JPS62297476A - Method and device for regenerating copper chloride etching waste solution - Google Patents
Method and device for regenerating copper chloride etching waste solutionInfo
- Publication number
- JPS62297476A JPS62297476A JP14173186A JP14173186A JPS62297476A JP S62297476 A JPS62297476 A JP S62297476A JP 14173186 A JP14173186 A JP 14173186A JP 14173186 A JP14173186 A JP 14173186A JP S62297476 A JPS62297476 A JP S62297476A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- etching waste
- waste liquid
- soln
- copper chloride
- 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
Links
- 238000005530 etching Methods 0.000 title claims abstract description 81
- 239000002699 waste material Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 26
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 title claims abstract description 18
- 230000001172 regenerating effect Effects 0.000 title claims description 15
- 239000010949 copper Substances 0.000 claims abstract description 46
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052802 copper Inorganic materials 0.000 claims abstract description 38
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 19
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 16
- 239000003085 diluting agent Substances 0.000 claims abstract description 14
- 239000012895 dilution Substances 0.000 claims abstract description 14
- 238000010790 dilution Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 71
- 239000000243 solution Substances 0.000 claims description 35
- 229910000831 Steel Inorganic materials 0.000 claims description 30
- 239000010959 steel Substances 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 238000007865 diluting Methods 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 239000000460 chlorine Substances 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 5
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 230000008929 regeneration Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- -1 chlorine ions Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 241001454694 Clupeiformes Species 0.000 description 1
- 235000019513 anchovy Nutrition 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical group I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 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
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
［産業上の利用分野］
この発明は、塩化鋼エッチング廃液の電解再生方法及び
その装置に関するものである。Detailed Description of the Invention 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method and apparatus for electrolytically regenerating chlorinated steel etching waste liquid.
［従来の技術］
従来、塩化鋼エッチング廃液の再生方法として、溶液中
に酸化剤を加え、溶液中のＣｕ （Ｉ ＞をＣｕ（ＩＩ
＞に酸化した後、溶液の組成を調整するため、塩酸や塩
化ナトリウム及び水を加えて再生する化学的処理法や、
電解により陰極で脱銅を行い、陽極でＣｕ （Ｉ ）を
Ｃｕ（ＩＩ＞に酸化する電気化学的処理法が知られてい
る。[Prior Art] Conventionally, as a method for regenerating chloride steel etching waste solution, an oxidizing agent is added to the solution, and Cu (I > in the solution is converted to Cu (II
After oxidizing to
An electrochemical treatment method is known in which copper is removed at the cathode by electrolysis and Cu (I ) is oxidized to Cu (II>) at the anode.
［発明が解決しようとする問題点］
このうち化学的処理法は、例えば過酸化水素と塩酸とを
用い
２ＣｕＣＪ！＋Ｈ２Ｏ２＋２ＨＣＪ！＝ ２Ｃｕ廊２
＋２８２０にて示されるように行われる方法であるが、
この方法は廃液より脱銅しておらず再生液中のＣｕ （
ＩＩ ＞の量が増加するため銅イオン濃度を同一濃度に
維持するためには他の試薬及び水を加えて調整すること
を必要とし、再生液の体積が増加するという欠点がある
。また電気化学的処理法により塩化鋼エッチング廃液の
再生を行う場合、エツチング液の銅濃度を一定にするた
めに、陰極で金属銅を還元析出させて回収するが、エツ
チング廃液の組成や各種イオン濃度が異なると金属鋼の
析出状態が異なり、特に銅イオンや塩素イオンの各濃度
が高濃度のエツチング廃液においては、殆ど銅の析出は
起きず電流効率は非常に小さな値になるという欠点があ
った。この発明は、電気化学的処理法を用いて、組成の
異なった塩化鋼エッチング廃液を、特に銅イオン濃度が
高濃度の廃液において、一様な状態で金属銅を析出させ
て再生する塩化鋼エッチング廃液再生方法及びその装置
を提供するものである。[Problems to be Solved by the Invention] Among these, the chemical treatment method uses, for example, hydrogen peroxide and hydrochloric acid to treat 2CuCJ! +H2O2+2HCJ! = 2Cu corridor 2
+2820 is a method performed as shown in
This method does not remove copper from the waste liquid, but Cu (
II> increases, it is necessary to adjust the copper ion concentration by adding other reagents and water in order to maintain the same concentration, and there is a drawback that the volume of the regenerating solution increases. Furthermore, when regenerating chloride steel etching waste liquid using an electrochemical treatment method, metal copper is reduced and precipitated at the cathode and recovered in order to maintain a constant copper concentration in the etching liquid. The precipitation state of the metal steel differs depending on the concentration of copper ions and chlorine ions, and in particular, in etching wastewater with high concentrations of copper ions and chloride ions, there is a disadvantage that almost no copper precipitation occurs and the current efficiency becomes a very small value. . This invention uses an electrochemical treatment method to regenerate chlorinated steel etching waste liquids with different compositions, particularly in waste liquids with high copper ion concentrations, by precipitating metallic copper in a uniform state. The present invention provides a waste liquid regeneration method and apparatus.
［問題点を解決するための手段］
本発明は塩化鋼エッチング廃液を電解により再生すると
ともに金属銅を回収する方法において、塩化鋼エッチン
グ廃液中に、この廃液と同じ塩素イオン濃度の塩酸−ア
ルカリ金属の塩化物溶液を加えて前記塩化鋼エッチング
廃液中の銅イオン濃度を希釈する第一工程と、隔膜で仕
切られた電解槽の陽極室に前記塩化鋼エッチング廃液を
導入し、かつ陰極室に第一工程で調製した希釈エツチン
グ廃液を導入して電解を行い、陰極室で金属鋼を還元析
出させ、かつ陽極室で銅イオンの酸化を行う第二工程と
、第二工程で得られる両極室の溶液を混合する第三工程
とを備えてなることを特徴とする塩化鋼エッチング廃液
の再生方法であり、またその再生装置は再生すべき塩化
鋼エッチング廃液を貯留する塩化鋼エッチング廃液貯槽
と、この塩化鋼エッチング廃液と同じ塩素イオン濃度の
塩酸−アルカリ金属の塩化物溶液よりなる希釈液を貯留
する希釈液貯槽と、前記塩化鋼エッチング廃液貯槽およ
び前記希釈液貯槽に接続し、塩化鋼エッチング廃液を希
釈液にて希釈する希釈槽と、前記塩化鋼エッチング廃液
貯槽に接続して塩化鋼エッチング廃液を収容する陽極室
および前記希釈槽に接続して希釈塩化鋼エッチング廃液
を収容する陰極室が隔膜で仕切られた電解槽と、この電
解槽の前記陰極室および前記陰極室に接続し、各極室の
電解液を混合する混合槽とを備えてなることを特徴とす
る。[Means for Solving the Problems] The present invention provides a method for regenerating chlorinated steel etching waste liquid by electrolysis and recovering metallic copper. A first step of diluting the copper ion concentration in the chloride steel etching waste solution by adding a chloride solution of The second step involves introducing the diluted etching waste solution prepared in the first step to perform electrolysis, reducing and precipitating the metal steel in the cathode chamber, and oxidizing copper ions in the anode chamber; A method for regenerating chlorinated steel etching waste liquid, comprising: a third step of mixing the solution; A diluent storage tank for storing a diluted solution made of hydrochloric acid-alkali metal chloride solution having the same chloride ion concentration as the chloride steel etching waste liquid is connected to the chloride steel etching waste liquid storage tank and the diluted liquid storage tank to store the chloride steel etching waste liquid. A dilution tank for diluting with a diluent, an anode chamber connected to the chloride steel etching waste liquid storage tank and accommodating the chloride steel etching waste liquid, and a cathode chamber connected to the dilution tank and accommodating the diluted chloride steel etching waste liquid are formed by a diaphragm. It is characterized by comprising a partitioned electrolytic cell, and a mixing tank that is connected to the cathode chamber and the cathode chamber of the electrolytic cell and mixes the electrolyte in each electrode chamber.
［実施例］
以下、本発明の再生装置の一実施例を図面を用いて説明
する。[Example] Hereinafter, an example of the reproducing apparatus of the present invention will be described with reference to the drawings.
第１図において、１は塩化鋼エッチング廃液貯槽、２は
廃液と同濃度の塩素イオンを含有する塩酸とアルカリ金
属塩化物の混合溶液を貯える希釈液貯槽である。塩化鋼
エッチング廃液貯槽１および希釈液貯槽２はそれぞれポ
ンプＰ１およびＰ２を介して塩化銅エッチング廃液およ
び希釈液を混合する希釈槽３に接続している。この希釈
槽３はポンプＰ４を介して、陽極室４１および陰極室４
３が隔膜４２で仕切られた電解槽４の陰極室４３に接続
すると共に、陽極室４１にはポンプＰ３を介して塩化鋼
エッチング廃液貯槽１が接続している。電解槽４の陰極
室４３および陽極室４１はそれぞれポンプＰ８およびＰ
５を介して両極室の液を混合する混合槽５に接続すると
共に、この混合槽５はポンプＰ６を介して塩化鋼エッチ
ング再生液貯槽６に接続している。また電解槽４の陰極
室４３はポンプＰ７を介して希釈液貯槽２に接続してい
る。In FIG. 1, 1 is a chloride steel etching waste liquid storage tank, and 2 is a diluted liquid storage tank that stores a mixed solution of hydrochloric acid and alkali metal chloride containing chloride ions at the same concentration as the waste liquid. The steel chloride etching waste liquid storage tank 1 and the dilution liquid storage tank 2 are connected via pumps P1 and P2, respectively, to a dilution tank 3 for mixing the copper chloride etching waste liquid and the dilution liquid. This dilution tank 3 is connected to an anode chamber 41 and a cathode chamber 4 via a pump P4.
3 is connected to a cathode chamber 43 of an electrolytic cell 4 partitioned by a diaphragm 42, and a chloride steel etching waste liquid storage tank 1 is connected to an anode chamber 41 via a pump P3. The cathode chamber 43 and anode chamber 41 of the electrolytic cell 4 are connected to pumps P8 and P, respectively.
The mixing tank 5 is connected via a pump P6 to a mixing tank 5 for mixing the liquids in both electrode chambers, and the mixing tank 5 is also connected to a chlorinated steel etching regeneration liquid storage tank 6 via a pump P6. Further, the cathode chamber 43 of the electrolytic cell 4 is connected to the diluent storage tank 2 via a pump P7.
以上のように構成された再生装置を用いる塩化鋼エッチ
ング廃液の再生は例えば次のようにして行なう。Regeneration of chlorinated steel etching waste liquid using the regeneration apparatus configured as described above is carried out, for example, as follows.
エツチング工程で生じるエツチング廃液を塩化鋼エッチ
ング廃液貯槽１に貯え、エツチング廃液の塩素濃度と等
しい■ご−Ｎａ（Ｉ！混合溶液（希釈液）を希釈液貯槽
２に貯えておく。これは、通常エツチング液は塩酸と塩
化ナトリウム液を用いて塩素イオン濃度が調整されてい
るためであるが、その他の試薬例えばＫ（、ｉ２が含ま
れている場合には、これも含まれている希釈液を用いる
のが望ましい。Etching waste liquid generated in the etching process is stored in the chloride steel etching waste liquid storage tank 1, and a mixed solution (diluted liquid) with a concentration of chlorine equal to the chlorine concentration of the etching waste liquid is stored in the diluted liquid storage tank 2. This is because the chloride ion concentration of the etching solution is adjusted using hydrochloric acid and sodium chloride solution, but if it contains other reagents such as K (, i2), use a diluted solution that also contains this. It is desirable to use
エツチング廃液の一部と希釈液を各々、ポンプＰ１、Ｐ
２により希釈槽３へ供給し、エツチング廃液の希釈を行
う。この希釈率は後に示すように銅イオン濃度にして０
．２ （ｍｏｆ ／ｆ ＞以下、０，０１（ｍｏｂ／β
〉以上になることが望ましい。希釈後のエツチング廃液
はポンプＰ４により電解１ｔ４の陰極室４３に送られ、
エツチング廃液の一部はポンプＰ３により電解槽４の陰
極室４１に送られる。陰極１４３の面積を陽極１４１の
面積より小さクシ隘）※１４３の電流密度を陽極１４１
のそれより大きくなるようにするのが望ましい。例えば
陰極１４３に１０ＯＡ／ｄｍ２ 、陽極１４１に２０Ａ
／ｄｍ２程度の電気を流すと、陰極１４３表面に針状の
金属銅が析出し、電極を交換可能な物を用いれば容易に
金属銅を回収することができる。また陽憧１４１では塩
素ガス発生反応は抑制され効率よ＜Ｃｕ（１）をＣｕ（
Ｉ［＞に酸化し再生する事ができる。一定量の金属銅を
析出させた後、電解を終了する。電解後の陽極液及び陰
極液の一部を各々ポンプＰ５、Ｐ８により混合槽５へ供
給し銅イオン濃度を所定値にする。残りの陰極液はポン
プＰ７により希釈液貯槽２へ送り返し再び希釈液として
用いる。銅濃度を調整された混合液は塩化鋼エッチング
再生液貯槽６ヘポンプＰ６により送られる。以上のよう
にしてエツチング廃液より所定の量の金属銅を回収し酸
化還元電位を調整したエツチング再生液を得ることがで
きる。Pumps P1 and P pumps a part of the etching waste liquid and a diluted liquid, respectively.
