JP3523727B2 - Etching waste liquid treatment method - Google Patents
Etching waste liquid treatment methodInfo
- Publication number
- JP3523727B2 JP3523727B2 JP26653095A JP26653095A JP3523727B2 JP 3523727 B2 JP3523727 B2 JP 3523727B2 JP 26653095 A JP26653095 A JP 26653095A JP 26653095 A JP26653095 A JP 26653095A JP 3523727 B2 JP3523727 B2 JP 3523727B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid
- chloride
- etching
- concentration
- ferric 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.)
- Expired - Fee Related
Links
- 239000007788 liquid Substances 0.000 title claims description 175
- 238000005530 etching Methods 0.000 title claims description 120
- 239000002699 waste material Substances 0.000 title claims description 70
- 238000000034 method Methods 0.000 title claims description 34
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 92
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 85
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 85
- 229960003280 cupric chloride Drugs 0.000 claims description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 42
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 41
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 41
- 239000010949 copper Substances 0.000 claims description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 33
- 229960002089 ferrous chloride Drugs 0.000 claims description 33
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 33
- 229910052802 copper Inorganic materials 0.000 claims description 32
- 238000000926 separation method Methods 0.000 claims description 19
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 11
- 230000001172 regenerating effect Effects 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 238000000151 deposition Methods 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 39
- 238000002425 crystallisation Methods 0.000 description 19
- 230000008025 crystallization Effects 0.000 description 19
- 229910052742 iron Inorganic materials 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000013078 crystal Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 10
- 230000008929 regeneration Effects 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 8
- 229910001882 dioxygen Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 238000000895 extractive distillation Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102220491117 Putative postmeiotic segregation increased 2-like protein 1_C23F_mutation Human genes 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 102220411551 c.74G>T Human genes 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229960003284 iron Drugs 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000010841 municipal wastewater Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- ing And Chemical Polishing (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、塩化第二鉄エッチ
ング液を用いて銅をエッチング処理した後のエッチング
廃液からエッチング液を再生するための、エッチング廃
液処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an etching waste liquid treatment method for regenerating an etching waste liquid from an etching waste liquid after etching copper with an ferric chloride etching liquid.
【０００２】[0002]
【従来の技術】塩化第二鉄エッチング液による銅プリン
ト基板のエッチングは、塩化第二鉄（ＦｅＣｌ3 ）液を
用いて銅（Ｃｕ）を溶解し、残した銅パタ−ンにより回
路を形成するものであり、一般に民生用、産業機器用な
ど幅広い分野で多く利用されている。このようなエッチ
ング反応は、下記の（１）式に示す反応式に従って進行
する。
Ｃｕ＋２ＦｅＣｌ3 → ＣｕＣｌ2 ＋２ＦｅＣｌ2 ・・・ （１）2. Description of the Related Art The etching of a copper printed circuit board with a ferric chloride etching solution dissolves copper (Cu) using a ferric chloride (FeCl 3 ) solution and forms a circuit by the remaining copper pattern. In general, it is widely used in a wide range of fields such as consumer products and industrial equipment. Such an etching reaction proceeds according to the reaction formula shown in the following formula (1). Cu + 2FeCl 3 → CuCl 2 + 2FeCl 2 (1)
【０００３】このためエッチング処理中のエッチング液
には、エッチング反応の生成物である塩化第二銅（Ｃｕ
Ｃｌ2 ）及び塩化第一鉄（ＦｅＣｌ2 ）と、未反応の塩
化第二鉄等が含まれており、処理が進むに連れてエッチ
ング液中の塩化第二銅と塩化第一鉄の濃度が高くなって
くる。ここで塩化第一鉄には銅の溶解能力（エッチング
能力）がほとんど無いため、このようにエッチング液中
の塩化第一鉄濃度が高くなると、エッチング速度（銅の
単位時間あたりの溶解量）が低下し、このためエッチン
グ処理の効率が著しく悪化する。Therefore, the etching solution during the etching process contains cupric chloride (Cu) which is a product of the etching reaction.
Cl 2 ) and ferrous chloride (FeCl 2 ) and unreacted ferric chloride, etc. are contained, and the concentration of cupric chloride and ferrous chloride in the etching solution increases as the treatment progresses. Getting higher. Here, since ferrous chloride has almost no copper dissolving ability (etching ability), if the concentration of ferrous chloride in the etching solution becomes high, the etching rate (dissolving amount of copper per unit time) will increase. And thus the efficiency of the etching process is significantly reduced.
【０００４】またエッチング処理後のエッチング廃液に
は比較的に価格の高い銅が上述のように塩化第二銅とし
て含まれていることから、従来より塩化第一鉄から塩化
第二鉄を再生すると共に、塩化第二銅を析出させて銅の
有効利用を図るために、エッチング廃液に鉄等の還元剤
を添加することにより、エッチング廃液を処理する方法
が採られている。Further, since the etching waste liquid after the etching treatment contains relatively expensive copper as cupric chloride as described above, ferric chloride is regenerated from ferrous chloride conventionally. At the same time, in order to precipitate cupric chloride to effectively use copper, a method of treating the etching waste liquid by adding a reducing agent such as iron to the etching waste liquid is adopted.
【０００５】この方法ではエッチング廃液は以下の
（２）〜（５）式に示す工程を経て処理される。即ちエ
ッチング廃液に含まれている塩化第二銅を鉄との反応に
より銅メタルとして析出させて回収すると共に（（３）
式）、鉄と塩化第二鉄との反応（（２）式）、鉄と塩化
第二銅との反応（（３）式）、鉄とエッチング液中に含
まれる塩化水素（ＨＣｌ）との反応（（４）式）によっ
て塩化第一鉄を生成し、この塩化第一鉄を塩素化
（（５）式）することにより塩化第二鉄液としてエッチ
ング液が再生される。
Ｆｅ＋２ＦｅＣｌ3 → ３ＦｅＣｌ2 ・・・ （２）
Ｆｅ＋ＣｕＣｌ2 → Ｃｕ＋ＦｅＣｌ2 ・・・ （３）
Ｆｅ＋２ＨＣｌ → ＦｅＣｌ2 ＋Ｈ2 ・・・ （４）
ＦｅＣｌ2 ＋１／２Ｃｌ2 → ＦｅＣｌ3 ・・・ （５）In this method, the etching waste liquid is processed through the steps shown in the following equations (2) to (5). That is, while the cupric chloride contained in the etching waste liquid is precipitated as copper metal by the reaction with iron and recovered ((3)
Formula), a reaction between iron and ferric chloride (formula (2)), a reaction between iron and cupric chloride (formula (3)), and a reaction between iron and hydrogen chloride (HCl) contained in the etching solution. The reaction (formula (4)) produces ferrous chloride, and by chlorinating the ferrous chloride (formula (5)), the etching solution is regenerated as ferric chloride solution. Fe + 2FeCl 3 → 3FeCl 2 (2) Fe + CuCl 2 → Cu + FeCl 2 ... (3) Fe + 2HCl → FeCl 2 + H 2 ... (4) FeCl 2 + 1 / 2Cl 2 → FeCl 3 ... (5)
【０００６】[0006]
【発明が解決しようとする課題】しかしながら従来のエ
ッチング廃液の処理方法では、再生処理工程が複雑であ
るので人手を多く必要とし、また再生後のエッチング液
の液量が再生前に比べて１．３〜１．５倍に増加してし
まう。その主因は前記塩化第二銅と鉄との反応の前に塩
化第二鉄と鉄との反応が起こり、この反応により塩化第
一鉄が生成されることにある。即ちこの反応では（２）
式に示すように、塩化第二鉄の１．５倍の塩化第一鉄が
生成されてしまうので、この反応での塩化第一鉄の増加
量にあわせて再生後の塩化第二鉄液が増加してしまう。However, the conventional method for treating the etching waste liquid requires a large amount of manpower because the regeneration treatment step is complicated, and the amount of the etching liquid after the regeneration is smaller than that before the regeneration. It will increase 3 to 1.5 times. The main reason is that the reaction between ferric chloride and iron occurs before the reaction between the cupric chloride and iron, and ferrous chloride is produced by this reaction. That is, in this reaction (2)
As shown in the formula, 1.5 times as much ferric chloride as ferric chloride is produced, so the ferric chloride solution after regeneration is adjusted according to the increase in ferrous chloride in this reaction. Will increase.
