JPH0461986A - Treatment of waste liquid of sulfuric acid/hydrogen peroxide etching - Google Patents

Treatment of waste liquid of sulfuric acid/hydrogen peroxide etching

Info

Publication number
JPH0461986A
JPH0461986A JP2169159A JP16915990A JPH0461986A JP H0461986 A JPH0461986 A JP H0461986A JP 2169159 A JP2169159 A JP 2169159A JP 16915990 A JP16915990 A JP 16915990A JP H0461986 A JPH0461986 A JP H0461986A
Authority
JP
Japan
Prior art keywords
copper
sulfuric acid
hydrogen peroxide
recovered
etching solution
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
Application number
JP2169159A
Other languages
Japanese (ja)
Inventor
Katsuhei Mizui
水井 勝平
Hideyuki Wakashima
若島 英幸
Mitsunori Tanaka
田中 三徳
Taizo Nagaoka
長岡 泰三
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.)
Nissan Engineering Ltd
NEC Toppan Circuit Solutions Toyama Inc
Original Assignee
Nissan Engineering Ltd
NEC Toppan Circuit Solutions Toyama Inc
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 Nissan Engineering Ltd, NEC Toppan Circuit Solutions Toyama Inc filed Critical Nissan Engineering Ltd
Priority to JP2169159A priority Critical patent/JPH0461986A/en
Publication of JPH0461986A publication Critical patent/JPH0461986A/en
Pending legal-status Critical Current

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  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Heat Treatment Of Water, Waste Water Or Sewage (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

PURPOSE:To reduce much treatment cost by a method wherein a raw etching solution is heated after a copper material is immersed in the raw etching solution to decompose residual hydrogen peroxide and this waste etching solution is subjected to electrolytic treatment to recover electrolytic copper and an aqueous sulfuric acid solution. CONSTITUTION:Metal copper 2 to be etched is dissolved in an etching solution. First, a copper material 3 is immersed in a waste etching solution 1 increased in the concn. of copper and, in this state, the waste etching solution is heated to decompose hydrogen peroxide exerting adverse effect on electrolysis. Next, high purity electrolytic copper 7 is precipitated and recovered on a cathode by electrolysis using a lead electrode 5 as an anode and a stainless steel electrode 6 as cathode. The electrolytic treatment solution 8 from which copper is removed is recovered as an aqueous sulfuric acid solution. By this method, electrolytic treatment efficiency can drastically be enhanced and treatment cost is reduced, and the enviromental pollution of a public water area is prevented and the purity of recovered copper and that of recovered sulfuric acid are enhanced and, further, the recycle of recovered sulfuric acid becomes possible.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、硫酸、過酸化水素及び水からなるエツチング
液を用いて、金属銅を溶解した後の銅濃度が高くなった
硫酸・過酸化水素エツチング廃液(以下単にエツチング
廃液と云う)の処理方法に関し、特に電解回収方式を用
いたエツチング廃液中の銅及び硫酸の回収方法に関する
[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to the use of sulfuric acid/peroxide with a high copper concentration after dissolving metallic copper using an etching solution consisting of sulfuric acid, hydrogen peroxide, and water. The present invention relates to a method for treating hydrogen etching waste liquid (hereinafter simply referred to as etching waste liquid), and in particular to a method for recovering copper and sulfuric acid from etching waste liquid using an electrolytic recovery method.

〔従来の技術〕[Conventional technology]

例えば硫酸100〜180 g / 1及び過酸化水素
18〜30 g / J2から成る硫酸・過酸化水素エ
ツチング液は銅を溶解する工程(以下エツチング工程と
云う)に用いられるが、銅の溶解により銅濃度の高くな
ったエツチング廃液(通常の銅濃度、50〜60 g 
/ (1)の処理方法としては、従来よりアルカリ凝集
沈澱法、硫酸銅冷却沈澱法及び電解法が主に採用されて
いる。以下図面を用いて説明する。
For example, a sulfuric acid/hydrogen peroxide etching solution consisting of 100 to 180 g/1 sulfuric acid and 18 to 30 g/J2 hydrogen peroxide is used in the step of dissolving copper (hereinafter referred to as the etching step). Etching waste liquid with high concentration (normal copper concentration, 50-60 g
/ As the treatment method for (1), the alkali coagulation precipitation method, copper sulfate cooling precipitation method, and electrolytic method have been mainly adopted. This will be explained below using the drawings.

