JP2015001000A - Method for recovering tin from tin-plating release waste liquor - Google Patents

Method for recovering tin from tin-plating release waste liquor Download PDF

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JP2015001000A
JP2015001000A JP2013125273A JP2013125273A JP2015001000A JP 2015001000 A JP2015001000 A JP 2015001000A JP 2013125273 A JP2013125273 A JP 2013125273A JP 2013125273 A JP2013125273 A JP 2013125273A JP 2015001000 A JP2015001000 A JP 2015001000A
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tin
waste liquid
sludge
stripping waste
liquid
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圭栄 樽谷
Yoshie Tarutani
圭栄 樽谷
賢治 久保田
Kenji Kubota
賢治 久保田
加藤　直樹
Naoki Kato
直樹 加藤
正之 相田
Masayuki Aida
正之 相田
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Mitsubishi Shindoh Co Ltd
Mitsubishi Materials Corp
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Mitsubishi Shindoh Co Ltd
Mitsubishi Materials Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02P10/00—Technologies related to metal processing
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Abstract

PROBLEM TO BE SOLVED: To provide a method for recovering Sn content from tin-plating release waste liquor of copper-based tinned material, the method enabling high quality Sn including little entrainment of a Cu content to be recovered.SOLUTION: The method for recovering tin from tin-plating release waste liquor is provided which comprise: an oxidation treatment step in which an oxidizer is added to the tin-plating release waste liquor of copper-based tinned material to oxidize the Sn ion in the liquor, thereby Sn sludge is produced and the Cu powder in the liquor is dissolved; and a coagulation treatment step in which the pH of the release waste liquor is neutralized to 0.5 to 2.5 and followed by adding a coagulant to the release waste liquor to coagulate the Sn sludge. Preferably, the oxidizer is used in an amount of 0.5 to 2.5 fold of the total amount (mol amount) of Sn(II) ion and Cu powder in the liquor. The method may further includes before the coagulation treatment step, an electrolytic treatment step in which the oxidized release waste liquor is electrolyzed to precipitate Cu.

Description

本発明は、錫めっき剥離廃液に含まれる錫を回収する方法において、Ｃｕ分の含有が少なく、高品位の錫を回収することができる方法に関する。 The present invention relates to a method for recovering tin contained in a tin plating stripping waste liquid, which can recover high-grade tin with less Cu content.

銅や銅合金の基材表面に錫めっきを施した銅基錫めっき材は電子機器や電気機器などにおいて広く利用されており、資源の有効活用の観点から、廃棄された銅基錫めっき材から錫や銅を効率よく回収することが求められる。 Copper-based tin-plated materials with tin plating on the surface of copper or copper alloy base materials are widely used in electronic equipment and electrical equipment. From the viewpoint of effective utilization of resources, It is required to efficiently recover tin and copper.

上記銅基錫めっき材から錫めっきを剥離する方法として、Ｃｕイオンと過酸化水素と硫酸等を含む剥離液に上記銅基錫めっき材を浸漬し、ＳｎをＣｕで置換して錫めっきを剥離する方法が従来から知られている（特許文献１）。また、カラムを使用し、銅基錫めっき材をカラムに充填し、Ｃｕイオンおよび硫酸を含む酸性剥離液をカラムに通じてＳｎを除去する方法が知られている（特許文献２）。 As a method for removing the tin plating from the copper-based tin plating material, the copper-based tin plating material is immersed in a release solution containing Cu ions, hydrogen peroxide, sulfuric acid, etc., and Sn is replaced with Cu to remove the tin plating. The method to do is known conventionally (patent document 1). Further, a method is known in which a column is used, a copper-based tin plating material is filled into the column, and an acidic stripping solution containing Cu ions and sulfuric acid is passed through the column to remove Sn (Patent Document 2).

特開昭６１−１５９５８０号公報JP-A 61-159580 特開平０５−１７１３０６号公報JP 05-171306 A

上記銅基錫めっき材から錫めっきを剥離した剥離廃液には、高濃度のＳｎ(II)イオンとＳｎＯ2粉体（通称Ｓｎスラッジ)が含まれており、Ｓｎ(II)イオンは液の中和処理によってＳｎ水酸化物ないしＳｎ酸化物の固体になるので、高分子凝集剤を添加してこれらをフロックにし、Ｓｎスラッジと共に回収することができる。 The stripping waste liquid from which the tin plating is stripped from the copper-based tin plating material contains high concentrations of Sn (II) ions and SnO 2 powder (commonly called Sn sludge), and the Sn (II) ions are contained in the liquid. Since the sum treatment results in a solid of Sn hydroxide or Sn oxide, a polymer flocculant can be added to make these floc and be recovered together with Sn sludge.

