KR20020045253A - Preparation of copper oxychloride from acidic copper etchant - Google Patents

Preparation of copper oxychloride from acidic copper etchant Download PDF

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KR20020045253A
KR20020045253A KR1020000074636A KR20000074636A KR20020045253A KR 20020045253 A KR20020045253 A KR 20020045253A KR 1020000074636 A KR1020000074636 A KR 1020000074636A KR 20000074636 A KR20000074636 A KR 20000074636A KR 20020045253 A KR20020045253 A KR 20020045253A
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copper chloride
copper
acidic
basic copper
particle size
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KR1020000074636A
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Korean (ko)
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어용선
김영희
김선진
김명훈
서규범
한정윤
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황의영
주식회사 명진화학
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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
    • C01G3/04—Halides
    • C01G3/05—Chlorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

PURPOSE: Provided is a preparation of copper oxychloride from acidic copper etchant. The prepared copper oxychloride crystal has high purity and even granularity. CONSTITUTION: The copper oxychloride is prepared by: treating copper chloride in acidic copper etchant with sodium hydroxide of pH 6-8 to obtain deposits, wherein reaction temperature is maintained to 18-40 deg.C; and maturing the deposits at 40-50 deg.C for 1-3 hours. The composition of acidic copper etchant is as follows: 19-25.5 wt.% of CuCl2; 7-10 wt.% of HCl; and 64.5-74 wt.% of H2O.

Description

ＰＣＢ 산업에서 배출되는 산성 염화구리 폐액으로부터 염기성 염화구리의 제조방법{PREPARATION OF COPPER OXYCHLORIDE FROM ACIDIC COPPER ETCHANT}Production method of basic copper chloride from acidic copper chloride waste liquid discharged from PCC industry {PREPARATION OF COPPER OXYCHLORIDE FROM ACIDIC COPPER ETCHANT}

본 발명은 PCB 산업에서 배출되는 산성 염화구리 폐액으로부터 염기성 염화구리를 제조하는 방법에 관한 것으로, 염기성 염화구리는 농약원료 등에 유용하게 사용할 수 있다.The present invention relates to a method for producing a basic copper chloride from the acidic copper chloride waste liquid discharged from the PCB industry, basic copper chloride can be usefully used in agrochemical raw materials.

PCB (Printed Circuit Board) 제조 산업은 구리를 소재로 한 전자부품 가공산업이다. PCB 제조에 있어서, 부식 과정 중에 다량의 구리가 함유된 에칭 폐액이 발생한다. 이러한 에칭 폐액은 산성 폐액 (염화 구리 폐액)과 염기성 폐액 (알파인동 폐액)으로 구분되며 각 폐액에는 구리농도가 약 10 ∼ 15 중량 % 함유되어 있다. 따라서 PCB 산업에서 배출되는 폐액으로부터 구리성분을 회수하는 회수기술은 원료의 재활용과 환경오염의 저감과 방지라는 관점에서 매우 중요한 기술이다.The PCB (Printed Circuit Board) manufacturing industry is an electronic component processing industry based on copper. In PCB fabrication, an etching waste liquid containing a large amount of copper is generated during the corrosion process. Such etching waste liquid is classified into an acidic waste liquid (copper chloride waste liquid) and a basic waste liquid (alpine copper waste liquid), and each waste liquid contains about 10 to 15% by weight of copper. Therefore, the recovery technology for recovering the copper component from the waste liquid discharged from the PCB industry is a very important technology in terms of recycling of raw materials and reducing and preventing environmental pollution.

일반적으로 염기성 염화구리를 제조하는 공지의 제조방법은 대별하여 산화법과 중화법으로 구분할 수 있는 바, 산화법은 염화구리 용액에서 금속 구리를 산소(공기), NaClO, KClO, NaClO3등의 산화제 존재하에 산화시키는 방법이며 다음과 같은 반응식으로 나타낼 수 있다.In general, known production methods for preparing basic copper chloride can be roughly divided into oxidation and neutralization methods. The oxidation method is performed in the presence of oxidants such as oxygen (air), NaClO, KClO, NaClO 3, etc. It is a method of oxidation and can be represented by the following reaction formula.

