residual chlorine standard of the manufactured copper sulfate is 30 ppm or less, and repetition of recrystallization or the like in order to meet the standard increases the manufacturing cost and thus the product competitiveness is weak.

따라서, 상기와 같이 계속 발생되는 염화동 폐액을 재활용하는 획기적인 방법은 제시되지 않고 있으며, 산업계에서는 이러한 문제의 해결이 절실히 요구되고 있다.Therefore, no groundbreaking method for recycling the copper chloride waste solution, which continues to be generated as described above, has not been proposed, and the industry is urgently required to solve such problems.

따라서, 본 발명자는 상기 문제점을 해결하기 위하여 예의 연구한 결과, 염산을 함유하는 염화동 폐액에 아연재(ZnO)를 사용하여 중화시키고, 여기에 황산아연을 가하여 염화동과 반응시킴으로서 고순도의 황산동과 염화아연을 얻을 수 있음을 발견하고, 본 발명을 완성하게 되었다.Therefore, the present inventors have diligently studied to solve the above problems, and as a result, neutralize the copper chloride waste solution containing hydrochloric acid using zinc (ZnO), and react with copper chloride by adding zinc sulfate to it to make copper sulfate and zinc chloride of high purity. It was found that can be obtained, to complete the present invention.

전자회로기판의 부식용 폐액은 전술한 바와 같이, 염화동의 함량이 약 15∼20%, 염산이 약 10∼12% 기타 불순물을 함유하는 강산성 액체이다.As described above, the waste liquid for corrosion of an electronic circuit board is a strongly acidic liquid containing about 15 to 20% of copper chloride and about 10 to 12% of hydrochloric acid.

이 염화동 폐액을 교반기가 부착된 반응기에 넣고, 교반하면서, 아연재(ZnO)를 투입하여 일차로 반응시키면, 폐액중의 염산이 아연재와 반응하여 염화아연을 생성함과 동시에 반응액이 중성으로 중화된다. 이를 화학식으로 표현하면 아래와 같다.When the copper chloride waste solution is put into a reactor with a stirrer and stirred, a zinc material (ZnO) is added and reacted firstly. The hydrochloric acid in the waste solution reacts with the zinc material to produce zinc chloride, and the reaction solution is neutral. Neutralized. If this is expressed as a chemical formula:

(CuCl2+ 2HCl) + ZnO → CuCl2+ ZnCl2+ H2O(CuCl 2 + 2HCl) + ZnO → CuCl 2 + ZnCl 2 + H 2 O

상기에서 얻어진 반응 생성액을 내식성이 양호한 SUS316, SUS304 등의 재질로 된 반응기에 넣고, 농축하여 수분을 조절한 후, 여기에 황산아연을 가하고, 교반한다. 이 때 첨가되는 황산아연의 양은 염화동과의 반응에 요하는 화학양론적 양, 또는 약간 과량으로 가하여도 좋다. 이 황산아연을 용해된 상태에서 가열 농축한다. 이 반응의 반응식은 아래와 같다.The reaction product solution obtained above is placed in a reactor made of SUS316, SUS304 or the like having good corrosion resistance, concentrated to adjust moisture, and then zinc sulfate is added thereto and stirred. The amount of zinc sulfate added at this time may be added in a stoichiometric amount required for the reaction with copper chloride or in a slight excess. The zinc sulfate is concentrated by heating in a dissolved state. The reaction scheme of this reaction is shown below.

