JPS6372893A - Cathode for recovering metal copper and method for recovering metal copper from solution containing hydrochloric acid and copper chloride - Google Patents
Cathode for recovering metal copper and method for recovering metal copper from solution containing hydrochloric acid and copper chlorideInfo
- Publication number
- JPS6372893A JPS6372893A JP21416186A JP21416186A JPS6372893A JP S6372893 A JPS6372893 A JP S6372893A JP 21416186 A JP21416186 A JP 21416186A JP 21416186 A JP21416186 A JP 21416186A JP S6372893 A JPS6372893 A JP S6372893A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- cathode
- electrolysis
- hydrochloric acid
- metal
- 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.)
- Pending
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 65
- 239000010949 copper Substances 0.000 title claims abstract description 65
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 18
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 title claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 title abstract description 18
- 239000002184 metal Substances 0.000 title abstract description 18
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 239000010419 fine particle Substances 0.000 abstract description 11
- 239000002699 waste material Substances 0.000 abstract description 10
- 238000005530 etching Methods 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 8
- 229910001431 copper ion Inorganic materials 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229960002089 ferrous chloride Drugs 0.000 description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
（１）発明の目的
〔産業上の利用分野〕
本発明は金属銅回収用陰極、特に塩酸及び塩化銅を含有
する溶液から電解により金属銅を回収するに通した陰極
並びにこれを用いた金属銅の回収方法に関するものであ
る。Detailed Description of the Invention (1) Purpose of the Invention [Field of Industrial Application] The present invention relates to a cathode for recovering metallic copper, particularly a cathode which is used to recover metallic copper from a solution containing hydrochloric acid and copper chloride by electrolysis. The present invention also relates to a method for recovering metallic copper using the same.
更に詳しくは、電解により金属銅を回収するに際し、陰
極の交換、抜き出し、電解の停止を行うことなく連続し
て金属銅の回収を行うことができる陰極及びこれを用い
た金属銅の回収方法に関するものであり、この陰極及び
回収方法は特にプリント配線基板製造工程で生成するよ
うな高濃度の塩酸を含む塩化銅廃液がら、銅を回収する
際に通したものである。More specifically, the present invention relates to a cathode that enables continuous recovery of copper metal when recovering metal copper by electrolysis without replacing or extracting the cathode or stopping electrolysis, and a method for recovering metal copper using the cathode. This cathode and recovery method are particularly used when recovering copper from copper chloride waste liquid containing high concentration hydrochloric acid, such as that produced in the printed wiring board manufacturing process.
塩酸及び塩化銅を含有する溶液、特に銅廃液から金属銅
を回収する方法としては、下式のようなイオン化傾向の
差を利用した銅イオンと金属鉄の置換反応が利用されて
いる。As a method for recovering metallic copper from a solution containing hydrochloric acid and copper chloride, particularly from a copper waste solution, a substitution reaction between copper ions and metallic iron using the difference in ionization tendency as shown in the following formula is used.
ＣｕＣ１２＋Ｆ ｅ−ｅｃｕ ＋Ｆ ｅ Ｃ１２ここで
得られる副生成物である塩化第１鉄水溶液は、更に塩素
ガスにより塩素化され、塩化第２鉄水溶液（過鉄）とし
て再利用されている。CuC12+F e-ecu +F e C12 The ferrous chloride aqueous solution, which is a by-product obtained here, is further chlorinated with chlorine gas and reused as a ferric chloride aqueous solution (perferrous).
しかし近年、銅エツチング廃液等の銅廃液の量が多いた
め、過鉄及びこの原料である塩化第１鉄水溶液は、過剰
気味である。However, in recent years, due to the large amount of copper waste liquid such as copper etching waste liquid, the amount of superferrous metal and its raw material, ferrous chloride aqueous solution, has become excessive.
このため銅廃液の処理方法として、副生物の塩化第１鉄
が生成せず、金属銅と塩素ガスが同時に回収できる電解
法が注目されている。For this reason, as a method for treating copper waste liquid, an electrolytic method that does not produce the by-product ferrous chloride and can recover metallic copper and chlorine gas at the same time is attracting attention.