【０００７】ここで塩化第二鉄液はエッチング液として
利用される以外に、都市下水、工業排水等の水処理の凝
集沈降剤としても利用されるが、近年その水処理用凝集
沈降剤が有機高分子系のものに変わりつつあるため、再
生塩化第二鉄液の増加分の用途は少なく、結局廃液とし
て廃棄しなければならない。しかし廃棄には中和処理な
どの廃液処理を経て産業廃棄物として処分するという面
倒な作業が必要であり、エッチング廃液の処理を行うこ
とによって、常に元の３０〜５０％の量のエッチング液
について面倒な廃棄処分を行わなければならないため、
手間やコストが増大すると共に、資源を無駄にしてしま
うという問題があった。このような背景の下では鉄等の
還元剤を使用せず、また再生エッチング液の液量の増加
を抑えたエッチング廃液の処理方法の確立が望まれてい
る。The ferric chloride solution is used not only as an etching solution but also as a coagulating sedimentation agent for water treatment of municipal wastewater, industrial wastewater and the like. In recent years, the coagulation sedimentation agent for water treatment is organic. Since it is changing to a polymer type, the increased amount of regenerated ferric chloride solution has little use and must be discarded as a waste solution. However, the disposal requires a troublesome work of disposing as an industrial waste through a waste liquid treatment such as a neutralization treatment. By treating the etching waste liquid, the original etching liquid of 30 to 50% is always consumed. Since it has to be a troublesome disposal,
There is a problem that the labor and cost increase and the resources are wasted. Under such a background, it is desired to establish a method for treating an etching waste liquid that does not use a reducing agent such as iron and that suppresses an increase in the amount of the regenerated etching liquid.
【０００８】本発明はこのような事情の下になされたも
のであり、その目的は鉄材等の還元剤を使用せず、また
再生エッチング液の液量の増加を抑えたエッチング廃液
の処理方法を提供することにある。The present invention has been made under such circumstances, and an object thereof is to provide a method for treating an etching waste liquid which does not use a reducing agent such as an iron material and which suppresses an increase in the amount of the regenerated etching liquid. To provide.
【０００９】[0009]
【課題を解決するための手段】請求項１の発明は、塩化
第二鉄エッチング液を用いて銅をエッチング処理した後
のエッチング廃液からエッチング液を再生する方法にお
いて、前記エッチング廃液中の塩化第二鉄濃度を高める
工程と、前記工程にて得られた被処理液に塩化水素を添
加して塩化第二銅を析出させ、分離する析出分離工程
と、を含むことを特徴とする。According to a first aspect of the present invention, there is provided a method for regenerating an etching solution from an etching waste solution after etching copper with an ferric chloride etching solution. It is characterized by including a step of increasing the concentration of diiron and a precipitation separation step of adding hydrogen chloride to the liquid to be treated obtained in the above step to precipitate cupric chloride and separating the solution.
【００１０】請求項２の発明は、塩化第二鉄エッチング
液を用いて銅をエッチング処理した後のエッチング廃液
からエッチング液を再生する方法において、前記エッチ
ング廃液を濃縮し塩化第二鉄濃度を高める濃縮工程と、
前記濃縮工程にて得られた被処理液を冷却する冷却工程
と、冷却された被処理液に塩化水素を添加して塩化第二
銅を析出させ、分離する析出分離工程と、を含むことを
特徴とする。According to a second aspect of the present invention, in a method of regenerating an etching liquid from an etching waste liquid after etching copper with an ferric chloride etching liquid, the etching waste liquid is concentrated to increase the ferric chloride concentration. A concentration step,
Cooling step for cooling the liquid to be treated obtained in the concentration step
And hydrogen chloride is added to the cooled liquid to be treated to precipitate cupric chloride, and the separation process is performed to separate the cupric chloride.
【００１１】請求項３の発明は、塩化第二鉄エッチング
液を用いて銅をエッチング処理した後のエッチング廃液
からエッチング液を再生する方法において、前記エッチ
ング廃液中の塩化第一鉄を塩化第二鉄に酸化する酸化工
程と、前記酸化工程にて得られた被処理液を濃縮して塩
化第二銅を析出させ、分離する工程と、を含むことを特
徴とする。According to a third aspect of the present invention, in the method of regenerating the etching liquid from the etching waste liquid after the etching treatment of copper with the ferric chloride etching liquid, the ferrous chloride in the etching waste liquid is changed to the second chloride. The method is characterized by including an oxidation step of oxidizing to iron and a step of concentrating the liquid to be treated obtained in the oxidation step to precipitate cupric chloride and separating it.
【００１２】請求項４の発明は、塩化第二鉄エッチング
液を用いて銅をエッチング処理した後のエッチング廃液
からエッチング液を再生する方法において、前記エッチ
ング廃液中の塩化第一鉄を塩化第二鉄に酸化する酸化工
程と、前記酸化工程にて得られた被処理液を濃縮し塩化
第二鉄濃度を高める濃縮工程と、前記濃縮された被処理
液を冷却する冷却工程と、冷却された被処理液に塩化水
素を添加して塩化第二銅を析出させ、分離する析出分離
工程と、を含むことを特徴とする。According to a fourth aspect of the present invention, in the method of regenerating the etching liquid from the etching waste liquid after etching copper with the ferric chloride etching liquid, the ferrous chloride in the etching waste liquid is converted to the second chloride. An oxidation step of oxidizing to iron, a concentration step of concentrating the liquid to be treated obtained in the oxidation step to increase the ferric chloride concentration, a cooling step of cooling the concentrated liquid to be treated, and a cooling step. A precipitation separation step of adding hydrogen chloride to the liquid to be treated to precipitate cupric chloride and separating the cupric chloride.
