JPH0533168A - Method for recovering hydrochloric acid and copper sulfate from waste copper chloride solution - Google Patents

Method for recovering hydrochloric acid and copper sulfate from waste copper chloride solution

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Publication number
JPH0533168A
JPH0533168A JP15925891A JP15925891A JPH0533168A JP H0533168 A JPH0533168 A JP H0533168A JP 15925891 A JP15925891 A JP 15925891A JP 15925891 A JP15925891 A JP 15925891A JP H0533168 A JPH0533168 A JP H0533168A
Authority
JP
Japan
Prior art keywords
hydrochloric acid
copper
copper sulfate
sulfuric acid
recover
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
JP15925891A
Other languages
Japanese (ja)
Other versions
JP3085549B2 (en
Inventor
Keita Yamada
慶太 山田
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.)
Asaka Riken Industrial Co Ltd
Original Assignee
Asaka Riken Industrial Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Asaka Riken Industrial Co Ltd filed Critical Asaka Riken Industrial Co Ltd
Priority to JP03159258A priority Critical patent/JP3085549B2/en
Publication of JPH0533168A publication Critical patent/JPH0533168A/en
Application granted granted Critical
Publication of JP3085549B2 publication Critical patent/JP3085549B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • ing And Chemical Polishing (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Heat Treatment Of Water, Waste Water Or Sewage (AREA)

Abstract

PURPOSE:To efficiently reutilize resources, to form an effective recycling line and to recover hydrochloric acid and copper sulfate by separating and recovering the useful hydrochloric acid and copper sulfate from a waste copper chloride soln. discharged from an etching stage. CONSTITUTION:Concd. sulfuric acid is allowed to react with a waste copper soln. contg. hydrochloric acid to recover hydrochloric acid, and the liq. mixture is heated and concentrated to liberate and recover hydrochloric acid. The concd. waste soln. is further crystallized, solid and liq. are separated, the liq. mixture of hydrochloric acid and sulfuric acid is recovered, and copper sulfate pentahydrate is crystallized and brought out. The hydrous crystal is refined to recover a copper sulfate crystal. The recovered hydrochloric acid and sulfuric acid are distilled to obtain >=35% aq. hydrochloric acid. Furthermore, sulfuric acid is added to the bottoms to obtain >=35% aq. hydrochloric acid.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、銅プリント基板のエッ
チング工程により排出される塩化銅廃液から塩酸及び硫
酸銅を分離回収する回収方法に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recovery method for separating and recovering hydrochloric acid and copper sulfate from a copper chloride waste liquid discharged in an etching process of a copper printed board.

【0002】[0002]

【従来の技術】従来、銅プリント配線基板のエッチング
には、塩化第二銅を主成分とし、これに塩酸及び過酸化
水素を添加したエッチング剤が多量に使用されている。
エッチング後、その廃液は塩化銅溶液と成って排出され
る。この塩化銅廃液からは、化学還元処理によって銅を
回収する方法が採られていた。
2. Description of the Related Art Conventionally, a large amount of an etching agent containing cupric chloride as a main component and hydrochloric acid and hydrogen peroxide added thereto has been used for etching a copper printed wiring board.
After etching, the waste liquid becomes a copper chloride solution and is discharged. A method of recovering copper from this copper chloride waste liquid by a chemical reduction treatment has been adopted.

【0003】[0003]