しかし、この場合、通常は生成物である金属銅は結晶状
で陰極上に析出するため、これを電解槽外へ抜き出すに
は気体や液体と異なり、人為的作業が必要であった。However, in this case, the product, metallic copper, is usually crystalline and deposited on the cathode, so unlike gas or liquid, manual work is required to extract it from the electrolytic cell.
例えば一定時間電解後、電解を停止して析出銅が付着し
た陰極を交換したり、或いは陰極上の析出銅を剥離させ
電解槽外へ取り出す等の作業を行わなければならず、時
間及び労力の点で好ましくなかった。For example, after electrolysis for a certain period of time, it is necessary to stop electrolysis and replace the cathode with deposited copper attached, or to peel off the deposited copper on the cathode and take it out of the electrolytic cell, which saves time and effort. I didn't like it in that respect.
これらの欠点を補うため、陰極から容易に剥離すること
ができる微粒子状の金属銅を、電解により析出させ、固
−液温送流（金属微粒子を懸濁させた溶液の流れ）とし
て電解槽外へ取り出す方法が提案されている。In order to compensate for these drawbacks, fine-particle metallic copper, which can be easily peeled off from the cathode, is deposited by electrolysis and sent outside the electrolytic cell as a solid-liquid hot flow (flow of a solution containing fine metal particles suspended). A method has been proposed to extract the
このプロセスで最も重要なことは陰極上で常に微粒子状
の金属銅が生成することである。The most important thing in this process is that fine particles of metallic copper are always produced on the cathode.
このような機能を有する陰極材質として、特開昭５６−
２９６８６にＴｉ或いはＴｉ合金からなる陰極が提案さ
れている。As a cathode material having such a function, JP-A-56-
No. 29686 proposes a cathode made of Ti or a Ti alloy.
この発明は銅を熔解した鉄液から、溶存する銅を電解析
出させる再に、チタンを陰極板として電解した場合に、
適切な条件下では、銅が極板に固着することがない、高
純度の、美麗な結晶相として析出する特別の効果がある
と述べている。This invention involves electrolytically depositing dissolved copper from an iron solution containing dissolved copper, and then electrolyzing titanium as a cathode plate.
It states that under appropriate conditions, copper has the special effect of precipitating as a highly pure, beautiful crystalline phase that does not stick to the electrode plate.
しかし、実際にはこの電極の機能は充分でなく、本発明
の比較例１に記載のように陰極表面に析出銅の強固な付
着が起こり、その剥離は困難であった。However, in reality, the function of this electrode was not sufficient, and as described in Comparative Example 1 of the present invention, deposited copper strongly adhered to the surface of the cathode, and it was difficult to peel it off.
又剥離しやすい銅微粒子を製造する電解方法として特開
昭５７−１９２２８３に陰極電流密度を陽極のそれの１
００〜５００倍として電解する方法が提案されている。In addition, as an electrolytic method for producing fine copper particles that are easy to peel off, Japanese Patent Application Laid-Open No. 192283/1983 reported that the current density at the cathode was one of that at the anode.
A method of electrolyzing with a magnification of 00 to 500 times has been proposed.
しかしこの方法は析出金属と同一の金冗板を可溶性陽極
として使用し金属微粒子を製造する方法に関するもので
あり、本発明のように陽極でガスの発生、陰極で金属銅
の回収を目的とするシステムに応用することは不可能に
近い。However, this method is related to a method for producing metal fine particles using the same gold plate as the deposited metal as a soluble anode, and as in the present invention, the purpose is to generate gas at the anode and recover metallic copper at the cathode. It is almost impossible to apply it to a system.
塩酸及び塩化銅を含有する溶液から電解により金属銅を
回収しようとする場合、通常は陰極表面上に結晶性の金
属銅が析出するため、これを電解槽外へ取り出すための
時間及び労力が必要であった。When attempting to recover metallic copper from a solution containing hydrochloric acid and copper chloride by electrolysis, crystalline metallic copper is usually deposited on the cathode surface, which requires time and effort to remove from the electrolytic cell. Met.
本発明は金属銅を微粒子状で析出させ、固−液温送流と
して電解槽外へ連続して抜き出すことを可能ならしめた
ものである。The present invention makes it possible to precipitate metallic copper in the form of fine particles and continuously extract it out of the electrolytic cell as a solid-liquid hot flow.
（２）発明の構成
〔問題点を解決するためのための手段〕本発明は塩酸及
び塩化銅を含有する溶液から電解により金属銅を回収す
るに際し、フッ化水素酸でエツチング処理されたＴ １
％ Ｚ ｒ −、Ｎ ｂ或いはＴａからなる陰極を用い
るごとによって上記の問題を解決したものであり、これ
に加えて本発明者等は更に研究を重ねた結果、水素発生
による電流効率の損失を１５〜５０％に維持しつつ電解
を行うと、より剥離性の優れた微粒子状の金属銅を析出
させ得るとの予想外の知見を得て、本発明を完成させた
ものである。(2) Structure of the Invention [Means for Solving Problems] The present invention uses T 1 etched with hydrofluoric acid when recovering metallic copper from a solution containing hydrochloric acid and copper chloride by electrolysis.
The above problem was solved by using a cathode made of %Zr-, Nb, or Ta.In addition, the inventors conducted further research and found that the loss of current efficiency due to hydrogen generation can be reduced. The present invention was completed based on the unexpected finding that if electrolysis is carried out while maintaining the concentration of copper at 15 to 50%, it is possible to precipitate metallic copper in the form of fine particles with better releasability.
本発明の陰極を用いた場合、微粒子状の金属銅が析出す
る理由は明確ではないが、走査型電子顕微鏡で調べると
、エツチング処理を施されたＴ ｉ ｓ Ｚ ｒ ％
Ｎ ｂ或いはＴａの表面は非常に平滑化されているのが
認められる。When using the cathode of the present invention, the reason why fine particles of metallic copper are precipitated is not clear, but when examined with a scanning electron microscope, the etched TisZr%
It is observed that the surface of Nb or Ta is extremely smooth.
このような平滑な電極表面に加え、発生した水素による
エロージョンの相乗効果、更に発生水素ガスの攪拌効果
に基づく銅イオン濃度の均−化等の効果により、剥離性
の優れた微粒子状の金属銅が析出するものと思われる。In addition to this smooth electrode surface, the synergistic effect of erosion caused by the generated hydrogen, and the equalization of the copper ion concentration based on the stirring effect of the generated hydrogen gas, make it possible to create fine particles of metallic copper with excellent removability. is expected to precipitate.
これらに加え、陰極を構成している金属の結晶構造や、
溶解性の水素化物が生成するという物性も関連している
と思われるが、詳細は不明である。In addition to these, the crystal structure of the metal that makes up the cathode,
The physical property of producing soluble hydrides is thought to be related, but the details are unknown.
本発明における陰極を製造するために行うエツチング処
理の望ましい条件は、対象とする金属の耐蝕性により異
なる。Desirable etching conditions for producing the cathode of the present invention vary depending on the corrosion resistance of the target metal.
例えば、５％（重量％：以下同じ）フッ化水素酸を用い
る場合、ＴｉおよびＺｒでは室温で１〜３分間浸漬すれ
ば充分であるが、Ｎｂでは６０℃で１時間前後の浸漬を
、Ｔａでは６０℃で３〜５時間程度の浸漬を行うことが
望ましい。For example, when using 5% (wt%) hydrofluoric acid, immersion for 1 to 3 minutes at room temperature is sufficient for Ti and Zr, but for Nb, immersion for about 1 hour at 60°C is sufficient for Ti and Zr. Then, it is desirable to perform immersion at 60° C. for about 3 to 5 hours.
又この浸漬時間は、フッ化水素酸の濃度及び温度により
ある程度コントロールすることができる。Moreover, this immersion time can be controlled to some extent by the concentration of hydrofluoric acid and temperature.
実際には、金属の活性熔解に基づく水素発生が顕著にな
るまでエツチング処理を行う方法を取ればよい。Actually, it is sufficient to carry out the etching process until hydrogen generation due to active melting of the metal becomes noticeable.
