JP5466273B2 - Electroless nickel plating wastewater treatment method - Google Patents

Electroless nickel plating wastewater treatment method Download PDF

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JP5466273B2
JP5466273B2 JP2012180974A JP2012180974A JP5466273B2 JP 5466273 B2 JP5466273 B2 JP 5466273B2 JP 2012180974 A JP2012180974 A JP 2012180974A JP 2012180974 A JP2012180974 A JP 2012180974A JP 5466273 B2 JP5466273 B2 JP 5466273B2
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nickel
plating wastewater
ethanol
electroless
nickel plating
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JP2013044052A (en
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ビョン−ソク，コ
ドン−ギュン，コ
ヒョン−ベク，コ
ミョン−モ，ソン
ジョン−ナム，ヤン
ドン−ファン，コ
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Sehwa Enstech Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5209—Regulation methods for flocculation or precipitation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Removal Of Specific Substances (AREA)
  • Heat Treatment Of Water, Waste Water Or Sewage (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Chemically Coating (AREA)

Description

本発明は、無電解ニッケルメッキ廃水中のニッケルを高純度の水酸化ニッケルとして回収し、蒸留工法を用いてメッキ廃水を工程水としてリサイクルする方法に関する。   The present invention relates to a method of recovering nickel in electroless nickel plating wastewater as high-purity nickel hydroxide and recycling the plating wastewater as process water using a distillation method.

近年、産業活動が盛んになるにつれて、無電解メッキ工法が各種機械装置及び部品の製造に非常に広範囲にわたって応用されている。無電解メッキは、電気メッキとは異なり、プラスチック或いはセラミックなどの電気不導体に対して金属コーティングを施す工法であって、産業的には各種機械及び電子部品の製造に用いられる無電解ニッケルメッキとＰＣＢ基板の製造に用いられる無電解銅メッキが最も普遍的であると知られている。   In recent years, the electroless plating method has been applied to a wide range of machines and parts in a very wide range as industrial activities become popular. Electroless plating, unlike electroplating, is a method of applying a metal coating to electrical non-conductors such as plastics or ceramics, and is an electroless nickel plating used for manufacturing various machines and electronic components industrially. Electroless copper plating used in the manufacture of PCB substrates is known to be the most universal.

ところが、最近、無電解ニッケルメッキへの需要が急増することにより、この過程で発生する無電解ニッケルメッキ廃水も毎年増えている。しかも、前記無電解ニッケルメッキ廃水には高価のニッケルが含有されており、それからニッケルを回収して製品化することが必要な状況である。   However, due to the recent rapid increase in demand for electroless nickel plating, the amount of electroless nickel plating wastewater generated in this process is increasing every year. Moreover, the electroless nickel plating wastewater contains expensive nickel, and it is necessary to recover the nickel from the wastewater to produce a product.

通常の無電解ニッケルメッキ廃水の処理方法としては、生石灰を添加し、廃水中のニッケルを始めとした次亜リン酸（ＰＯ２ ３−）及び亜リン酸（ＰＯ３ ３−）などのリン化合物と各種有機酸をカルシウム化合物で沈殿させて除去する方法が採用されている。ところが、前記無電解ニッケルメッキ廃水の処理方法は、廃水中に含有された高価のニッケル資源を回収することができず、そのまま廃棄させる問題があるのはもとより、カルシウム化合物の生成により莫大な量のスラッジが発生するという欠点がある。 As an ordinary electroless nickel plating wastewater treatment method, phosphorus compounds such as hypophosphorous acid (PO 2 3− ) and phosphorous acid (PO 3 3− ), including nickel in the waste water, are added. And various organic acids are precipitated with a calcium compound and removed. However, the electroless nickel plating wastewater treatment method cannot recover expensive nickel resources contained in the wastewater, and has a problem of discarding it as it is. There is a disadvantage that sludge is generated.

上述した単純中和法の問題点を克服し、かつ廃水に含有されたニッケルを高純度の製品として回収するためには、まず、無電解ニッケルメッキ廃水に含有された様々な成分のうちニッケル以外の成分を効果的に分離させる技術が求められているが、現在まで開発されたイオン交換法、溶媒抽出法及び膜分離法などは、費用があまり高く、ニッケル回収率が６０％以下と低いことが欠点として指摘されている。   In order to overcome the problems of the simple neutralization method described above and to recover the nickel contained in the wastewater as a high-purity product, first of all various components contained in the electroless nickel plating wastewater other than nickel However, the ion exchange method, solvent extraction method, and membrane separation method that have been developed so far are too expensive and the nickel recovery rate is as low as 60% or less. Has been pointed out as a drawback.

