JP2769774B2 - Method and apparatus for regenerating electroless nickel plating wastewater - Google Patents

Method and apparatus for regenerating electroless nickel plating wastewater

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Publication number
JP2769774B2
JP2769774B2 JP5294053A JP29405393A JP2769774B2 JP 2769774 B2 JP2769774 B2 JP 2769774B2 JP 5294053 A JP5294053 A JP 5294053A JP 29405393 A JP29405393 A JP 29405393A JP 2769774 B2 JP2769774 B2 JP 2769774B2
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JP
Japan
Prior art keywords
phosphite
nickel plating
electroless nickel
plating
tank
Prior art date
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JP5294053A
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Japanese (ja)
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JPH07126855A (en
Inventor
哲男 斎藤
康二 戸室
進一 桑名
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Tochigi Prefecture
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Tochigi Prefecture
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Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【産業上の利用分野】本発明は、無電解ニッケルめっき
廃液を再生して循環的に再利用できる方法とその装置に
関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for regenerating and recycling a waste electroless nickel plating waste solution.

【0002】[0002]

【発明の背景】無電解ニッケルめっきは、還元剤の化学
反応を利用してめっき皮膜を形成することができる為、
導電性のないセラミックやプラスチックにめっき皮膜が
形成でき、又、電気めっきに比較してめっき皮膜の付き
廻り性に優れ、ピンホ−ルのない均一な皮膜が得られる
為、大型コンピュ−タ−部品、自動車用燃料供給部品、
カメラ部品、印刷用ロ−ル部品等に広く利用されてい
る。しかし、めっき時に副生する反応阻害成分が蓄積す
ると、めっき反応が阻害され良好なめっきができなくな
り、その廃液は、全量産業廃棄物として業者に委託して
処分している現状にある。それらめっき廃液は、年間約
10万トンも発生し、現在その90%が海洋投棄されて
おり、その処理方法の開発が急務となっている。
BACKGROUND OF THE INVENTION Since electroless nickel plating can form a plating film by utilizing a chemical reaction of a reducing agent,
Plating film can be formed on non-conductive ceramics and plastics. Also, compared with electroplating, the plating film has excellent coverage and a uniform film without pinholes can be obtained. , Automotive fuel supply parts,
Widely used for camera parts, printing roll parts and the like. However, if a reaction inhibitory component by-produced during plating accumulates, the plating reaction is inhibited, and good plating cannot be performed, and the entire waste liquid is now being disposed of by a contractor as industrial waste. About 100,000 tons of these plating waste liquids are generated annually, and 90% of them are currently dumped in the ocean.

【0003】[0003]

【従来の技術】現在、無電解めっき廃液の再利用法とし
て検討が進められている主な技術に、(a)逆浸透膜或
いは次亜リン酸を結合させたイオン交換膜を用い、めっ
き液中の亜リン酸成分を除去する逆浸透法及びイオン交
換膜法、(b)亜リン酸をリン酸に酸化する電解法等が
ある。又、無電解ニッケルめっきとは対象を異にする
が、無電解錫めっき浴の再生方法として、めっき浴にア
ルカリ土類金属塩を添加して、アルカリ土類金属の錫酸
塩を沈殿させるステップと、めっき浴から前記錫酸塩の
沈殿を除去するステップを含んで錫めっき浴を再生させ
る手段も提案されている(特開昭63−192876号
公報)。
2. Description of the Related Art The main technologies currently being studied as a method for reusing an electroless plating waste solution include (a) a plating solution using a reverse osmosis membrane or an ion exchange membrane to which hypophosphorous acid is bound. There are a reverse osmosis method and an ion-exchange membrane method for removing phosphorous acid components therein, and (b) an electrolytic method for oxidizing phosphorous acid to phosphoric acid. In addition, although the target is different from electroless nickel plating, as a method for regenerating an electroless tin plating bath, a step of adding an alkaline earth metal salt to a plating bath to precipitate a stannate of an alkaline earth metal. A means for regenerating a tin plating bath including a step of removing the precipitate of the stannate from the plating bath has also been proposed (JP-A-63-192876).

【0004】[0004]

【発明が解決しようとする課題】しかし、(a)逆浸透
法及びイオン交換膜法は、亜リン酸の除去率が30〜5
0%と低く、又、(b)電解法は、リン酸の蓄積量の増
加に伴い比重及び粘性が増大してめっき皮膜形成ができ
難くなる等の欠点を有し、いずれの方法においても複雑
で高価な装置を必要とし、再生処理コストがかかりすぎ
処理効率も悪く、また、排水処理においてもBOD成分
の除去等に対する充分な対応が困難なため、実用化され
ずに現在に至っている。
However, in the reverse osmosis method and the ion exchange membrane method, the removal rate of phosphorous acid is 30 to 5 (a).
0%, and the (b) electrolysis method has the drawback that the specific gravity and viscosity increase with the increase in the amount of accumulated phosphoric acid, making it difficult to form a plating film. In addition, the cost of regeneration treatment is too high and the treatment efficiency is low, and it is difficult to sufficiently cope with the removal of BOD components in wastewater treatment.

【0005】又、無電解錫を対象とした浴の再生方法
は、該技術が両性金属である錫を対象とした処理技術で
あることから上記手段で再生処理が可能となるが、これ
を無電解ニッケルめっきの廃液に応用しようとすると、
添加したアルカリ土類金属塩の影響で、無電解ニッケル
めっき液中のニッケルイオンが難溶性の水酸化ニッケル
として沈殿を生成してしまうため、ニッケルイオンの欠
けためっき液としての価値がなくなるという重大な欠点
を含み、そのままでは無電解ニッケルめっきへの応用が
不可能である。
In the method of regenerating a bath for electroless tin, since the technique is a processing technique for tin, which is an amphoteric metal, regeneration can be performed by the above-described means. When trying to apply it to electrolytic nickel plating wastewater,
Due to the effect of the added alkaline earth metal salt, nickel ions in the electroless nickel plating solution form precipitates as poorly soluble nickel hydroxide, and the value as a plating solution lacking nickel ions is lost. However, it cannot be applied to electroless nickel plating as it is.