【発明が解決しようとする課題】しかし、かかる従来の
処理方法では、銅は回収されるが、その後の廃液処理に
問題があった。すなわち、かかる廃液は酸性が強く、こ
のまま放流することはできず、中和法により中和して廃
棄放流しなければならなかった。そのため、中和費用が
嵩むばかりでなく、たとえ中和したとしても継続的かつ
大量の処理水及び大量の金属スラッジは、環境に与える
影響も無視できない状態にある。また、廃液処理の許容
量を越えた所謂未処理廃液のダブつきは、製品のエッチ
ング加工量にも影響を及ぼすようになってきており、逆
にエッチング加工量は、廃液の処理能力如何に係わるの
が現状となってきていた。また近年の流れとして、工業
生産過程における地域環境保全や資源の効率的利用への
対応は、重要な問題となってきていた。このようなな現
状から、エッチング加工業界にあっては、かかる廃液の
効率的処理、および公害の未然防止が長年の懸案と成っ
ていた。
However, in such a conventional treatment method, although copper was recovered, there was a problem in the subsequent waste liquid treatment. That is, such a waste liquid has a strong acidity and cannot be discharged as it is. Therefore, the waste liquid must be neutralized by the neutralization method and discharged. Therefore, not only the neutralization cost is high, but even if the neutralization is performed, the continuous and large amount of treated water and the large amount of metal sludge have a non-negligible effect on the environment. In addition, the so-called dubbing of so-called unprocessed waste liquid, which exceeds the allowable amount of waste liquid treatment, has come to affect the etching amount of the product. Was becoming the current situation. In addition, as a trend in recent years, it has become an important issue to cope with regional environmental conservation and efficient use of resources in the industrial production process. From such a current situation, in the etching processing industry, efficient treatment of such waste liquid and prevention of pollution have been a long-standing concern.

【0004】そこで、本発明は、これら問題点の解決を
目的として成されたもので、エッチング処理工程から排
出される塩化銅廃液から、有用性のある塩酸及び硫酸銅
を分離回収することにより、効率的な資源の再利用を計
り、無駄のないリサイクル循環系を形成することのでき
る、塩化銅廃液からの塩酸及び硫酸銅の回収方法を提供
するものである。
Therefore, the present invention has been made for the purpose of solving these problems, and by separating and recovering useful hydrochloric acid and copper sulfate from the copper chloride waste liquid discharged from the etching process, It is intended to provide a method for recovering hydrochloric acid and copper sulfate from a copper chloride waste liquid, capable of efficiently recycling resources and forming a recycling cycle without waste.

【0005】[0005]

【課題を解決するための手段】本発明は、上記目的を達
成するため次の工程を採る。図1は、その工程の概略フ
ローを示す図である。先ず、銅プリント配線基板のエッ
チング工程により排出される塩化水素、塩化第二銅を含
む塩酸含有銅廃液を原料とする。この塩酸含有銅廃液
に、濃硫酸を添加混合して反応させ、発生する塩酸を回
収すると共に、該混合液を濃縮塔で加熱濃縮して、発生
する気体を液化し塩酸を取り出し回収する。この濃縮後
の濃縮液には、まだ塩酸が残存しており、硫酸と混合し
た銅濃縮廃液と成っている。
The present invention employs the following steps in order to achieve the above object. FIG. 1 is a diagram showing a schematic flow of the process. First, a hydrochloric acid-containing copper waste liquid containing hydrogen chloride and cupric chloride discharged in the etching process of a copper printed wiring board is used as a raw material. Concentrated sulfuric acid is added to and mixed with this hydrochloric acid-containing copper waste liquid to react, and the generated hydrochloric acid is recovered, and the mixed liquid is heated and concentrated in a concentrating tower to liquefy the generated gas and collect and recover the hydrochloric acid. Hydrochloric acid still remains in the concentrated liquid after the concentration, which is a copper concentrated waste liquid mixed with sulfuric acid.

