JP2827210B2 - Regeneration method of ferric chloride etching waste liquid - Google Patents
Regeneration method of ferric chloride etching waste liquidInfo
- Publication number
- JP2827210B2 JP2827210B2 JP926088A JP926088A JP2827210B2 JP 2827210 B2 JP2827210 B2 JP 2827210B2 JP 926088 A JP926088 A JP 926088A JP 926088 A JP926088 A JP 926088A JP 2827210 B2 JP2827210 B2 JP 2827210B2
- Authority
- JP
- Japan
- Prior art keywords
- waste liquid
- ferric chloride
- etching
- etching waste
- iron ions
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は金属のエッチングに使用した塩化第二鉄エッ
チング廃液から、不要な重金属成分を除去してエッチン
グ能力を回復させる方法に関するものである。Description: TECHNICAL FIELD The present invention relates to a method for recovering etching ability by removing unnecessary heavy metal components from ferric chloride etching waste liquid used for metal etching.
塩化第二鉄エッチング液は、鋼、銅、ステンレス鋼、
ニッケル合金等の金属表面をエッチング処理するための
エッチング液として用いられる。しかし、このエッチン
グ液は繰返し使用すると、エッチング時に溶解する重金
属の濃度が次第に高まり、また三価の鉄イオンが二価に
還元されて塩化第二鉄は塩化第一鉄となり、エッチング
能力が低下する。エッチング能力の低下した液は廃液と
して廃棄するか、再生して再利用している。しかし、廃
棄するには公害防止上解決すべき問題があり、再生して
利用することが望まれている。Ferric chloride etching solution is used for steel, copper, stainless steel,
It is used as an etchant for etching a metal surface such as a nickel alloy. However, when this etching solution is used repeatedly, the concentration of heavy metals dissolved during etching gradually increases, and trivalent iron ions are reduced to divalent, and ferric chloride becomes ferrous chloride, and the etching ability decreases. . The liquid with reduced etching ability is discarded as a waste liquid, or is recycled and reused. However, there are problems to be solved in terms of pollution prevention for disposal, and it is desired to recycle and use them.
塩化第二鉄エッチング廃液（以下エッチング廃液とい
う）の再生方法としては本発明者らが先に提案した特開
昭62−130285号公報技術がある。すなわち、同公報技術
では重金属を含有するエッチング廃液を予め60〜120℃
に加熱し、この加熱廃液に金属鉄を加え反応させ、析出
した重金属成分を除去し、次いで廃液に塩素ガスを吹き
込むことにより二価の鉄イオンを三価の鉄イオンにて再
生し、再利用を行なっている。As a method for regenerating ferric chloride etching waste liquid (hereinafter referred to as etching waste liquid), there is a technique disclosed in Japanese Patent Application Laid-Open No. Sho 62-130285 previously proposed by the present inventors. In other words, according to the publication technology, an etching waste liquid containing heavy metals is previously heated to 60 to 120 ° C.
To the heated waste liquid, add metallic iron to react, remove the precipitated heavy metal components, and then blow chlorine gas into the waste liquid to regenerate divalent iron ions with trivalent iron ions and reuse them Are doing.
特開昭62−130285号公報技術によってエッチング廃液
の再生、再利用が可能となったが、同公報技術では再生
液中のNi量が新液に比べ多いため、エッチング液用とし
ては支障はないが他の目的に使用する場合（例えば凝集
剤に使用する場合）は受け入れ準備に合致しないという
問題点があった。また、２段処理して新液同様の液を作
る方法は確立しているが、コストがかかるという問題点
もあり、工数を増加させずに再生液中のNi量を新液と同
レベルまで減少できるエッチング廃液の再生方法が望ま
れていた。Japanese Patent Application Laid-Open No. Sho 62-130285 discloses a technique for recycling and reusing an etching waste liquid. However, the technique disclosed in the Japanese Patent Laid-Open Publication No. 62-130285 does not hinder the use of an etching liquid because the amount of Ni in the regenerating liquid is larger than that of a new liquid. However, when it is used for another purpose (for example, when it is used for a flocculant), there is a problem that it does not meet the preparation for acceptance. In addition, although a method to produce a liquid similar to the new liquid by two-stage processing has been established, there is a problem that the cost is high, and the amount of Ni in the regenerating liquid is reduced to the same level as the new liquid without increasing the number of steps. There has been a demand for a method of regenerating an etching waste liquid that can be reduced.