【0006】本発明は、従来の無電解めっき廃液処理技
術が持つ以上のような欠点を解決し、実効性のある無電
解めっき廃液再生処理技術を開発することを目的とす
る。
An object of the present invention is to solve the above-mentioned drawbacks of the conventional electroless plating wastewater treatment technology and to develop an effective electroless plating wastewater recycling technology.

【0007】[0007]

【課題を解決するための手段】本発明の対象とするの
は、無電解ニッケルめっき浴中で、ニッケル皮膜形成に
より次亜リン酸塩が酸化された塩を含むめっき廃液であ
る。当該液が廃液とされるのは、還元剤の還元反応を利
用して金属めっき皮膜を形成するため、めっき皮膜形成
反応により、還元剤自体の酸化が進み、還元力を失った
亜リン酸塩がめっき液中に多量に蓄積されることにな
り、この酸化された還元剤は、めっき皮膜形成反応を阻
害するため、蓄積量が増加しためっき液ではめっきがで
きなくなる為である。
An object of the present invention is a plating waste solution containing a salt obtained by oxidizing hypophosphite by forming a nickel film in an electroless nickel plating bath. The liquid is a waste liquid because the metal plating film is formed by utilizing the reduction reaction of the reducing agent, so that the oxidation of the reducing agent itself proceeds by the plating film forming reaction, and the phosphite which has lost the reducing power is reduced. Is accumulated in the plating solution in a large amount, and the oxidized reducing agent inhibits a plating film forming reaction, so that plating cannot be performed with the plating solution having an increased accumulated amount.

【0008】そこで、亜リン酸塩に反応して沈殿を生じ
させる手段を検討したところ、カルシウムの水酸化物を
亜リン酸塩の処理剤として無電解ニッケルめっき廃液に
添加すると、亜リン酸塩が生成し、これを沈殿物として
除去できることが確認され、同様の性質から、バリウム
又はストロンチウムの水酸化物にも応用が可能となる。
即ち、例えば水酸化カルシウム,水酸化バリウム,水酸
化ストロンチウム等の水酸化物を廃液中に添加すると、
亜リン酸カルシウム,亜リン酸バリウム,亜リン酸スト
ロンチウム等の化合物が生成され、当該化合物は固化し
て溶液中から沈殿として沈積し、これを分離することで
除去できることを見出した。
[0008] Then, the means for reacting with phosphite to form a precipitate was examined. When calcium hydroxide was added to the electroless nickel plating waste solution as a phosphite treatment agent, phosphite was added. Is generated, and it is confirmed that it can be removed as a precipitate. From the same properties, application to barium or strontium hydroxide is possible.
That is, for example, when hydroxides such as calcium hydroxide, barium hydroxide, and strontium hydroxide are added to the waste liquid,
It has been found that compounds such as calcium phosphite, barium phosphite, and strontium phosphite are produced, and the compounds are solidified, deposited as a precipitate from the solution, and can be removed by separation.

【0009】しかし、上記方法のままでは、水酸化物を
添加すると、処理液のpHが10以上のアルカリとな
り、無電解ニッケルめっき液中のニッケルイオンが、難
溶性の水酸化ニッケルとして沈殿を生成してしまい、液
のゲル化が進むと共に主成分たるニッケルイオンが除去
された液は、めっき液としての価値がなく、再利用の目
的が損われてしまう。
However, in the above method, when a hydroxide is added, the pH of the processing solution becomes alkali of 10 or more, and nickel ions in the electroless nickel plating solution form precipitates as poorly soluble nickel hydroxide. As a result, the solution from which the gelation of the solution has progressed and the nickel ions as the main component have been removed has no value as a plating solution, and the purpose of reuse is impaired.

【0010】そこで、ニッケルイオンを沈殿させること
なく亜リン酸化合物のみを選択的に沈殿させる手段を鋭
意研究した結果、廃液中に存在するニッケルイオン1モ
ルに対し水酸化アンモニウムを0.2〜4モルの割合、
より望ましくは1.8〜2.2モルの割合で添加する
と、アンモニウムイオンとニッケルイオンとの間に結合
関係が生成し、アルカリ性でも極めて安定な可溶性錯イ
オンとしてめっき廃液中に溶存でき、且つ、それが亜リ
ン酸化合物の沈殿の促進を妨害しないことを見い出し
た。即ち、廃液中に存在するニッケルイオン1モルに対
し水酸化アンモニウムを0.2〜4モルの割合で添加す
ると、アンモニウムイオンとニッケルイオンとの間に、
錯イオンが形成され、その形態は(NH42Ni(SO
42・6H2Oと推測されるが、これが溶液中に可溶性
物質として安定に存在する為、ニッケルイオンが水酸化
物として沈殿してしまう虞がなくなる。このとき、水酸
化アンモニウムが0.2モル以下では、ニッケルイオン
が沈殿してしまい、4.0モル以上では再生めっき液が
分解してめっき皮膜が形成できないものとなる。一方、
0.2〜0.8モルでめっき皮膜の形成が可能となるが
未だ光沢の少ない状態で、2.2〜4.0モルではやは
りめっき皮膜は形成されるがザラ付きの多い状態で、
1.8〜2.2モルの範囲において光沢のある良好な皮
膜が形成され、最適な範囲であることが確認された。
Therefore, as a result of intensive studies on a means for selectively precipitating only the phosphite compound without precipitating nickel ions, ammonium hydroxide was added in an amount of 0.2 to 4 mol per mol of nickel ions present in the waste liquid. Mole percentage,
More preferably, when added at a ratio of 1.8 to 2.2 mol, a bonding relationship is formed between the ammonium ion and the nickel ion, and the compound can be dissolved in the plating waste solution as a soluble complex ion which is extremely stable even under alkaline conditions. It has been found that it does not hinder the promotion of the precipitation of the phosphite compound. That is, when ammonium hydroxide is added at a ratio of 0.2 to 4 moles relative to 1 mole of nickel ions present in the waste liquid, between the ammonium ions and nickel ions,
A complex ion is formed, and its form is (NH 4 ) 2 Ni (SO
4) it is estimated to 2 · 6H 2 O, which is to exist stably as soluble material in solution, there is no fear that the nickel ions will be precipitated as the hydroxide. At this time, if the amount of ammonium hydroxide is 0.2 mol or less, nickel ions precipitate, and if the amount is 4.0 mol or more, the regenerated plating solution is decomposed and a plating film cannot be formed. on the other hand,
With 0.2 to 0.8 mol, a plating film can be formed but still has little luster. With 2.2 to 4.0 mol, a plating film is still formed but with a lot of roughness.
A good glossy film was formed in the range of 1.8 to 2.2 mol, and it was confirmed that the film was in an optimum range.

【0011】更に、同様の趣旨で、亜リン酸化合物を選
択的に沈殿させる方法を研究したところ、無電解ニッケ
ルめっき皮膜形成により次亜リン酸塩が酸化された塩を
含む無電解ニッケルめっき廃液に対し、廃液中の亜リン
酸濃度と等モルのカルシウム,バリウム又はストロンチ
ウムの水酸化物から成る群の少なくとも一つ以上を含む
亜リン酸処理剤を添加し、一定時間攪拌して亜リン酸成
分を可及的に沈殿させ、次いでpHを4〜6に調整し、
ニッケルイオンを沈殿させることなく亜リン酸化合物の
みを選択的に除去することを見い出した。即ち、後述の
実施例3に記す如く、廃液中の亜リン酸濃度と等モルの
水酸化カルシウムを添加し、一定時間溶液に攪拌を加え
つつ、亜リン酸塩と水酸化カルシウムとの反応を促し、
一定時間内はニッケルイオンを沈殿させることなく亜リ
ン酸成分を可及的に多量に沈殿させる。更に、溶液内の
亜リン酸塩を取除くため、先ず、亜リン酸カルシウム溶
解量とpHとの関係を調べたところ、図1に示す如く、
約pH3近傍から亜リン酸カルシウムの溶解量が著しく
低下することが判った。一方、ニッケルイオンの水酸化
物との反応とpHとの関係を実験したところ、表1に示
す如くで、pH6以下では全く沈殿を生じることがな
く、pH7〜8で6%程度の沈殿を生成し、pH9で2
8%、pH10以上では99%沈殿を生成することが判
明した。この結果から、処理液のpHを亜リン酸カルシ
ウムの溶解量の少ないpH4以上でニッケルイオンの沈
殿の全く生じない6以下に調整し、ニッケルを沈殿させ
ることなく、亜リン酸化合物の沈殿を最大とし、つま
り、亜リン酸化合物のみを選択的に沈殿させ、これを除
去することが可能となった。
Further, a phosphorous acid compound is selected for the same purpose.
After studying the method of selective precipitation, the electroless nickel
The salt of hypophosphite oxidized by plating film formation
Containing phosphorus electrolyte in wastewater
Calcium, barium, or strontium equimolar to the acid concentration
Containing at least one of the group consisting of
Add a phosphite treatment agent, stir for a certain period of time,
As much as possible, then adjust the pH to 4-6,
Phosphorous compounds without precipitation of nickel ions
Have been found to selectively remove only That is,
As described in Example 3, the concentration of phosphorous acid in the waste liquid is equimolar.
Add calcium hydroxide and stir the solution for a certain period of time
While promoting the reaction between phosphite and calcium hydroxide,
For a certain period of time, the sub-
The acid component is precipitated as much as possible. Furthermore, in the solution
In order to remove phosphite , first, the relationship between the amount of calcium phosphite dissolved and the pH was examined. As shown in FIG.
It was found that the dissolution amount of calcium phosphite was remarkably reduced from about pH 3. On the other hand, when the relationship between the reaction of nickel ions with hydroxide and pH was tested, as shown in Table 1, no precipitation occurred at pH 6 or lower, and about 6% precipitation was generated at pH 7 to 8. And at pH 9 2
It was found that a precipitate of 99% was formed at a pH of 8% and a pH of 10 or more. From these results, the pH of the treatment solution was adjusted to
At pH 4 or higher where the amount of dissolved
It is possible to maximize the precipitation of the phosphite compound without precipitating nickel by adjusting it to 6 or less at which no phosphite compound is generated, that is, it is possible to selectively precipitate only the phosphite compound and remove it. became.

【0012】[0012]

【表1】 条件)NiCl2 を0.1N HClに溶解し、Ni2+
として10ppmに調整した調整液を作製し、これに
pH調整用試薬を投与して、沈殿が生成した後の溶液中
のNiの残留濃度を測定した。
[Table 1] Conditions) NiCl 2 is dissolved in 0.1N HCl, and Ni 2+
Was prepared, and a pH adjusting reagent was administered thereto, and the residual concentration of Ni in the solution after the formation of the precipitate was measured.

【0013】上記沈殿した亜リン酸化合物は、後述の遠
心分離装置等を含む分離手段で分離する。このとき、上
記亜リン酸処理剤をカルシウムとした場合には、過剰の
カルシウムイオンが残留し、これをそのまま再生めっき
液として使用すると、皮膜の光沢が失われる傾向があ
る。そこで、亜リン酸化合物の沈殿除去後に、フッ素化
合物例えば、フッ化アンモニウム(NH4F)を添加
し、残留カルシウムと反応させてフッ化カルシウムとし
て沈殿を生成し、これを分離除去するのが望ましい。こ
のとき、フッ素化合物は沈殿生成を促すばかりでなく、
めっき皮膜の光沢を増すので好適である。
The precipitated phosphite compound is separated by separation means including a centrifugal separator and the like described below. At this time, when calcium is used as the phosphite treatment agent, excessive calcium ions remain, and if this is used as it is as a regenerating plating solution, the gloss of the film tends to be lost. Therefore, it is preferable to add a fluorine compound, for example, ammonium fluoride (NH 4 F), react with residual calcium to form a precipitate as calcium fluoride, and separate and remove the precipitate after removing the precipitate of the phosphite compound. . At this time, the fluorine compound not only promotes precipitation, but also
It is suitable because it increases the gloss of the plating film.

【0014】上記沈殿分離後の濾液はそのまま再度の無
電解ニッケルめっき液として利用することもできるが、
より望ましくは、処理液の成分を分析し、硫酸ニッケ
ル,次亜リン酸,及び有機酸等が不足する場合には、こ
れを補って完全なめっき液として再生するのが望まし
い。
[0014] The filtrate after the precipitation and separation can be used as it is as an electroless nickel plating solution again.
More desirably, the components of the processing solution are analyzed, and when nickel sulfate, hypophosphorous acid, organic acid, and the like are insufficient, it is desirable to make up for this and to regenerate as a complete plating solution.

【0015】斯して得られた再生処理液を用いて無電解
ニッケルめっきを行なったところ、皮膜の析出速度、皮
膜の均一析出性、皮膜の硬さ、皮膜の耐食性及び皮膜の
密着力等の特性値において、新しいめっき浴と遜色のな
い値を示し、物性的にも優れたものであることが確認さ
れた。
When electroless nickel plating was performed using the thus obtained regenerating solution, the deposition rate of the film, uniform deposition of the film, hardness of the film, corrosion resistance of the film, adhesion of the film, etc. The characteristic values were comparable to those of a new plating bath, and were confirmed to be excellent in physical properties.

【0016】次に、上記方法を具現するための無電解ニ
ッケルめっき廃液の再生装置は、無電解ニッケルめっき
廃液を溜める貯留槽と、該廃液と水酸化アンモニウム及
び亜リン酸処理剤の反応を促し亜リン酸化合物を選択的
に生成させる反応槽と、当該反応によって生じた沈殿物
を除去する分離槽と、該分離槽からの分離液を昇温させ
て亜リン酸処理剤をカルシウムとした場合の水酸化カル
シウムの更なる沈殿を促す加温槽とから成る。望ましく
は、加温槽の後に処理液に不足する薬剤を投入する調整
槽を配設して成る。
Next, an apparatus for regenerating an electroless nickel plating waste solution for realizing the above method comprises a storage tank for storing the electroless nickel plating waste solution, and a reaction between the waste solution, ammonium hydroxide and a phosphite treatment agent. When a reaction tank for selectively generating a phosphite compound, a separation tank for removing a precipitate generated by the reaction, and a temperature of a separated solution from the separation tank, and the phosphite treatment agent is calcium. And a heating tank for promoting further precipitation of calcium hydroxide. Desirably, an adjusting tank is provided after the heating tank for charging the insufficient chemical into the processing liquid.

【0017】当該再生装置の作用を説明すると、先ず、
めっき廃液を溜めた貯留槽から送られた液を、反応槽内
で薬剤槽から投入された亜リン酸処理剤及び水酸化アン
モニウムと混合し、又は、pH調整を行いニッケルイオ
ンの沈殿を回避しつつ、亜リン酸化合物の生成反応を促
す。該反応が終了したら処理液を分離槽に送り、該分離
槽内の遠心分離機で比重の大なる沈殿物を遠心分離作用
で分離除去すると、めっき阻害成分としての亜リン酸化
合物を除去することができる。該処理液を加温槽に入
れ、液温を上昇させ、その昇温効果によりカルシウムの
溶解度を低下させ、液中の未だ溶解したままの水酸化カ
ルシウムをも析出させると、除去を完全ならしめること
ができる。更に完全を期すため、調整槽に投入して薬品
槽から、硫酸ニッケル、次亜リン酸、有機酸等のめっき
浴としての不足成分を補給し、斯かる処理液をめっき槽
に戻して再利用することができる。
The operation of the reproducing apparatus will be described first.
The solution sent from the storage tank that stores the plating waste solution is mixed with the phosphating agent and ammonium hydroxide charged from the chemical tank in the reaction tank, or the pH is adjusted to avoid precipitation of nickel ions. While promoting the reaction of forming a phosphorous acid compound. When the reaction is completed, the treatment solution is sent to a separation tank, and a sediment having a large specific gravity is separated and removed by a centrifugal separator in a centrifuge in the separation tank to remove a phosphite compound as a plating inhibiting component. Can be. The treatment liquid is put into a heating bath, the temperature of the liquid is raised, the solubility of calcium is lowered by the temperature raising effect, and the calcium hydroxide which is still dissolved in the liquid is precipitated, thereby completely removing the calcium hydroxide. be able to. For further perfection, put into the adjustment tank and replenish the plating bath with insufficient components such as nickel sulfate, hypophosphorous acid, organic acid, etc. from the chemical tank, and return such processing solution to the plating tank for reuse. can do.

【0018】[0018]

【発明の効果】本発明は、以上の構成及び作用に基づ
き、めっき主成分としてのニッケル濃度の減少率を極少
に留めつつ、めっき阻害成分としての亜リン酸を大幅に
減少させることができるという選択的除去が可能とな
り、めっき皮膜形成に必要な成分が確保されて再利用が
可能になるという画期的効果を奏する。又、遠心分離装
置及び加温槽等を装備した本発明装置は、めっきの阻害
成分である亜リン酸成分を充分に除去することができ再
生処理装置として最適であると共に、複雑で高価な装置
を必要とせず、簡潔で効率的な機構となる等極めて有益
な発明である。
According to the present invention, based on the above constitution and operation, it is possible to greatly reduce phosphorous acid as a plating inhibiting component while keeping the rate of reduction of nickel concentration as a plating main component to a minimum. Selective removal is possible, and an epoch-making effect is achieved in that components necessary for plating film formation are secured and reuse becomes possible. The apparatus of the present invention equipped with a centrifugal separator, a heating tank, and the like is capable of sufficiently removing a phosphorous acid component, which is a plating-inhibiting component, and is optimal as a reprocessing apparatus, and is a complicated and expensive apparatus. This is an extremely useful invention that does not require a device and provides a simple and efficient mechanism.

【0019】[0019]

【実施例】【Example】

(実施例1)めっき阻害成分の亜リン酸100g/Lを
含む無電解ニッケルめっき廃液に、廃液中のニッケルイ
オン1モルに対する水酸化アンモニウムを各濃度を変え
て添加し、攪拌後、スラリ−状に調整した水酸化カルシ
ウムを廃液中の亜リン酸濃度と等モルの60gを加え、
30分間攪拌を行った後、3時間放置後遠心分離により
固液を分離した。次に、分離液を精密濾過し、濾液に硫
酸を加えて、pHを4.5に調整し、液温を70℃に昇
温して30分間加熱後、ただちに精密濾過を行った。そ
の濾液を無電解めっき再生液として用い、めっき皮膜形
成を行った。その結果を示すと表2の通りで、水酸化ア
ンモニウムの濃度が廃液中のニッケルイオン1モルに対
し0.2〜4.0モルの範囲でめっき皮膜の形成が可能
であるが、光沢のあるもっとも良好な皮膜が形成される
のは1.8〜2.2モルの範囲であり、かかる範囲が最
適範囲であることが判った。
(Example 1) Ammonium hydroxide was added to a waste solution of electroless nickel plating containing 100 g / L of phosphorous acid as a plating inhibiting component at various concentrations with respect to 1 mol of nickel ions in the waste solution. 60 g of calcium hydroxide adjusted to the same concentration as the phosphorous acid concentration in the waste liquid was added,
After stirring for 30 minutes, the mixture was allowed to stand for 3 hours and then separated into solid and liquid by centrifugation. Next, the separated solution was subjected to microfiltration, sulfuric acid was added to the filtrate to adjust the pH to 4.5, the temperature of the solution was raised to 70 ° C., and after heating for 30 minutes, microfiltration was immediately performed. Using the filtrate as a regenerating solution for electroless plating, a plating film was formed. The results are shown in Table 2. As shown in Table 2, it is possible to form a plating film when the concentration of ammonium hydroxide is in the range of 0.2 to 4.0 mol with respect to 1 mol of nickel ions in the waste liquid. The best film was formed in the range of 1.8 to 2.2 mol, and it was found that this range was the optimum range.

【0020】[0020]

【表2】 [Table 2]

【0021】(実施例2)めっき阻害成分の亜リン酸1
00g/Lを含む無電解ニッケルめっき廃液に水酸化ア
ンモニウム2.0モルを加え、攪拌後、スラリ−状に調
整した水酸化カルシウムを廃液中の亜リン酸濃度と等モ
ルの60gを加え、30分間攪拌を行った後、3時間放
置後遠心分離により固液を分離した。次に、分離液を精
密濾過し、濾液に硫酸を加えて、pHを4.5に調整
し、液温を70℃に昇温して30分間加熱後、ただちに
精密濾過を行った。比較のために、無電解ニッケルめっ
きを行うために新規に調製しためっき浴(以下新浴と呼
ぶ)と水酸化アンモニウムを添加せずに処理したときの
濾液の成分を分析した。その結果を示すと表3の通り
で、めっき廃液に水酸化アンモニウムを添加した試料で
は、めっきを阻害する亜リン酸成分の除去率が92%に
達する一方、ニッケルイオンは94%が保持され、優れ
て選択的に除去されていることが判った。これに対し、
水酸化アンモニウムを含まないめっき廃液では、ニッケ
ルイオンの96%が除去されてしまい、殆どめっき液の
再利用には適さないことが判った。
(Example 2) Phosphorous acid 1 as a plating inhibiting component
2.0 mol of ammonium hydroxide was added to the electroless nickel plating waste solution containing 00 g / L, and after stirring, calcium hydroxide adjusted to a slurry state was added with 60 g of an equimolar concentration of the phosphorous acid concentration in the waste solution to obtain 30 g After stirring for 3 minutes, the mixture was allowed to stand for 3 hours, and then separated into solid and liquid by centrifugation. Next, the separated solution was subjected to microfiltration, sulfuric acid was added to the filtrate to adjust the pH to 4.5, the temperature of the solution was raised to 70 ° C., and after heating for 30 minutes, microfiltration was immediately performed. For comparison, the components of a plating bath newly prepared for performing electroless nickel plating (hereinafter referred to as a new bath) and the components of the filtrate obtained when the treatment was performed without adding ammonium hydroxide were analyzed. The results are as shown in Table 3. In the sample in which ammonium hydroxide was added to the plating waste liquid, the removal rate of the phosphorous acid component that inhibits plating reached 92%, while 94% of nickel ions were retained. It was found to be excellent and selectively removed. In contrast,
In the plating waste solution containing no ammonium hydroxide, 96% of the nickel ions were removed, and it was found that almost no plating solution was suitable for reuse.