CuCl2+ ZnSO4→ CuSO4+ ZnCl2 CuCl 2 + ZnSO 4 → CuSO 4 + ZnCl 2

즉, 과잉의 염산은 아연재에 의해 중화되고, 염화동의 당량비에 해당하는 황산아연을 투입하여 복분해시키고, 이 과정이 완료되면 농축하여 무수물 상태, 또는 수분이 10% 이하로 한 상태에서 농축을 중단하고, 반응생성물을 꺼내 알코올에 붓는다. 여기서 알코올이란, 메탄올 또는 에탄올을 의미하며, 메탄올이 바람직하며, 그의 농도는 95%이상이 바람직하다. 상기 반응생성물을 알코올로 추출하는 경우, 염화아연의 알코올에 대한 용해도는 알코올 1.3㎖에 염화아연 1 g이 용해하므로 생성되는 염화아연에 대해 1.3∼1.5배량으로 추출하면 염화아연은 생성되는 황산동과 분리된다. 얻어진 황산동을 건조한 후, 물에 재결정시키면 황산동 5수화물이 얻어진다.That is, excess hydrochloric acid is neutralized by zinc material, and it is double-decomposed by adding zinc sulfate corresponding to the equivalent ratio of copper chloride, and when this process is completed, it is concentrated to stop the concentration in the anhydride state or the water to 10% or less. The reaction product is taken out and poured into alcohol. Alcohol means methanol or ethanol here, methanol is preferable and its density | concentration is 95% or more. In the case of extracting the reaction product with alcohol, the solubility of zinc chloride in alcohol is 1 g of zinc chloride in alcohol 1.3 ml, so zinc chloride is separated from the copper sulfate produced by extracting 1.3 to 1.5 times the amount of zinc chloride. do. The obtained copper sulfate is dried and then recrystallized in water to obtain copper sulfate pentahydrate.

또한, 염화아연을 함유하는 알코올을 증류하여 알코올을 회수하고, 염화아연을 재결정하면 고순도의 염화아연을 얻을 수 있다.In addition, by distilling the alcohol containing zinc chloride to recover the alcohol, and recrystallization of zinc chloride it is possible to obtain a high purity zinc chloride.

본 발명에 의하면 종래 처리하기 어려웠던 염화동을 함유하는 PCB 기판 부식 폐액을 아연재(ZnO)로 중화시키고, 여기에 황산아연을 첨가하여 염화동과 복분해시키고, 생성된 염화아연과 황산동을 알코올로 처리하여 고순도의 염화아연과 황산동을 회수할 수 있다.According to the present invention, the PCB substrate containing waste copper, which has been difficult to treat conventionally, is neutralized with zinc (ZnO), and zinc sulfate is added thereto to metathesis with copper chloride, and the resulting zinc chloride and copper sulfate are treated with alcohol to obtain high purity. Zinc chloride and copper sulfate can be recovered.

이하, 실시예를 들어 본 발명은 더 구체적으로 설명한다. 그러나, 이들 실시예가 본 발명의 범위를 한정하는 것은 아니다.Hereinafter, an Example is given and this invention is demonstrated further more concretely. However, these examples do not limit the scope of the present invention.

실시예 1Example 1

염산 12%, 염화동 20%을 함유하는 폐액 1 리터를 반응기에 넣고, 교반하면서, 아연재 140 g을 넣고 반응액의 산성도를 확인하면서 교반하였다. 중성인 것을 확인한 후, 황산아연 240 g을 넣고, 용해한 후, 50℃에서 30분 동안 가열하여 반응시킴과 동시에 농축하여 전량을 5% 함수상태로 하였다. 반응생성물을 꺼내 95%메탄올 500 g에 넣고, 40℃에서 1시간 교반한 후, 여과하여 분리하였다. 분리된 고체상의 황산동을 다시 메탄올 100cc로 세정하고, 건조하고, 물로 재결정하여 황산동 5수화물 370 g을 얻었다. 이를 분석하여 본 결과, 염소함량은 5 ppm 이하이었다.1 liter of a waste liquid containing 12% hydrochloric acid and 20% copper chloride was placed in a reactor, and while stirring, 140 g of zinc material was added and stirred while checking the acidity of the reaction solution. After confirming to be neutral, 240 g of zinc sulfate was added, dissolved, and heated at 50 ° C. for 30 minutes to react, and concentrated to make the whole amount 5% water-containing. The reaction product was taken out and poured into 500 g of 95% methanol, stirred at 40 ° C. for 1 hour, and then separated by filtration. The separated solid copper sulfate was washed again with 100 cc of methanol, dried and recrystallized with water to obtain 370 g of copper sulfate pentahydrate. As a result of analyzing this, the chlorine content was 5 ppm or less.

한편, 상기 염화아연이 함유된 알코올 용액을 합하고 증류하여 알코올을 회수하고, 정제하여 염화아연 분말(순도: 99.5%) 202 g을 얻었다.Meanwhile, the alcohol solution containing zinc chloride was combined and distilled to recover the alcohol, and purified to obtain 202 g of zinc chloride powder (purity: 99.5%).