2, the etching waste liquid is supplied to the dilution tank 3 and diluted. As shown later, this dilution rate is 0 when the copper ion concentration is
．． 2 (mof /f > below, 0,01(mob/β
〉 or more is desirable. The etching waste solution after dilution is sent to the cathode chamber 43 of the electrolyzer 1t4 by the pump P4,
A part of the etching waste liquid is sent to the cathode chamber 41 of the electrolytic cell 4 by the pump P3. The area of the cathode 143 is smaller than the area of the anode 141) *The current density of the cathode 143 is set to
It is desirable to make it larger than that of . For example, 10 OA/dm2 for the cathode 143 and 20 A for the anode 141.
When electricity of about /dm2 is applied, acicular copper metal is deposited on the surface of the cathode 143, and if an electrode with a replaceable electrode is used, the metal copper can be easily recovered. In addition, in Yodo 141, the chlorine gas generation reaction is suppressed, and the efficiency is lower than Cu(1) to Cu(
It can be oxidized to I[> and regenerated. After depositing a certain amount of metallic copper, the electrolysis is terminated. Parts of the anolyte and catholyte after electrolysis are supplied to the mixing tank 5 by pumps P5 and P8, respectively, to bring the copper ion concentration to a predetermined value. The remaining catholyte is sent back to the diluent storage tank 2 by the pump P7 and used as a diluent again. The mixed solution with adjusted copper concentration is sent to the chloride steel etching regenerating solution storage tank 6 by a pump P6. In the manner described above, it is possible to recover a predetermined amount of metallic copper from the etching waste liquid and obtain an etching regenerating liquid whose oxidation-reduction potential has been adjusted.
次に銅イオン濃度と陰極の電流密度に関して説明する。Next, the copper ion concentration and the current density of the cathode will be explained.
実験によると銅を析出するに要する最低の電流密度があ
り、銅イオン濃度必るいは塩素イオン）９度が大きいほ
ど、この最低電流密度は大きくなる傾向におることが確
かめられた。そしてこの電′ａ密度以下では、金属銅の
析出は殆ど起きずＣｕ （ＩＩ ）をＣ１Ｊ （工）に
還元するのみで電流効率は著しく低下する。また銅イオ
ン濃度が小さい場合には、過剰な電流密度で電解をする
と、陰極では銅の析出反応とともに水素発生が生じ、析
出銅はポーラスな状態となり、電極表面より離脱しやす
く、回収しにくいことが確かめられた。希釈液をくり返
し使用するという観点から、希釈の仕方（陰極室の電解
液の調整）は以下のようにするのが望ましい。即ち廃液
中に含まれる塩素イオン濃度と同じ濃度で、かつ塩酸と
塩化ナトリウムのモル比が廃液のモル比と同じである混
合液（希釈液〉を用いて（もし廃液中ににし等が含まれ
ていれば、そのモル比になるように調整された希釈液）
、陰極で回収したい銅の量（エツチング工程で溶解した
銅の量）を過不足なく含有し、鋼イオン濃度が０．２〜
０．０１ （ｍｏｉ） ／１ ）になるように希釈す
る。Experiments have confirmed that there is a minimum current density required to deposit copper, and this minimum current density tends to increase as the copper ion concentration (or chlorine ion) increases. Below this electric density, metal copper is hardly precipitated and Cu (II) is only reduced to C1J (E), resulting in a significant decrease in current efficiency. In addition, when the copper ion concentration is low, if electrolysis is carried out at an excessive current density, hydrogen will be generated at the cathode along with the copper precipitation reaction, and the deposited copper will become porous, easily detached from the electrode surface, and difficult to recover. was confirmed. From the viewpoint of using the diluted solution repeatedly, it is desirable to dilute it (adjust the electrolytic solution in the cathode chamber) as follows. In other words, using a mixed solution (diluent) that has the same concentration of chlorine ions as the waste solution and the same molar ratio of hydrochloric acid and sodium chloride as the waste solution (if the waste solution contains anchovies, etc.), diluted solution adjusted to achieve that molar ratio)
, contains exactly the amount of copper that is desired to be recovered at the cathode (the amount of copper dissolved in the etching process), and has a steel ion concentration of 0.2~
Dilute to 0.01 (moi)/1).