本発明は上記した従来技術が抱える課題を考慮してな
されたもので、重金属を含有する塩化第二鉄エッチング
廃液を予め加熱し、該加熱廃液に水酸化鉄を加えて残存
している三価の鉄イオンを二価の鉄イオンとし、次に塊
状の金属を加えて重金属をスラッジとして析出除去する
ことにより不純物の少ない塩化第一鉄液とし、更に塩素
ガスを吹き込むことにより、再度三価の鉄イオンとする
ことを特徴とする塩化第二鉄エッチング廃液の再生方法
を提供し、従来技術の課題を全て解消するものである。The present invention has been made in view of the above-mentioned problems of the prior art, and heats a ferric chloride etching waste liquid containing a heavy metal in advance, and adds iron hydroxide to the heated waste liquid to remove residual trivalent chloride. Iron ions into divalent iron ions, and then add a lump of metal to precipitate and remove heavy metals as sludge to obtain a ferrous chloride solution with less impurities, and then blow chlorine gas again to form trivalent iron ions again. An object of the present invention is to provide a method for regenerating ferric chloride etching waste liquid, which is characterized by using iron ions, thereby solving all the problems of the prior art.
つぎに本発明を実施例に基づいて詳細に説明する。 Next, the present invention will be described in detail based on examples.
図面は実施例に於いて用いたエッチング廃液の再生工
程を示すフローチャートである。廃液槽１に貯えられた
エッチング廃液は加熱器２に送られて100℃に加熱され
る。加熱器２の熱源は本再生工程では少量だが水素ガス
の発生があるので水素爆発の危険があり、これを避ける
目的でスチーム源３から供給されるスチームである。ス
チームにより100℃に加熱されたエッチング廃液は反応
器の反応槽４に於いて、水酸化鉄５が加えられ、エッチ
ング廃液中の塩化第二鉄は全て塩化第一鉄に還元され
る。水酸化鉄５が添加されたエッチング廃液は還元反応
を促進させるため適当な方法（例えば撹拌翼）によって
撹拌するのが好ましい。尚、水酸化鉄５とともに後述す
る別途回収される塩素分を多量に含有するスラッジ10を
触媒として添加し、反応をより効率よく進めることが可
能である、塩化第二鉄を塩化第一鉄に還元されたエッチ
ング廃液は析出容器６に送られ、塊状の金属（例えば
鉄）７が加えられ、エッチング廃液中の重金属成分（例
えばNi、Cr、Cuなど）は該金属と反応して、一部は該金
属表面に金属８として析出し、他は水酸化物として析出
沈澱する。析出した水酸化物を含有するエッチング廃液
はフィルタープレス９に送られ、濾過されてスラッジ10
と濾液11に分離される。スラッジ10の組成（重量部）を
第１表に示す。The drawing is a flowchart showing a process of regenerating the etching waste liquid used in the embodiment. The etching waste liquid stored in the waste liquid tank 1 is sent to the heater 2 and heated to 100 ° C. The heat source of the heater 2 is a steam supplied from the steam source 3 for the purpose of avoiding a hydrogen explosion due to the generation of hydrogen gas although a small amount is generated in this regeneration process. The etching waste liquid heated to 100 ° C. by steam is added with iron hydroxide 5 in a reaction tank 4 of the reactor, and all ferric chloride in the etching waste liquid is reduced to ferrous chloride. It is preferable that the etching waste liquid to which the iron hydroxide 5 is added is stirred by an appropriate method (for example, a stirring blade) in order to promote a reduction reaction. In addition, it is possible to add, as a catalyst, a sludge 10 containing a large amount of separately recovered chlorine, which will be described later, together with the iron hydroxide 5 so that the reaction can proceed more efficiently. The reduced etching waste liquid is sent to the deposition vessel 6, where a lump of metal (eg, iron) 7 is added, and heavy metal components (eg, Ni, Cr, Cu, etc.) in the etching waste liquid react with the metal to form a part. Precipitates on the metal surface as metal 8, and the others precipitate as hydroxides. The etching waste liquid containing the precipitated hydroxide is sent to a filter press 9 where it is filtered to form sludge 10.