一方、上記剥離廃液には、Ｓｎ(II)イオンと共にＣｕ(II)イオンおよび剥離工程で材料から脱落した固体のＣｕ粉が含まれており、Ｃｕ(II)イオンは液の中和処理によってＣｕ水酸化物の固体になるので、液中に含まれるＳｎ分を凝集フロックにして回収しようとすると、この凝集フロックにＣｕ水酸化物やＣｕ粉が取り込まれ、回収したＳｎの品位が大幅に低下する。 On the other hand, the exfoliation waste liquid contains Sn (II) ions and Cu (II) ions and solid Cu powder that has fallen from the material in the exfoliation process. Since it becomes a hydroxide solid, when trying to collect the Sn content contained in the liquid as an aggregated floc, Cu hydroxide or Cu powder is taken into the aggregated floc and the quality of the recovered Sn is greatly reduced. To do.

本発明は、従来のＳｎ回収方法における上記課題を解決したものであり、銅基錫めっき材の錫めっき剥離廃液からＳｎ分を回収する方法において、Ｃｕ分の含有が少なく、高品位のＳｎを回収することができる方法を提供する。 This invention solves the said subject in the conventional Sn collection | recovery method, In the method of collect | recovering Sn content from the tin plating peeling waste liquid of a copper base tin plating material, there is little content of Cu content and high quality Sn is obtained. Provide a method that can be recovered.

本発明によれば、以下の構成によって上記課題を解決したＳｎの回収方法が提供される。
〔１〕銅基錫めっき材の錫めっき剥離廃液に酸化剤を添加して液中のＳｎイオンを酸化してＳｎスラッジを生成させると共に液中のＣｕ粉を溶解し（酸化処理）、次いで該剥離廃液のｐＨを０.５〜２.５に中和した後に凝集剤を添加してＳｎスラッジを凝集させる（凝集処理）ことを特徴とする錫めっき剥離廃液からの錫の回収方法。
〔２〕酸化剤の添加量が、液中のＳｎ(II)イオンとＣｕ粉の合計量(mol量)の０.５〜２.５倍量(mol量)である上記[１]に記載する錫の回収方法。
〔３〕剥離廃液に酸化剤を添加して酸化処理した後に、該剥離廃液を電気分解してＣｕを析出させて回収し（電解処理）、次いで該剥離廃液のｐＨを０.５〜２．５に中和した後に凝集剤を添加してＳｎスラッジを凝集させる（凝集処理）上記[１]または上記[２]に記載する錫の回収方法。 According to the present invention, there is provided a method for recovering Sn that solves the above problems by the following configuration.
[1] An oxidizing agent is added to the tin plating stripping waste liquid of the copper-based tin plating material to oxidize Sn ions in the liquid to produce Sn sludge and dissolve Cu powder in the liquid (oxidation treatment), A method for recovering tin from a tin plating stripping waste liquid, comprising neutralizing the pH of the stripping waste liquid to 0.5 to 2.5 and then adding a flocculant to agglomerate Sn sludge (aggregation treatment).
[2] The above-mentioned [1], wherein the addition amount of the oxidizing agent is 0.5 to 2.5 times (mol amount) the total amount (mol amount) of Sn (II) ions and Cu powder in the liquid. To recover tin.
[3] After oxidizing the stripping waste liquid by adding an oxidizing agent, the stripping waste liquid is electrolyzed and Cu is deposited and recovered (electrolytic treatment), and then the pH of the stripping waste liquid is 0.5-2. 5. The method for recovering tin according to [1] or [2] above, wherein the flocculant is added after neutralization to 5 to aggregate Sn sludge (aggregation treatment).