CuCl2+ 3Cu + 3/2O2+ 3H2O → 2[CuCl(OH)3]CuCl 2 + 3Cu + 3 / 2O 2 + 3H 2 O → 2 [CuCl (OH) 3 ]

한편, 중화법은 일반적으로 염화구리 화합물을 알칼리와 반응시켜 금속의 염기성 염화물 (basic chloride)을 제조하는 방법으로서, 사용되는 알칼리는 NaOH, Na2CO3, NaHCO3, CaCO3, 암모니아 등이 사용된다. 이 반응은 염소기를 전부 수산화기로 치환시키는 것이 아니라 부분적으로 치환시키는 것이다.In general, the neutralization method is a method for preparing a basic chloride of a metal by reacting a copper chloride compound with an alkali, and the alkali used is NaOH, Na 2 CO 3 , NaHCO 3 , CaCO 3 , or ammonia. do. This reaction does not replace all the chlorine groups with hydroxyl groups, but partially replaces them.

4CuCl2+ 6NaOH → CuCl2·3Cu(OH)2+ 6NaCl4CuCl 2 + 6NaOH → CuCl 2 · 3Cu (OH) 2 + 6NaCl

다른 금속들은 처음부터 침전물로 침전되어지나 구리의 경우에는 염기성 염화물의 용해도가 낮기 때문에 이것이 먼저 석출된다. 그러나 알칼리 용액을 첨가할 때 수산화나트륨과 같은 강한 알칼리를 첨가하면 국부적으로 젤라틴형의 수산화 구리가 석출되어 이것이 쉽게 검은 색의 산화 구리로 생성되어 혼재하게 될 수도 있다. 알칼리로서 역시 PCB 산업에서 배출되는 알칼리성 염화구리 폐액 [조성: Cu(NH3)Cl, NH4NO3, (NH4)2CO3그리고NH4OH]을 사용하는 방법도 있다.Other metals precipitate from the outset, but in the case of copper, it is precipitated first because of the low solubility of basic chlorides. However, the addition of strong alkalis, such as sodium hydroxide, when adding an alkaline solution, locally precipitates gelatinous copper hydroxide, which can easily form black copper oxide and mix. There is also the use of alkaline copper chloride waste liquids (composition: Cu (NH 3 ) Cl, NH 4 NO 3 , (NH 4 ) 2 CO 3 and NH 4 OH) as alkalis.

농약으로 사용하기 위한 초기의 염화구리 제조방법은 주로 산화법을 사용하였다. 염화구리의 폐액을 사용하는 경우, 부분 중화법도 많이 사용되고 있다. 수산화나트륨을 첨가하는 방법은 알칼리 염화구리 폐액을 사용하는 것보다 생산 코스트가 높게 투입되나 고 순도의 염기성 염화구리를 얻을 수 있는 장점을 가지고 있다.The initial method for producing copper chloride for use as a pesticide mainly used the oxidation method. In the case of using the waste liquid of copper chloride, the partial neutralization method is also used a lot. The method of adding sodium hydroxide has a higher production cost than using alkaline copper chloride waste solution, but has the advantage of obtaining basic copper chloride of high purity.

본 발명자들은 공지 기술과는 달리 환경 친화적이며 순도가 높은 동시에 균일한 입자 크기를 가지는 염기성 염화구리의 제조 공정을 개발하기 위하여 연구하던 차산성 염화구리 폐액을 사용하여 pH와 온도를 조절하면서 수산화나트륨으로 중화시키면 연녹색의 염기성 염화구리와 부산물로 염화나트륨(소금)만이 생성되고, 초기에 얻은 침전물을 40 ∼ 50oC에서 숙성시킨 후, 여과 및 세척과정을 거쳐 건조시키면 산화구리와 같은 다른 구리화합물 결정이 혼재되어 있지 않고, 입도 분포가 균일한 염기성 염화구리를 제조할 수 있음을 발견하고 본 발명을 완성하게 되었다.The present inventors, unlike the known art, used sodium hydroxide while adjusting pH and temperature using a secondary acidic copper chloride waste solution, which was studied to develop a process for producing basic copper chloride having high purity and uniform particle size. When neutralized, only sodium chloride (salt) is produced as a basic product of light green basic copper chloride and by-products. The precipitate obtained is aged at 40 to 50 o C, then filtered and washed to dry other copper compound crystals such as copper oxide. The present invention has been completed by discovering that basic copper chloride, which is not mixed and has a uniform particle size distribution, can be produced.