And the filtrate 11 is separated. Table 1 shows the composition (parts by weight) of the sludge 10.
第１表から判る様にスラッジ10はNi含量が多いためNi
資源として利用可能であり、また該スラッジ10は販述し
た様に反応器の反応槽４に水酸化鉄５とともに加えら
れ、触媒として反応を促進させることも可能である。重
金属成分の殆んどが除去された塩化第一鉄の濃度の極め
て高い濾液11は、適量の水12が添加されて濃度調整さ
れ、塩素ガス反応槽13に送られ、塩素ガス14を吹き込ま
れる。濾液中の第一鉄イオンは吹き込まれた塩素ガス14
によって第二鉄イオンに酸化されるので、塩化第一鉄液
は塩化第二鉄液となり、エッチング廃液は再生されて貯
槽15に貯えられる。 As can be seen from Table 1, sludge 10 has a high Ni content,
The sludge 10 can be used as a resource, and the sludge 10 can be added to the reaction tank 4 of the reactor together with the iron hydroxide 5 as described above to promote the reaction as a catalyst. The filtrate 11 having a very high concentration of ferrous chloride from which most of the heavy metal components have been removed is adjusted to a concentration by adding an appropriate amount of water 12, sent to a chlorine gas reaction tank 13, and blown with chlorine gas 14. . Ferrous ions in the filtrate are blown chlorine gas14
As a result, the ferrous chloride solution becomes a ferric chloride solution, and the etching waste solution is regenerated and stored in the storage tank 15.
以上のプロセスによって再生されたエッチング液の組
成を、新液および廃液の組成とともに第２表に示す。Table 2 shows the composition of the etching solution regenerated by the above process together with the compositions of the new solution and the waste solution.
第２表より再生液の組は新液に比べるとて差はなく、
Ni量も特開昭62−130285号公報技術の再生液に比べて大
幅に減少し、新液と殆んど変らない。 According to Table 2, there is no difference between the set of regenerating solution and the new solution.
The amount of Ni is also greatly reduced as compared with the regenerating solution of Japanese Patent Application Laid-Open No. 62-130285, and is almost the same as the new solution.
尚、フィルタープレス９は反応器の反応槽４の前工
程、または後工程にも設けることが可能である。Incidentally, the filter press 9 can be provided in a step before or after the reaction tank 4 of the reactor.