【0022】[0022]

【表3】 [Table 3]

【0023】(実施例3)硫酸ニッケル25 g/L,次亜
リン酸28 g/L,錯化剤55 g/L,亜リン酸120 g/L
からなる組成のめっき廃液を用い、これに硫酸を加え
てpHを4.6に調整し、次いで、廃液中の亜リン酸濃
度と等モルの水酸化カルシウム71gを添加し、30分
攪拌後、硫酸を加え、処理液のpHを6.0に調整し、
3時間放置後実施例1と同様の処理を行った。その結果
は、表4に示す通りで、亜リン酸成分の除去率が99%
に達する一方、ニッケルイオンは88%が保持され、や
はり優れて選択的に除去されていることが判明した。一
方、比較のため廃液にそのまま水酸化カルシウムを添加
した場合には、処理液のpHが10.5となり、そのま
まの状態では、液のゲル化が進むと共に廃液中にニッケ
ルイオンが水酸化ニッケルとして徐々に沈殿してしま
い、再利用が不可能なものであった。
Example 3 Nickel sulfate 25 g / L, hypophosphorous acid 28 g / L, complexing agent 55 g / L, phosphorous acid 120 g / L
A sulfuric acid was added to the solution to adjust the pH to 4.6. Then, 71 g of calcium hydroxide having an equimolar concentration to the phosphorous acid concentration in the waste solution was added, and the mixture was stirred for 30 minutes. Sulfuric acid was added to adjust the pH of the treatment solution to 6.0,
After leaving for 3 hours, the same processing as in Example 1 was performed. The results are as shown in Table 4, and the removal rate of the phosphorous acid component was 99%.
, While 88% of the nickel ions were retained, again showing excellent and selective removal. On the other hand, when calcium hydroxide was directly added to the waste liquid for comparison, the pH of the treatment liquid became 10.5. In this state, the gelation of the liquid proceeded and nickel ions were converted into nickel hydroxide in the waste liquid. It gradually settled out and could not be reused.

【0024】[0024]

【表4】 [Table 4]

【0025】(実施例4)実施例1及び2の再生液を用
いてニッケルめっき皮膜を形成し、新浴を用いて作製し
たニッケルめっき皮膜との特性の相違について検討し
た。その結果を示すと表5の通りで、再生液を用いて作
製したニッケルめっき皮膜の種々の特性値は、新浴で形
成した皮膜に劣らない優れた値を示し、これら再生液は
各種産業分野でのめっき加工に利用が可能なことが明ら
かとなった。
(Example 4) A nickel plating film was formed using the regenerating solutions of Examples 1 and 2, and a difference in characteristics from a nickel plating film produced using a new bath was examined. The results are shown in Table 5. As shown in Table 5, various characteristic values of the nickel plating film prepared using the regenerating solution show excellent values not inferior to the film formed by the new bath. It was clarified that it can be used for plating in steel.

【0026】[0026]

【表5】 [Table 5]

【0027】(再生装置の実施例)次に、上記再生方法
に対しこれを具現する装置の実施例を説明する。1が無
電解ニッケルめっきの廃液を溜め置く貯留槽で、pH管
理の為のpHメ−タ−を配設する。2が、該廃液中の亜
リン酸塩と水酸化アンモニウム又はpH調整された液中
で亜リン酸処理剤との反応を促す反応槽で、槽上部に薬
剤槽3を配設し、その投下口3aを反応槽2に臨ませ、
該反応槽2の低部には反応の均一化を図るための攪拌羽
根2aを配する。
(Embodiment of Reproducing Apparatus) Next, an embodiment of an apparatus for realizing the above-mentioned reproducing method will be described. Reference numeral 1 denotes a storage tank for storing a waste liquid of electroless nickel plating, in which a pH meter for pH control is provided. 2 is a reaction tank for promoting the reaction between the phosphite in the waste liquid and the ammonium hydroxide or the phosphite treatment agent in the pH-adjusted liquid. With the mouth 3a facing the reaction tank 2,
In the lower part of the reaction tank 2, a stirring blade 2a for making the reaction uniform is arranged.

【0028】該反応槽2の隣に、当該反応槽2で生成さ
れた沈殿物を除去する為の分離槽4を配し、該分離槽4
内には約1mφの遠心分離装置4aを配し比重の大なる
沈殿物を遠心作用で分離する。該分離槽4は、濾紙等を
配しても良いが、亜リン酸化合物の沈殿は粒子が小さい
ため目づまりが起こり易く、連続処理には、前記遠心分
離装置4aが好適である。
Next to the reaction tank 2, a separation tank 4 for removing the precipitate generated in the reaction tank 2 is arranged.
Inside, a centrifugal separator 4a of about 1 mφ is disposed, and a sediment having a large specific gravity is separated by a centrifugal action. The separation tank 4 may be provided with filter paper or the like. However, the precipitation of the phosphite compound tends to be clogged because the particles are small, and the centrifugal separator 4a is suitable for continuous processing.

【0029】5が、沈殿物を除去した後の処理液を一時
的に貯留する為の貯留槽で、該貯留槽5の液を濾過機6
を通して加温槽7に送るが、該濾過機6は、前記分離槽
5でも分離されなかった微細な沈殿粒子を濾すものであ
る。
Reference numeral 5 denotes a storage tank for temporarily storing the processing liquid from which the precipitate has been removed, and the liquid in the storage tank 5 is filtered by a filter 6.
To the heating tank 7, and the filter 6 filters fine precipitated particles that are not separated in the separation tank 5.