こうすれば回収後の陰極液には殆ど銅イオンを含まず、
またナトリウムイオンと水素イオンのモル比が廃液と等
しいため、再び希釈液として再利用することが可能とな
る。なお銅の析出にともない、鋼イオン濃度は小さくな
るが、これに従って電流密度を小さくさせて（電流を小
さくして）水素発生を抑えることが望ましい。In this way, the catholyte after collection contains almost no copper ions,
Furthermore, since the molar ratio of sodium ions and hydrogen ions is the same as that of the waste liquid, it becomes possible to reuse it as a diluent again. Note that as copper is deposited, the steel ion concentration decreases, and it is desirable to reduce the current density accordingly (by reducing the current) to suppress hydrogen generation.
以下に本発明による電解再生法の一実施例と本発明によ
らない電解再生法の一例を示し、本発明の効果を明らか
にする。An example of an electrolytic regeneration method according to the present invention and an example of an electrolytic regeneration method not according to the present invention will be shown below to clarify the effects of the present invention.
第２図及び第３図に、各々エツチング工程から再生に至
るまでの、エツチング液中の組成、酸化還元電位及び実
験条件等の流れ図を示す。第２図の実施例１ではエツチ
ング工程で６．４ｇ（０，１ｍｏβ）の銅が溶解してあ
り、これを回収するにはエツチング廃液約１００ｍ１に
含まれる銅を回収する必要かあり、陰）へ室に１００彪
の廃液と９０（７の塩酸と塩化ナトリウムの混合液（塩
素；装置６ｘ１）を加え１０倍に希釈を行い銅イオン濃
度にして約０．１１ ｊ〜１、塩素イオン温度にして６
Ｍとした。実験によるとこの希釈エツチング廃液は５０
Ａ／ｄｍ２以上で電解すると銅が析出することから陰極
電流密度１００Ａ／ｄｍ２で電解を行い、銅５．８ｇを
析出したところで電解を終了した。このときの電流効率
は８２％であった。FIGS. 2 and 3 are flowcharts showing the composition of the etching solution, redox potential, experimental conditions, etc. from the etching process to regeneration, respectively. In Example 1 shown in Figure 2, 6.4 g (0.1 moβ) of copper was dissolved in the etching process, and to recover it, it was necessary to recover the copper contained in about 100 ml of etching waste liquid. Add 100 m2 of waste liquid and 90 (7) mixed solution of hydrochloric acid and sodium chloride (chlorine; apparatus 6 x 1) to the chamber and dilute 10 times to bring the copper ion concentration to about 0.11 J to 1 and the chlorine ion temperature. Te6
It was set as M. According to experiments, this diluted etching waste solution has a
Since copper precipitates when electrolyzed at A/dm2 or more, electrolysis was performed at a cathode current density of 100 A/dm2, and the electrolysis was terminated when 5.8 g of copper was deposited. The current efficiency at this time was 82%.
電解後隅極液９００ｄと陰極液１００ｍ１を混合し酸化
還元電位１０１００Ｏ（ＶＳ −ＡＱ −ＡｇＣＪ ）
以上の再生液１０００ｄを得た。この酸化還元電位の値
は、エツチング液のエツチング能力を示す目安となるも
のでエツチング液の組成や濃度により異なるが、おおよ
そ７００ｍＶ （ｖｓ −Ａｇ−ＡｇｃＩｌ）以上で精
度良いエツチングが可能となる。After electrolysis, 900 d of corner electrolyte and 100 ml of catholyte were mixed to give an oxidation-reduction potential of 10,100 O (VS -AQ -AgCJ)
1000 d of the above regenerated liquid was obtained. This oxidation-reduction potential value is a measure of the etching ability of the etching solution, and varies depending on the composition and concentration of the etching solution, but accurate etching is possible at approximately 700 mV (vs -Ag-AgcIl) or higher.