【００１３】請求項５の発明は、請求項１、２、３又は
４記載の発明において、塩化第二鉄濃度を高めた後のエ
ッチング廃液又は被処理液中の塩化第二鉄濃度は４０％
以上であることを特徴とする。According to a fifth aspect of the present invention, in the first, second, third or fourth aspect of the invention, the ferric chloride concentration in the etching waste liquid or the liquid to be treated after the ferric chloride concentration is increased is 40%.
The above is characterized.
【００１４】請求項６の発明は、請求項２又は４記載の
発明において、濃縮工程は、塩化第二銅を析出させる工
程を含むことを特徴とする。The invention of claim 6 is characterized in that, in the invention of claim 2 or 4, the concentration step includes a step of precipitating cupric chloride.
【００１５】[0015]
【発明の実施の形態】次に本発明の実施の形態について
説明する。図１は本発明方法を実施するエッチング廃液
処理装置の一形態を示す構成図である。図中１は酸化槽
であり、この槽にはエッチング廃液貯槽１１が廃液供給
管Ｔ１１を介して接続されている。また酸化槽１には塩
化第一鉄を塩化第二鉄に酸化するための酸化ガス例えば
塩素ガスの供給源である塩素ガス源１２がエジェクタ−
１３が介設された塩素ガス供給管Ｔ１２を介して設けら
れると共に、槽内のエッチング廃液をエジェクタ−１３
に循環供給する循環管Ｔ１０が設けられている。BEST MODE FOR CARRYING OUT THE INVENTION Next, embodiments of the present invention will be described. FIG. 1 is a block diagram showing an embodiment of an etching waste liquid treatment apparatus for carrying out the method of the present invention. In the figure, 1 is an oxidation tank, and an etching waste liquid storage tank 11 is connected to this tank via a waste liquid supply pipe T11. Further, in the oxidation tank 1, a chlorine gas source 12 which is a supply source of an oxidizing gas such as chlorine gas for oxidizing ferrous chloride to ferric chloride is ejector.
13 is provided via a chlorine gas supply pipe T12 in which the etching waste liquid in the tank is ejected.
A circulation pipe T10 is provided for circulating the supply.
【００１６】前記酸化槽１の下流側には配管Ｔ１を介し
て濃縮槽２が設けられており、この槽には熱交換器２１
が介設された循環管Ｔ２０が、濃縮液を槽内に循環供給
するように設けられていると共に、排気管Ｔ２２を介し
て減圧手段２２が接続されている。濃縮槽２の下流側に
は配管Ｔ２、Ｔ３０を介して撹拌機３０を備えた晶析槽
３が設けられると共に、配管Ｔ２１、循環管Ｔ２０より
分岐する配管Ｔ２３を介して第１の分離回収手段が設け
られている。A concentration tank 2 is provided on the downstream side of the oxidation tank 1 through a pipe T1, and the heat exchanger 21 is installed in this tank.
A circulating pipe T20 is provided so as to circulate and supply the concentrated liquid into the tank, and a depressurizing means 22 is connected through an exhaust pipe T22. A crystallization tank 3 equipped with a stirrer 30 is provided on the downstream side of the concentration tank 2 via pipes T2 and T30, and a first separation and recovery means is provided via a pipe T21 and a pipe T23 branched from a circulation pipe T20. Is provided.
【００１７】前記晶析槽３には塩化水素ガス源３１がエ
ジェクタ−３２が介設された塩化水素ガス供給管Ｔ３２
を介して設けられると共に、熱交換器３３が設けられて
おり、エジェクタ−３２と熱交換器３３とは槽内の液が
熱交換器３３を介してエジェクタ−３２に循環供給され
るように循環管Ｔ３０により接続されている。In the crystallization tank 3, a hydrogen chloride gas source 31 is provided with a hydrogen chloride gas source 31 and an ejector 32 interposed therebetween.
And the heat exchanger 33 is provided, and the ejector 32 and the heat exchanger 33 circulate so that the liquid in the tank is circulated and supplied to the ejector 32 via the heat exchanger 33. It is connected by a tube T30.
【００１８】この晶析槽３の下流側には循環管Ｔ３０か
ら分岐する配管Ｔ３１を介して第２の分離回収手段４２
が設けられており、この第２の分離回収手段４２の下流
側には配管Ｔ４を介して調整槽５が設けられている。調
整槽５には酸素ガス源５１がエジェクタ−５２が介設さ
れた酸素ガス供給管Ｔ５１を介して設けられると共に、
槽内の液をエジェクタ−５２に循環供給する循環管Ｔ５
０が設けられている。またこの槽には塩化第一鉄貯槽５
３及び貯水槽５４が夫々塩化第一鉄供給管Ｔ５３、水供
給管Ｔ５４を介して接続されている。図中Ｖはバルブ
を、Ｐはポンプを夫々示している。A second separating / collecting means 42 is provided downstream of the crystallization tank 3 via a pipe T31 branched from a circulation pipe T30.
Is provided, and the adjusting tank 5 is provided on the downstream side of the second separating and collecting means 42 through a pipe T4. An oxygen gas source 51 is provided in the adjusting tank 5 via an oxygen gas supply pipe T51 in which an ejector 52 is provided, and
Circulation pipe T5 for circulating and supplying the liquid in the tank to the ejector 52
0 is provided. In addition, the ferrous chloride storage tank 5
3 and the water storage tank 54 are connected via a ferrous chloride supply pipe T53 and a water supply pipe T54, respectively. In the figure, V indicates a valve, and P indicates a pump.
【００１９】このようなエッチング廃液処理装置では、
先ずエッチング廃液貯槽１１から酸化槽２に、例えば銅
４％、塩化第一鉄１０％と塩化第二鉄１９％等を含むエ
ッチング廃液を供給し、この槽内においてエッチング廃
液の酸化工程を実施する。即ち塩素ガス源１２からエジ
ェクタ−１３に塩素ガスを供給する一方、槽内のエッチ
ング廃液をエジェクタ−１３を介して循環させ、エッチ
ング廃液に塩素ガスを添加する。ここで塩素ガスの供給
量は例えば酸化還元電位等で制御する。この工程におい
てエッチング廃液中の塩化第一鉄は塩化第二鉄に酸化さ
れ、エッチング廃液中の塩化第二鉄濃度は例えば３１％
程度まで高められる。In such an etching waste liquid treatment apparatus,
First, an etching waste liquid containing, for example, 4% copper, 10% ferrous chloride and 19% ferric chloride is supplied from the etching waste liquid storage tank 11 to the oxidation tank 2, and the oxidation step of the etching waste liquid is carried out in this tank. . That is, while chlorine gas is supplied from the chlorine gas source 12 to the ejector 13, the etching waste liquid in the tank is circulated through the ejector 13, and chlorine gas is added to the etching waste liquid. Here, the supply amount of chlorine gas is controlled by, for example, the redox potential. In this process, ferrous chloride in the etching waste liquid is oxidized to ferric chloride, and the concentration of ferric chloride in the etching waste liquid is, for example, 31%.