【0030】7が、該処理液を加温する為の加温槽で、
水酸化カルシウムは温度の上昇と共にその溶解度が低下
するという特性を有する為、亜リン酸処理剤をカルシウ
ムとした場合には、この特性を利用して蒸気加熱等で液
温を80〜90℃に昇温させ、溶解度の低下に伴う沈殿
作用を促して水酸化カルシウムの沈積を図る。
7 is a heating tank for heating the processing solution,
Since calcium hydroxide has the property that its solubility decreases with increasing temperature, when calcium is used as the phosphite treatment agent, this property is used to raise the liquid temperature to 80 to 90 ° C. by steam heating or the like. The temperature is raised to promote the precipitation effect associated with the decrease in solubility to promote the deposition of calcium hydroxide.

【0031】8は、該沈殿物を濾す濾過機で、調整槽9
に連結し、該調整槽9は、めっき阻害物質としての亜リ
ン酸化合物が除去された後の処理液を、再度無電解ニッ
ケルめっき溶液として利用するためのもので、硫酸ニッ
ケル,硫酸,次亜リン酸,水酸化アンモニウム,有機酸
等を装備した薬品槽10と連通し、該処理液に不足する
薬品を補充して調整し、より望ましい形での再生液とす
る。該調整槽9は、循環的に再生処理が行えるようめっ
き槽に連通させる。
Reference numeral 8 denotes a filter for filtering the sediment.
The adjustment tank 9 is used to reuse the treatment solution after the removal of the phosphite compound as a plating inhibitor as an electroless nickel plating solution. It communicates with a chemical tank 10 equipped with phosphoric acid, ammonium hydroxide, an organic acid, etc., and replenishes and adjusts the processing solution with a deficient chemical to obtain a regenerating solution in a more desirable form. The adjusting tank 9 is communicated with the plating tank so that the regenerating process can be performed cyclically.

【0032】(再生装置実施例の作用)該実施例の作用
を説明すると、めっき廃液を溜めた貯留槽1からポンプ
で送られた処理液は、反応槽2内で、先ず、薬剤槽3か
ら投入された亜リン酸処理剤例えば水酸化カルシウムが
アンモニア水中で、又は、pH調整液中で混合され、そ
の中でニッケルイオンの沈殿を回避しつつ、亜リン酸化
合物の生成反応を促す。
(Operation of Embodiment of Recycling Apparatus) The operation of this embodiment will be described. The processing liquid pumped from the storage tank 1 storing the plating waste liquid is supplied from the chemical tank 3 to the reaction tank 2 first. The added phosphite treatment agent, for example, calcium hydroxide, is mixed in aqueous ammonia or in a pH-adjusting solution, and promotes a phosphite compound formation reaction while avoiding precipitation of nickel ions therein.

【0033】反応時間は、30分から1時間程度で、該
反応が終了したら沈殿物の混ざった処理液を分離槽4に
送り、該分離槽4内の遠心分離機4aで比重の大なる沈
殿物を遠心分離作用で分離する。このとき、遠心分離機
4aは、亜リン酸化合物の沈殿物が微細でも目詰り等を
起こすことなく連続処理が可能となる。
The reaction time is about 30 minutes to 1 hour. When the reaction is completed, the treatment liquid mixed with the precipitate is sent to the separation tank 4, and the sediment having a large specific gravity is centrifuged by the centrifuge 4a in the separation tank 4. Is separated by centrifugation. At this time, the centrifugal separator 4a can perform continuous processing without causing clogging or the like even if the precipitate of the phosphite compound is fine.

【0034】次いで、亜リン酸化合物の除去された処理
液は、一時貯留槽5に入り、瀘過機6で残留した微細粒
子を濾した後、加温槽7に入る。該加温槽7では、蒸気
加熱により液温を80〜90℃に保ち、その昇温効果に
より水酸化カルシウムの溶解度を低下させ、液中の未だ
溶解したままの水酸化カルシウムをも析出させ、瀘過機
8にて、除去作用を完全ならしめる。
Next, the processing solution from which the phosphite compound has been removed enters the temporary storage tank 5, and after filtering the remaining fine particles with the filter 6, enters the heating tank 7. In the heating tank 7, the liquid temperature is maintained at 80 to 90 ° C. by steam heating, the solubility of calcium hydroxide is reduced by the temperature increasing effect, and calcium hydroxide still dissolved in the liquid is precipitated. In the filter 8, the removal action is completely completed.

【0035】斯して得られた処理液は、めっき阻害成分
としての亜リン酸化合物が除去されている一方ニッケル
イオン成分を充分に保持している為、そのままでも再度
無電解ニッメルめっきに利用できるが、更に完全を期す
ため、調整槽9に投入して薬品槽10から、硫酸ニッケ
ル、硫酸、次亜リン酸、水酸化アンモニウム、有機酸等
のめっき浴としての不足成分を補給する。斯かる処理液
をめっき槽へと戻して再利用すれば循環的にめっき廃液
を利用することができる。
The treatment solution thus obtained removes the phosphite compound as a plating-inhibiting component and sufficiently retains the nickel ion component, so that it can be reused as it is for electroless nipmel plating. However, in order to further improve the completeness, the components are charged into the adjusting tank 9 and replenished from the chemical tank 10 with insufficient components as a plating bath such as nickel sulfate, sulfuric acid, hypophosphorous acid, ammonium hydroxide, and organic acids. If such a treatment solution is returned to the plating tank and reused, the plating waste solution can be recycled.

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

【図1】本発明装置を示す模式図。FIG. 1 is a schematic view showing a device of the present invention.

【図2】亜リン酸カルシウムの溶解量を示すグラフ図。FIG. 2 is a graph showing the amount of calcium phosphite dissolved.

【符号の説明】[Explanation of symbols]

1 貯留槽 2 反応槽 3 薬剤槽 4 分離槽 4a 遠心分離装置 5 貯留槽 6 濾過機 7 加温槽 8 濾過機 9 調整槽 10 薬品槽 DESCRIPTION OF SYMBOLS 1 Storage tank 2 Reaction tank 3 Chemical tank 4 Separation tank 4a Centrifugal separator 5 Storage tank 6 Filtration machine 7 Heating tank 8 Filtration machine 9 Adjustment tank 10 Chemical tank

Claims (6)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 無電解ニッケルめっき皮膜形成により次
亜リン酸塩が酸化された塩を含む無電解ニッケルめっき
廃液に、該廃液中に存在するニッケルイオン1モルに対
し水酸化アンモニウムを0.2〜4モルの割合、より望
ましくは1.8〜2.2モルの割合で添加し、次いでカ
ルシウム,バリウム又はストロンチウムの水酸化物から
成る群の少なくとも一つ以上を含む亜リン酸処理剤を添
加し、ニッケルイオンを沈殿させることなく亜リン酸化
合物を選択的に除去することを特徴とする無電解ニッケ
ルめっき廃液の再生方法。
1. An electroless nickel plating waste solution containing a salt in which hypophosphite has been oxidized by forming an electroless nickel plating film, ammonium hydroxide is added in an amount of 0.2 mol per mol of nickel ions present in the waste solution. 44 mol, more preferably 1.812.2 mol, and then a phosphite treatment agent containing at least one of the group consisting of calcium, barium or strontium hydroxide is added. And selectively removing a phosphite compound without causing precipitation of nickel ions.
【請求項2】 無電解ニッケルめっき皮膜形成により次
亜リン酸塩が酸化された塩と錯化剤として有機酸を含む
無電解ニッケルめっき廃液に対し、廃液中の亜リン酸濃
度と等モルのカルシウム,バリウム又はストロンチウム
の水酸化物から成る群の少なくとも一つ以上を含む亜リ
ン酸処理剤を添加し、一定時間攪拌して亜リン酸成分を
可及的に多量沈殿させ、次いでpHを4〜6に調整し、
ニッケルイオンを沈殿させることなく亜リン酸化合物の
みを選択的に除去することを特徴とする無電解ニッケル
めっき廃液の再生方法。
2. The concentration of phosphorous acid in wastewater of electroless nickel plating wastewater containing a salt obtained by oxidizing hypophosphite by forming an electroless nickel plating film and an organic acid as a complexing agent. And a phosphite treating agent containing at least one of the group consisting of hydroxides of calcium, barium or strontium in equimolar amounts, and stirred for a certain period of time to precipitate the phosphite component as much as possible, Then adjust the pH to 4-6,
A method for regenerating an electroless nickel plating waste liquid, comprising selectively removing only a phosphite compound without precipitating nickel ions.
【請求項3】 無電解ニッケルめっき廃液に、有機酸を
添加する請求項2記載の無電解ニッケルめっき廃液の再
生方法。
3. The method according to claim 2, wherein an organic acid is added to the electroless nickel plating waste liquid.
【請求項4】 亜リン酸処理剤をカルシウムとした場合
に、亜リン酸化合物の沈殿除去後にフッ素化合物を添加
してフッ化カルシウムの沈殿を生成し、これを分離除去
する請求項1ないし3項のうちいずれか1項記載の無電
解ニッケルめっき廃液の再生方法。
4. When calcium is used as the phosphite-treating agent, a fluorine compound is added to remove a precipitate of the phosphite compound to form a precipitate of calcium fluoride, which is separated and removed. The method for regenerating an electroless nickel plating waste liquid according to any one of the above items.
【請求項5】 無電解ニッケルめっき廃液を溜める貯留
槽と、該廃液とアンモニア及び亜リン酸処理剤の反応を
促し亜リン酸化合物を選択的に生成させる反応槽と、当
該反応によって生じた沈殿物を除去する分離槽と、該分
離槽からの分離液を昇温させて水酸化カルシウムの更な
る沈殿を促す加温槽とから成る無電解ニッケルめっき廃
液の再生装置。
5. A storage tank for storing an electroless nickel plating waste liquid, a reaction tank for promoting a reaction between the waste liquid and ammonia and a phosphite treatment agent to selectively generate a phosphite compound, and a precipitate formed by the reaction. An apparatus for regenerating an electroless nickel plating waste liquid, comprising: a separation tank for removing substances; and a heating tank for raising the temperature of the separated liquid from the separation tank to promote further precipitation of calcium hydroxide.
【請求項6】 加温槽の後に処理液に不足する薬剤を投
入する調整槽を配設した請求項5記載の無電解ニッケル
めっき廃液の再生装置。
6. The apparatus according to claim 5, further comprising an adjusting tank for introducing a chemical insufficient in the processing liquid after the heating tank.
JP5294053A 1993-10-29 1993-10-29 Method and apparatus for regenerating electroless nickel plating wastewater Expired - Fee Related JP2769774B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP5294053A JP2769774B2 (en) 1993-10-29 1993-10-29 Method and apparatus for regenerating electroless nickel plating wastewater

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP5294053A JP2769774B2 (en) 1993-10-29 1993-10-29 Method and apparatus for regenerating electroless nickel plating wastewater

Publications (2)

Publication Number Publication Date
JPH07126855A JPH07126855A (en) 1995-05-16
JP2769774B2 true JP2769774B2 (en) 1998-06-25

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7892603B2 (en) 2005-07-12 2011-02-22 Murata Co., Ltd. Regeneration apparatus and regeneration method for electroless plating

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9802042D0 (en) * 1998-01-31 1998-03-25 Classic Chemicals Limited Improvements in electroless nickel plating

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7892603B2 (en) 2005-07-12 2011-02-22 Murata Co., Ltd. Regeneration apparatus and regeneration method for electroless plating
US7968149B2 (en) 2005-07-12 2011-06-28 Murata Co., Ltd. Regeneration apparatus and regeneration method for electroless plating

Also Published As

Publication number Publication date
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