第３図の実施例２ではエツチング工程で０．６４ｇ（０
，０１ｍｏｆりの銅が溶解しており、これを回収′する
にはエツチング廃液的１０７に含まれる銅を回収する必
要があり、陰極室に１０ｍの廃液と９９０威の塩酸と塩
化ナトリウムの混合液（塩素濃度６Ｍ＞を加え１００倍
に希釈を行い銅イオン濃度にして約０．０１１Ｍ、塩素
イオン濃度にして６Ｍとした。実験によると、この希釈
エツチング廃液は数Ａ／ｄｍ２以上で電解すると銅が析
出することから陰極電流密度５０Ａ／ｄｍ２で電解を行
い銅０．６４Ｃｌ析出したところで電解を終了した。こ
のときの電流効率は９９％であった。Ｎ前後陽極液９９
０ｄと陰極液１０ｒｄ、を混合し酸化還元電位１０１０
０Ｏ（ｖｓ −Ａｇ−Ａｇ［，２＞以上の再生液１００
０Ｉｎｌを得た。第４図及び第５図に各々比較例１及び
比較例２の流れ図を示す。比較例１は実施例１と同組成
の廃液を、比較例２は実施例２と同組成の廃液を、各々
再生した例で両者とも希釈せずに電解を行った。この結
果どちらの場合も銅を回収することはできなかった。な
お電解後の陽極液の酸化還元電位はどちらも１０００ｍ
Ｖ以上であったが陰極液を混合すると比較例１では４０
０ｍＶ、比較例２では４７０ｍＶとなり、エツチング液
として使用できないことが判明した
第２図及び第３日に示したように本発明による再生方法
及び再生装置によれば、塩化鋼エッチング廃液より所定
の量の銅を回収し、かつ再生液を得ることができ、特に
銅イオン濃度が高濃度のエツチング廃液の再生において
も効率良く銅を回収することができる。しかしながら、
比較例に示したように本発明によらない再生方法及び再
生装置では、銅濃度が高いため銅を回収することはでき
ず、もし回収するにしても数百Ａ／ｄｍ２という高電流
を必要とし実用上問題点がある。In Example 2 shown in Figure 3, 0.64 g (0.0
,01mof of copper is dissolved, and in order to recover it, it is necessary to recover the copper contained in the etching waste liquid.Into the cathode chamber, a mixed solution of 10m of waste liquid, 990m of hydrochloric acid, and sodium chloride is added. (Chlorine concentration: 6M) was added to dilute the etching 100 times, resulting in a copper ion concentration of approximately 0.011M and a chlorine ion concentration of 6M.According to experiments, this diluted etching waste solution was electrolyzed at several A/dm2 or higher, resulting in copper was precipitated, so electrolysis was carried out at a cathode current density of 50 A/dm2, and the electrolysis was terminated when 0.64 Cl of copper was precipitated.The current efficiency at this time was 99%.
Mix 0d and catholyte 10rd to obtain an oxidation-reduction potential of 1010
0O(vs -Ag-Ag[,2> or more regeneration liquid 100
0 Inl was obtained. Flowcharts of Comparative Example 1 and Comparative Example 2 are shown in FIG. 4 and FIG. 5, respectively. Comparative Example 1 was an example in which a waste liquid having the same composition as in Example 1 was regenerated, and Comparative Example 2 was an example in which a waste liquid having the same composition as in Example 2 was regenerated, and both were electrolyzed without being diluted. As a result, copper could not be recovered in either case. The oxidation-reduction potential of the anolyte after electrolysis is 1000m in both cases.
V or more, but when the catholyte was mixed, in Comparative Example 1, it was 40
0mV, and 470mV in Comparative Example 2, and it was found that it could not be used as an etching solution.As shown in FIG. of copper can be recovered and a regenerated solution can be obtained. In particular, copper can be efficiently recovered even in the regeneration of etching waste liquid with a high concentration of copper ions. however,
As shown in the comparative example, with the regeneration method and regeneration device not according to the present invention, copper cannot be recovered due to the high copper concentration, and even if it were to be recovered, a high current of several hundred A/dm2 would be required. There are practical problems.
［発明の効果１
このように本発明による塩化鋼エッチング廃液の再生方
法及び再生装置によればエツチング液の組成や濃度にか
かわらず、所望の希釈条件で希釈することにより、効率
良く銅を回収し再生できるとともに、希釈液を再利用で
きるので、エツチング工程からエツチング廃液再生の工
程まで、はとんど他からの物質（試薬や水）の流入及び
他への物質（廃液）の流出のないクローズシステムとし
て期待できるものである。[Effect of the invention 1] As described above, according to the method and apparatus for regenerating chlorinated steel etching waste liquid according to the present invention, copper can be efficiently recovered by diluting the etching liquid under desired dilution conditions, regardless of the composition and concentration of the etching liquid. Since it can be regenerated and the diluted solution can be reused, from the etching process to the process of regenerating the etching waste liquid, it is a closed process where there is no inflow of substances (reagents or water) from other sources or outflow of substances (waste liquid) to other areas. This is a promising system.