アルカリ凝集沈澱法は、まず第3図(a)に示すように
、エツチング工程で金属銅2をエツチングし銅濃度の高
くなったエツチング廃液1は、第3図(b)に示すよう
に、反応工程で苛性ソーダ11の添加により銅成分を水
酸化銅とし、次で第3図(c)に示すように、凝集沈澱
工程でアニオン系高分子の凝集剤12の添加により水酸
化銅16として凝集させ、クラリファイヤ13を用いて
凝集沈澱させる。この後、上澄液14を第3図(d)に
示すように、中和工程で塩酸15添加により中和し公共
水域へ放流する。又、沈降分離した水酸化銅16は第3
図(e)に示す脱水工程で、脱水機17を用いて脱水し
水酸化銅スラッジ18として回収するものである。
In the alkali coagulation precipitation method, first, as shown in FIG. 3(a), the etching waste liquid 1, which has a high copper concentration after etching metal copper 2 in the etching process, undergoes a reaction as shown in FIG. 3(b). In the process, the copper component is converted into copper hydroxide by adding caustic soda 11, and then, as shown in FIG. , and coagulate and precipitate using a clarifier 13. Thereafter, as shown in FIG. 3(d), the supernatant liquid 14 is neutralized by adding 15 liters of hydrochloric acid in a neutralization step and is discharged into public waters. In addition, the copper hydroxide 16 separated by sedimentation is
In the dehydration step shown in FIG. 1(e), the sludge is dehydrated using a dehydrator 17 and recovered as copper hydroxide sludge 18.

硫酸銅冷却析出法は、第4図(a)に示すように、エツ
チング工程で金属銅の溶解により銅濃度の高くなったエ
ツチング廃液1を、硫酸銅冷却工程で冷却熱交換器19
により5°C以下に冷却することにより、結晶硫酸銅2
0として回収する。更に結晶硫酸銅回収後のエツチング
廃液1は、第4図(b)に示す薬注工程で硫酸9及び過
酸化水素10を補充して各濃度を調整し、再びエツチン
グ工程で再利用するものである。
In the copper sulfate cooling precipitation method, as shown in FIG. 4(a), the etching waste liquid 1, which has a high copper concentration due to the dissolution of metallic copper in the etching process, is passed through a cooling heat exchanger 19 in the copper sulfate cooling process.
By cooling to below 5°C, crystalline copper sulfate 2
Collected as 0. Furthermore, the etching waste solution 1 after recovering crystalline copper sulfate is refilled with sulfuric acid 9 and hydrogen peroxide 10 in the chemical injection process shown in FIG. 4(b) to adjust each concentration, and then reused in the etching process. be.

電解法は第5図に示すように、エツチング工程で金属銅
の溶解により銅濃度の高くなったエツチング廃液1は、
陽極として鉛電極5.陰極としてステンレス電極6を用
いた電解工程で電気分解により、陰極に電解銅7を析出
させ回収する。又、銅が除去された電解処理液8は、硫
酸水溶液として回収するものである。
As shown in Fig. 5, the electrolytic method uses the etching waste liquid 1, which has a high copper concentration due to the dissolution of metallic copper during the etching process.
5. Lead electrode as anode. Electrolytic copper 7 is deposited on the cathode and recovered by electrolysis in an electrolytic process using the stainless steel electrode 6 as the cathode. Further, the electrolytically treated solution 8 from which copper has been removed is recovered as an aqueous sulfuric acid solution.

〔発明が解決しようとする課題〕[Problem to be solved by the invention]

上述した従来の処理方法のうち、アルカリ凝集沈澱法は
、多くの処理費用(苛性ソーダ、凝集剤等の処理薬品及
び電力等)と、産業廃棄物処理が必要であり、又、処理
液には塩(硫酸ソーダ等)が含有しているため、排出先
である公共水域の環境負荷にもなっていた。
Among the conventional treatment methods mentioned above, the alkaline coagulation-sedimentation method requires a lot of treatment costs (processing chemicals such as caustic soda, flocculants, electricity, etc.) and industrial waste treatment, and the treatment liquid does not contain salt. Because it contains substances such as sodium sulfate, it also poses an environmental burden to public water bodies where it is discharged.