以上説明した様に本発明になる塩化第二鉄エッチング
廃液の再生方法は、重金属を含有する該エッチング廃液
を予め加熱し、該加熱液に水酸化鉄等を加えて残存して
いる三価の鉄イオンを一旦二価の鉄イオンに還元した
後、塊状の金属を加えて廃液中の重金属をスラッジとし
て析出除去するので、純度の高い塩化第一鉄液が得られ
る。本発明では純度の高い塩化第一鉄に塩素ガスを吹き
込んで廃液中の塩化第一鉄を酸化してエッチング能力を
持つ塩化第二鉄を得るので純度の高い塩化第二鉄液が得
られる。この様にして再生された塩化第二鉄エッチング
液はNi成分が従来法に比べ大幅に減少しており、新液と
変らないエッチング能力がある。残存塩化第二鉄は水酸
化第一鉄および第二鉄、その他と反応するため水素ガス
の発生が少なく、その分危険が減少する。As described above, in the method for regenerating the ferric chloride etching waste liquid according to the present invention, the etching waste liquid containing a heavy metal is preliminarily heated, and iron hydroxide or the like is added to the heated liquid to remove the remaining trivalent chloride. After the iron ions are once reduced to divalent iron ions, a massive metal is added to precipitate and remove heavy metals in the waste liquid as sludge, so that a highly pure ferrous chloride solution can be obtained. In the present invention, a chlorine gas is blown into high-purity ferrous chloride to oxidize the ferrous chloride in the waste liquid to obtain ferric chloride having an etching ability, so that a high-purity ferric chloride solution can be obtained. The ferric chloride etching solution thus regenerated has a significantly reduced Ni component compared to the conventional method, and has an etching ability that is not different from that of the new solution. The remaining ferric chloride reacts with ferrous hydroxide, ferric hydroxide, and the like, so that less hydrogen gas is generated, and the danger is reduced accordingly.
第１図は本発明の一実施例を示すフローチャートであ
る。 １……廃液槽、２……加熱器、 ３……スチーム源、４……反応槽、 ５……水酸化鉄、６……析出容器、 7,8……金属、９……フィルタープレス、 10……スラッジ、11……濾液、 12……水、13……反応槽、 14……塩素ガス、15……貯槽。FIG. 1 is a flowchart showing an embodiment of the present invention. 1 ... waste liquid tank, 2 ... heater, 3 ... steam source, 4 ... reaction tank, 5 ... iron hydroxide, 6 ... precipitation vessel, 7,8 ... metal, 9 ... filter press, 10 ... sludge, 11 ... filtrate, 12 ... water, 13 ... reaction tank, 14 ... chlorine gas, 15 ... storage tank.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭62−130285（ＪＰ，Ａ) 特開 昭51−121956（ＪＰ，Ａ) 特開 昭51−124051（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C23F 1/00 - 3/06──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-130285 (JP, A) JP-A-51-221956 (JP, A) JP-A-51-224051 (JP, A) (58) Field (Int.Cl. 6 , DB name) C23F 1/00-3/06
Claims (1)
液を予め加熱し、該加熱廃液に水酸化鉄を加えて残存し
ている三価の鉄イオンを二価の鉄イオンとし、次に塊状
の金属を加えて重金属をスラッジとして析出除去するこ
とにより不純物の少ない塩化第一鉄液とし、更に塩素ガ
スを吹き込むことにより、再度三価の鉄イオンとするこ
とを特徴とする塩化第二鉄エッチング廃液の再生方法。1. A ferric chloride etching waste liquid containing a heavy metal is heated in advance, and iron hydroxide is added to the heated waste liquid to convert the remaining trivalent iron ions into divalent iron ions. Ferric chloride etching, characterized in that ferrous chloride liquid with few impurities is obtained by adding heavy metals to precipitate and remove heavy metals as sludge, and then trivalent iron ions are again blown by blowing chlorine gas. How to recycle waste liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP926088A JP2827210B2 (en) | 1988-01-19 | 1988-01-19 | Regeneration method of ferric chloride etching waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP926088A JP2827210B2 (en) | 1988-01-19 | 1988-01-19 | Regeneration method of ferric chloride etching waste liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01184284A JPH01184284A (en) | 1989-07-21 |
| JP2827210B2 true JP2827210B2 (en) | 1998-11-25 |
Family
ID=11715457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP926088A Expired - Fee Related JP2827210B2 (en) | 1988-01-19 | 1988-01-19 | Regeneration method of ferric chloride etching waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2827210B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100406619C (en) * | 2002-02-06 | 2008-07-30 | 新光电气工业株式会社 | Electrolytic recycling device |
-
1988
- 1988-01-19 JP JP926088A patent/JP2827210B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01184284A (en) | 1989-07-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |