JPH08246157A - Device for recovering valuable component in chemical copper plating solution - Google Patents
Device for recovering valuable component in chemical copper plating solutionInfo
- Publication number
- JPH08246157A JPH08246157A JP8081095A JP8081095A JPH08246157A JP H08246157 A JPH08246157 A JP H08246157A JP 8081095 A JP8081095 A JP 8081095A JP 8081095 A JP8081095 A JP 8081095A JP H08246157 A JPH08246157 A JP H08246157A
- Authority
- JP
- Japan
- Prior art keywords
- waste liquid
- copper plating
- chemical copper
- chelating agent
- recovered
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Chemically Coating (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、プリント配線板の製造
プロセス等に用いる化学銅めっき液の老化廃液中の金属
イオン、キレート剤、およびギ酸イオンを回収し、再資
源化する装置に係り、特に、銅イオンを回収した化学銅
めっき液の廃液から、有価成分を回収し再資源化する装
置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a device for recovering and recycling metal ions, chelating agents, and formate ions in an aged waste liquid of a chemical copper plating solution used in a printed wiring board manufacturing process, etc. In particular, it relates to an apparatus for recovering valuable components from a waste liquid of a chemical copper plating solution in which copper ions have been recovered and recycling them.
【０００２】[0002]
【従来の技術】コンピューターの部品であるプリント配
線板の製造プロセスを例に挙げれば、スルーホール銅、
導体パターンの形成に化学銅めっき液を用いている。化
学銅めっき液は析出反応により液中の銅イオンを金属銅
として析出すると、析出量に対比してめっき液中の銅イ
オン、還元剤、ｐＨ調整剤が減少するため、減少量に応
じて銅イオン、還元剤、ｐＨ調整剤を補給して、化学銅
めっき液の成分濃度を一定に維持し作業を継続してい
る。一般的に銅イオンの補給源としては硫酸銅溶液を用
いており、また、硫酸銅溶液に替えてギ酸銅溶液を用い
ることも試みられている。還元剤、ｐＨ調整剤としてホ
ルマリン、苛性ソーダ溶液を用いている。しかし、化学
銅めっきの欠点として、前記の析出反応、すなわち、 ＣｕＳＯ4＋４ＮａＯＨ＋２ＨＣＨＯ→ Ｃｕ↓＋Ｈ2↑
＋Ｎａ2ＳＯ4＋２ＮａＣＯＯＨ により化学銅めっき液中にギ酸ソーダ、硫酸ソーダが生
じ蓄積する。これ等の塩が蓄積し高濃度になると、析出
するめっき皮膜は物性が劣る脆いめっき皮膜となる。ま
た、析出するめっき皮膜にはコブ状（ノジュール）の突
起が発生しやすくなる傾向にある。そのため、化学銅め
っき液中に蓄積するギ酸ソーダ、硫酸ソーダ等の塩濃度
を管理し、一定量に達すると廃棄して新しい液に更新す
る必要がある。2. Description of the Related Art As an example of a manufacturing process of a printed wiring board which is a computer part, through-hole copper,
A chemical copper plating solution is used to form the conductor pattern. When chemical copper plating solution deposits copper ions in the solution as metallic copper by the precipitation reaction, the copper ions, reducing agent, and pH adjusting agent in the plating solution decrease in comparison with the amount of precipitation. Ions, reducing agents and pH adjusters are replenished to maintain the chemical copper plating solution at a constant concentration, and the work is continued. Generally, a copper sulfate solution is used as a supply source of copper ions, and it has been attempted to use a copper formate solution instead of the copper sulfate solution. Formalin and caustic soda solution are used as a reducing agent and a pH adjusting agent. However, as a drawback of chemical copper plating, the above-mentioned precipitation reaction, that is, CuSO 4 + 4NaOH + 2HCHO → Cu ↓ + H 2 ↑
+ Na 2 SO 4 + 2NaCOOH generates and accumulates sodium formate and sodium sulfate in the chemical copper plating solution. When these salts accumulate and become high in concentration, the deposited plating film becomes a brittle plating film with poor physical properties. In addition, bump-like (nodule) protrusions tend to be easily generated in the deposited plating film. Therefore, it is necessary to manage the salt concentration of sodium formate, sodium sulfate, etc. accumulated in the chemical copper plating solution, and to discard it when a certain amount is reached and to replace it with a new solution.