【0006】この濃縮廃液を晶析させ、気相に塩酸、液
相には塩酸と硫酸の混合物、固相には硫酸銅五水和物
(CuSO4 5H2O) を得る。かかる気相の塩酸は回収され、
また、かかる液相と固相は分離され、液相の塩酸と硫酸
の混合物は、分離後、母液として濃縮缶に戻される。固
相の硫酸銅五水和物には、未だ塩化水素が含有するた
め、次の工程を行う。硫酸銅五水和物を塩酸を除去した
硫酸含有銅廃液に溶解し、これを晶析して取り出した硫
酸銅五水和物を、さらに洗浄水で洗浄して遠心分離機を
用いて生成して、塩化水素が低減されて精製された硫酸
銅結晶を回収すことができる。残りは、前出の硫酸銅五
水和物の溶解に使用されて循環することになる。これに
より、塩酸含有銅廃液を、塩酸と硫酸銅とに分離し回収
することができる。
This concentrated waste liquid is crystallized to obtain hydrochloric acid in the gas phase, a mixture of hydrochloric acid and sulfuric acid in the liquid phase, and copper sulfate pentahydrate (CuSO 4 5H 2 O) in the solid phase. Such vapor phase hydrochloric acid is recovered,
Further, the liquid phase and the solid phase are separated, and the liquid-phase mixture of hydrochloric acid and sulfuric acid is separated and then returned to the concentration canister as a mother liquor. Since the solid-phase copper sulfate pentahydrate still contains hydrogen chloride, the next step is performed. Copper sulfate pentahydrate was dissolved in a sulfuric acid-containing copper waste liquid from which hydrochloric acid had been removed, and the copper sulfate pentahydrate taken out by crystallization was further washed with washing water and produced using a centrifuge. Thus, purified copper sulfate crystals with reduced hydrogen chloride can be recovered. The rest will be used to circulate the copper sulphate pentahydrate mentioned above and circulate. Thereby, the hydrochloric acid-containing copper waste liquid can be separated into hydrochloric acid and copper sulfate and collected.

【0007】次に、前記の回収した塩化水素及び塩酸の
濃度を上げるため、さらに上記工程に次の工程を付加す
る。前記工程で回収した塩化水素及び塩酸を蒸留する。
これにより、留出液は、濃度35%以上の塩酸とするこ
とができる。ここで用いられる蒸留装置は、通常一般的
な公知のものが用いられている。さらに、上記工程の
後、蒸留塔底の蒸留缶またはボトムから系外に抜き出さ
れたいわゆる缶出液には、もはや蒸留では回収すること
のできない、共沸状態の塩酸が存在するため、これを更
に、塩酸を回収するため抽出蒸留工程を付加する。共沸
剤として硫酸を添加し、共沸点を移動させて塩酸を回収
する。これにより濃度35%以上の塩酸を取り出すこと
が可能となる。共沸剤として用いられる硫酸は、当初は
共沸剤として硫酸が添加されるが、抽出蒸留の缶出液に
は希釈された硫酸が含まれ、これを濃縮することによ
り、以後これを共沸剤として使用する。
Next, in order to increase the concentrations of the recovered hydrogen chloride and hydrochloric acid, the following steps are added to the above steps. The hydrogen chloride and hydrochloric acid recovered in the above step are distilled.
As a result, the distillate can be hydrochloric acid having a concentration of 35% or more. As the distillation apparatus used here, a commonly known distillation apparatus is generally used. Further, after the above step, the so-called bottom liquid extracted from the distillation can or bottom at the bottom of the distillation column to the outside of the system contains azeotropic hydrochloric acid which can no longer be recovered by distillation. Further, an extractive distillation step is added to recover hydrochloric acid. Sulfuric acid is added as an azeotropic agent, and the azeotropic point is moved to recover hydrochloric acid. This makes it possible to take out hydrochloric acid having a concentration of 35% or more. Sulfuric acid used as an azeotropic agent is initially added as an azeotropic agent, but the bottom liquid of extractive distillation contains diluted sulfuric acid, which is then azeotroped by concentrating it. Used as an agent.

【0008】なお、各工程の反応条件は、特に限定的な
ものではなく、それぞれの工程の対象物の組成により適
宜、最適の温度、圧力が決定される。
The reaction conditions in each step are not particularly limited, and the optimum temperature and pressure are appropriately determined depending on the composition of the object of each step.

