JP2001355027A - Method for recovering copper in aqueous solution containing hydrochloric acid and copper chloride - Google Patents

Method for recovering copper in aqueous solution containing hydrochloric acid and copper chloride

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Publication number
JP2001355027A
JP2001355027A JP2000175656A JP2000175656A JP2001355027A JP 2001355027 A JP2001355027 A JP 2001355027A JP 2000175656 A JP2000175656 A JP 2000175656A JP 2000175656 A JP2000175656 A JP 2000175656A JP 2001355027 A JP2001355027 A JP 2001355027A
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JP
Japan
Prior art keywords
copper
hydrochloric acid
aqueous solution
chloride
solution containing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2000175656A
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Japanese (ja)
Other versions
JP3536787B2 (en
Inventor
Keizo Hayashi
桂三 林
Akihiro Sakata
昭博 坂田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toagosei Co Ltd
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Toagosei Co Ltd
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    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Manufacture And Refinement Of Metals (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide an efficient method for reducing the amount of an iron material to be used and also suppressing the generation of hydrogen as for a method by which metallic copper is recovered from an aqueous solution containing hydrochloric acid and copper chloride such as an etching waste solution, and by which an aqueous solution of ferrous chloride is obtained. SOLUTION: In a method in which an aqueous solution containing hydrochloric acid and copper chloride is brought into reaction with an iron material to recover metallic copper precipitated on the surface of the iron material, the aqueous solution containing hydrochloric acid and copper chloride is previously brought into reaction with iron oxyhydroxide to remove free hydrochloric acid and is threafter brought into reaction with the iron material.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は塩酸および塩化銅を
含有する水溶液から、銅分を鉄材にて金属銅として回収
する方法において、予め塩酸分をオキシ水酸化鉄により
中和除去させることにより、金属銅回収工程での鉄材の
使用量を減少させると共に水素発生を防止することを目
的とする塩酸および塩化銅含有水溶液中の銅の回収方法
に関するもので、特に塩化第二鉄水溶液をエッチング工
程に用いた後のエッチング廃液の再生に適したものであ
る。The present invention relates to a method for recovering copper from an aqueous solution containing hydrochloric acid and copper chloride as metallic copper with an iron material, wherein the hydrochloric acid is neutralized and removed with iron oxyhydroxide in advance. The present invention relates to a method for recovering copper in an aqueous solution containing hydrochloric acid and copper chloride for the purpose of reducing the amount of iron material used in the metal copper recovery process and preventing the generation of hydrogen. It is suitable for regenerating the etching waste liquid after use.

【０００２】[0002]

【従来の技術】塩化第二鉄水溶液は無機系凝集剤として
使用される他、各種の金属をエッチングするためのエッ
チャントとして使用されている。2. Description of the Related Art An aqueous ferric chloride solution is used not only as an inorganic coagulant but also as an etchant for etching various metals.

【０００３】塩化第二鉄水溶液の製造方法としては、鉄
（くず鉄）を塩酸に溶解して得られた塩化第一鉄水溶液
に塩素ガスを吹き込む等の酸化反応をさせて得る方法が
挙げられる。現在では鉄鋼の酸洗廃液に鉄（くず鉄）を
投入した後、塩素を吹き込み塩化第二鉄水溶液とする等
の廃棄物のリサイクルによって得ることが多い。As a method for producing an aqueous ferric chloride solution, there is a method obtained by subjecting an aqueous ferrous chloride solution obtained by dissolving iron (waste iron) to an oxidation reaction such as blowing a chlorine gas into the aqueous solution. At present, iron (scrap iron) is thrown into a pickling waste liquid of iron and steel, and chlorine is then blown into the ferric chloride aqueous solution to obtain an aqueous ferric chloride solution.