It can be raised to a certain degree.
【００２０】続いて酸化された被処理液を濃縮槽２に送
液し、この槽において濃縮工程を実施する。即ち減圧手
段２２により槽内の圧力を減圧しながら、槽内の液を熱
交換器２１により加熱して被処理液の濃縮を行なう。こ
のように被処理液を濃縮すると、次第に被処理液の量が
減少し、液中の塩化第二鉄濃度と塩化第二銅濃度が高ま
ってきて、ある程度濃縮が進むと塩化第二銅を主とし、
塩化第二鉄等を含む結晶が析出してくる。そこで被処理
液を配管Ｔ２１を介して第１の固液分離手段４１へ送液
し、析出した結晶を分離しながら濃縮を行なう。Subsequently, the oxidized liquid to be treated is sent to the concentration tank 2, and the concentration step is carried out in this tank. That is, while reducing the pressure in the tank by the pressure reducing means 22, the liquid in the tank is heated by the heat exchanger 21 to concentrate the liquid to be treated. By concentrating the liquid to be treated in this way, the amount of the liquid to be treated gradually decreases, the concentration of ferric chloride and cupric chloride in the liquid increases, and when the concentration proceeds to a certain extent, the cupric chloride is mainly age,
Crystals containing ferric chloride and the like are deposited. Therefore, the liquid to be treated is sent to the first solid-liquid separation means 41 through the pipe T21, and concentrated while separating the precipitated crystals.
【００２１】ここで濃縮の終了時のタイミングは例えば
被処理液の比重に基づいて制御され、被処理液の比重を
検出し、この値が設定範囲になった段階で濃縮工程を終
了する。このようにして塩化第二鉄濃度が例えば６５％
〜７５％程度となるまで濃縮する。このとき被処理液の
量は例えば１／２〜１／３程度まで減少し、液中には例
えば塩化第二鉄が７３％、銅が０．１８％程度含まれて
いる。Here, the timing at the end of the concentration is controlled, for example, based on the specific gravity of the liquid to be treated, the specific gravity of the liquid to be treated is detected, and the concentration process is terminated when this value falls within the set range. In this way, the ferric chloride concentration is, for example, 65%
Concentrate to ~ 75%. At this time, the amount of the liquid to be treated is reduced to, for example, about 1/2 to 1/3, and the liquid contains, for example, ferric chloride 73% and copper 0.18%.
【００２２】次いで濃縮された被処理液を晶析槽３に送
液し、この槽において晶析工程を実施する。即ち塩化水
素ガス源３１からエジェクタ−３２に塩化水素ガスを供
給する一方、槽内の被処理液を熱交換器３３により例え
ば３０℃程度に冷却しながら、エジェクタ−３２を介し
て循環させ、被処理液に塩化水素ガスを例えば８％程度
になるまで供給する。なお塩化水素ガスの供給量は例え
ば被処理液の比重や電導度に基づいて制御される。Next, the concentrated liquid to be treated is sent to the crystallization tank 3, and the crystallization step is carried out in this tank. That is, while supplying the hydrogen chloride gas from the hydrogen chloride gas source 31 to the ejector 32, the liquid to be treated in the tank is circulated through the ejector 32 while being cooled to about 30 ° C. by the heat exchanger 33. Hydrogen chloride gas is supplied to the treatment liquid until it reaches, for example, about 8%. The supply amount of hydrogen chloride gas is controlled based on, for example, the specific gravity or conductivity of the liquid to be treated.
【００２３】このように塩化第二鉄濃度が６５％〜７５
％程度となるまで濃縮された被処理液を３０℃程度に冷
却しながら、塩化水素ガスを８％程度添加すると、被処
理液中に微量含まれている塩化第二銅が析出してくる。
即ち図２に示す塩化第二鉄の状態図により明らかなよう
に、塩化第二鉄は濃度が６５％〜７５％程度であれば３
０℃程度の温度では液体の状態で存在し、さらにこの状
態で塩化水素が存在すると錯体（ＨＦｅＣｌ4 ）を形成
するので溶解度が高くなり、より低い温度でも液体の状
態で存在する。一方塩化第二銅は塩化水素が存在しても
錯体を形成しないので、塩化第二銅と塩化第二鉄の塩化
水素存在下の溶解度の違いにより、被処理液中に微量含
まれている塩化第二銅が析出する。但し被処理液には塩
化第二鉄がかなり高い濃度で含まれているので塩化第二
鉄等も多少析出する。Thus, the ferric chloride concentration is 65% to 75%.
When hydrogen chloride gas is added at about 8% while the liquid to be treated concentrated to about 30% is cooled to about 30 ° C., cupric chloride contained in a small amount in the liquid to be treated is precipitated.
That is, as is clear from the phase diagram of ferric chloride shown in FIG. 2, if the concentration of ferric chloride is about 65% to 75%,
It exists in a liquid state at a temperature of about 0 ° C., and if hydrogen chloride exists in this state, it forms a complex (HFeCl 4 ), so that the solubility becomes high, and it exists in a liquid state even at a lower temperature. On the other hand, cupric chloride does not form a complex even in the presence of hydrogen chloride, and due to the difference in solubility of cupric chloride and ferric chloride in the presence of hydrogen chloride, a small amount of chloride Cupric acid precipitates. However, the liquid to be treated contains ferric chloride at a considerably high concentration, and thus ferric chloride and the like are also precipitated to some extent.
【００２４】続いて塩化第二銅等を含む結晶が析出した
被処理液を第二の固液分離手段４２に送液して結晶を分
離し、結晶分離後の被処理液を調整槽５に送液する。こ
こで結晶分離後の被処理液には例えば塩化第二鉄が６５
〜６８％、塩化水素が８〜１０％、銅が５０〜２００ｐ
ｐｍ程度含まれている。この実施の形態では晶析槽３と
第１の固液分離手段４１、第２の固液分離手段４２とに
より析出分離工程が実施される。Subsequently, the liquid to be treated in which crystals containing cupric chloride and the like are deposited is sent to the second solid-liquid separation means 42 to separate the crystals, and the liquid to be treated after the crystal separation is placed in the adjusting tank 5. Send the liquid. Here, for example, ferric chloride is contained in the liquid to be treated after crystal separation is 65
~ 68%, hydrogen chloride 8 ~ 10%, copper 50 ~ 200p
pm is included. In this embodiment, the crystallization tank 3, the first solid-liquid separation means 41, and the second solid-liquid separation means 42 carry out the precipitation separation step.