結晶硫酸銅回収後は、結晶回収装置の管理が複雑なこと
、又、硫酸銅が有価物として価値がなく地域に依っては
産業廃棄物となる等の課題を有していた。
After recovery of crystalline copper sulfate, there are problems such as the complicated management of the crystal recovery equipment and the fact that copper sulfate has no value as a valuable resource and becomes industrial waste depending on the region.

電解法は、処理液であるエツチング廃液に含まれる過酸
化水素が電解装置の陽極としての鉛板の溶出に影響を与
える。それにより鉛電極の寿命が短かく又、回収する電
解銅及び硫酸水溶液の純度も劣る。特に硫酸水溶液につ
いては、純度が低いため有価物としての価値がなく、ア
ルカリ凝集沈澱法等の廃水処理が必要であった。
In the electrolytic method, hydrogen peroxide contained in the etching waste solution, which is the processing solution, affects the elution of the lead plate used as the anode of the electrolytic device. As a result, the life of the lead electrode is shortened, and the purity of the recovered electrolytic copper and sulfuric acid aqueous solution is also poor. In particular, sulfuric acid aqueous solutions have low purity and are therefore of no value as valuables, requiring wastewater treatment such as alkaline coagulation and precipitation.

本発明は、かかる従来課題を解決したエツチング廃液の
処理方法を提供することにある。
The object of the present invention is to provide a method for treating etching waste liquid that solves the problems of the prior art.

〔課題を解決するための手段〕[Means to solve the problem]

本発明の硫酸・過酸化水素エツチング廃液の処理方法は
、硫酸と過酸化水素を含むエツチング廃液に銅材を浸漬
させたのち加熱して残存する過酸化水素を分解させる工
程と、過酸化水素を分解したこのエツチング廃液を電解
処理して電解銅と硫酸水溶液を回収する工程とを含んで
構成される。
The method of treating sulfuric acid/hydrogen peroxide etching waste liquid of the present invention includes a step of immersing a copper material in an etching waste liquid containing sulfuric acid and hydrogen peroxide, and then heating it to decompose the remaining hydrogen peroxide. The method includes a step of electrolytically treating the decomposed etching waste solution to recover electrolytic copper and an aqueous sulfuric acid solution.

〔実施例〕〔Example〕

次に、本発明について図面を参照して説明する。 Next, the present invention will be explained with reference to the drawings.

第1図は本発明の第1の実施例を説明するための処理槽
の模式断面図である。
FIG. 1 is a schematic sectional view of a processing tank for explaining a first embodiment of the present invention.

第1図(a)に示すように、エツチング対象の金属銅2
は、エツチング工程でエツチング液(WL酸100〜1
80 g / II 、過酸化水素18〜30g/()
にて溶解される。銅濃度の高くなったエツチング廃液1
(通常の銅濃度、50〜60g/l)は、まず第1図(
b)に示すように、前処理工程で触媒として銅材3を浸
漬し、加熱ヒータ4を用い40〜60℃で1〜2時間加
熱して電解に悪影響を与える過酸化水素を分解する。反
応は下記(1)及び(2)の反応式がらなり、分解後の
過酸化水素濃度は5 g / II以下とすることが出
来る。
As shown in FIG. 1(a), the metal copper 2 to be etched
In the etching process, an etching solution (WL acid 100-1
80 g/II, hydrogen peroxide 18-30 g/()
It is dissolved in Etching waste liquid with high copper concentration 1
(Normal copper concentration, 50 to 60 g/l) is first shown in Figure 1 (
As shown in b), in the pretreatment step, a copper material 3 is immersed as a catalyst and heated using a heater 4 at 40 to 60° C. for 1 to 2 hours to decompose hydrogen peroxide that adversely affects electrolysis. The reaction has the following reaction formulas (1) and (2), and the hydrogen peroxide concentration after decomposition can be 5 g/II or less.