상술한 바와 같이, 본 발명에 의하면 염화동 및 염산을 함유하는 PCB 기판 부식 폐액을 아연재(ZnO)로 중화시키고, 여기에 황산아연을 첨가하여 염화동과 복분해시키고, 생성된 염화아연과 황산동을 알코올로 처리하여 고순도의 염화아연과 황산동을 회수할 수 있다. 이렇게 얻어진 염화아연과 황산동은 순도가 높고 경제적으로 유리하게 동시에 얻을 수 있다. 이러한 본 발명의 방법에 의하여 종래 해결하기 어려웠던 염산을 함유하는 염화철 폐액을 처리하여 고가의 황산동과 염화아연을 얻을 수 있다.As described above, according to the present invention, the PCB substrate corrosion waste liquid containing copper chloride and hydrochloric acid is neutralized with zinc (ZnO), and zinc sulfate is added thereto to metathesize with copper chloride, and the resulting zinc chloride and copper sulfate are converted into alcohol. By treatment, high purity zinc chloride and copper sulfate can be recovered. The zinc chloride and copper sulfate thus obtained can be obtained simultaneously with high purity and economically. By the method of the present invention, expensive copper sulfate and zinc chloride can be obtained by treating the iron chloride waste solution containing hydrochloric acid, which has been difficult to solve conventionally.

Claims (2)

염산과 염화동을 함유하는 전자회로기판의 부식용 폐액으로부터 염화아연과 황산동을 제조하는 방법에 있어서,In the method for producing zinc chloride and copper sulfate from the waste liquid for corrosion of an electronic circuit board containing hydrochloric acid and copper chloride, 기판 염화동 폐액에 함유된 염산을 아연재(ZnO)로 중화시킨 후, 황산아연을 첨가하여 염화동과 복분해시키고, 생성된 염화아연과 황산동을 알코올로 처리하여 염화아연과 황산동을 분리함을 특징으로 하는 염화아연 및 황산동의 동시 제조방법.The hydrochloric acid contained in the substrate copper chloride waste solution is neutralized with zinc (ZnO), and then zinc zinc sulfate is added to metathesis with copper chloride, and the resulting zinc chloride and copper sulfate are treated with alcohol to separate zinc chloride and copper sulfate. Simultaneous production of zinc chloride and copper sulfate. 제 1항에 있어서, 알코올이 95% 이상의 메탄올임을 특징으로 하는 방법.The method of claim 1 wherein the alcohol is at least 95% methanol.
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KR100504235B1 (en) * 2002-10-14 2005-07-27 서안켐텍 주식회사 Process for preparing mono hydrate copper chloride soln.
KR100936433B1 (en) * 2008-03-11 2010-01-14 김철한 Process for preparing potassium sulfate and zinc chloride from zinc sulfate and potassium chloride

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Publication number Priority date Publication date Assignee Title
KR20020094180A (en) * 2001-06-12 2002-12-18 김수태 Process for preparing double salt of copper sulfate and sodium chloride

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GB2250507A (en) * 1990-12-03 1992-06-10 Compeq Manufacturing Co Limite Method for producing copper sulfate from waste copper-containing-liquid
JPH0533168A (en) * 1991-06-29 1993-02-09 Asaka Riken Kogyo Kk Method for recovering hydrochloric acid and copper sulfate from waste copper chloride solution
CN1225899A (en) * 1999-01-19 1999-08-18 李海滨 Process for production of copper sulfate using waste liquid of copper dichloride

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Publication number Priority date Publication date Assignee Title
JPH0489316A (en) * 1990-08-01 1992-03-23 Toagosei Chem Ind Co Ltd Method for recovering copper sulfate from aqueous copper chloride solution containing hydrochloric acid
GB2250507A (en) * 1990-12-03 1992-06-10 Compeq Manufacturing Co Limite Method for producing copper sulfate from waste copper-containing-liquid
JPH0533168A (en) * 1991-06-29 1993-02-09 Asaka Riken Kogyo Kk Method for recovering hydrochloric acid and copper sulfate from waste copper chloride solution
CN1225899A (en) * 1999-01-19 1999-08-18 李海滨 Process for production of copper sulfate using waste liquid of copper dichloride

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100504235B1 (en) * 2002-10-14 2005-07-27 서안켐텍 주식회사 Process for preparing mono hydrate copper chloride soln.
KR100936433B1 (en) * 2008-03-11 2010-01-14 김철한 Process for preparing potassium sulfate and zinc chloride from zinc sulfate and potassium chloride

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