そこで、本発明は、前述した問題点を解決するためになされたもので、その目的は、従来の生石灰の添加による単純中和法で無電解ニッケルメッキ廃水を処理する方法に代えて、メッキ廃水中のニッケルを高純度の製品として回収し、メッキ廃水を工程水としてリサイクルことができる、経済的かつ効果的な無電解ニッケルメッキ廃水の処理方法を提供することにある。   Therefore, the present invention has been made to solve the above-described problems, and its purpose is to replace the conventional method of treating electroless nickel plating wastewater with a simple neutralization method by the addition of quicklime, and plating wastewater. An object of the present invention is to provide an economical and effective method for treating electroless nickel plating wastewater, which can recover nickel contained therein as a high-purity product and recycle the plating wastewater as process water.

上記目的を達成するために、本発明は、無電解ニッケルメッキ廃水に塩化ナトリウム又は硝酸ナトリウムを添加した後、エタノールを混合して各種有機酸塩を沈殿させて除去する第１段階と、前記第１段階の工程を介して無電解メッキ廃水中のニッケル以外の各種成分を沈殿及び除去させたエタノール混合溶液に苛性ソーダを添加し、ニッケルを水酸化ニッケルとして沈殿させて回収する第２段階と、前記第２段階でニッケルを分離して残った混合溶液を対象として、蒸留工法を用いてエタノールと水を分離する第３段階とを含んでなることを特徴とする、無電解ニッケルメッキ廃水の処理方法を提供することにある。   In order to achieve the above object, the present invention includes a first step of adding sodium chloride or sodium nitrate to electroless nickel plating wastewater and then mixing ethanol to precipitate and remove various organic acid salts, A second stage in which caustic soda is added to an ethanol mixed solution in which various components other than nickel in the electroless plating wastewater are precipitated and removed through a one-stage process, and nickel is precipitated and recovered as nickel hydroxide; An electroless nickel plating wastewater treatment method comprising a third step of separating ethanol and water using a distillation method for a mixed solution remaining after separation of nickel in the second step Is to provide.

前記塩化ナトリウム又は硝酸ナトリウムは、無電解ニッケルメッキ廃水に含有されたニッケル含量に対するモル比で２〜５倍添加することを特徴とし、前記エタノールを体積比で無電解メッキ廃水：エタノール＝１：１〜１：４の範囲となるように混合することを特徴とし、前記苛性ソーダを混合溶液のｐＨが８〜１０の範囲となるように添加することを特徴とする。   The sodium chloride or sodium nitrate is added 2 to 5 times in molar ratio to the nickel content contained in electroless nickel plating wastewater, and the ethanol is electroless plating wastewater by volume ratio: ethanol = 1: 1. It mixes so that it may become the range of -1: 4, The said caustic soda is added so that the pH of a mixed solution may be the range of 8-10.

本発明に係る無電解ニッケルメッキ廃水を処理する場合、生石灰を添加する単純中和法で処理する従来の方法と比較して、高価の金属資源であるニッケルを高純度の製品として９７％以上回収することにより経済的付加価値を向上させることができるという利点がある。さらに、従来の方法と比較して、カルシウム成分を添加しないためスラッジ発生量を５０％以上節減することができるという特徴がある。特に、従来の方法では中和処理されたメッキ廃水をそのまま放流したが、本発明の方法では、蒸留工法を用いてメッキ廃水を工程水としてリサイクルすることができるため、水質汚染を防止し且つ水資源を節約することができるという利点がある。   When treating the electroless nickel plating wastewater according to the present invention, more than 97% of nickel, which is an expensive metal resource, is recovered as a high-purity product compared to the conventional method of treating by the simple neutralization method of adding quick lime. By doing so, there is an advantage that economic added value can be improved. Furthermore, compared with the conventional method, since the calcium component is not added, the amount of sludge generation can be reduced by 50% or more. In particular, the neutralization-treated plating wastewater is discharged as it is in the conventional method. However, in the method of the present invention, the plating wastewater can be recycled as process water using the distillation method, so that water pollution is prevented and water is removed. There is an advantage that resources can be saved.

以下、本発明に係る無電解ニッケルメッキ廃水処理方法をより具体的に説明する。   Hereinafter, the electroless nickel plating wastewater treatment method according to the present invention will be described in more detail.