【００２５】調整槽５では結晶分離後の被処理液をエッ
チング液として調整する工程を実施する。即ち被処理液
に含まれる塩化水素をエッチング液として必要な量を残
して除去すると共に塩化第二鉄濃度を調整して、エッチ
ング液を再生する。具体的には塩化第一鉄貯槽５３から
例えば３３％塩化第一鉄液を槽内に供給すると共に、酸
素ガス源５１からエジェクタ−５２に酸素ガスを供給す
る一方、槽内の被処理液をエジェクタ−５２を介して循
環させ、被処理液に酸素ガスを供給する。このように被
処理液に塩化第一鉄と酸素ガスとを添加すると、以下の
（６）式に示すように、被処理液中に存在する塩化水素
が塩化第一鉄と反応し除去される。
４ＦｅＣｌ2 ＋４ＨＣｌ＋Ｏ2 → ４ＦｅＣｌ3 ＋２Ｈ2 Ｏ ・・・ （６）In the adjusting tank 5, a step of adjusting the liquid to be treated after the crystal separation as an etching liquid is carried out. That is, hydrogen chloride contained in the liquid to be treated is removed while leaving a necessary amount as an etching liquid, and the concentration of ferric chloride is adjusted to regenerate the etching liquid. Specifically, while supplying, for example, a 33% ferrous chloride solution from the ferrous chloride storage tank 53 into the tank, and supplying oxygen gas from the oxygen gas source 51 to the ejector 52, the liquid to be treated in the tank is treated. Oxygen gas is supplied to the liquid to be processed by circulating it through the ejector 52. When ferrous chloride and oxygen gas are added to the liquid to be treated in this way, hydrogen chloride present in the liquid to be treated reacts with ferrous chloride and is removed, as shown in the following equation (6). . 4FeCl 2 + 4HCl + O 2 → 4FeCl 3 + 2H 2 O (6)
【００２６】ここで槽内に供給される塩化第一鉄の量
は、被処理液中に存在する塩化水素の量と当量か当量よ
りも多少多い量であるが、この供給量は例えば被処理液
の酸化還元電位に基づいて制御される。また塩化第一鉄
の供給量が塩化水素の量よりも多い場合には、例えば塩
化水素除去後の被処理液に塩素ガスを供給して、残存す
る塩化第一鉄を塩化第二鉄に酸化する。続いて塩化水素
が除去された被処理液に貯水槽５４から水を添加し、塩
化第二鉄濃度を用途に応じて調整し、このようにして例
えば塩化第二鉄が３７％〜５５％、塩化水素が０．１％
程度のエッチング液が再生される。The amount of ferrous chloride supplied into the bath here is an amount equivalent to or slightly larger than the amount of hydrogen chloride present in the liquid to be treated. It is controlled based on the redox potential of the liquid. If the amount of ferrous chloride supplied is greater than the amount of hydrogen chloride, chlorine gas is supplied to the liquid to be treated after removal of hydrogen chloride, and the remaining ferrous chloride is oxidized to ferric chloride. To do. Subsequently, water is added from the water storage tank 54 to the liquid to be treated from which hydrogen chloride has been removed, and the ferric chloride concentration is adjusted according to the application. In this way, for example, ferric chloride is 37% to 55%, 0.1% hydrogen chloride
The etching solution of a certain degree is regenerated.
【００２７】なお分離回収した塩化第二銅は所定の処理
を経て例えば銅粉として取り出されるが、この処理にて
得られる塩化第一鉄液を調整槽５に供給するようにして
もよい。The separated and collected cupric chloride is taken out as copper powder after a predetermined treatment, but the ferrous chloride liquid obtained by this treatment may be supplied to the adjusting tank 5.
【００２８】ここで前記濃縮工程においては、上述のよ
うに被処理液中の塩化第二鉄濃度が４０％以上となるま
で濃縮することが望ましく、特に６５％〜７５％の濃度
となるまで濃縮することが望ましい。その理由は塩化第
二鉄濃度が４０％以下では、晶析工程で塩化第二鉄の錯
体を形成させながら、塩化第二銅を析出させるためには
多量の塩化水素が必要となるからである。In the concentration step, it is desirable to concentrate the ferric chloride in the liquid to be treated to a concentration of 40% or more as described above, and particularly to a concentration of 65% to 75%. It is desirable to do. The reason is that when the ferric chloride concentration is 40% or less, a large amount of hydrogen chloride is required to precipitate cupric chloride while forming a complex of ferric chloride in the crystallization process. .
【００２９】また上述の状態図より塩化第二鉄濃度が６
０％を越えると塩化第二鉄が液体状態で存在できる温度
が低くなり始め、６５％では３０℃程度、７０％では２
５℃程度まで低くなる。従って塩化第二鉄濃度が６５％
以上となるまで濃縮すると、塩化第二鉄の溶解度が高く
なるので、塩化第二銅との溶解度差が大きくなり、塩化
第二銅を析出させやすくなるからである。但し塩化第二
鉄濃度が７５％以上になると液体状態で存在できる温度
が高くなり始めるので７５％程度まで濃縮することが望
ましい。From the above state diagram, the ferric chloride concentration was 6
If it exceeds 0%, the temperature at which ferric chloride can exist in a liquid state begins to decrease, and at 65% it is about 30 ° C, and at 70% it is 2
It goes down to around 5 ° C. Therefore, the ferric chloride concentration is 65%
When concentrated to the above level, the solubility of ferric chloride increases, and the solubility difference with cupric chloride increases, which facilitates the precipitation of cupric chloride. However, when the concentration of ferric chloride becomes 75% or more, the temperature at which it can exist in the liquid state begins to rise, so it is desirable to concentrate to about 75%.
【００３０】さらに晶析工程にて添加される塩化水素ガ
スの量は、再生エッチング液に含まれる銅濃度をどの程
度まで低減するかにより異なるが、２００ｐｐｍ以下を
目的とする場合には、本発明者らの実験結果から８〜１
０％程度であれば塩化第二鉄濃度が６５％程度の場合、
０℃まで被処理液を冷却しても塩化第二鉄が析出するお
それは少ないことが確認され、これにより８〜１０％程
度であることが望ましい。また晶析工程では塩化水素ガ
スを添加することにより塩化第二銅を析出させている
が、このときの晶析温度は１０℃〜５０℃であることが
望ましく、特に塩化第二銅が析出しやすい状態としなが
ら、冷却コストを低下させるためには２０℃〜３０℃で
あることが望ましい。Further, the amount of hydrogen chloride gas added in the crystallization step varies depending on the extent to which the copper concentration contained in the regenerated etching solution is reduced, but when the target is 200 ppm or less, the present invention is used. 8 to 1 from the results of their experiments
If the ferric chloride concentration is about 65% if it is about 0%,
It has been confirmed that ferric chloride is less likely to precipitate even if the liquid to be treated is cooled to 0 ° C., and thus it is preferably about 8 to 10%. Further, in the crystallization step, cupric chloride is deposited by adding hydrogen chloride gas, but the crystallization temperature at this time is preferably 10 ° C to 50 ° C, and particularly cupric chloride is deposited. In order to reduce the cooling cost while maintaining the easy state, the temperature is preferably 20 ° C to 30 ° C.