第１図は本発明の塩化鋼エッチング廃液の再生装置の一
実施例を示す構成図、第２図はその再生装置を用いた再
生方法の一実施例を示す工程図、第３図はその他の一実
施例を示す工程図、第４図は従来の再生装置を用いた再
生方法の一例を示す工程図、第５図はその他の一例を示
す工程図である。
１・・・塩化鋼エッチング廃液貯槽
２・・・希釈液貯槽 ３・・・希釈槽４・・・電
解槽 ５・・・混合槽６・・・塩化鋼エッチ
ング再生液貯槽
４１・・・陽極室 ４２・・・隔膜４３・・
・陰極室 １４１・・・陽極１４３・・・陰
極 Ｐ１〜Ｐ８・・・ポンプ第３図Fig. 1 is a configuration diagram showing an embodiment of a regeneration device for chlorinated steel etching waste liquid of the present invention, Fig. 2 is a process diagram showing an embodiment of a regeneration method using the regeneration device, and Fig. 3 is a diagram showing an example of a regeneration method using the regeneration device. FIG. 4 is a process diagram showing an example of a regeneration method using a conventional regeneration device, and FIG. 5 is a process diagram showing another example. 1... Steel chloride etching waste liquid storage tank 2... Diluent storage tank 3... Dilution tank 4... Electrolytic tank 5... Mixing tank 6... Steel chloride etching regeneration liquid storage tank 41... Anode chamber 42...Diaphragm 43...
・Cathode chamber 141...Anode 143...Cathode P1-P8...Pump Fig. 3
Claims (3)
もに金属銅を回収する方法において、塩化銅エッチング
廃液中に、この廃液と同じ塩素イオン濃度の塩酸−アル
カリ金属の塩化物溶液を加えて前記塩化銅エッチング廃
液中の銅イオン濃度を希釈する第一工程と、隔膜で仕切
られた電解槽の陽極室に前記塩化銅エッチング廃液を導
入し、かつ陰極室に第一工程で調製した希釈エッチング
廃液を導入して電解を行い、陰極室で金属銅を還元析出
させ、かつ陽極室で銅イオンの酸化を行う第二工程と、
第二工程で得られる両極室の溶液を混合する第三工程と
を備えてなることを特徴とする塩化銅エッチング廃液の
再生方法。(1) In a method of regenerating a copper chloride etching waste liquid by electrolysis and recovering metallic copper, a hydrochloric acid-alkali metal chloride solution having the same chlorine ion concentration as the waste liquid is added to the copper chloride etching waste liquid to recover the copper chloride. A first step of diluting the copper ion concentration in the etching waste solution, introducing the copper chloride etching waste solution into the anode chamber of the electrolytic cell separated by a diaphragm, and introducing the diluted etching waste solution prepared in the first step into the cathode chamber. a second step in which electrolysis is performed to reduce and precipitate metallic copper in the cathode chamber, and oxidation of copper ions in the anode chamber;
A method for regenerating a copper chloride etching waste solution, comprising a third step of mixing the solution in the bipolar chamber obtained in the second step.
許請求の範囲第一項記載の塩化銅エッチング廃液の再生
方法。(2) The method for regenerating copper chloride etching waste liquid according to claim 1, wherein the alkali metal chloride is sodium chloride.