【０００４】塩化第二鉄水溶液の別の製造方法として
は、プリント基板等の金属銅をエッチングした後の廃液
の再生が挙げられる。ここで、前記エッチングには２種
類の方法があり、その一つは、塩酸含有塩化第二鉄水溶
液によるエッチングである。この場合の廃液は、塩化第
二鉄、塩化第一鉄、塩化銅および塩酸を含む。もう一つ
は、塩酸によるエッチングである。この場合の廃液は、
塩化銅と塩酸を含む。いずれにせよこれらの廃液には、
塩酸分が数〜数１０質量％含まれる。[0004] Another method for producing an aqueous ferric chloride solution is to regenerate a waste liquid after etching metallic copper on a printed circuit board or the like. Here, there are two types of etching, one of which is etching using an aqueous solution of ferric chloride containing hydrochloric acid. The waste liquid in this case contains ferric chloride, ferrous chloride, copper chloride and hydrochloric acid. The other is etching with hydrochloric acid. The waste liquid in this case is
Contains copper chloride and hydrochloric acid. In any case, these waste liquids
Hydrochloric acid content is several to several tens mass%.

【０００５】これらの廃液を再生して、塩化第二鉄を製
造する方法としては、鉄材を利用する方法が一般的であ
る。即ち、これらの廃液と鉄材を反応させると、下記の
反応により金属銅の析出と共に、塩化第一鉄水溶液が得
られる。 ２FeCl3 ＋ Fe → ３ＦｅＣｌ2 ＣｕＣｌ2 ＋ Ｆｅ → Ｃｕ↓ ＋ ＦｅＣｌ2 ２ＨＣｌ ＋ Ｆｅ → ＦｅＣｌ2 ＋ Ｈ2↑As a method for producing ferric chloride by regenerating these waste liquids, a method using an iron material is generally used. That is, when these waste liquids are reacted with an iron material, an aqueous ferrous chloride solution is obtained together with the precipitation of metallic copper by the following reaction. 2FeCl 3 + Fe → 3FeCl 2 CuCl 2 + Fe → Cu ↓ + FeCl 2 2HCl + Fe → FeCl 2 + H 2 ↑

【０００６】析出した金属銅を回収すると共に、塩化第
一鉄は塩素等による酸化により塩化第二鉄として再利用
する。このプロセス自体は非常に簡単ではあるが、塩酸
除去のために鉄材の使用量が多くなること、並びに多量
の水素が発生することが問題となる。[0006] The precipitated metallic copper is recovered, and ferrous chloride is reused as ferric chloride by oxidation with chlorine or the like. Although this process itself is very simple, there are problems in that an increased amount of iron material is used for removing hydrochloric acid and a large amount of hydrogen is generated.

【０００７】[0007]

【発明が解決しようとする課題】本発明の課題は、エッ
チング廃液等の塩酸および塩化銅を含有する水溶液か
ら、金属銅を回収しかつ塩化第一鉄水溶液を得る方法に
関して、鉄材の使用量を減少させ、かつ水素の発生を抑
制する効率的な方法を提供することである。An object of the present invention is to provide a method for recovering metallic copper and obtaining an aqueous ferrous chloride solution from an aqueous solution containing hydrochloric acid and copper chloride, such as an etching waste liquid, by reducing the amount of iron material used. An object of the present invention is to provide an efficient method for reducing the amount of hydrogen and suppressing the generation of hydrogen.

【０００８】[0008]

【課題を解決するための手段】本発明者等は、前記課題
を解決すべく鋭意検討を重ね、エッチング廃液等の塩酸
および塩化銅含有水溶液から金属銅を回収しかつ塩化第
一鉄水溶液を得る工程だけでなく、塩化第一鉄水溶液を
酸化して塩化第二鉄水溶液を得る工程までも含めたエッ
チング廃液処理の全工程を総合的に検討した結果、本発
明を完成するに至った。Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and recover copper metal from aqueous solution containing hydrochloric acid and copper chloride such as etching waste liquid and obtain an aqueous ferrous chloride solution. As a result of comprehensively examining not only the process but also the entire process of etching waste liquid treatment including the process of oxidizing the ferrous chloride aqueous solution to obtain the ferric chloride aqueous solution, the present invention was completed.

【０００９】即ち本発明は、塩酸および塩化銅を含有す
る水溶液を鉄材と反応させ、鉄材表面に析出する金属銅
を回収する方法において、前記塩酸および塩化銅含有水
溶液を予めオキシ水酸化鉄と反応させて遊離の塩酸を除
去した後に鉄材と反応させることを特徴とする塩酸およ
び塩化銅含有水溶液中の銅の回収方法である。That is, the present invention provides a method for recovering metallic copper deposited on the surface of an iron material by reacting an aqueous solution containing hydrochloric acid and copper chloride with an iron material, wherein the aqueous solution containing hydrochloric acid and copper chloride is reacted with iron oxyhydroxide in advance. This is a method for recovering copper from an aqueous solution containing hydrochloric acid and copper chloride, wherein the free hydrochloric acid is removed to react with an iron material.

【００１０】[0010]

【発明の実施の形態】本発明の具体的手段は次のとおり
である。まず、銅エッチング廃液等の塩酸および塩化銅
含有水溶液を、オキシ水酸化鉄と反応させて、水溶液中
の遊離の塩酸を除去する。この反応は以下のとおりであ
る。 ３ＨＣｌ ＋ ＦｅＯＯＨ → ＦｅＣｌ3 ＋ ２Ｈ2Ｏ （１ ）DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific means of the present invention are as follows. First, an aqueous solution containing hydrochloric acid and copper chloride such as a copper etching waste liquid is reacted with iron oxyhydroxide to remove free hydrochloric acid in the aqueous solution. This reaction is as follows. 3HCl + FeOOH → FeCl 3 + 2H 2 O (1)

【００１１】次に鉄材を反応させると、以下の反応によ
り金属銅の析出と塩化第一鉄の生成が起こる。 ２ＦｅＣｌ3 ＋ Ｆｅ → ３ＦｅＣｌ2 （２） ＣｕＣｌ2 ＋ Ｆｅ → Ｃｕ↓ ＋ ＦｅＣｌ2 （３）Next, when an iron material is reacted, the following reaction causes precipitation of metallic copper and formation of ferrous chloride. 2FeCl 3 + Fe → 3FeCl 2 (2) CuCl 2 + Fe → Cu ↓ + FeCl 2 (3)

【００１２】更に金属銅を除去した後、塩化第一鉄水溶
液を塩素等で酸化して塩化第二鉄水溶液を得る。この反
応は以下のとおりである。 ２ＦｅＣｌ2 ＋ Ｃｌ2 → ２ＦｅＣｌ3 （４）After the metallic copper is further removed, the aqueous ferrous chloride solution is oxidized with chlorine or the like to obtain an aqueous ferric chloride solution. This reaction is as follows. 2FeCl 2 + Cl 2 → 2FeCl 3 (4)

【００１３】遊離の塩酸を除去する（１）の反応に使用
するオキシ水酸化鉄は、（２）あるいは（３）の反応で
得られた塩化第一鉄水溶液の一部または全部を用いて、
酸素含有気体を通気して、下記（５）の反応を起こして
得ることができる。この方法を用いると新たな薬剤の入
手する必要はなく、一連のエッチング廃液の処理工程に
組み入れることができるので効率的である。酸素含有気
体としては、空気等が挙げられる。 12FeCl2 + 3O2 + 2H2O → 8FeCl3 + 4FeOOH （５）The iron oxyhydroxide used in the reaction (1) for removing free hydrochloric acid is obtained by using a part or all of the aqueous ferrous chloride solution obtained in the reaction (2) or (3).
It can be obtained by aeration of an oxygen-containing gas to cause the following reaction (5). By using this method, there is no need to obtain a new chemical, and the method can be incorporated in a series of processing steps of the waste etching solution, which is efficient. Examples of the oxygen-containing gas include air. 12FeCl 2 + 3O 2 + 2H 2 O → 8FeCl 3 + 4FeOOH (5)

【００１４】この反応を効率的に行うためには、エジェ
クターを用いて、酸素含有気体を塩化第一鉄水溶液に供
給する方式が安価であると共に温和な条件ながら高い反
応率を示すので好ましい。反応で析出するオキシ水酸化
鉄を含有するスラリーをフィルタープレス等で濾別した
後に、（１）で示される工程に使用する。In order to carry out this reaction efficiently, it is preferable to use an ejector to supply an oxygen-containing gas to an aqueous ferrous chloride solution because it is inexpensive and exhibits a high reaction rate under mild conditions. After the slurry containing iron oxyhydroxide precipitated by the reaction is filtered off with a filter press or the like, it is used in the step (1).