본 발명은 염화구리 폐액에 포함된 염화구리를 수산화나트륨과 반응시켜 염기성 염화구리를 제조함에 있어서, 산화구리 등 다른 형태의 구리화합물이 혼재되어 있지 않은 결정형태이며 또한 균일한 입도 분포를 가진 염기성 염화구리를 제조하는 방법에 관한 것이다. 본 발명에 의한 염기성 염화구리는 순도가 높기 때문에 농약원료로 사용할 수 있다.In the present invention, in the preparation of basic copper chloride by reacting copper chloride contained in the copper chloride waste solution with sodium hydroxide, basic chloride having a uniform particle size distribution and a crystal form in which other copper compounds such as copper oxide are not mixed It relates to a method of producing copper. The basic copper chloride according to the present invention can be used as a pesticide raw material because of its high purity.

본 발명은 염화구리 폐액에 포함된 염화구리를 수산화나트륨과 반응시켜 염기성 염화구리를 제조함에 있어서, 산화구리 등 다른 형태의 구리화합물이 혼재되어 있지 않은 결정형태이며 또한 균일한 입도 분포를 가진 염기성 염화구리를 제조하는 방법에 관한 것이다.In the present invention, in the preparation of basic copper chloride by reacting copper chloride contained in the copper chloride waste solution with sodium hydroxide, basic chloride having a uniform particle size distribution and a crystal form in which other copper compounds such as copper oxide are not mixed It relates to a method of producing copper.

일반적으로 산성 염화구리 폐액은 CuCl2: 19 ∼ 25.5 중량 %, HCl: 7 ∼ 10 중량 %, H2O: 64.5 ∼ 74 중량 %의 조성으로 이루어져 있으며, 다량의 염산을 포함하고 있다. 산성 염화구리 폐액에 수산화나트륨 용액을 첨가할 때에는 반응온도를 조절하지 않으면 산-염기 중화반응에 의하여 다량의 열이 발생하게 되어 반응기의 온도가 80oC까지 올라가게 된다. 반응 초기에 생성된 침전물은 용액의 온도가 높으면 탈수가 일어나 반응 중 산화구리로 전환된다. 따라서, 반응 온도를 조절하지 않으면 산성 염화구리 폐액으로부터 고 순도의 염기성 염화구리를 얻을 수 없다.Generally, the acidic copper chloride waste liquid is composed of CuCl 2 : 19 to 25.5% by weight, HCl: 7 to 10% by weight, H 2 O: 64.5 to 74% by weight, and contains a large amount of hydrochloric acid. When the sodium hydroxide solution is added to the acidic copper chloride waste solution, if the reaction temperature is not controlled, a large amount of heat is generated by the acid-base neutralization reaction, thereby increasing the temperature of the reactor to 80 ° C. The precipitate formed at the beginning of the reaction is dehydrated when the solution temperature is high and converted to copper oxide during the reaction. Therefore, high purity basic copper chloride cannot be obtained from the acidic copper chloride waste liquid without controlling the reaction temperature.