【００３１】以上において本発明では、酸化工程及び調
整工程は上述の構成に限らず、例えば酸化工程はエッチ
ング廃液中に塩化水素がある程度存在する場合には、酸
素ガスをエッチング廃液中に添加することにより、実施
するようにしてもよい。また調整工程は、抽出蒸留等に
より被処理液から塩化水素を除去することにより、当該
液中の塩化水素濃度を調整するようにしてもよく、この
ようにすれば塩化第一鉄液を添加して調整する場合に比
べて添加した塩化第一鉄分の液量増加が抑えられ、塩化
第二鉄液の再生倍率をより低くすることができる。また
このようにして除去した塩化水素を回収し、晶析工程に
おいて再使用するようにしてもよい。In the above, in the present invention, the oxidizing step and the adjusting step are not limited to the above-mentioned constitutions. For example, in the oxidizing step, when hydrogen chloride is present to some extent in the etching waste liquid, oxygen gas is added to the etching waste liquid. May be carried out. In the adjusting step, the concentration of hydrogen chloride in the liquid may be adjusted by removing hydrogen chloride from the liquid to be treated by extractive distillation or the like. In this way, ferrous chloride liquid is added. The increase in the amount of the added ferrous chloride component can be suppressed as compared with the case of adjusting by the above adjustment, and the regeneration ratio of the ferric chloride liquid can be further lowered. Further, the hydrogen chloride thus removed may be recovered and reused in the crystallization step.
【００３２】このようなエッチング廃液処理方法では、
鉄等の還元剤を用いずに、エッチング廃液から塩化第二
銅を回収することができると共に、銅濃度が２００ｐｐ
ｍ以下という極めて低い濃度のエッチング液を再生する
ことができる。またエッチング液を再生するにあたっ
て、塩化第二鉄と鉄との反応による塩化第一鉄生成に伴
う液量の増加という事態は起こらないので、還元剤とし
て鉄を用いてエッチング廃液を処理する場合に比べて、
エッチング液の再生倍率（再生後のエッチング液の増加
率）を低くすることができ、特に調整工程において抽出
蒸留にて塩化水素を除去した場合には大幅に低くするこ
とができる。In such an etching waste liquid treatment method,
Cupric chloride can be recovered from the etching waste liquid without using a reducing agent such as iron, and the copper concentration is 200 pp.
It is possible to regenerate an etching solution having an extremely low concentration of m or less. Also, when regenerating the etching solution, there is no possibility that the amount of the solution will increase due to the ferrous chloride formation due to the reaction between ferric chloride and iron, so when treating the etching waste solution using iron as the reducing agent. Compared to,
The regeneration ratio of the etching solution (the rate of increase of the etching solution after the regeneration) can be reduced, and particularly when hydrogen chloride is removed by extractive distillation in the adjusting step, it can be significantly reduced.
【００３３】このようにエッチング廃液処理の前後にお
けるエッチング液の量をほとんど増加させることなくエ
ッチング廃液処理を行なうことができるので、廃液処理
にて増加した塩化第二鉄液の廃棄処分を行なう必要がな
くなるか、または廃棄処分の回数を大幅に低減すること
ができ、この廃棄処分に要する手数やコストを削減する
ことができる。As described above, since the etching waste liquid treatment can be performed without substantially increasing the amount of the etching liquid before and after the etching waste liquid treatment, it is necessary to dispose of the ferric chloride liquid increased by the waste liquid treatment. It can be eliminated or the number of times of disposal can be significantly reduced, and the number of steps and costs required for this disposal can be reduced.
【００３４】また被処理液を濃縮して塩化第二鉄濃度を
高めてから、晶析工程にて塩化水素ガスを添加して塩化
第二銅を析出させるようにしたので、塩化第二鉄と塩化
第二銅との溶解度差が大きくなり、塩化第二鉄濃度が高
い溶液から微量の塩化第二銅を析出させることができ、
再生液中の銅濃度を低くすることができる。さらに塩化
第二鉄濃度を６５％程度まで高めると、塩化第二鉄が液
体状態で存在できる温度が高くなることから、塩化第二
鉄の錯体を形成するのに必要な塩化水素の量が少くなる
と共に、被処理液を濃縮することによって析出する塩化
第二銅の量が増加することから、塩化第二銅の析出に必
要な塩化水素の量も減少する。さらにまた晶析工程で塩
化水素を添加することにより塩化第二銅を析出させてい
るので、２０℃〜３０℃程度のある程度高い温度で晶析
を行なうことができ、冷却が容易であり、装置も簡易な
構造にすることができる。Further, after concentrating the liquid to be treated to increase the concentration of ferric chloride, hydrogen chloride gas was added in the crystallization step to precipitate cupric chloride. The solubility difference with cupric chloride becomes large, and trace amounts of cupric chloride can be precipitated from a solution having a high ferric chloride concentration,
The copper concentration in the regenerant can be lowered. Further, if the concentration of ferric chloride is increased to about 65%, the temperature at which ferric chloride can exist in a liquid state becomes high, so that the amount of hydrogen chloride required to form a complex of ferric chloride is small. At the same time, the amount of cupric chloride precipitated by concentrating the liquid to be treated increases, so that the amount of hydrogen chloride required for precipitation of cupric chloride also decreases. Furthermore, since cupric chloride is deposited by adding hydrogen chloride in the crystallization step, crystallization can be performed at a somewhat high temperature of about 20 ° C. to 30 ° C., cooling is easy, and the apparatus is Can also have a simple structure.