【００１５】本発明を、工程図を用いて更に詳しく説明
する。図１は従来法による工程を示す。図１において、
塩酸および塩化銅含有水溶液１は、銅析出反応槽２に供
給され、ここで鉄材３と反応し、前記式（２）（３）の
反応に従って金属銅４の析出と塩化第一鉄水溶液５が生
成される。更に、塩化第一鉄水溶液５は、酸化反応槽６
にて塩素によって酸化され、塩化第二鉄水溶液を得る。The present invention will be described in more detail with reference to a process chart. FIG. 1 shows a conventional process. In FIG.
The aqueous solution 1 containing hydrochloric acid and copper chloride is supplied to a copper deposition reaction tank 2, where it reacts with the iron material 3, and the precipitation of metallic copper 4 and the aqueous ferrous chloride solution 5 are formed according to the above-mentioned equations (2) and (3). Generated. Further, the ferrous chloride aqueous solution 5 is supplied to the oxidation reaction tank 6.
At the same time to obtain an aqueous ferric chloride solution.

【００１６】図２は本発明による工程の一例を示す。塩
酸および塩化銅含有水溶液７は、中和槽８に供給され、
ここでオキシ水酸化鉄９と反応させ、水溶液中の塩酸が
中和される。中和後の水溶液は、銅析出反応槽１０に供
給され、ここで鉄材１１と反応し、金属銅１２の析出と
塩化第一鉄水溶液１３が生成する。更に塩化第一鉄水溶
液１３は、酸化反応槽１４にて塩素により酸化され、塩
化第二鉄水溶液を得る。FIG. 2 shows an example of a process according to the present invention. The aqueous solution 7 containing hydrochloric acid and copper chloride is supplied to a neutralization tank 8,
Here, it reacts with iron oxyhydroxide 9 to neutralize hydrochloric acid in the aqueous solution. The neutralized aqueous solution is supplied to a copper deposition reaction tank 10 where it reacts with the iron material 11 to precipitate metallic copper 12 and produce an aqueous ferrous chloride solution 13. Further, the ferrous chloride aqueous solution 13 is oxidized by chlorine in the oxidation reaction tank 14 to obtain a ferric chloride aqueous solution.

【００１７】更に塩化第一鉄水溶液１３の一部は、空気
酸化槽１５に送られ、ここで空気等の酸素含有気体と反
応させ、オキシ水酸化鉄９を生成させ、濾過後に中和槽
８にリサイクルする。濾液は、塩化第二鉄と未反応の塩
化第一鉄を含むが、これは酸化反応槽１４に送られる。Further, a part of the aqueous ferrous chloride solution 13 is sent to an air oxidation tank 15, where it reacts with an oxygen-containing gas such as air to form iron oxyhydroxide 9, and after filtration, the neutralization tank 8 To recycle. The filtrate contains ferrous chloride and unreacted ferrous chloride, which is sent to the oxidation reaction tank 14.

【００１８】中和槽における反応温度は、４０〜１００
℃が好ましく、更に好ましくは６０〜９０℃である。ま
た攪拌を行うことにより反応を速やかに行うことができ
る。エジェクターにより塩化第一鉄水溶液に酸素含有気
体を供給することによるオキシ水酸化鉄の製造について
は、特開平３−６０４３２号に記載された方法および条
件で行うことができる。オキシ水酸化鉄は他の金属塩不
純物が含まれていても用いることができる。しかし、本
発明で銅を回収した後の塩化鉄水溶液を再生して得られ
る塩化第二鉄水溶液を、不純物による汚染を嫌う上水用
の凝集剤用途等に使用する場合には、前記オキシ水酸化
鉄は不純物のないものを使用することが好ましい。The reaction temperature in the neutralization tank is 40 to 100
C is preferable, and more preferably 60 to 90C. The reaction can be performed promptly by stirring. The production of iron oxyhydroxide by supplying an oxygen-containing gas to an aqueous ferrous chloride solution by an ejector can be performed under the method and conditions described in JP-A-3-60432. Iron oxyhydroxide can be used even if it contains other metal salt impurities. However, when the ferric chloride aqueous solution obtained by regenerating the iron chloride aqueous solution after recovering the copper in the present invention is used for a flocculant use for water supply or the like that dislikes contamination by impurities, the oxywater It is preferable to use iron oxide having no impurities.

【００１９】[0019]

【実施例】以下実施例により本発明を具体的に説明す
る。但し、本発明は実施例のみに限定されるものではな
い。The present invention will be described in detail with reference to the following examples. However, the present invention is not limited only to the examples.

【００２０】実施例１ 塩酸および塩化銅含有水溶液（塩化銅２０質量％、遊離
塩酸１０．６質量％）１００ｇに対して、特開平３−６
０４３２号に記載された方法に基づき、塩化第一鉄水溶
液中にエジェクターにより空気を吹き込むことにより得
られたオキシ水酸化鉄５ｇ（塩酸に対して過剰）を加
え、室温（２０℃）および８５℃にて反応させた。攪拌
下および無攪拌下における遊離塩酸の分解率を測定した
結果を表１に示した。No.４に示したとおり反応温度を
高くし、攪拌することにより遊離塩酸を速やかに除去で
きることが分かった。Example 1 A 100 g aqueous solution containing hydrochloric acid and copper chloride (20% by mass of copper chloride, 10.6% by mass of free hydrochloric acid) was added to JP-A-3-6.
Based on the method described in No. 0432, 5 g (excess of hydrochloric acid) of iron oxyhydroxide obtained by blowing air with an ejector into an aqueous ferrous chloride solution was added, and room temperature (20 ° C.) and 85 ° C. Was reacted. Table 1 shows the results of measuring the decomposition rate of free hydrochloric acid under stirring and without stirring. As shown in No. 4, it was found that free hydrochloric acid could be quickly removed by increasing the reaction temperature and stirring.

【００２１】[0021]

【表１】 [Table 1]

【００２２】No.４で４時間反応させた後の液を８０℃
に加温し、これに鉄材を過剰に加えたところ、僅かに気
泡（水素）が発生しただけで、鉄材表面に析出した銅を
回収できた。After the reaction at No. 4 for 4 hours, the solution was heated to 80 ° C.
Then, when the iron material was excessively added thereto, only slight bubbles (hydrogen) were generated, and copper precipitated on the surface of the iron material could be recovered.

【００２３】比較例１ オキシ水酸化鉄と反応させない塩酸および塩化銅含有水
溶液（塩化銅２０質量％、遊離塩酸１０．６質量％）を
８０℃に加温し、これに鉄材を過剰に加えた。反応温度
が上昇すると共に気泡（水素）が多量に発生した。最終
的に鉄材表面に析出した銅を回収できたが、鉄材のかな
りの部分が塩酸の除去に消費されていることが分かっ
た。COMPARATIVE EXAMPLE 1 An aqueous solution containing hydrochloric acid and copper chloride (20% by mass of copper chloride and 10.6% by mass of free hydrochloric acid) not reacted with iron oxyhydroxide was heated to 80 ° C., and an excess amount of iron material was added thereto. . As the reaction temperature rose, a large amount of bubbles (hydrogen) was generated. Although copper precipitated on the surface of the iron material was finally recovered, it was found that a considerable portion of the iron material was consumed for removing hydrochloric acid.

【００２４】[0024]

【発明の効果】本発明によれば、エッチング廃液等の塩
酸および塩化銅含有水溶液から、金属銅を回収しかつ塩
化第一鉄水溶液を得る方法において、鉄材の使用量を減
少させ、かつ水素の発生を抑制することが可能となる。According to the present invention, in a method for recovering metallic copper and obtaining an aqueous ferrous chloride solution from an aqueous solution containing hydrochloric acid and copper chloride such as an etching waste liquid, the amount of iron material used is reduced and the amount of hydrogen is reduced. Generation can be suppressed.

【図面の簡単な説明】[Brief description of the drawings]

【図１】 従来法による塩酸および塩化銅含有水溶液か
ら銅を回収する工程を示した工程図である。FIG. 1 is a process diagram showing a process of recovering copper from an aqueous solution containing hydrochloric acid and copper chloride according to a conventional method.

【図２】 本発明による塩酸および塩化銅含有水溶液か
ら銅を回収する工程を示した工程図である。FIG. 2 is a process diagram showing a process of recovering copper from an aqueous solution containing hydrochloric acid and copper chloride according to the present invention.