본 발명자들은 PCB 산업에서 배출되는 산성 염화구리 폐액으로부터 염화구리, 산화구리와 같은 다른 형태의 구리화합물 결정이 혼재되어 있지 않으며 또한 입도가 균일한 염기성 염화구리를 제조하는 방법을 집중적으로 연구한 결과 산성 염화구리 폐액에 온도를 18 ∼ 40oC 이하로 유지시키면서 pH가 6 ∼ 8, 바람직하게는 6.5 ∼ 7.5 사이가 될 때까지 수산화나트륨을 첨가하여 연록색의 염기성 염화구리 슬러리를 만든 후, 이 슬러리를 40 ∼ 50oC 에서 1 ∼ 3 시간동안 숙성하면 다른 형태의 구리화합물이 혼재되어 있지 않은 연녹색의 순수한 염기성 염화구리를 얻을 수 있음을 발견하였다. 이 방법에 따르면 순도가 95.0 중량 % 이상이며 입도가 매우 균일한 염기성 염화구리를 제조 할 수 있는 장점을 가진다. 생성된 침전물은 통상의 방법으로 여과 후 순수 또는 증류수를 사용하여 세척하면 된다. 건조과정에서는 염기성 염화구리의 분해를 막기 위하여 100 ∼ 150oC에서 건조시키는 것이 바람직하다.The inventors intensively studied how to produce basic copper chloride crystals having no particle size and other copper compounds, such as copper chloride and copper oxide, from acidic copper chloride waste liquid discharged from the PCB industry. The copper chloride waste solution was added with sodium hydroxide until the pH was between 6 and 8, preferably between 6.5 and 7.5, while maintaining the temperature at 18 to 40 ° C. or lower to form a light green basic copper chloride slurry. After aging at 40 to 50 ° C. for 1 to 3 hours, it was found that pure green copper chloride, which is light green, does not contain other types of copper compounds. According to this method, the basic copper chloride having a purity of 95.0% by weight or more and a very uniform particle size can be produced. The produced precipitate may be washed with pure water or distilled water after filtration in a conventional manner. In the drying process, it is preferable to dry at 100 ~ 150 o C to prevent decomposition of basic copper chloride.

다음 실시 예는 본 발명을 더욱 자세히 설명할 것이나, 이는 예시적인 의미로서 본 발명의 보호범위가 이들 실시 예에 한정되지 아니한다.The following examples will explain the present invention in more detail, but this is by way of example and the scope of protection of the present invention is not limited to these examples.

실시예 1Example 1

산성 염화구리 폐액 (22 중량 % CuCl2, 11중량 % HCl, 67 중량 % H2O 및 중금속은 검출한계 이하) 1.2 리터에 온도를 40oC 이하로 유지시키면서 50 중량 % 수산화나트륨 수용액 360 g을 서서히 첨가하여 연록색의 염기성 염화구리 슬러리를 만들었다. 본 실험에 사용된 산성 염화구리 폐액에는 CuCl222 중량%, HCl 11 중량%가 함유되어 있으므로 이를 중화시키기 위하여 이론적으로 362.6 g의 50 중량 % 수산화 나트륨 수용액을 첨가하였다. 반응 종결시 용액의 pH는 6.7이었으며 이 슬러리를 45 ± 5oC에서 2 시간동안 가열하여 숙성시켜 연녹색의 염기성 염화구리 결정을 얻었다. 이를 여과 후, 순수를 사용하여 세척하고, 100 ∼ 110 ℃의 오븐에서 2 시간 동안 건조하였다. X-선 회절도에 의하면 제조된 염기성 염화구리는 국제적인 X-선 회절도 자료인 JCPDS No. 18-0439의 CuCl2·3Cu(OH)2와일치하였다. CIPAC(국제공동농약분석위원회, Collaborative International Pesticide Analytical Council) 방법에 의한 시험결과 구리함량, 수용성구리, 수용성 염화물은 물론, 극미량 함유된 중금속들이 농약으로 사용할 수 있는 기준에 만족하였다. 또한 CuCl2·3Cu(OH)2로 환산한 염기성 염화구리의 순도는 97 중량 % 이상이었다. 입도 분석기를 사용하여 입도를 측정한 결과 1 ∼ 10 ㎛의 입도 분포를 보여 주었다.360 g of 50% by weight aqueous sodium hydroxide solution is maintained at 1.2 liters of an acidic copper chloride waste solution (22% by weight CuCl 2 , 11% by weight HCl, 67% by weight H 2 O and heavy metals below the detection limit) while maintaining the temperature below 40 o C. Slow addition was made to yield a light green basic copper chloride slurry. The acidic copper chloride waste solution used in this experiment contained 22 wt% CuCl 2 and 11 wt% HCl, so in order to neutralize it, 362.6 g of 50 wt% sodium hydroxide aqueous solution was theoretically added. At the end of the reaction, the pH of the solution was 6.7 and the slurry was aged at 45 ± 5 o C for 2 hours to give light green basic copper chloride crystals. After filtration, the mixture was washed with pure water and dried in an oven at 100 to 110 ° C for 2 hours. According to the X-ray diffractogram, the prepared basic copper chloride was prepared by JCPDS No. 18-0439 CuCl 2 .3Cu (OH) 2 was matched. Tests by the Collaborative International Pesticide Analytical Council (CIPAC) method met the criteria for the use of trace metals as well as copper, soluble copper and soluble chlorides. Also CuCl 2 · 3Cu purity of the basic copper chloride in terms of (OH) 2 was no less than 97% by weight. The particle size was measured using a particle size analyzer showed a particle size distribution of 1 ~ 10 ㎛.