本発明における電極は、Ｔｔ、Ｚｒ、ＮｂあるいはＴａ
からなるものであれば、形状は特に規定はなく、板状、
ラス網状、スダレ状等が使用可能であるが、エツチング
処理の簡便さ及び溶接部分の耐蝕性等の点から、板状が
好ましい形状である。The electrode in the present invention is made of Tt, Zr, Nb or Ta.
As long as it is made of
A lath net shape, a sag shape, etc. can be used, but a plate shape is preferable from the viewpoint of ease of etching treatment and corrosion resistance of the welded portion.
本発明の電解による金属銅の回収法においては、副反応
である水素発生に基づ（電流効率の損失を１５〜５０％
に維持しつつ電解を行うことが好ましい。The method of recovering metallic copper by electrolysis of the present invention is based on hydrogen generation as a side reaction (loss of current efficiency is reduced by 15 to 50%).
It is preferable to perform electrolysis while maintaining the temperature at
具体的には通ｆｆ１ｆｆｌに対して５０〜８５％当量の
銅イオンを含む塩酸含有鋼溶液を電解槽に供給して、通
電量の１５〜５０％を強制的に水素発生で消費させる方
法が取られる。Specifically, a method is adopted in which a hydrochloric acid-containing steel solution containing 50 to 85% equivalent of copper ions per ffl of current is supplied to the electrolytic cell, and 15 to 50% of the current is forcibly consumed by hydrogen generation. It will be done.
通電量に対して水素発生の割合が１５％未満では剥離性
の優れた銅微粒子が生成しにくく、５０％を超えると銅
回収に要する電力原単位の悪化および設備の大型化に直
結し好ましくない。If the ratio of hydrogen generation to the amount of electricity applied is less than 15%, copper fine particles with excellent releasability will be difficult to generate, and if it exceeds 50%, it will directly lead to a worsening of the electricity consumption rate required for copper recovery and an increase in the size of the equipment, which is undesirable. .
最も好ましい水素発生に基づく電流効率の損失の割合は
２０〜４０％である。The most preferred rate of current efficiency loss due to hydrogen generation is 20-40%.
本発明の金属銅の回収方法に用いる塩酸及び塩化銅を含
有する溶液としては、特にｆ！ｉ類は問わないが、塩酸
含有銅廃液、特にプリント配線基板のエツチング等で生
じる塩酸含有銅廃液は、不純物が少なくかつ廃液の生産
量が多いので、技術的、経済的に最も好ましいものであ
る。Especially f! Although type i does not matter, hydrochloric acid-containing copper waste liquid, especially hydrochloric acid-containing copper waste liquid generated from etching of printed wiring boards, etc., is technically and economically the most preferable because it has few impurities and produces a large amount of waste liquid. .
以下に実施例及び比較例を挙げて本発明をさらに詳しく
説明する。The present invention will be explained in more detail by giving examples and comparative examples below.
実施例１
１０ ｃｍＸ ２０ ｃｍのＴｉ板（ＪＩＳ規格１種品
）を５％フッ化水素酸水溶液に室温で２分間浸漬し、水
洗後１０ｃｗＸＩＯｃｍだけ電解液に接するようにテー
ピングした。Example 1 A 10 cm x 20 cm Ti plate (JIS standard type 1 product) was immersed in a 5% hydrofluoric acid aqueous solution at room temperature for 2 minutes, and after washing with water, was taped so that it was in contact with the electrolyte by 10 cw x IO cm.
これをフルオロカーボン陽イオン交換１９ｉＮａｆｉｏ
ｎ−１１７（Ｄｕ Ｐｏｎｔ社製）を隔膜とする電解
槽の陰極とした。Fluorocarbon cation exchange 19iNafio
The cathode of the electrolytic cell was made of n-117 (manufactured by Du Pont) as a diaphragm.
陽極にはＲｕＯ２ＴｉＯ２型金属陽極を用い、銅の電解
試験を行った。A copper electrolysis test was conducted using a RuO2TiO2 type metal anode as the anode.