【０００３】現在、この化学銅めっきの老化廃液処理と
しては、産業廃棄物処理業者に処理を委託したり、もし
くは、プリント配線板の製造業者自身が有する排水処理
施設において、金属イオンを凝集沈降し固液分離し希釈
放流している。しかし、この化学銅めっき液の成分は、
金属イオン以外にも大量のキレート剤、反応生成物のギ
酸ソーダ等が含まれているため、近年、環境汚染の問題
や廃液中の有価資源の回収、再利用という観点から、化
学銅めっき液の老化廃液中の有価資源である、銅イオン
は金属銅とし、また、キレート剤は晶析分離して回収す
る等の再資源化、再利用化が積極的に行われるようにな
ってきた。だが、反応生成物であるギ酸ソーダ、硫酸ソ
ーダ等は、従来から有価資源として回収、再利用は行な
われていないのが現状である。特に、ギ酸ソーダを未回
収のまま、一般排水として河川に放流するとＣＯＤ（化
学酸素消費量）成分が高くなり水質汚染の原因となる。
そのため、水質基準に定める濃度以下にＣＯＤ成分を処
理して河川に放流する必要がある。従来のＣＯＤ成分の
処理方法は、いくつか有るが一般的には以下の方法で行
われている。東京教育情報センター発行の『水質関係の
基礎知識』第２節の汚水処理の方式〔生物化学的処理〕
に述べられているように、ＣＯＤ成分は生物化学的に処
理する。At present, as the aging waste liquid treatment of this chemical copper plating, the treatment is outsourced to an industrial waste treatment company, or metal ions are coagulated and settled in a waste water treatment facility owned by a printed wiring board manufacturer. Solid-liquid separation is performed and diluted and discharged. However, the components of this chemical copper plating solution are
In addition to metal ions, a large amount of chelating agents, reaction products such as sodium formate, etc. are contained, so in recent years, from the viewpoint of environmental pollution problems and recovery and reuse of valuable resources in waste liquid, Copper ion, which is a valuable resource in the aging waste liquid, is changed to metallic copper, and the chelating agent has been actively recycled and reused by crystallization separation and recovery. However, the reaction products such as sodium formate and sodium sulfate have not been recovered and reused as valuable resources in the present situation. In particular, if sodium formate is not recovered yet and is discharged into a river as general wastewater, COD (chemical oxygen consumption) component becomes high, which causes water pollution.
Therefore, it is necessary to process COD components to a concentration below the water quality standards and discharge them into rivers. There are several conventional methods for treating COD components, but the following methods are generally used. Method of sewage treatment [Biochemical treatment] in Section 2 of "Basic knowledge on water quality" published by Tokyo Education Information Center
The COD component is biochemically processed as described in.
【０００４】[0004]
【発明が解決しようとする課題】化学めっきの老化廃液
中のギ酸ソーダの処理は、一般的には上記したような方
法で行われている。しかし、従来の方法である生物処理
は効率が悪いため、処理に時間がかかり施設の規模が大
きくなるという欠点がある。さらに処理施設の運転も専
従員を必要とする等、投資金額、ランニング費が大き
く、また、廃液処理物中から有価成分を回収し、資源の
有効活用、環境対策という点では効果が得られないとい
える。本発明は、上記の課題を解決するものであり、化
学銅めっきの老化廃液中に含まれる金属イオンの回収後
の廃液中から、キレート剤を回収し、キレート剤回収後
の廃液からギ酸ソーダをギ酸として回収することにあ
る。The treatment of sodium formate in the aging waste liquid of chemical plating is generally performed by the method as described above. However, the conventional method of biological treatment is inefficient, and thus has a drawback that the treatment takes time and the scale of the facility becomes large. In addition, the operation of the treatment facility requires a full-time employee, which results in large investment costs and running costs. Also, valuable components are recovered from the waste liquid treatment product, effective use of resources, and environmental measures are not effective. Can be said. The present invention is to solve the above problems, from the waste liquid after the recovery of metal ions contained in the aging waste liquid of chemical copper plating, recovering the chelating agent, sodium formate from the waste liquid after recovering the chelating agent. It is to collect it as formic acid.