もに、金属銅を回収する装置において、再生すべき塩化
銅エッチング廃液を貯留する塩化銅エッチング廃液貯槽
と、この塩化鋼エッチング廃液と同じ塩素イオン濃度の
塩酸−アルカリ金属の塩化物溶液よりなる希釈液を貯留
する希釈液貯槽と、前記塩化銅エッチング廃液貯槽およ
び前記希釈液貯槽に接続し、塩化銅エッチング廃液を希
釈液にて希釈する希釈槽と、前記塩化鋼エッチング廃液
貯槽に接続して塩化銅エッチング廃液を収容する陽極室
および前記希釈槽に接続して希釈塩化銅エッチング廃液
を収容する陰極室が隔膜で仕切られた電解槽と、この電
解槽の前記陰極室および前記陽極室に接続し、各極室の
電解液を混合する混合槽とを備えてなることを特徴とす
る塩化銅エッチング廃液の再生装置。(3) In a device that regenerates copper chloride etching waste liquid by electrolysis and recovers metallic copper, there is a copper chloride etching waste liquid storage tank that stores the copper chloride etching waste liquid to be regenerated, and a copper chloride etching waste liquid storage tank that has the same chloride ion concentration as this chloride steel etching waste liquid. a diluent storage tank for storing a diluent made of a hydrochloric acid-alkali metal chloride solution; a dilution tank connected to the copper chloride etching waste liquid storage tank and the diluent storage tank and diluting the copper chloride etching waste liquid with the diluent; An electrolytic cell having an anode chamber connected to the steel chloride etching waste liquid storage tank and containing the copper chloride etching waste liquid and a cathode chamber connected to the dilution tank and containing the diluted copper chloride etching waste liquid separated by a diaphragm, and this electrolytic cell. An apparatus for regenerating copper chloride etching waste liquid, comprising: a mixing tank that is connected to the cathode chamber and the anode chamber and mixes the electrolyte in each electrode chamber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14173186A JPS62297476A (en) | 1986-06-17 | 1986-06-17 | Method and device for regenerating copper chloride etching waste solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14173186A JPS62297476A (en) | 1986-06-17 | 1986-06-17 | Method and device for regenerating copper chloride etching waste solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62297476A true JPS62297476A (en) | 1987-12-24 |
| JPS6353267B2 JPS6353267B2 (en) | 1988-10-21 |
Family
ID=15298898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14173186A Granted JPS62297476A (en) | 1986-06-17 | 1986-06-17 | Method and device for regenerating copper chloride etching waste solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62297476A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04285182A (en) * | 1990-11-16 | 1992-10-09 | Macdermid Inc | Improved reclaiming process of ammoniacal chloride etchant |
| JPH04314899A (en) * | 1990-11-16 | 1992-11-06 | Macdermid Inc | Method and device for electrolytically sampling heavy metal from waste bath |
| WO2012163238A1 (en) * | 2011-05-31 | 2012-12-06 | 无锡尚德太阳能电力有限公司 | Recycling system and method for treating used etching solution |
| CN103422154A (en) * | 2012-05-24 | 2013-12-04 | 叶福祥 | Cuprous chloride (Cu+, cuCL) ion diaphragm electrodeposition regeneration of circuit board acidic waste etching solution |
| CN103757635A (en) * | 2013-12-13 | 2014-04-30 | 陶克（苏州）机械设备有限公司 | Electrolytic bath, acid etching liquid regenerating equipment and method using electrolytic bath |
| CN105177584A (en) * | 2015-09-09 | 2015-12-23 | 成都虹华环保科技股份有限公司 | Acidic waste etching solution cyclic regeneration system with regenerated liquid treatment function |
-
1986
- 1986-06-17 JP JP14173186A patent/JPS62297476A/en active Granted
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04285182A (en) * | 1990-11-16 | 1992-10-09 | Macdermid Inc | Improved reclaiming process of ammoniacal chloride etchant |
| JPH04314899A (en) * | 1990-11-16 | 1992-11-06 | Macdermid Inc | Method and device for electrolytically sampling heavy metal from waste bath |
| WO2012163238A1 (en) * | 2011-05-31 | 2012-12-06 | 无锡尚德太阳能电力有限公司 | Recycling system and method for treating used etching solution |
| CN103422154A (en) * | 2012-05-24 | 2013-12-04 | 叶福祥 | Cuprous chloride (Cu+, cuCL) ion diaphragm electrodeposition regeneration of circuit board acidic waste etching solution |
| CN103757635A (en) * | 2013-12-13 | 2014-04-30 | 陶克（苏州）机械设备有限公司 | Electrolytic bath, acid etching liquid regenerating equipment and method using electrolytic bath |
| CN103757635B (en) * | 2013-12-13 | 2016-11-23 | 陶克（苏州）机械设备有限公司 | Electrolysis bath and use regenerated acidic etching solution equipment and the renovation process of this electrolysis bath |
| CN105177584A (en) * | 2015-09-09 | 2015-12-23 | 成都虹华环保科技股份有限公司 | Acidic waste etching solution cyclic regeneration system with regenerated liquid treatment function |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6353267B2 (en) | 1988-10-21 |
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