第１段階では、まず、無電解ニッケルメッキ廃水に塩化ナトリウム（ＮａＣｌ）或いは硝酸ナトリウム（ＮａＮＯ３）を添加した後、エタノールを混合して次亜リン酸ナトリウム（ＮａＨ２ＰＯ２）、亜リン酸ナトリウム（Ｎａ２ＨＰＯ３）及び各種有機酸塩などを沈殿させて除去する。前記第１段階の主目的は、無電解メッキ廃水に生石灰などのカルシウム成分を添加せず、ニッケル以外の各種成分を除去することにある。本発明では、無電解メッキ廃水にエタノールを混合する場合、アルコールに不溶性の各種成分が沈殿する現象を見出した。前記第１段階で塩化ナトリウム或いは硝酸ナトリウムを添加する理由は、メッキ廃水中のニッケルイオンと塩素イオン或いは硝酸イオンとが互いに結合して生成されたＮｉＣｌ２或いはＮｉ（ＮＯ３）２がアルコールに対しても溶解性であるから、沈殿せずにそのまま溶液に残留するためである。もし塩化ナトリウム或いは硝酸ナトリウムを添加しなければ、エタノールを混合したときに他の成分と同様にニッケルも沈殿するという問題が発生する。 In the first stage, first, sodium chloride (NaCl) or sodium nitrate (NaNO 3 ) is added to the electroless nickel plating wastewater, and then ethanol is mixed with sodium hypophosphite (NaH 2 PO 2 ), phosphorous acid. Sodium (Na 2 HPO 3 ) and various organic acid salts are precipitated and removed. The main purpose of the first stage is to remove various components other than nickel without adding calcium components such as quicklime to the electroless plating wastewater. In the present invention, the inventors have found a phenomenon in which various components insoluble in alcohol are precipitated when ethanol is mixed with electroless plating wastewater. The reason for adding sodium chloride or sodium nitrate in the first step is that NiCl 2 or Ni (NO 3 ) 2 produced by combining nickel ions and chlorine ions or nitrate ions in the plating wastewater with respect to the alcohol. This is because it remains soluble without being precipitated. If sodium chloride or sodium nitrate is not added, there is a problem that nickel is precipitated like other components when ethanol is mixed.

前記第１段階で、塩化ナトリウム或いは硝酸ナトリウムの添加量は、無電解ニッケルメッキ廃水に含有されたニッケルの含量に対するモル比で２〜５倍となるようにする。塩化ナトリウム或いは硝酸ナトリウムの添加比率が前記範囲より低ければ、エタノール添加の際にニッケルが一部沈殿するという問題が発生し、前記範囲より高ければ、無駄に薬品消費量が増えるという問題が発生する。また、エタノール混合比率においては、体積比で無電解メッキ廃水：エタノール＝１：１〜１：４の範囲が適正である。前記範囲よりエタノールの添加量が低ければ、無電解メッキ廃水中の各種成分がまともに沈殿しないという問題が発生し、前記範囲より高ければ、エタノール消耗量が無駄に過多となるという問題が発生する。前記本発明の第１段階で、アルコールの種類をエタノール以外の他のものにしてもよいが、本発明ではアルコールの種類を特定のものに特に限定しない。   In the first step, the amount of sodium chloride or sodium nitrate added is 2 to 5 times as much as the molar ratio of nickel contained in the electroless nickel plating wastewater. If the addition ratio of sodium chloride or sodium nitrate is lower than the above range, there is a problem that nickel is partially precipitated during the addition of ethanol, and if it is higher than the above range, there is a problem that the amount of chemical consumption is unnecessarily increased. . In addition, regarding the ethanol mixing ratio, the volume ratio of electroless plating wastewater: ethanol = 1: 1 to 1: 4 is appropriate. If the amount of ethanol added is lower than the above range, there will be a problem that various components in the electroless plating wastewater will not settle properly. If it is higher than the above range, there will be a problem that the amount of ethanol consumption is excessively increased. . In the first stage of the present invention, the type of alcohol may be other than ethanol, but in the present invention, the type of alcohol is not particularly limited to a specific type.