【０００５】[0005]
【課題を解決するための手段】上記目的を達成するた
め、本発明は、化学銅めっき液から銅イオンが回収され
た老化廃液を収容する老化廃液貯槽と、老化廃液からキ
レート剤を晶析させるため前記老化廃液貯槽内に硫酸を
添加する添加機構と、前記老化廃液貯槽内の老化廃液を
撹拌する撹拌機構と、キレート剤濾過用の濾過器と、老
化廃液を前記老化廃液貯槽から前記濾過器に移送する移
送機構と、濾過器で濾過した老化廃液を減圧蒸留する減
圧蒸留器と、減圧蒸留により気化したギ酸を液化する冷
却器を備えるようにしている。In order to achieve the above object, the present invention provides an aging waste liquid storage tank for storing an aging waste liquid in which copper ions are recovered from a chemical copper plating solution, and a chelating agent is crystallized from the aging waste liquid. Therefore, an addition mechanism for adding sulfuric acid in the aging waste liquid storage tank, a stirring mechanism for stirring the aging waste liquid in the aging waste liquid storage tank, a filter for filtering a chelating agent, and an aging waste liquid from the aging waste liquid storage tank to the filtration device A transfer mechanism for transferring the waste liquid to the container, a vacuum distiller for distilling the aged waste liquid filtered by the filter under reduced pressure, and a cooler for liquefying the formic acid vaporized by vacuum distillation.
【０００６】[0006]
【作用】上記手段により、化学銅めっきの老化廃液中の
銅イオンを、金属銅として析出させ回収した後の液に、
硫酸を添加しｐＨ２以下にすることにより、キレ−ト剤
であるエチレンジアミンテトラアセテートは晶析する。
晶析したエチレンジアミンテトラアセテートを固液分離
し、ろ液を硫酸酸性で減圧蒸留することにより、化学銅
めっきの老化廃液中のギ酸ソ−ダをギ酸として蒸留回収
する。By the above means, the copper ion in the aging waste liquid of chemical copper plating is deposited as metallic copper and collected in the liquid,
By adding sulfuric acid to adjust the pH to 2 or less, ethylenediaminetetraacetate as a chelating agent is crystallized.
The crystallized ethylenediaminetetraacetate is subjected to solid-liquid separation, and the filtrate is distilled under reduced pressure with sulfuric acid acidity to distill and recover soda formate in the aging waste liquid of chemical copper plating as formic acid.