비교 예 1Comparative Example 1

산성 염화구리 폐액 (22 중량 % CuCl2, 11중량 % HCl 그리고 67 중량 % H2O) 1.2 리터에 온도를 조절하지 않고 50 중량 %의 수산화나트륨 용액 360 g을 첨가하였다. 산-염기 중화반응에 의하여 다량의 열이 발생하게 되어 반응기의 온도가 80oC까지 상승되었다. 반응 초기에 생성된 침전물은 이 온도에서 탈수가 일어나 반응 중 산화구리로 전환되어 검은색으로 변하였다. 반응 종결시 용액의 pH는 6.5이었으며 이 슬러리를 45 ± 5oC에서 2시간동안 더 숙성하여 반응을 완결하였다. 이를 여과 후, 순수를 사용하여 세척하고, 100 ∼ 110 ℃의 오븐에서 2 시간 동안 건조하였다. 생성물은 어두운 녹색을 띠고 있었으며, X-선 회절기를 사용하여 분석한 결과 염기성 염화구리에 산화구리가 혼재되어 있었다.To 1.2 liters of acidic copper chloride waste liquor (22 wt% CuCl 2 , 11 wt% HCl and 67 wt% H 2 O) was added 360 g of 50 wt% sodium hydroxide solution without temperature control. A large amount of heat was generated by the acid-base neutralization reaction, and the temperature of the reactor was raised to 80 ° C. The precipitate formed at the beginning of the reaction dehydrated at this temperature, converted to copper oxide during the reaction, and turned black. At the end of the reaction the pH of the solution was 6.5 and the slurry was further aged at 45 ± 5 o C for 2 hours to complete the reaction. After filtration, the mixture was washed with pure water and dried in an oven at 100 to 110 ° C for 2 hours. The product was dark green in color and was analyzed using an X-ray diffractometer.

본 발명은 PCB 산업에서 배출되는 산성 염화구리 폐액으로부터 염화구리나 산화구리와 같은 다른 종류의 구리화합물을 함유하지 않으며 순도가 높고 또한 균일한 입도 분포를 가진 염기성 염화구리를 제조하는 기술로서 농약원료 생산기술에 활용될 수 있다.The present invention is a technology for producing basic copper chloride, which contains a high purity and uniform particle size distribution, containing no other copper compound such as copper chloride or copper oxide, from acidic copper chloride waste liquid discharged from the PCB industry. It can be used for technology.

Claims (5)