第２段階では、第１段階の工程を介して無電解メッキ廃水中のニッケル以外の各種成分を沈殿及び除去させたエタノール混合溶液に苛性ソーダ（ＮａＯＨ）を添加し、ニッケルを水酸化ニッケル（Ｎｉ（ＯＨ）２）として沈殿させて回収する。前記第２段階で生成される水酸化ニッケルは、不純物の含量が非常に少ない高純度の水酸化ニッケルであって、本発明の方法によってニッケルを回収する場合、従来の方法に比べて非常に経済的に無電解ニッケルメッキ廃水中のニッケルを分離回収することができる。前記第２段階で、苛性ソーダの添加量は混合溶液のｐＨが８〜１０の範囲となるように添加する。ｐＨが前記範囲より低ければ、ニッケルが完全に沈殿しないため回収率が低下するという問題が発生し、ｐＨが前記範囲より高ければ、苛性ソーダが無駄に消耗されるという欠点がある。前記第２段階で沈殿した水酸化ニッケルは、濾過してクリーンな水で洗浄した後、乾燥させて水酸化ニッケル製品として生産する。 In the second stage, caustic soda (NaOH) is added to the ethanol mixed solution in which various components other than nickel in the electroless plating wastewater are precipitated and removed through the process of the first stage, and nickel is converted into nickel hydroxide (Ni ( Precipitate as OH) 2 ) and collect. The nickel hydroxide produced in the second stage is a high-purity nickel hydroxide with a very low impurity content. When nickel is recovered by the method of the present invention, it is much more economical than the conventional method. In particular, nickel in the electroless nickel plating wastewater can be separated and recovered. In the second stage, caustic soda is added so that the pH of the mixed solution is in the range of 8-10. If the pH is lower than the above range, there is a problem that nickel is not completely precipitated and the recovery rate is lowered. If the pH is higher than the above range, caustic soda is wasted. The nickel hydroxide precipitated in the second stage is filtered, washed with clean water, and then dried to produce a nickel hydroxide product.

第３段階では、第２段階でニッケルを分離回収して残った混合溶液を対象として、蒸留工程を用いてエタノールと水を分離する。第３段階の蒸留工法は、水とエタノールとの混合溶液を加熱して沸かすと、沸点の低いエタノールが先に気化し、ついで沸点の高い水が気化するため、これをそれぞれ凝縮させると、水とエタノールを分離して回収することができるという基本的な原理に基づいたものである。本発明では、第３段階の蒸留工法において特別な蒸留方法又は蒸留装置を使用することに制限しない。すなわち、第３段階の水とエタノールの分離のための蒸留工法では商用化されている通常の蒸留方法、蒸留条件及び蒸留装置を使用すれば十分である。前記第３段階の蒸留工法を介して得たエタノールと水はそれぞれリサイクルし、最後に残った各種塩成分含有濃縮液は廃棄する。   In the third stage, ethanol and water are separated using a distillation process for the mixed solution remaining after separation and recovery of nickel in the second stage. In the third stage distillation method, when a mixed solution of water and ethanol is heated and boiled, ethanol with a low boiling point is vaporized first, and then water with a high boiling point is vaporized. It is based on the basic principle that ethanol can be separated and recovered. In this invention, it does not restrict | limit to using a special distillation method or a distillation apparatus in the 3rd stage distillation method. That is, in the third stage distillation method for separating water and ethanol, it is sufficient to use a commercially available ordinary distillation method, distillation conditions and distillation apparatus. Ethanol and water obtained through the third stage distillation method are recycled, and the remaining salt component-containing concentrates are discarded.

以下、実際無電解ニッケルメッキ廃水を対象とした本発明の具体的な条件及び特徴を下記の実施例によって詳細に説明する。   Hereinafter, specific conditions and features of the present invention for actual electroless nickel plating wastewater will be described in detail by the following examples.