【０００７】[0007]
【実施例】以下に本実施例について図１を用いて説明す
る。化学銅めっきの析出反応で生じた、ギ酸ソーダ、硫
酸ソーダ等の塩濃度が、管理限界に達した化学銅めっき
槽１の化学銅めっき液２は、ポンプ３で配管４を経由し
て廃液貯槽５に移送される。廃液貯槽５の化学銅めっき
液２は、加温用ヒータ６でめっき反応に最適な温度まで
昇温する。廃液貯槽５には化学銅めっきの析出反応に必
要な十分な量の還元剤（ホルマリン）、ｐＨ調整剤（苛
性ソーダ）を添加する。化学銅めっき液２は、ポンプ７
で配管８を経由し、金属イオンを析出させる触媒となる
金属を付着させたフィルター９を装填した濾過器１０を
通過し廃液貯槽５に戻る。一定の時間循環濾過を行うこ
とにより化学銅めっき液中の銅イオンは、フィルター９
に金属銅として析出する。EXAMPLE This example will be described below with reference to FIG. The chemical copper plating solution 2 in the chemical copper plating tank 1 in which the salt concentration of sodium formate, sodium sulfate, etc., generated in the precipitation reaction of the chemical copper plating has reached the control limit, is passed through the pipe 4 by the pump 3 to the waste liquid storage tank. Transferred to 5. The chemical copper plating solution 2 in the waste solution storage tank 5 is heated by the heater 6 for heating to a temperature optimum for the plating reaction. A sufficient amount of reducing agent (formalin) and pH adjusting agent (caustic soda) necessary for the chemical copper plating precipitation reaction are added to the waste liquid storage tank 5. Chemical copper plating solution 2 is pump 7
Then, after passing through the pipe 8, it passes through the filter 10 loaded with the filter 9 to which the metal serving as the catalyst for depositing metal ions is attached, and returns to the waste liquid storage tank 5. By performing circulation filtration for a certain period of time, the copper ions in the chemical copper plating solution are filtered by the filter 9
Precipitates as metallic copper.
【０００８】次に、銅イオンが除去された廃液貯槽５の
液を、ポンプ１１で配管１２を経由して晶析槽１４に移
送する。硫酸タンク１７の硫酸１８をポンプ１５で配管
１６を経由し添加し撹拌機１３で撹拌しながら、ｐＨを
２以下に下げて銅イオンを除去した化学銅めっき液２に
含まれているキレート剤を晶析させる。その後、ポンプ
１９で配管２０を経由しフィルター２１を装着した濾過
器２２に送液し固液分離する。ろ液は配管２０から減圧
蒸留器２４に送くられ、沸点７０〜８０℃になるように
圧力を減じた、減圧蒸留器２４で蒸留する。気化したギ
酸は冷却器２３で液化し、ギ酸受槽２５に回収する。回
収したギ酸は、酸化銅を添加し撹拌することにより、酸
化銅がギ酸に溶解してギ酸銅なる。このギ酸銅は化学銅
めっきに使用することができる。Next, the liquid in the waste liquid storage tank 5 from which the copper ions have been removed is transferred by the pump 11 to the crystallization tank 14 via the pipe 12. While adding sulfuric acid 18 in the sulfuric acid tank 17 via the pipe 16 with the pump 15 and stirring with the stirrer 13, the chelating agent contained in the chemical copper plating solution 2 in which the pH was lowered to 2 or less to remove copper ions was added. Allow to crystallize. After that, the liquid is sent by the pump 19 through the pipe 20 to the filter 22 equipped with the filter 21 for solid-liquid separation. The filtrate is sent from the pipe 20 to the vacuum distillation device 24, and is distilled in the vacuum distillation device 24 whose pressure is reduced so that the boiling point becomes 70 to 80 ° C. The vaporized formic acid is liquefied in the cooler 23 and collected in the formic acid receiving tank 25. By adding copper oxide and stirring the recovered formic acid, the copper oxide is dissolved in formic acid to become copper formate. This copper formate can be used for chemical copper plating.