산성 염화구리 폐액 (조성: CuCl2: 19 ∼ 25.5 중량 %, HCl: 7 ∼ 10 중량 %, H2O: 64.5 ∼ 74 중량 %)을 수산화나트륨과 반응시켜 연녹색의 염기성 염화구리 슬러리를 제조하고 이 슬러리를 숙성시키는 것을 특징으로 하는 95.0 중량% 이상의 순도와 균일한 입도의 염기성 염화구리의 제조방법.An acidic copper chloride waste solution (composition: CuCl 2 : 19 to 25.5 wt%, HCl: 7 to 10 wt%, H 2 O: 64.5 to 74 wt%) was reacted with sodium hydroxide to prepare a light green basic copper chloride slurry. A method for producing a basic copper chloride of at least 95.0% by weight purity and uniform particle size, characterized in that the slurry is aged. 제 1항에 있어서, 반응온도를 18 ∼ 40oC의 온도에서 수행하는 것을 특징으로 하는 95.0 중량% 이상의 순도와 균일한 입도의 염기성 염화구리의 제조방법.The method for producing basic copper chloride having a purity of 95.0 wt% or more and a uniform particle size according to claim 1, wherein the reaction temperature is performed at a temperature of 18 to 40 ° C. 제 1항에 있어서, pH 6 ∼ 8의 범위에서 수행하는 것을 특징으로 하는 95.0 중량% 이상의 순도와 균일한 입도의 염기성 염화구리의 제조방법.The method for producing a basic copper chloride having a purity of 95.0% by weight or more and a uniform particle size according to claim 1, which is performed in a range of pH 6-8. 제 1항에 있어서, 염기성 염화구리 슬러리를 40 ∼ 50oC의 온도에서 1 ∼ 3 시간 숙성시키는 것을 특징으로 하는 95.0 중량% 이상의 순도와 균일한 입도의 염기성 염화구리의 제조방법.The method for producing a basic copper chloride having a purity of 95.0% by weight or more and a uniform particle size according to claim 1, wherein the basic copper chloride slurry is aged at a temperature of 40 to 50 ° C. for 1 to 3 hours. 제 1항에 있어서, 통상의 방법으로 여과 및 세척한 결정을 100 ∼ 150oC의 건조온도에서 건조시키는 것을 특징으로 하는 95.0 중량% 이상의 순도와 균일한 입도의 염기성 염화구리의 제조방법.The method for producing basic copper chloride having a purity and uniform particle size of 95.0 wt% or more according to claim 1, wherein the crystals filtered and washed by a conventional method are dried at a drying temperature of 100 to 150 ° C.
KR1020000074636A 2000-12-08 2000-12-08 Preparation of copper oxychloride from acidic copper etchant KR20020045253A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100707930B1 (en) * 2005-02-18 2007-04-16 (주)화백엔지니어링 Method and Apparatus of Treatment for the Recycle of Etchant waste
CN108423704A (en) * 2018-03-29 2018-08-21 东莞市恒建环保科技有限公司 The production method of basic copper chloride
CN114680135A (en) * 2020-12-25 2022-07-01 广州科城环保科技有限公司 King copper, preparation method and application thereof, and bactericide
KR102666478B1 (en) * 2024-01-29 2024-05-16 용진환경주식회사 Method for manufacturing deodorant using copper chloride waste liquid

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Publication number Priority date Publication date Assignee Title
JPS5841721A (en) * 1981-09-08 1983-03-11 Nippon Chem Ind Co Ltd:The Preparation of cupric hydroxide
JPH0489315A (en) * 1990-07-30 1992-03-23 Toagosei Chem Ind Co Ltd Method for recovering copper sulfate and alkali chloride from aqueous copper chloride solution containing hydrochoric acid
JPH05319825A (en) * 1992-05-25 1993-12-03 Nippon Kagaku Sangyo Kk Production of cuprous oxide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5841721A (en) * 1981-09-08 1983-03-11 Nippon Chem Ind Co Ltd:The Preparation of cupric hydroxide
JPH0489315A (en) * 1990-07-30 1992-03-23 Toagosei Chem Ind Co Ltd Method for recovering copper sulfate and alkali chloride from aqueous copper chloride solution containing hydrochoric acid
JPH05319825A (en) * 1992-05-25 1993-12-03 Nippon Kagaku Sangyo Kk Production of cuprous oxide

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100707930B1 (en) * 2005-02-18 2007-04-16 (주)화백엔지니어링 Method and Apparatus of Treatment for the Recycle of Etchant waste
CN108423704A (en) * 2018-03-29 2018-08-21 东莞市恒建环保科技有限公司 The production method of basic copper chloride
CN114680135A (en) * 2020-12-25 2022-07-01 广州科城环保科技有限公司 King copper, preparation method and application thereof, and bactericide
KR102666478B1 (en) * 2024-01-29 2024-05-16 용진환경주식회사 Method for manufacturing deodorant using copper chloride waste liquid

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