〔具体的な説明〕
本発明は、銅基錫めっき材の錫めっき剥離廃液に酸化剤を添加して液中のＳｎイオンを酸化してＳｎスラッジを生成させると共に液中のＣｕ粉を溶解し（酸化処理）、次いで該剥離廃液のｐＨを０.５〜２.５に中和した後に凝集剤を添加してＳｎスラッジを凝集させる（凝集処理）ことを特徴とする錫めっき剥離廃液からの錫の回収方法である。 [Specific description]
In the present invention, an oxidizing agent is added to a tin plating stripping waste liquid of a copper-based tin plating material to oxidize Sn ions in the liquid to generate Sn sludge and dissolve Cu powder in the liquid (oxidation treatment), A method for recovering tin from a tin plating stripping waste liquid, wherein the pH of the stripping waste liquid is neutralized to 0.5 to 2.5 and then a flocculant is added to agglomerate Sn sludge (flocculation treatment). .

本発明の回収方法において、銅基錫めっき材とは銅基材または銅合金基材の表面に錫めっきが施されている材料である。錫めっき剥離廃液とは上記銅基めっき材から錫めっきを剥離した液であり、この剥離廃液には高濃度のＳｎ(II)イオンと、Ｃｕ(II)イオン、および固体のＣｕ粉、ＳｎＯ2粉体（通称Ｓｎスラッジ）が含まれている。また、硫酸酸性の剥離液に由来する硫酸が含まれており、概ねｐＨ１以下、通常はｐＨ０.３〜ｐＨ０.６の強酸性溶液である。 In the recovery method of the present invention, the copper-based tin plating material is a material in which tin plating is applied to the surface of a copper base material or a copper alloy base material. The tin plating stripping waste liquid is a liquid obtained by stripping tin plating from the copper-based plating material. The stripping waste liquid contains high concentrations of Sn (II) ions, Cu (II) ions, solid Cu powder, and SnO 2. Powder (commonly known as Sn sludge) is included. Moreover, the sulfuric acid derived from a sulfuric acid acidic stripping solution is contained, and it is a strongly acidic solution having a pH of approximately 1 or less, usually pH 0.3 to pH 0.6.

〔酸化処理〕
本発明の回収方法は、錫めっき剥離廃液に酸化剤を添加して液中に含まれるＳｎイオンを酸化してＳｎスラッジを生成させる。具体的には、剥離廃液に酸化剤を添加することによって、液中のＳｎ(II)イオンがＳｎ(IV)イオンに酸化され、このＳｎ(IV)イオンは速やかに加水分解してＳｎＯ2（固体）のＳｎスラッジになる。また、液中に含まれるＣｕ粉は酸化されて溶解する。 [Oxidation treatment]
In the recovery method of the present invention, an oxidizing agent is added to the tin plating stripping waste liquid to oxidize Sn ions contained in the liquid to produce Sn sludge. Specifically, by adding an oxidizing agent to the stripping waste liquid, Sn (II) ions in the liquid are oxidized to Sn (IV) ions, and these Sn (IV) ions are rapidly hydrolyzed to SnO 2 ( Solid) Sn sludge. Moreover, Cu powder contained in the liquid is oxidized and dissolved.

酸化剤としては硝酸、過酸化水素、酸素、オゾン、ペルオキソ二硫酸イオン、Ｆｅ(III)イオンなどを用いることができる。これらの中で、反応速度が高く、電解採取に影響を与えにくい過酸化水素が好ましい。酸化剤の添加量は、液中のＳｎ(II)イオンとＣｕ粉の合計量(mol量)の０.５〜２.５倍量(mol量)が良く、１〜２倍量(mol量)が好ましい。酸化剤の添加量が上記合計量の０.５倍量より少ないと、Ｓｎ(II)イオンおよびＣｕ粉の酸化が不十分になり、一方、酸化剤の添加量が２.５倍量より多くても効果は実質的に変わらない。 As the oxidizing agent, nitric acid, hydrogen peroxide, oxygen, ozone, peroxodisulfate ion, Fe (III) ion, or the like can be used. Among these, hydrogen peroxide is preferable because it has a high reaction rate and hardly affects the electrowinning. The addition amount of the oxidizing agent is preferably 0.5 to 2.5 times (mol amount) of the total amount (mol amount) of Sn (II) ions and Cu powder in the liquid, and 1 to 2 times (mol amount). ) Is preferred. If the amount of oxidizer added is less than 0.5 times the total amount, the oxidation of Sn (II) ions and Cu powder becomes insufficient, while the amount of oxidizer added is more than 2.5 times the amount. However, the effect is not substantially changed.