【０００９】具体的な処理条件を示すと、廃液貯槽５の
化学銅めっき液量は、約５０００ｌで廃液中の銅濃度は
２．６ｇ／ｌ、キレート剤であるエチレンジアミンテト
ラアセテートは３１ｇ／ｌ、反応生成物であるギ酸ソー
ダは５１ｇ／ｌである。廃液の液温は６５〜７５℃に昇
温し、ポンプ７で１分間当り５００〜６００ｌを濾過器
１０に送液した。フィルター９は市販の２０インチのカ
ートリッジタイプで、フィルターのメッシュは１０ミク
ロンメータを用いた。フィルターは、あらかじめ市販の
パラジウム触媒に２〜３分間浸漬したのち、２〜３分間
流水中で水洗し、水洗中から取り出し３〜４分間液きり
を行ったのち、洗浄水を循環できる濾過器に装填し１０
〜１５分間水洗したのち、濾過器１０に２０本装填し
た。化学銅めっき液２の循環は１２０分間行なった。銅
イオン除去後の廃液貯槽５の液中の銅イオン濃度は１ｐ
ｐｍ以下となり、約１３ｋｇの銅が回収できた。The specific treatment conditions are as follows: the amount of chemical copper plating solution in the waste liquid storage tank 5 is about 5000 l, the copper concentration in the waste liquid is 2.6 g / l, and the chelating agent ethylenediaminetetraacetate is 31 g / l. The reaction product, sodium formate, is 51 g / l. The liquid temperature of the waste liquid was raised to 65 to 75 ° C., and the pump 7 sent 500 to 600 l per minute to the filter 10. The filter 9 was a commercially available 20-inch cartridge type, and the mesh of the filter was a 10 micron meter. The filter is immersed in a commercially available palladium catalyst for 2 to 3 minutes in advance, washed with running water for 2 to 3 minutes, taken out from the rinsed water and drained for 3 to 4 minutes. Loaded 10
After washing for 15 minutes with water, 20 bottles were loaded in the filter 10. The chemical copper plating solution 2 was circulated for 120 minutes. The copper ion concentration in the liquid in the waste liquid storage tank 5 after removal of copper ions is 1 p
It became pm or less, and about 13 kg of copper could be recovered.
【００１０】銅イオンを除去した廃液貯槽５の液を晶析
槽１４に移し、２５℃以下に冷却し、７５％の硫酸を添
加し撹拌しながらｐＨ１．５に調整し、エチレンジアミ
ンテトラアセテートを晶析させ濾過器で固液分離した。
フィルターは市販の２０インチのカートリッジタイプ
で、フィルターメッシュは５ミクロンメータを用いた。
ろ液中のエチレンジアミンテトラアセテート濃度は０．
３ｇ／ｌ以下となり、約１５０ｋｇ回収できた。ろ液を
減圧蒸留器２４で沸点７０〜８０℃で蒸留し、ギ酸受槽
２５に回収した。この時、化学銅めっきの老化廃液５０
００ｌから、ギ酸が約１００ｋｇ回収出来た。従来、５
０００ｌ（約５６００ｋｇ）の産業廃棄物量を５００ｋ
ｇに減量出来た。The liquid in the waste liquid storage tank 5 from which the copper ions have been removed is transferred to the crystallization tank 14, cooled to 25 ° C. or lower, 75% sulfuric acid is added and the pH is adjusted to 1.5 with stirring to crystallize ethylenediamine tetraacetate. It was precipitated and solid-liquid separated with a filter.
The filter was a commercially available 20-inch cartridge type, and the filter mesh used was a 5 micron meter.
The concentration of ethylenediaminetetraacetate in the filtrate was 0.
It was 3 g / l or less, and about 150 kg could be recovered. The filtrate was distilled with a vacuum distiller 24 at a boiling point of 70 to 80 ° C. and collected in a formic acid receiving tank 25. At this time, chemical copper plating aging waste liquid 50
About 100 kg of formic acid could be recovered from 001. Conventional 5
Amount of industrial waste of 000 l (about 5600 kg) is 500 k
I was able to reduce to g.
【００１１】[0011]
【発明の効果】以上説明したように本発明によれば、化
学めっきの老化廃液からの有価成分のキレート剤、ギ酸
の回収を、低コストの設備投資、ランニング費で可能と
する。また、回収したギ酸に銅を溶解することにより、
化学銅めっきの銅イオンの補給に再利用することが可能
である。As described above, according to the present invention, it is possible to recover the chelating agent, which is a valuable component, and formic acid from the aging waste liquid of chemical plating with a low cost of equipment investment and running cost. Also, by dissolving copper in the recovered formic acid,
It can be reused for the supply of copper ions for chemical copper plating.