<実施例１>
ニッケル含量１２００ｍｇ／Ｌの無電解ニッケルメッキ廃水を１Ｌ採取して反応器に仕込み、攪拌を行いながら塩化ナトリウム（ＮａＣｌ）をモル比でニッケル含量の２倍となるように添加した。塩化ナトリウムが全て溶解した後、エタノールを４Ｌ混合してから十分に沈殿物が生成されるように３０分攪拌する。前記沈殿物を濾過及び除去して第１段階の工程が終わると、第２段階の工程では苛性ソーダを添加して混合溶液のｐＨを８となるように調節する。前記ｐＨの調節によって混合溶液中のニッケルを水酸化ニッケルとして沈殿させる。この際のニッケル回収率は混合溶液中の初期ニッケル含量を基準として９７．４％に達した。沈殿した水酸化ニッケルを濾過してクリーンな水で洗浄し乾燥させる方法で水酸化ニッケル製品を生産することができた。この際、生産された水酸化ニッケルの純度は表１に示すように９９．８％以上であった。最後に、第３段階では、ニッケルを分離して残った混合溶液から蒸留工法を用いてエタノールと水を分離する。前記第３段階の蒸留工法を介して得たエタノールと水はそれぞれリサイクルし、最後に残った各種塩成分含有濃縮液は廃棄する。 <Example 1>
1 L of electroless nickel plating wastewater having a nickel content of 1200 mg / L was collected and charged into the reactor, and sodium chloride (NaCl) was added in a molar ratio so as to double the nickel content while stirring. After all the sodium chloride is dissolved, 4 L of ethanol is mixed and then stirred for 30 minutes so that a precipitate is sufficiently formed. When the first step is completed by filtering and removing the precipitate, caustic soda is added to adjust the pH of the mixed solution to 8 in the second step. By adjusting the pH, nickel in the mixed solution is precipitated as nickel hydroxide. At this time, the nickel recovery rate reached 97.4% based on the initial nickel content in the mixed solution. The nickel hydroxide product could be produced by filtering the precipitated nickel hydroxide, washing with clean water and drying. At this time, the purity of the produced nickel hydroxide was 99.8% or more as shown in Table 1. Finally, in the third stage, ethanol and water are separated from the mixed solution remaining after separation of nickel using a distillation method. Ethanol and water obtained through the third stage distillation method are recycled, and the remaining salt component-containing concentrates are discarded.

Figure 0005466273
Figure 0005466273

<実施例２>
実施例１で使用したものと同一の無電解ニッケルメッキ廃水を１Ｌ採取して反応器に仕込み、攪拌を行いながら塩化ナトリウムをモル比でニッケル含量の５倍となるように添加した。塩化ナトリウムが全て溶解した後、エタノールを１Ｌ混合してから十分に生成物が生成されるように３０分攪拌する。前記沈殿物を濾過及び除去して第１段階の工程が終わると、第２段階の工程では苛性ソーダを添加して混合溶液のｐＨを１０となるように調節する。前記ｐＨ調節によって混合溶液中のニッケルを水酸化ニッケルとして沈殿させる。この際のニッケル回収率は混合溶液中の初期ニッケル含量を基準として９８．７％に達した。前記沈殿した水酸化ニッケルを実施例１と同様の方法で濾過してクリーンな水で洗浄し乾燥させる方法で水酸化ニッケル製品を生産することができた。この際、生産された水酸化ニッケルの純度は表２に示すように９９．６％以上であった。最後に、第３段階では、ニッケルを分離して残った混合溶液から実施例１と同様に蒸留工法を用いてエタノールと水を分離する。前記第３段階の蒸留工法を介して得たエタノールと水はそれぞれリサイクルし、最後に残った各種塩成分含有濃縮液は実施例１と同様に廃棄する。 <Example 2>
1 L of the same electroless nickel plating wastewater as that used in Example 1 was collected and charged into the reactor, and sodium chloride was added in a molar ratio so as to be 5 times the nickel content while stirring. After all the sodium chloride is dissolved, 1 L of ethanol is mixed and then stirred for 30 minutes so that the product is sufficiently formed. When the first step is completed by filtering and removing the precipitate, caustic soda is added to adjust the pH of the mixed solution to 10 in the second step. By the pH adjustment, nickel in the mixed solution is precipitated as nickel hydroxide. At this time, the nickel recovery rate reached 98.7% based on the initial nickel content in the mixed solution. The precipitated nickel hydroxide was filtered by the same method as in Example 1, washed with clean water and dried to produce a nickel hydroxide product. At this time, the purity of the produced nickel hydroxide was 99.6% or more as shown in Table 2. Finally, in the third stage, ethanol and water are separated from the mixed solution remaining after the nickel separation using the distillation method in the same manner as in Example 1. Ethanol and water obtained through the third stage distillation method are recycled, and the various salt component-containing concentrates remaining at the end are discarded as in Example 1.