【0009】[0009]

【作用】かかる工程により、塩酸含有銅廃液は、硫酸の
添加により塩化銅を硫酸銅に換え、硫酸銅の結晶物を得
ると共に、濃縮及び晶析の工程で気相又は液相として生
じる塩酸は、蒸留により濃度35%以上の塩酸が取り出
され、かつ缶出液に残留する塩酸は、抽出蒸留によって
濃縮され濃度35%以上の塩酸を取り出される。この時
の缶出液は、濃縮され再び共沸剤として、再利用され
る。
In this process, the hydrochloric acid-containing copper waste liquid is converted from copper chloride to copper sulfate by the addition of sulfuric acid to obtain copper sulfate crystals, and the hydrochloric acid produced in the vapor phase or liquid phase in the concentration and crystallization steps is eliminated. The hydrochloric acid having a concentration of 35% or more is removed by distillation, and the hydrochloric acid remaining in the bottom liquid is concentrated by extractive distillation to remove the hydrochloric acid having a concentration of 35% or more. The bottom solution at this time is concentrated and reused again as an azeotropic agent.

【0010】[0010]

【効果】以上の構成により、本発明は以下のような効果
を奏する。塩酸含有銅廃液に硫酸を添加して、硫酸銅と
塩酸を分離して回収するため、エッチング工程で排出さ
れた廃液を、廃棄放流することがなく、有効に活用する
ことができる。精製した硫酸銅は、顔料、メッキ液、試
薬、及び農薬、等の原料として付加価値の高い製品とし
て有効に活用することができる。また、分離回収した塩
酸も、本発明の蒸留、抽出蒸留工程を経ることにより濃
度の高い塩酸とすることができるため、工業的利用性の
ある塩酸溶液として再利用が可能となる。
[Effect] With the above structure, the present invention has the following effects. Since sulfuric acid is added to the hydrochloric acid-containing copper waste liquid to separate and collect copper sulfate and hydrochloric acid, the waste liquid discharged in the etching step can be effectively used without being discharged and discharged. Purified copper sulfate can be effectively used as a product with high added value as a raw material for pigments, plating solutions, reagents, agricultural chemicals, and the like. Further, the separated and recovered hydrochloric acid can be converted into a highly concentrated hydrochloric acid by the distillation and extractive distillation steps of the present invention, and can be reused as a hydrochloric acid solution having industrial utility.

【0011】さらに、添加する硫酸は、銅と結合して硫
酸銅の結晶として使用されるもの以外は、母液として系
内に戻して再利用されるため、消費した分のみを補充す
るだけでよい。したがって、廃液はすべて有用な硫酸銅
と塩酸に換えられ、資源の効率的な回収をすることがで
きる。硫酸は消費分のみが補充され、及び僅かの排水が
排出されるのみであるため、閉鎖したリサイクル循環系
を形成することができ、無駄に破棄される含有成分が無
くなる利点がある。
Further, the sulfuric acid to be added is returned to the system as a mother liquor and reused except for those used as crystals of copper sulfate by combining with copper, so that only the consumed amount needs to be replenished. . Therefore, all the waste liquid can be replaced with useful copper sulfate and hydrochloric acid, and the resources can be efficiently recovered. Since sulfuric acid is replenished only with the consumed amount and a small amount of waste water is discharged, there is an advantage that it is possible to form a closed recycle circulation system and there is no waste component to be discarded.

【0012】中和法により中和して廃液を処理するもの
でないため、コスト節減に役立つばかりでなく、公害防
止、及び環境保全にも寄与するものである。
Since the waste liquid is not neutralized by the neutralization method, it not only contributes to cost reduction but also contributes to pollution prevention and environmental protection.

【0013】[0013]

【実施例】以下に、本発明の実施例を示すが、本発明は
これに限定されるものではない。表1に示す実施例No.1
〜No.7は、塩化水素aと、塩化第二銅bを含む銅プリン
ト配線基板のエッチングで生じた塩酸含有の銅廃液cに
濃硫酸dを加え、濃縮塔で濃縮した後に、回収した塩酸
eの濃度と回収量、及び塩酸・硫酸混合の銅濃縮廃液量
fを示したものである。なお、この時の濃縮塔での濃縮
条件は、最適値の一つであるP=265.8 Torr、T=25°
Cとした。
EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. Example No. 1 shown in Table 1
No. 7 is hydrochloric acid recovered after adding concentrated sulfuric acid d to hydrochloric acid-containing copper waste liquid c generated by etching a copper printed wiring board containing hydrogen chloride a and cupric chloride b and concentrating in a concentrating tower. The figure shows the concentration and recovery amount of e, and the copper concentrated waste liquid amount f of a mixture of hydrochloric acid and sulfuric acid. The concentration conditions in the concentration tower at this time are one of the optimum values, P = 265.8 Torr, T = 25 °
It was set to C.

【0014】[0014]

【表1】 表2は、濃縮塔から回収された塩酸・硫酸混合の銅濃
縮廃液fを、更に晶析して得た塩酸gの濃度と回収量、
及び晶析塔から取り出された硫酸銅五水和物hの重量
と、これに含まれる塩化水素iの量を示したものであ
る。なお、ここで晶析塔における晶析条件は、最適値の
一つであるP=15.5 Torr 、T=30°Cとした。
[Table 1] Table 2 shows the concentration and recovery amount of hydrochloric acid g obtained by further crystallization of the copper concentrated waste liquid f containing a mixture of hydrochloric acid and sulfuric acid recovered from the concentration tower.
And the weight of copper sulfate pentahydrate h taken out from the crystallization tower and the amount of hydrogen chloride i contained therein. Here, the crystallization conditions in the crystallization tower were P = 15.5 Torr and T = 30 ° C., which are one of the optimum values.

【0015】[0015]

【表2】 表3は、晶析塔から取り出された硫酸五水和物hの塩
化水素iの量(表2と同一。)を低減させるため、硫酸
五水和物hの約4倍重量相当の塩酸を除去した硫酸含有
銅廃液jに当該硫酸五水和物hを溶解し、その溶液を、
さらに別の晶析塔で晶析して回収した硫酸銅五水和物k
と、その中の塩化水素lの量を示したものである。
[Table 2] Table 3 shows that in order to reduce the amount of hydrogen chloride i in the sulfuric acid pentahydrate h taken out from the crystallization column (same as in Table 2), about 4 times the weight of hydrochloric acid equivalent to sulfuric acid pentahydrate h was added. The sulfuric acid pentahydrate h is dissolved in the removed sulfuric acid-containing copper waste liquid j, and the solution is
Copper sulphate pentahydrate k which was recovered by crystallization in another crystallization tower
And the amount of hydrogen chloride in it.

【0016】[0016]

【表3】 表4は、上記別の晶析塔で晶析して回収した硫酸銅五
水和物kをさらに低減させるために、その等重量相当の
水mで洗浄し、遠心分離機にて遠心分離をさせた場合
の、硫酸銅五水和物nと、その中の塩化水素oの量を示
したものである。
[Table 3] Table 4 shows that in order to further reduce the copper sulfate pentahydrate k crystallized and recovered in another crystallization tower, water was washed with an equivalent weight of water m and centrifugation was performed with a centrifuge. It shows the amount of copper sulfate pentahydrate n and the amount of hydrogen chloride o therein in the case of being allowed to do so.

【0017】[0017]

【表4】 表5は、濃縮で得た塩酸eと、晶析で得た塩酸gとの
混合液を蒸留塔で蒸留し、得られた留出液中の塩酸p
と、缶出液中の塩酸qの重量及び濃度を示したものであ
る。
[Table 4] Table 5 shows that hydrochloric acid p in the distillate obtained by distilling a mixed solution of hydrochloric acid e obtained by concentration and hydrochloric acid g obtained by crystallization in a distillation column.
And the weight and concentration of hydrochloric acid q in the bottom solution.

【0018】[0018]

【表5】 表6は、缶出液中の塩酸qに共沸剤としての硫酸を添
加して抽出蒸留塔で抽出蒸留した結果得られた、塩酸r
の濃度及び重量を示したものである。
[Table 5] Table 6 shows that hydrochloric acid r obtained by adding sulfuric acid as an azeotropic agent to hydrochloric acid q in the bottom liquid and performing extractive distillation in the extractive distillation column
It shows the concentration and weight of.

【0019】[0019]

【表6】 [Table 6]

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

【図1】本発明の回収方法の工程概略を表わすフロー図
である。
FIG. 1 is a flowchart showing an outline of steps of a recovery method of the present invention.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 C23G 1/36 7308−4K H05K 3/06 Z 6921−4E ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C23G 1/36 7308-4K H05K 3/06 Z 6921-4E

Claims (3)

【特許請求の範囲】[Claims] 【請求項1】エッチング工程により排出される塩化銅廃
液に硫酸を反応させ、該反応液を濃縮させて塩化水素を
回収し、その後、晶析工程により該濃縮液を塩酸と硫酸
銅結晶とに分離し回収することを特徴とする塩化銅廃液
からの塩酸及び硫酸銅の回収方法。
1. A copper chloride waste solution discharged in an etching step is reacted with sulfuric acid to concentrate the reaction solution to recover hydrogen chloride, and then the concentrated solution is converted into hydrochloric acid and copper sulfate crystals in a crystallization step. A method for recovering hydrochloric acid and copper sulfate from a copper chloride waste liquid, characterized by separating and recovering.
【請求項2】前記塩化水素及び塩酸の回収工程の後にさ
らに蒸留工程を付加し、濃塩酸の留出液を回収すること
を特徴とする請求項1記載の塩化銅廃液からの塩酸及び
硫酸銅の回収方法。
2. The hydrochloric acid and copper sulfate from the copper chloride waste liquid according to claim 1, further comprising a distillation step after the step of recovering hydrogen chloride and hydrochloric acid to recover a distillate of concentrated hydrochloric acid. Recovery method.
【請求項3】前記蒸留工程の缶出液に、共沸剤として硫
酸を添加して抽出蒸留を行い、濃塩酸を留出液として回
収すると共に、液相の硫酸を濃縮して前記抽出蒸留の共
沸剤として用いることを特徴とする請求項2記載の塩化
銅廃液からの塩酸及び硫酸銅の回収方法。
3. Extractive distillation is carried out by adding sulfuric acid as an azeotropic agent to the bottom liquid of the distillation step to recover concentrated hydrochloric acid as a distillate and to concentrate the liquid phase sulfuric acid to carry out the extractive distillation. The method for recovering hydrochloric acid and copper sulfate from a copper chloride waste liquid according to claim 2, which is used as an azeotropic agent.
JP03159258A 1991-06-29 1991-06-29 Recovery method of hydrochloric acid and copper sulfate from copper chloride waste liquid Expired - Lifetime JP3085549B2 (en)

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Cited By (15)