【符号の説明】[Explanation of symbols]

１ 塩酸および塩化銅含有水溶液 ２ 銅析出反応槽 ３ 鉄材 ４ 金属銅 ５ 塩化第一鉄水溶液 ６ 酸化反応槽 ７ 塩酸および塩化銅含有水溶液 ８ 中和槽 ９ オキシ水酸化鉄 １０ 銅析出反応槽 １１ 鉄材 １２ 金属銅 １３ 塩化第一鉄水溶液 １４ 酸化反応槽 １５ 空気酸化槽 Reference Signs List 1 aqueous solution containing hydrochloric acid and copper chloride 2 copper deposition reaction tank 3 iron material 4 metallic copper 5 ferrous chloride aqueous solution 6 oxidation reaction tank 7 aqueous solution containing hydrochloric acid and copper chloride 8 neutralization tank 9 iron oxyhydroxide 10 copper precipitation reaction tank 11 iron material 12 Copper metal 13 Ferrous chloride aqueous solution 14 Oxidation reaction tank 15 Air oxidation tank

Claims (4)

【特許請求の範囲】[Claims] 【請求項1】 塩酸および塩化銅を含有する水溶液を鉄
材と反応させ、鉄材表面に析出する金属銅を回収する方
法において、前記塩酸および塩化銅含有水溶液を予めオ
キシ水酸化鉄と反応させて遊離の塩酸を除去した後に鉄
材と反応させることを特徴とする塩酸および塩化銅含有
水溶液中の銅の回収方法。1. A method for reacting an aqueous solution containing hydrochloric acid and copper chloride with an iron material and recovering metallic copper precipitated on the surface of the iron material, wherein the aqueous solution containing hydrochloric acid and copper chloride is reacted with iron oxyhydroxide in advance to release the copper solution. A method for recovering copper from an aqueous solution containing hydrochloric acid and copper chloride, wherein the copper is reacted with an iron material after removing hydrochloric acid. 【請求項2】 オキシ水酸化鉄が、塩化第一鉄含有水溶
液を酸素含有気体で酸化して得られたものである請求項
１の塩酸および塩化銅含有水溶液中の銅の回収方法。2. The method for recovering copper in an aqueous solution containing hydrochloric acid and copper chloride according to claim 1, wherein the iron oxyhydroxide is obtained by oxidizing an aqueous solution containing ferrous chloride with an oxygen-containing gas. 【請求項3】 酸化が、エジェクターにより塩化第一鉄
含有水溶液への酸素含有気体への供給により行うことを
特徴とする請求項２の塩酸および塩化銅含有水溶液中の
銅の回収方法。3. The method for recovering copper in an aqueous solution containing hydrochloric acid and copper chloride according to claim 2, wherein the oxidation is performed by supplying an oxygen-containing gas to the aqueous solution containing ferrous chloride by an ejector. 【請求項４】 塩化第一鉄含有水溶液が、塩酸および塩
化銅含有水溶液を鉄材と反応させ、金属銅を表面に析出
させた鉄材を分離することにより得られたものである請
求項２または３の塩酸および塩化銅含有水溶液中の銅の
回収方法。4. The ferrous chloride-containing aqueous solution is obtained by reacting an aqueous solution containing hydrochloric acid and copper chloride with an iron material and separating the iron material having metallic copper deposited on its surface. Of copper in aqueous solution containing hydrochloric acid and copper chloride.
JP2000175656A 2000-06-12 2000-06-12 Method for recovering copper in aqueous solution containing hydrochloric acid and copper chloride Expired - Lifetime JP3536787B2 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105018732A (en) * 2015-07-01 2015-11-04 夏栋 Novel method for comprehensive recovery of etching waste liquid and waste residues
WO2016122280A1 (en) * 2015-01-30 2016-08-04 한경옥 Production method for copper using industrial wastewater
JP7453002B2 (en) 2020-01-22 2024-03-19 大口電子株式会社 How to collect silver

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016122280A1 (en) * 2015-01-30 2016-08-04 한경옥 Production method for copper using industrial wastewater
CN105018732A (en) * 2015-07-01 2015-11-04 夏栋 Novel method for comprehensive recovery of etching waste liquid and waste residues
JP7453002B2 (en) 2020-01-22 2024-03-19 大口電子株式会社 How to collect silver

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