【００３５】以上において本発明は、エッチング廃液中
の塩化第二鉄濃度を高めるにあたってはエッチング廃液
の酸化工程のみによって行なってもよいし、エッチング
廃液中の塩化第一鉄濃度が低い場合等には濃縮工程のみ
によって行なってもよい。またエッチング廃液の濃縮工
程では濃縮が進むと塩化第二銅の析出量が多くなって、
被処理液中の銅濃度が低くなり、例えば塩化第二鉄濃度
を７０〜７５％程度まで濃縮すると、被処理液中の銅濃
度は１０００ｐｐｍ程度に減少する。従って濃縮工程で
塩化第二銅を析出させることによって、被処理液中の銅
濃度を所定の濃度まで低減できる場合には晶析工程を実
施しなくてもよい。In the above, according to the present invention, the concentration of ferric chloride in the etching waste liquid may be increased only by the oxidation step of the etching waste liquid, or when the concentration of ferrous chloride in the etching waste liquid is low. It may be performed only by the concentration step. Also, in the process of concentrating the etching waste liquid, the amount of cupric chloride deposited increases as the concentration proceeds,
The copper concentration in the liquid to be treated becomes low. For example, when the ferric chloride concentration is concentrated to about 70 to 75%, the copper concentration in the liquid to be treated is reduced to about 1000 ppm. Therefore, if the copper concentration in the liquid to be treated can be reduced to a predetermined concentration by precipitating cupric chloride in the concentration step, the crystallization step need not be performed.
【００３６】[0036]
【実施例】以下本発明の実施例と比較例とを記載する。
実施例１
塩化第二鉄を１９％、塩化第一鉄を１０％、銅を４％、
塩化水素を３％含む溶液１０００ｇをエッチング廃液の
模擬液として使用し、塩素ガスを添加してエッチング廃
液を酸化して塩化第二鉄濃度を３１％程度とした後（酸
化工程）、塩化第二鉄濃度が７３％となるまで濃縮し
た。この濃縮により結晶が析出し、析出した結晶の組成
を調べたところ、塩化第二銅は６５％、塩化第二鉄は１
９％含まれていた。また濃縮により液量は３９６ｇとな
り、当初の量の約２／５程度に減少した（濃縮工程）。EXAMPLES Examples of the present invention and comparative examples will be described below. Example 1 19% ferric chloride, 10% ferrous chloride, 4% copper,
After using 1000 g of a solution containing 3% of hydrogen chloride as a simulated etching waste liquid, chlorine gas was added to oxidize the etching waste liquid to a ferric chloride concentration of about 31% (oxidation step), and then the second chloride It concentrated until the iron concentration became 73%. Crystals were precipitated by this concentration, and the composition of the precipitated crystals was examined. As a result, cupric chloride was 65% and ferric chloride was 1%.
9% was included. Further, the liquid amount became 396 g by the concentration, which was reduced to about 2/5 of the initial amount (concentration step).
【００３７】次いでこの液を２０℃まで冷却し、塩化水
素ガスを３５ｇ（８．８％）添加した。この操作により
結晶が析出し、析出した結晶の組成を調べたところ、塩
化第二銅は６７％、塩化第二鉄は３１％含まれていた。
一方析出した結晶を分離した後の液の組成を調べたとこ
ろ、塩化第二鉄は６７％、銅は９１ｐｐｍであった（晶
析工程）。Next, this liquid was cooled to 20 ° C., and 35 g (8.8%) of hydrogen chloride gas was added. Crystals were deposited by this operation, and the composition of the deposited crystals was examined. As a result, 67% of cupric chloride and 31% of ferric chloride were contained.
On the other hand, when the composition of the liquid after separating the precipitated crystals was examined, ferric chloride was 67% and copper was 91 ppm (crystallization step).
【００３８】この後結晶分離後の液に酸素ガスを添加し
ながら、３３％塩化第一鉄液を、液中の塩化水素量の
１．２倍当量である４７０ｇ供給し、８０℃で１時間撹
拌を続け、液中の塩化水素を除去した。続いて液に塩素
ガスを添加して、過剰に供給した塩化第一鉄を塩化第二
鉄に酸化すると共に、水を加えて塩化第二鉄濃度を３７
％に調整し、塩化第二鉄液を再生した。再生された塩化
第二鉄液は、銅を５０ｐｐｍ含み、液量は１３２４ｇで
あった（調整工程）。Then, while adding oxygen gas to the liquid after crystal separation, 33% ferrous chloride liquid was supplied at 470 g, which is 1.2 times the equivalent of the amount of hydrogen chloride in the liquid, and the mixture was heated at 80 ° C. for 1 hour. The stirring was continued to remove hydrogen chloride in the liquid. Subsequently, chlorine gas was added to the solution to oxidize the ferrous chloride supplied in excess to ferric chloride, and water was added to adjust the ferric chloride concentration to 37%.
%, And the ferric chloride solution was regenerated. The regenerated ferric chloride liquid contained 50 ppm of copper, and the liquid amount was 1324 g (adjustment step).
【００３９】実施例２
実施例１と同様の条件で、酸化工程、濃縮工程、晶析工
程を実施した後、結晶分離後の被処理液から抽出蒸留に
より塩化水素を除去すると共に、残存する塩化水素を実
施例１と同様の方法で除去し、水を加えて塩化第二鉄濃
度を３７％に調整し、塩化第二鉄液を再生した（調整工
程）。再生された塩化第二鉄液は、銅を５０ｐｐｍ含
み、液量は９００ｇであった。Example 2 Under the same conditions as in Example 1, after carrying out an oxidation step, a concentration step and a crystallization step, hydrogen chloride was removed from the liquid to be treated after the crystal separation by extractive distillation, and residual chlorine was removed. Hydrogen was removed in the same manner as in Example 1, water was added to adjust the ferric chloride concentration to 37%, and the ferric chloride solution was regenerated (adjustment step). The regenerated ferric chloride liquid contained 50 ppm of copper and had a liquid amount of 900 g.
【００４０】比較例１
実施例１と同様の組成のエッチング廃液模擬液に鉄材を
還元剤として添加して、従来技術の項に記載した方法に
より廃液処理を行なった。再生された３７％塩化第二鉄
液は、液量は１５４０ｇであり、銅は５０ｐｐｍ以下で
あった。Comparative Example 1 An iron waste material was added as a reducing agent to a simulated etching waste liquid having the same composition as in Example 1, and the waste liquid was treated by the method described in the section of the prior art. The regenerated 37% ferric chloride solution had a liquid amount of 1540 g and copper content of 50 ppm or less.
【００４１】この実施例により、鉄等の還元剤を用いず
に、エッチング廃液から塩化第二銅を回収することがで
きると共に、銅濃度が１００ｐｐｍ以下という極めて低
い濃度のエッチング液を再生することができることが確
認された。また比較例１に記載した鉄材を用いて廃液処
理を行なう場合に比べて、エッチング液の再生倍率を低
くすることができ、特に実施例２に記載した抽出蒸留に
て塩化水素を除去する方法により調整工程を行なえば再
生倍率を大幅に低くすることができることが確認され
た。さらに晶析工程においては、２０℃程度の温度で塩
化第二銅が析出し、除去できることが確認された。According to this embodiment, cupric chloride can be recovered from the etching waste liquid without using a reducing agent such as iron, and the etching liquid having an extremely low copper concentration of 100 ppm or less can be regenerated. It was confirmed that it was possible. In addition, the regeneration rate of the etching solution can be lowered as compared with the case of performing the waste liquid treatment using the iron material described in Comparative Example 1, and in particular, the method for removing hydrogen chloride by the extractive distillation described in Example 2 is used. It was confirmed that the reproduction ratio can be significantly reduced by performing the adjustment process. Further, it was confirmed that cupric chloride was precipitated and could be removed at a temperature of about 20 ° C. in the crystallization step.