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EP0739228A4 (en) * 1994-01-12 1998-05-20 Fsi Int Recycling of wafer cleaning substances
KR20000058364A (en) * 2000-05-02 2000-10-05 정진동 The methods of copper sulpate extract from copper erodibility waste sludge in the electronic circuit board panel.
KR100352378B1 (en) * 2000-03-09 2002-09-11 서안켐텍 주식회사 Process for simultaneously preparing cupric sulfate and zinc chloride
KR100351942B1 (en) * 2000-03-17 2002-09-12 김수태 Process for simultaneously preparing cupric sulfate and calcium chloride from cupric chloride waste
KR20020094180A (en) * 2001-06-12 2002-12-18 김수태 Process for preparing double salt of copper sulfate and sodium chloride
KR100380033B1 (en) * 2000-03-09 2003-04-14 서안켐텍 주식회사 Process for preparing pure cupric sulphate from waste cupric chloride
KR100380030B1 (en) * 2000-05-10 2003-05-09 서안켐텍 주식회사 Process for preparing curric sulfate using the mixture of methyl acetate and methanol
KR20040033146A (en) * 2002-10-11 2004-04-21 김영준 The recovery equipment and method of copper sulfate from spent soft etching solution for recycling etching solution
KR100440469B1 (en) * 2001-12-22 2004-07-14 삼성전기주식회사 Recycling method of waste sulfuric acid etching solution, waste chloric acid etching solution and waste nitric acid etching solution
KR100504235B1 (en) * 2002-10-14 2005-07-27 서안켐텍 주식회사 Process for preparing mono hydrate copper chloride soln.
KR100620112B1 (en) * 2004-11-04 2006-09-12 이재철 The making method of watery copper sulphate and making device
JP2006291352A (en) * 2005-03-04 2006-10-26 Phibro-Tech Inc Regeneration of cupric etchants and recovery of copper sulfate
JP2007117874A (en) * 2005-10-27 2007-05-17 Ebara Corp Method and apparatus for treating wastewater containing component to be crystallized
JP2010172845A (en) * 2009-01-30 2010-08-12 Densho Engineering Co Ltd Etching waste liquid treatment method
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EP0739228A4 (en) * 1994-01-12 1998-05-20 Fsi Int Recycling of wafer cleaning substances
KR100352378B1 (en) * 2000-03-09 2002-09-11 서안켐텍 주식회사 Process for simultaneously preparing cupric sulfate and zinc chloride
KR100380033B1 (en) * 2000-03-09 2003-04-14 서안켐텍 주식회사 Process for preparing pure cupric sulphate from waste cupric chloride
KR100351942B1 (en) * 2000-03-17 2002-09-12 김수태 Process for simultaneously preparing cupric sulfate and calcium chloride from cupric chloride waste
KR20000058364A (en) * 2000-05-02 2000-10-05 정진동 The methods of copper sulpate extract from copper erodibility waste sludge in the electronic circuit board panel.
KR100380030B1 (en) * 2000-05-10 2003-05-09 서안켐텍 주식회사 Process for preparing curric sulfate using the mixture of methyl acetate and methanol
KR20020094180A (en) * 2001-06-12 2002-12-18 김수태 Process for preparing double salt of copper sulfate and sodium chloride
KR100440469B1 (en) * 2001-12-22 2004-07-14 삼성전기주식회사 Recycling method of waste sulfuric acid etching solution, waste chloric acid etching solution and waste nitric acid etching solution
KR20040033146A (en) * 2002-10-11 2004-04-21 김영준 The recovery equipment and method of copper sulfate from spent soft etching solution for recycling etching solution
KR100504235B1 (en) * 2002-10-14 2005-07-27 서안켐텍 주식회사 Process for preparing mono hydrate copper chloride soln.
KR100620112B1 (en) * 2004-11-04 2006-09-12 이재철 The making method of watery copper sulphate and making device
JP2006291352A (en) * 2005-03-04 2006-10-26 Phibro-Tech Inc Regeneration of cupric etchants and recovery of copper sulfate
JP2007117874A (en) * 2005-10-27 2007-05-17 Ebara Corp Method and apparatus for treating wastewater containing component to be crystallized
JP4503523B2 (en) * 2005-10-27 2010-07-14 荏原エンジニアリングサービス株式会社 A method and apparatus for treating wastewater containing a crystallization target component.
JP2010172845A (en) * 2009-01-30 2010-08-12 Densho Engineering Co Ltd Etching waste liquid treatment method
CN113402096A (en) * 2021-06-17 2021-09-17 遂宁市星河环境技术有限公司 Stripping and hanging waste liquid treatment method for PCB factory

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