陽極室には２Ｎ−ＨＣｌを５００ ｃｃ／ ｌｌｒで供
給し、陰極室には銅廃液としてｌＩＣ１１２ｇ／ｌ、Ｃ
ｕＣｌ２３７ ｇ／ｌを含む液（産廃液の１０倍希釈’
ｅ、、＞を５００ ｃｃ／ Ｈｒで供給し、室温、電解
電流１０Ａで電解を行った。2N-HCl was supplied to the anode chamber at 500 cc/llr, and the cathode chamber was supplied with 112 g/l of lIC and C as copper waste liquid.
Liquid containing uCl237 g/l (10-fold dilution of industrial waste liquid)
e, ,> was supplied at 500 cc/Hr, and electrolysis was performed at room temperature with an electrolytic current of 10 A.
２４時間電解後に、陰極室流出液の流量、キレート滴定
法及びＫＭｎＯ４酸化還元滴定法の併用による同波中の
第１銅イオン及び第２銅イオンの濃度及び水素発生に基
づく電流効率の損失を測定した。この測定結果を表１に
示すが、陰極室流出液中に銅イオンは殆ど認められなか
った。After 24 hours of electrolysis, we measured the flow rate of the cathode chamber effluent, the concentration of cuprous ions and cupric ions in the same wave using a combination of chelate titration and KMnO4 redox titration, and the loss of current efficiency due to hydrogen generation. did. The measurement results are shown in Table 1, and almost no copper ions were observed in the cathode chamber effluent.
又析出銅の大部分は、電解液中にフロック状で浮遊し、
陰極に付着していた析出銅も電極に軽い振動を与えると
容易に脱落した。In addition, most of the deposited copper is suspended in the electrolyte in the form of flocs,
The deposited copper adhering to the cathode also easily fell off when the electrode was subjected to light vibration.
実施例２
１０ｃ、ｍＸ２０ｃｍのＺｒ板（純度９９．９％）を用
いた以外は、実施例１と同じ条件でエツチングと電解試
験を行った。Example 2 Etching and electrolysis tests were carried out under the same conditions as in Example 1, except that a 10 cm x 20 cm Zr plate (purity 99.9%) was used.
この測定結果を表１に示すが、陰極室流出液中に銅イオ
ンは殆ど認められながった。The measurement results are shown in Table 1, and it was found that almost no copper ions were observed in the cathode chamber effluent.
又析出銅の大部分は、電解液中にフロック状で浮遊し、
陰極に付着していた析出銅も電極に軽い振動を与えると
容易に脱落した。In addition, most of the deposited copper is suspended in the electrolyte in the form of flocs,
The deposited copper adhering to the cathode also easily fell off when the electrode was subjected to light vibration.
実施例３
１０ ｃｍＸ ２０ ｃｍのＮｂ板（純度９９．９％）
を５％フッ化水素酸水溶液に６０’ｃで１時間浸漬し、
水洗後、実施例１と同じ条件で電解試験を行った。Example 3 10 cm x 20 cm Nb plate (purity 99.9%)
immersed in 5% hydrofluoric acid aqueous solution at 60'C for 1 hour,
After washing with water, an electrolytic test was conducted under the same conditions as in Example 1.
この測定結果を表１に示すが、陰極室流出液中に銅イオ
ンは殆ど認められなかった。The measurement results are shown in Table 1, and almost no copper ions were observed in the cathode chamber effluent.
又析出銅の大部分は、電解液中にフロック状で浮遊し、
陰極に付着していた析出鋼も電極に軽い振動を与えると
容易にｙ！Ａ落した。In addition, most of the deposited copper is suspended in the electrolyte in the form of flocs,
The precipitated steel attached to the cathode can be easily removed by applying light vibration to the electrode. I dropped A.
実施例４
１０ｃｍＸ２０ｃｍのＴｉ板（ＪＩＳ規格品）を５％フ
ッ化水素酸水溶液に６０℃で５時間浸漬し、水洗後、実
施例１と同じ条件で電解試験を行った。Example 4 A 10 cm x 20 cm Ti plate (JIS standard product) was immersed in a 5% aqueous hydrofluoric acid solution at 60° C. for 5 hours, and after washing with water, an electrolytic test was conducted under the same conditions as in Example 1.