H2SO4+H2O2+Cu  −”  CuSO4+
2H20(1,)2H20□ → 2H20+ 02 
       (2)次に第1図(C)に示す電解工程
で、陽極として鉛電8i!5を、陰極としてステンレス
電極6を用いた電気分解く電流密度;1〜2A/dm2
、電解所要時間;20〜30H)により陰極に高純度の
電解銅7を析出させ回収する。又、銅が除去された電解
処理液8は、硫酸水溶液として回収する。
H2SO4+H2O2+Cu −”CuSO4+
2H20(1,)2H20□ → 2H20+ 02
(2) Next, in the electrolytic process shown in FIG. 1(C), lead electrode 8i! Current density during electrolysis using stainless steel electrode 6 as a cathode; 1 to 2 A/dm2
, electrolysis time required; 20 to 30 hours), high-purity electrolytic copper 7 is deposited on the cathode and recovered. Further, the electrolytically treated liquid 8 from which copper has been removed is recovered as an aqueous sulfuric acid solution.

第2図は本発明の第2の実施例を説明するための処理槽
の模式断面図である。
FIG. 2 is a schematic sectional view of a processing tank for explaining a second embodiment of the present invention.

まず第1の実施例と同様に、エツチングにより銅濃度の
高くなったエツチング廃液1中に銅材を浸漬して加熱す
ることにより過酸化水素を分解する。次で第2図(a>
に示すように、鉛電[i5及びステンレス電極6を用い
る電気分解により電解銅7を回収する。
First, as in the first embodiment, hydrogen peroxide is decomposed by immersing a copper material in the etching waste liquid 1 whose copper concentration has been increased by etching and heating it. Next, Figure 2 (a>
As shown in FIG. 2, electrolytic copper 7 is recovered by electrolysis using a lead electrode [i5] and a stainless steel electrode 6.

この電解工程で回収した電解処理液8は第2図(b)に
示す薬注工程で、微量の硫酸9及び過酸化水素10(1
8〜30g/ρ)を補充して各濃度を調整し、新液と同
等のエツチング液としてエツチング工程で再利用する。
The electrolytically treated solution 8 recovered in this electrolytic process is used in the chemical injection process shown in FIG.
8 to 30 g/ρ) to adjust each concentration, and reused in the etching process as an etching solution equivalent to a new solution.

〔発明の効果〕〔Effect of the invention〕

以上説明した様に本発明は、エツチング廃液の過酸化水
素を分解した後に電解処理を行うことにより、電解処理
効率を飛躍的に高めることが出来、従来の方式であるア
ルカリ凝集沈澱法、硫酸銅冷却析出法、電解法に比べ、
処理費用が低減され、産業廃棄物としての処理が不要と
なり、公共水域の環境汚染の防止に役立ち、回収する銅
と硫酸の純度を向上させることができ、更に回収する硫
酸のリサイクルが可能であるという効果がある。
As explained above, the present invention dramatically improves the efficiency of electrolytic treatment by performing electrolytic treatment after decomposing hydrogen peroxide in etching waste liquid. Compared to the cooling precipitation method and electrolytic method,
Processing costs are reduced, treatment as industrial waste is no longer necessary, it helps prevent environmental pollution of public water bodies, the purity of the recovered copper and sulfuric acid can be improved, and the recovered sulfuric acid can be recycled. There is an effect.

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

第1図及び第2図は本発明の第1及び第2の実施例を説
明するための処理槽の模式断面図、第3図〜第5図は従
来の処理方法を説明するための処理槽の模式断面図であ
る。 1・・・エツチング廃液、2・・・金属銅、3・・・銅
材、4・・・加熱ヒータ、5・・・鉛電極、6・・・ス
テンレス電極、7・・・電解銅、8・・・電解処理液、
9・・・硫酸、10・・・過酸化水素、11・・・苛性
ソーダ、12・・・凝集剤、13・・・クラリファイヤ
、14・・・上澄液、15・・・塩酸、16・・・水酸
化銅、17・・・脱水機、18・・・水酸化銅スラッジ
、1つ・・・冷却熱交換器、20・・・結晶硫酸銅。
1 and 2 are schematic sectional views of processing tanks for explaining the first and second embodiments of the present invention, and FIGS. 3 to 5 are processing tanks for explaining conventional processing methods. FIG. DESCRIPTION OF SYMBOLS 1... Etching waste liquid, 2... Metallic copper, 3... Copper material, 4... Heater, 5... Lead electrode, 6... Stainless steel electrode, 7... Electrolytic copper, 8 ...electrolytic treatment solution,
9... Sulfuric acid, 10... Hydrogen peroxide, 11... Caustic soda, 12... Flocculant, 13... Clarifier, 14... Supernatant liquid, 15... Hydrochloric acid, 16... ...Copper hydroxide, 17...Dehydrator, 18...Copper hydroxide sludge, 1...Cooling heat exchanger, 20...Crystalline copper sulfate.