Figure 0005466273
Figure 0005466273

<実施例３>
実施例１で使用したものと同一の無電解ニッケルメッキ廃水を１Ｌ採取して反応器に仕込み、攪拌を行いながら硝酸ナトリウム（ＮａＮＯ３）をモル比でニッケル含量の２倍となるように添加した。硝酸ナトリウムが全て溶解した後、エタノールを１Ｌ混合してから十分に沈殿物が生成されるように３０分攪拌する。前記沈殿物を濾過及び除去して第１段階の工程が終わると、第２段階の工程では苛性ソーダを添加して混合溶液のｐＨを１０となるように調節する。前記ｐＨ調節によって混合溶液中のニッケルを水酸化ニッケルとして沈殿させる。この際、ニッケル回収率は混合溶液中の初期ニッケル含量を基準として９８．４％に達した。前記沈殿した水酸化ニッケルを実施例１と同様の方法で濾過してクリーンな水で洗浄し乾燥させる方法で水酸化ニッケル製品を生産することができた。この際、生産された水酸化ニッケルの純度は表３に示すように９９．７％以上であった。最後に、第３段階では、ニッケルを分離して残った混合溶液から実施例１と同様に蒸留工法を用いてエタノールと水を分離する。前記第３段階の蒸留工法を介して得たエタノールと水はそれぞれリサイクルし、最後に残った各種塩成分含有濃縮液は実施例１と同様に廃棄する。 <Example 3>
1 L of the same electroless nickel plating wastewater as used in Example 1 was collected and charged into the reactor, and sodium nitrate (NaNO 3 ) was added in a molar ratio so as to double the nickel content while stirring. . After all the sodium nitrate is dissolved, 1 L of ethanol is mixed and then stirred for 30 minutes so that a precipitate is sufficiently formed. When the first step is completed by filtering and removing the precipitate, caustic soda is added to adjust the pH of the mixed solution to 10 in the second step. By the pH adjustment, nickel in the mixed solution is precipitated as nickel hydroxide. At this time, the nickel recovery rate reached 98.4% based on the initial nickel content in the mixed solution. The precipitated nickel hydroxide was filtered by the same method as in Example 1, washed with clean water and dried to produce a nickel hydroxide product. At this time, the purity of the produced nickel hydroxide was 99.7% or more as shown in Table 3. Finally, in the third stage, ethanol and water are separated from the mixed solution remaining after the nickel separation using the distillation method in the same manner as in Example 1. Ethanol and water obtained through the third stage distillation method are recycled, and the various salt component-containing concentrates remaining at the end are discarded as in Example 1.

Figure 0005466273
Figure 0005466273

Claims (4)

無電解ニッケルメッキ廃水に塩化ナトリウム又は硝酸ナトリウムを添加した後、エタノールを混合して各種有機酸塩を沈殿させて除去する第１段階と、
前記第１段階の工程を介して無電解メッキ廃水中のニッケル以外の各種成分を沈殿及び除去させたエタノール混合溶液に苛性ソーダを添加し、ニッケルを水酸化ニッケルとして沈殿させて回収する第２段階と、
前記第２段階でニッケルを分離して残った混合溶液を対象として、蒸留工法を用いてエタノールと水を分離する第３段階とを含んでなることを特徴とする、無電解ニッケルメッキ廃水の処理方法。 After adding sodium chloride or sodium nitrate to the electroless nickel plating wastewater, ethanol is mixed to precipitate and remove various organic acid salts;
A second stage in which caustic soda is added to the ethanol mixed solution in which various components other than nickel in the electroless plating wastewater are precipitated and removed through the first stage process, and nickel is precipitated and recovered as nickel hydroxide; ,
A treatment of electroless nickel plating wastewater, comprising a third step of separating ethanol and water using a distillation method for the mixed solution remaining after separation of nickel in the second step. Method. 前記塩化ナトリウム又は硝酸ナトリウムは無電解ニッケルメッキ廃水に含有されたニッケルの含量に対するモル比で２〜５倍添加することを特徴とする、請求項１に記載の無電解ニッケルメッキ廃水の処理方法。   2. The method of treating electroless nickel plating wastewater according to claim 1, wherein the sodium chloride or sodium nitrate is added in a molar ratio of 2 to 5 times the content of nickel contained in the electroless nickel plating wastewater. 前記エタノールを体積比で無電解メッキ廃水：エタノール＝１：１〜１：４の範囲となるように混合することを特徴とする、請求項１に記載の無電解ニッケルメッキ廃水の処理方法。   2. The method of treating electroless nickel plating wastewater according to claim 1, wherein the ethanol is mixed so that the volume ratio of electroless plating wastewater: ethanol = 1: 1 to 1: 4. 前記苛性ソーダを混合溶液のｐＨが８〜１０の範囲となるように添加することを特徴とする、請求項１に記載の無電解ニッケルメッキ廃水の処理方法。   The method for treating electroless nickel plating wastewater according to claim 1, wherein the caustic soda is added so that the pH of the mixed solution is in the range of 8 to 10.
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