この測定結果を表１に示すが、陰極室流出液中に銅イオ
ンは殆ど認められなかった。The measurement results are shown in Table 1, and almost no copper ions were observed in the cathode chamber effluent.
又析出銅の大部分は、電解液中にフロック状で浮遊し、
陰極に付着していた析出銅も電極に軽い振動を与えると
容易に脱落した。In addition, most of the deposited copper is suspended in the electrolyte in the form of flocs,
The deposited copper adhering to the cathode also easily fell off when the electrode was subjected to light vibration.
比較例１
１０ ｃａＸ ２０ ｃｍのＴｉ板（ＪＩＳ規格１種品
）を１０ｃｍＸ１０ｃｍだけ電解液に接するようにテー
ピングし、陰極液の供給速度を６８０ ｃｃ／ Ｈｒと
した以外は、実施例１と同じ条件で電解試験を行った。Comparative Example 1 Same conditions as Example 1, except that a 10 ca x 20 cm Ti plate (JIS standard 1 type product) was taped so that it was in contact with the electrolyte by 10 cm x 10 cm, and the catholyte supply rate was 680 cc/Hr. An electrolytic test was conducted.
この測定結果を表１に示すが、水素発生による電流効率
の損失は１１％で、陰掻上に析出銅が強固に付着してい
た。The measurement results are shown in Table 1, and the loss in current efficiency due to hydrogen generation was 11%, and the deposited copper was firmly attached to the scratches.
比較例２
陰極液の供給速度を５００ ｃｃ／ ｌｌｒとした以外
は、比較例１と同じ条件で電解試験を行った。Comparative Example 2 An electrolytic test was conducted under the same conditions as Comparative Example 1 except that the catholyte supply rate was 500 cc/llr.
この測定結果を表１に示す。The measurement results are shown in Table 1.
陰極室流出液中に銅イオンは殆ど認められなかったが、
陰極に析出銅が付着しており、電極に軽い撮動を与えて
も剥離はしなかった。Although almost no copper ions were observed in the cathode chamber effluent,
Precipitated copper adhered to the cathode, and did not peel off even when the electrode was subjected to light imaging.
実施例５
陰極液の供給速度を６８０ ｃｃ／ ｌｌｒとした以外
は、実施例１と同じ条件で電解試験を行った。Example 5 An electrolytic test was conducted under the same conditions as in Example 1, except that the catholyte supply rate was 680 cc/llr.
この測定結果を表１に示すが、水素発生による電流効率
の損失は１２％で、陰極表面に銅粉がフィルム状に付着
していた。The measurement results are shown in Table 1, and the loss in current efficiency due to hydrogen generation was 12%, and copper powder was attached to the cathode surface in the form of a film.
電極に軽い振動を与えても、この銅粉は剥離しなかった
。Even when the electrode was subjected to slight vibrations, this copper powder did not peel off.
表１
（３）発明の効果
塩酸及び塩化銅を含有する溶液から電解により金属銅を
回収するに際し、本発明の陰極を用い並びに本発明の金
Ｂ銅の回収方法を利用すれば、軽い振動を与えることに
よって容易にａ落する微粒子状の金属銅を析出させるこ
とができ、これを固−液温送流として、電解槽外へ抜き
出すことが可能となった。Table 1 (3) Effects of the Invention When recovering metallic copper by electrolysis from a solution containing hydrochloric acid and copper chloride, by using the cathode of the present invention and the method of recovering gold B copper of the present invention, light vibrations can be suppressed. By applying this, it was possible to precipitate metallic copper in the form of fine particles that easily fall off, and it became possible to extract this as a solid-liquid heated flow to the outside of the electrolytic cell.