【００４２】[0042]
【発明の効果】本発明によれば、還元剤を使用せず、比
較的高い温度で塩化第二銅を晶析させて分離することが
できると共に、再生後のエッチング液の液量の増加を抑
えながら、エッチング廃液処理を行なうことができる。EFFECTS OF THE INVENTION According to the present invention, cupric chloride can be crystallized and separated at a relatively high temperature without using a reducing agent, and the amount of the etching solution after regeneration can be increased. It is possible to perform the etching waste liquid treatment while suppressing it.
【図１】本発明方法を実施するエッチング廃液処理装置
の一形態を示す構成図である。FIG. 1 is a configuration diagram showing an embodiment of an etching waste liquid treatment apparatus for carrying out the method of the present invention.
【図２】塩化第二鉄の状態図である。FIG. 2 is a phase diagram of ferric chloride.
１ 酸化槽 ２ 濃縮槽 ３ 晶析槽 ４１ 第１の固液分離手段 ４２ 第２の固液分離手段 ５ 調整槽 1 oxidation tank 2 concentration tank 3 crystallization tank 41 First Solid-Liquid Separation Means 42 Second solid-liquid separation means 5 adjusting tank
───────────────────────────────────────────────────── フロントページの続き (72)発明者 木村 克弘 神奈川県横浜市鶴見区末広町１−７ 鶴 見曹達株式会社内 (56)参考文献 特開 平６−146023（ＪＰ，Ａ) 特開 平７−138773（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C23F 1/46 C25F 7/02 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Katsuhiro Kimura 1-7 Suehiro-cho, Tsurumi-ku, Yokohama-shi, Kanagawa Within Tsurumi Soda Co., Ltd. (56) Reference JP-A-6-14023 (JP, A) JP-A 7-138773 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C23F 1/46 C25F 7/02
Claims (6)
ッチング処理した後のエッチング廃液からエッチング液
を再生する方法において、 前記エッチング廃液中の塩化第二鉄濃度を高める工程
と、 前記工程にて得られた被処理液に塩化水素を添加して塩
化第二銅を析出させ、分離する析出分離工程と、 を含むことを特徴とするエッチング廃液処理方法。1. A method of regenerating an etching liquid from an etching waste liquid after etching copper with an ferric chloride etching liquid, comprising the steps of increasing the concentration of ferric chloride in the etching waste liquid: A method for treating etching waste liquid, comprising: a precipitation separation step in which hydrogen chloride is added to the liquid to be treated thus obtained to precipitate cupric chloride and then separated.
ッチング処理した後のエッチング廃液からエッチング液
を再生する方法において、 前記エッチング廃液を濃縮し塩化第二鉄濃度を高める濃
縮工程と、 前記濃縮工程にて得られた被処理液を冷却する冷却工程
と、 冷却された被処理液 に塩化水素を添加して塩化第二銅を
析出させ、分離する析出分離工程と、 を含むことを特徴とするエッチング廃液処理方法。2. A method for regenerating an etching solution from an etching waste solution after etching copper with an ferric chloride etching solution, comprising a concentration step of concentrating the etching waste solution to increase a ferric chloride concentration. Cooling step for cooling the liquid to be treated obtained in the concentration step
And a precipitation / separation step of adding hydrogen chloride to the cooled liquid to be treated to precipitate cupric chloride and separating the liquid.
ッチング処理した後のエッチング廃液からエッチング液
を再生する方法において、 前記エッチング廃液中の塩化第一鉄を塩化第二鉄に酸化
する酸化工程と、 前記酸化工程にて得られた被処理液を濃縮して塩化第二
銅を析出させ、分離する工程と、 を含むことを特徴とするエッチング廃液処理方法。3. A method for regenerating an etching liquid from an etching waste liquid after etching copper with an ferric chloride etching liquid, the method comprising oxidizing ferrous chloride in the etching waste liquid to ferric chloride. And a step of concentrating the liquid to be treated obtained in the oxidation step to precipitate cupric chloride and separating the same, the etching waste liquid treatment method.
ッチング処理した後のエッチング廃液からエッチング液
を再生する方法において、 前記エッチング廃液中の塩化第一鉄を塩化第二鉄に酸化
する酸化工程と、 前記酸化工程にて得られた被処理液を濃縮し塩化第二鉄
濃度を高める濃縮工程と、 前記濃縮された被処理液を冷却する冷却工程と、 冷却された被処理液 に塩化水素を添加して塩化第二銅を
析出させ、分離する析出分離工程と、 を含むことを特徴とするエッチング廃液処理方法。4. A method for regenerating an etching liquid from an etching waste liquid after copper is etched using a ferric chloride etching liquid, the method comprising oxidizing ferrous chloride in the etching waste liquid to ferric chloride. A step, a concentration step of concentrating the liquid to be treated obtained in the oxidation step to increase the concentration of ferric chloride, a cooling step of cooling the concentrated liquid to be treated, and a chlorination of the cooled liquid to be treated. A method for treating an etching waste liquid, comprising: a precipitation separation step of adding hydrogen to precipitate cupric chloride and separating the cupric chloride.
廃液又は被処理液中の塩化第二鉄濃度は４０％以上であ
ることを特徴とする請求項１、２、３又は４記載のエッ
チング廃液処理方法。5. The ferric chloride concentration in the etching waste liquid or the liquid to be treated after increasing the ferric chloride concentration is 40% or more, according to claim 1, 2, 3 or 4. Etching waste liquid treatment method.
程を含むことを特徴とする請求項２又は４記載のエッチ
ング廃液処理方法。6. The etching waste liquid treatment method according to claim 2, wherein the concentration step includes a step of depositing cupric chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26653095A JP3523727B2 (en) | 1995-09-20 | 1995-09-20 | Etching waste liquid treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26653095A JP3523727B2 (en) | 1995-09-20 | 1995-09-20 | Etching waste liquid treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0978266A JPH0978266A (en) | 1997-03-25 |
| JP3523727B2 true JP3523727B2 (en) | 2004-04-26 |
Family
ID=17432166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26653095A Expired - Fee Related JP3523727B2 (en) | 1995-09-20 | 1995-09-20 | Etching waste liquid treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3523727B2 (en) |
-
1995
- 1995-09-20 JP JP26653095A patent/JP3523727B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0978266A (en) | 1997-03-25 |
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