【図１】化学銅めっき液から有価成分の銅、キレート
剤、ギ酸を回収する回収装置の構成を示す。FIG. 1 shows the configuration of a recovery device for recovering valuable components of copper, a chelating agent, and formic acid from a chemical copper plating solution.
１ 化学銅めっき槽 ２ 化学銅めっき液 ３ ポンプ ４ 配管 ５ 廃液貯槽 ６ 加温用ヒータ ７ ポンプ ８ 配管 ９ フィルター １０ 濾過器 １１ ポンプ １２ 配管 １３ 撹拌機 １４ 晶析槽 １５ ポンプ １６ 配管 １７ 硫酸タンク １８ 硫酸 １９ ポンプ ２０ 配管 ２１ フィルター ２２ 濾過器 ２３ 冷却器 ２４ 減圧蒸留器 ２５ ギ酸受槽 ２６ ギ酸 1 Chemical Copper Plating Tank 2 Chemical Copper Plating Solution 3 Pump 4 Piping 5 Waste Liquid Storage Tank 6 Heating Heater 7 Pump 8 Piping 9 Filter 10 Filter 11 Pump 12 Piping 13 Stirrer 14 Crystallizer 15 Pump 16 Piping 17 Sulfuric Acid Tank 18 Sulfuric acid 19 Pump 20 Piping 21 Filter 22 Filter 23 Cooler 24 Vacuum distiller 25 Formic acid receiving tank 26 Formic acid
Claims (1)
た老化廃液を収容する老化廃液貯槽と、老化廃液からキ
レート剤を晶析させるため前記老化廃液貯槽内に硫酸を
添加する添加機構と、前記老化廃液貯槽内の老化廃液を
撹拌する撹拌機構と、キレート剤濾過用の濾過器と、老
化廃液を前記老化廃液貯槽から前記濾過器に移送する移
送機構と、濾過器で濾過した老化廃液を減圧蒸留する減
圧蒸留器と、減圧蒸留により気化したギ酸を液化する冷
却器を備えることを特徴とする化学銅めっき液の有価成
分回収装置。1. An aging waste liquid storage tank for storing an aging waste liquid in which copper ions are recovered from a chemical copper plating solution, and an addition mechanism for adding sulfuric acid into the aging waste liquid storage tank for crystallizing a chelating agent from the aging waste liquid, A stirring mechanism for stirring the aging waste liquid in the aging waste liquid storage tank, a filter for filtering the chelating agent, a transfer mechanism for transferring the aging waste liquid from the aging waste liquid storage tank to the filter, and the aging waste liquid filtered by the filter. An apparatus for recovering valuable components of a chemical copper plating solution, comprising a vacuum distiller for vacuum distillation and a cooler for liquefying formic acid vaporized by vacuum distillation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7080810A JP3020137B2 (en) | 1995-03-13 | 1995-03-13 | Equipment for recovering valuable components of chemical plating solutions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7080810A JP3020137B2 (en) | 1995-03-13 | 1995-03-13 | Equipment for recovering valuable components of chemical plating solutions |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30080499A Division JP3312299B2 (en) | 1995-03-13 | 1999-10-22 | Apparatus and method for recovering valuable component of chemical plating solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08246157A true JPH08246157A (en) | 1996-09-24 |
| JP3020137B2 JP3020137B2 (en) | 2000-03-15 |
Family
ID=13728833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7080810A Expired - Fee Related JP3020137B2 (en) | 1995-03-13 | 1995-03-13 | Equipment for recovering valuable components of chemical plating solutions |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3020137B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107130229A (en) * | 2017-05-17 | 2017-09-05 | 齐鲁理工学院 | A kind of chemical plating appts |
-
1995
- 1995-03-13 JP JP7080810A patent/JP3020137B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107130229A (en) * | 2017-05-17 | 2017-09-05 | 齐鲁理工学院 | A kind of chemical plating appts |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3020137B2 (en) | 2000-03-15 |
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