このため従来析出金属銅回収のために行っていた陰極の
交換、抜き出し、電解の停止等が不要となり、連続して
金属銅を回収することができ、金属銅の電解回収の時間
および労力が大幅に削減できるものである。This eliminates the need for replacing the cathode, extracting the cathode, stopping electrolysis, etc. that were conventionally required to recover precipitated metallic copper, allowing continuous recovery of metallic copper, which significantly reduces the time and labor required for electrolytic recovery of metallic copper. This can be reduced to
Claims (1)
Ｎｂ或いはＴａからなる金属銅回収用陰極。 ２、塩酸及び塩化銅を含有する溶液から電解により金属
銅を回収する方法において、フッ化水素酸でエッチング
処理されたＴｉ、Ｚｒ、Ｎｂ或いはＴａからなる陰極を
使用することを特徴とする金属銅を回収する方法。 ３、水素発生による電流効率の損失を、１５〜５０％に
維持しつつ電解を行うことを特徴とする特許請求の範囲
第２項記載の金属銅を回収する方法。[Claims] 1. Ti, Zr etched with hydrofluoric acid,
A cathode for recovering metallic copper made of Nb or Ta. 2. A method for recovering metallic copper from a solution containing hydrochloric acid and copper chloride by electrolysis, characterized by using a cathode made of Ti, Zr, Nb or Ta that has been etched with hydrofluoric acid. How to recover. 3. The method for recovering metallic copper according to claim 2, wherein the electrolysis is carried out while maintaining the loss of current efficiency due to hydrogen generation at 15 to 50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21416186A JPS6372893A (en) | 1986-09-12 | 1986-09-12 | Cathode for recovering metal copper and method for recovering metal copper from solution containing hydrochloric acid and copper chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21416186A JPS6372893A (en) | 1986-09-12 | 1986-09-12 | Cathode for recovering metal copper and method for recovering metal copper from solution containing hydrochloric acid and copper chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6372893A true JPS6372893A (en) | 1988-04-02 |
Family
ID=16651244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21416186A Pending JPS6372893A (en) | 1986-09-12 | 1986-09-12 | Cathode for recovering metal copper and method for recovering metal copper from solution containing hydrochloric acid and copper chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6372893A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04131393A (en) * | 1990-09-21 | 1992-05-06 | Power Reactor & Nuclear Fuel Dev Corp | Method and device for recovering palladium by electrolysis method |
| JPH04314899A (en) * | 1990-11-16 | 1992-11-06 | Macdermid Inc | Method and device for electrolytically sampling heavy metal from waste bath |
| JP2020160065A (en) * | 2019-03-25 | 2020-10-01 | 住友金属鉱山株式会社 | Copper valence fractionation quantification method and copper quantification device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4916167A (en) * | 1972-06-09 | 1974-02-13 | ||
| JPS5210823A (en) * | 1975-07-15 | 1977-01-27 | Kobe Steel Ltd | Cathode plate made of titanium for electrolysis of copper |
| JPS531603A (en) * | 1976-06-29 | 1978-01-09 | Asahi Glass Co Ltd | Pretreatment of cathode to be used at deposition of metal by electrolysis from solution containing metal salt |
| JPS5394218A (en) * | 1977-01-28 | 1978-08-18 | Inco Ltd | Method of electrolytically recovering nickel or cobalt |
-
1986
- 1986-09-12 JP JP21416186A patent/JPS6372893A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4916167A (en) * | 1972-06-09 | 1974-02-13 | ||
| JPS5210823A (en) * | 1975-07-15 | 1977-01-27 | Kobe Steel Ltd | Cathode plate made of titanium for electrolysis of copper |
| JPS531603A (en) * | 1976-06-29 | 1978-01-09 | Asahi Glass Co Ltd | Pretreatment of cathode to be used at deposition of metal by electrolysis from solution containing metal salt |
| JPS5394218A (en) * | 1977-01-28 | 1978-08-18 | Inco Ltd | Method of electrolytically recovering nickel or cobalt |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04131393A (en) * | 1990-09-21 | 1992-05-06 | Power Reactor & Nuclear Fuel Dev Corp | Method and device for recovering palladium by electrolysis method |
| JPH04314899A (en) * | 1990-11-16 | 1992-11-06 | Macdermid Inc | Method and device for electrolytically sampling heavy metal from waste bath |
| JP2020160065A (en) * | 2019-03-25 | 2020-10-01 | 住友金属鉱山株式会社 | Copper valence fractionation quantification method and copper quantification device |
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