JPH0461986A - Treatment of waste liquid of sulfuric acid/hydrogen peroxide etching - Google Patents
Treatment of waste liquid of sulfuric acid/hydrogen peroxide etchingInfo
- 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
Links
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 51
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000005530 etching Methods 0.000 title claims abstract description 41
- 239000002699 waste material Substances 0.000 title claims abstract description 25
- 239000007788 liquid Substances 0.000 title claims description 20
- 239000010949 copper Substances 0.000 claims abstract description 37
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 abstract description 7
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 5
- 239000010935 stainless steel Substances 0.000 abstract description 5
- 239000003984 copper intrauterine device Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 230000002411 adverse Effects 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 9
- 229910000365 copper sulfate Inorganic materials 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 6
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 5
- 239000005750 Copper hydroxide Substances 0.000 description 5
- 229910001956 copper hydroxide Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 239000002440 industrial waste Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
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.
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.
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.
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.
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.
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.
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)
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.
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)
| 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 |
-
1990
- 1990-06-27 JP JP2169159A patent/JPH0461986A/en active Pending
Cited By (7)
| 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 |
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| 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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