Claims (1)

【特許請求の範囲】[Claims] 硫酸と過酸化水素を含むエッチング廃液に銅材を浸漬さ
せたのち加熱して残存する過酸化水素を分解させる工程
と、過酸化水素を分解したこのエッチング廃液を電解処
理して電解銅と硫酸水溶液を回収する工程とを含むこと
を特徴とする硫酸・過酸化水素エッチング廃液の処理方
法。
The copper material is immersed in an etching waste solution containing sulfuric acid and hydrogen peroxide, then heated to decompose the remaining hydrogen peroxide, and the etching waste solution that has decomposed the hydrogen peroxide is electrolytically treated to form an electrolytic copper and sulfuric acid aqueous solution. 1. A method for treating sulfuric acid/hydrogen peroxide etching waste liquid, the method comprising the step of recovering sulfuric acid/hydrogen peroxide etching waste.
JP2169159A 1990-06-27 1990-06-27 Treatment of waste liquid of sulfuric acid/hydrogen peroxide etching Pending JPH0461986A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2169159A JPH0461986A (en) 1990-06-27 1990-06-27 Treatment of waste liquid of sulfuric acid/hydrogen peroxide etching

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2169159A JPH0461986A (en) 1990-06-27 1990-06-27 Treatment of waste liquid of sulfuric acid/hydrogen peroxide etching

Publications (1)

Publication Number Publication Date
JPH0461986A true JPH0461986A (en) 1992-02-27

Family

ID=15881374

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2169159A Pending JPH0461986A (en) 1990-06-27 1990-06-27 Treatment of waste liquid of sulfuric acid/hydrogen peroxide etching

Country Status (1)

Country Link
JP (1) JPH0461986A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002081380A1 (en) * 2001-04-09 2002-10-17 Ak Properties, Inc. Apparatus and method for removing hydrogen peroxide from spent pickle liquor
JP2006080559A (en) * 2005-10-31 2006-03-23 Toshiba Corp Method for manufacturing semiconductor apparatus, semiconductor manufacturing apparatus and semiconductor apparatus
JP2009004807A (en) * 2008-09-12 2009-01-08 Toshiba Corp Method of manufacturing semiconductor device and apparatus for manufacturing the semiconductor device
JP2009160486A (en) * 2007-12-28 2009-07-23 Mitsubishi Gas Chem Co Inc Treatment apparatus for copper etching waste liquid containing hydrogen peroxide
CN104150569A (en) * 2014-08-20 2014-11-19 成都飞创科技有限公司 Method and apparatus for processing purified desulfurization waste water
CN112708885A (en) * 2020-12-16 2021-04-27 华润环保发展有限公司 Recycling method and system for copper-etching waste nitric acid

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002081380A1 (en) * 2001-04-09 2002-10-17 Ak Properties, Inc. Apparatus and method for removing hydrogen peroxide from spent pickle liquor
JP2004532104A (en) * 2001-04-09 2004-10-21 エイケイ・プロパティーズ・インコーポレイテッド Apparatus and method for removing hydrogen peroxide from pickling waste liquid
JP2006080559A (en) * 2005-10-31 2006-03-23 Toshiba Corp Method for manufacturing semiconductor apparatus, semiconductor manufacturing apparatus and semiconductor apparatus
JP2009160486A (en) * 2007-12-28 2009-07-23 Mitsubishi Gas Chem Co Inc Treatment apparatus for copper etching waste liquid containing hydrogen peroxide
JP2009004807A (en) * 2008-09-12 2009-01-08 Toshiba Corp Method of manufacturing semiconductor device and apparatus for manufacturing the semiconductor device
CN104150569A (en) * 2014-08-20 2014-11-19 成都飞创科技有限公司 Method and apparatus for processing purified desulfurization waste water
CN112708885A (en) * 2020-12-16 2021-04-27 华润环保发展有限公司 Recycling method and system for copper-etching waste nitric acid

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