剥離廃液に酸化剤を添加し、液温１０℃〜６０℃で１時間以上、酸化処理を行うと良い。液温が１０℃未満では上記酸化反応が遅く、６０℃より高いと酸化剤の自己分解が進むため酸化反応が不十分になり、Ｓｎ(II)イオンが残存する。また、処理時間が１時間未満では酸化反応が不十分になる。 It is preferable to add an oxidizing agent to the stripping waste liquid and perform an oxidation treatment at a liquid temperature of 10 ° C. to 60 ° C. for 1 hour or longer. When the liquid temperature is less than 10 ° C., the oxidation reaction is slow. When the liquid temperature is higher than 60 ° C., self-decomposition of the oxidant proceeds, so that the oxidation reaction becomes insufficient and Sn (II) ions remain. Further, if the treatment time is less than 1 hour, the oxidation reaction becomes insufficient.

なお、通常、錫めっきの剥離液には酸化剤が含まれているが、この酸化剤は錫めっきの剥離に消費されるので、剥離されたＳｎ(II)イオンは十分に酸化されず、剥離後の剥離廃液には多量のＳｎ(II)イオンが含まれている。本発明の回収方法は、この剥離廃液に酸化剤を添加し、液中のＳｎ(II)イオンを十分に酸化してＳｎスラッジを生成させてＳｎの回収率を高め、またＣｕ粉を溶解してＣｕの混入を防ぐ。 Usually, the tin plating stripper contains an oxidizing agent, but since this oxidizing agent is consumed for stripping of the tin plating, the stripped Sn (II) ions are not sufficiently oxidized and stripped. The later stripping waste liquid contains a large amount of Sn (II) ions. In the recovery method of the present invention, an oxidizing agent is added to the stripping waste liquid, Sn (II) ions in the liquid are sufficiently oxidized to produce Sn sludge to increase the Sn recovery rate, and the Cu powder is dissolved. To prevent Cu contamination.

〔電解処理〕
本発明の回収方法は、剥離廃液に酸化剤を添加して酸化処理した後に、該剥離廃液を電気分解してＣｕを析出させて回収（電解処理）した後に、Ｓｎスラッジを凝集処理する態様を含む。剥離廃液から電解によってＣｕを除去した後に、液中のＳｎスラッジ分を凝集させれば、高品位のＳｎを安易なプロセスで回収することができる。また、剥離廃液を酸化処理し、Ｓｎ(II)イオンを酸化して固体のＳｎスラッジにした後に電気分解を行うことによって、Ｓｎの共析を防止することができ、Ｓｎ混入量の少ない高品位のＣｕを電解で回収することができる。 [Electrolytic treatment]
In the recovery method of the present invention, after oxidizing the stripping waste liquid by adding an oxidizing agent, the stripping waste liquid is electrolyzed, Cu is deposited and recovered (electrolytic processing), and then Sn sludge is agglomerated. Including. After removing Cu from the stripping waste liquid by electrolysis, if Sn sludge in the liquid is agglomerated, high quality Sn can be recovered by an easy process. In addition, it is possible to prevent Sn co-deposition by oxidizing the stripping waste liquid and oxidizing Sn (II) ions to form solid Sn sludge. Cu can be recovered by electrolysis.

Ｃｕの電解採取は、例えば、ＳＵＳ３１６をカソード、酸化イリジウムコートチタン板をアノードにし、浴温３５℃、電流密度２Ａ/ｄｍ2にて４８時間程度行うと良い。 For example, the electrolytic extraction of Cu may be performed for about 48 hours at a bath temperature of 35 ° C. and a current density of 2 A / dm 2 using SUS316 as a cathode and an iridium oxide-coated titanium plate as an anode.

Ｃｕの電解採取は、芳香族スルホン酸、芳香族スルホン酸塩、芳香族カルボン酸、芳香族カルボン酸塩からなるグループから選択された少なくとも一つの結晶粒微細化剤と、アルキルベンゼンスルホン酸、アルキルベンゼンスルホン酸塩からなるグループから選択された少なくとも一つの界面活性剤とを該剥離廃液に添加して行うと良い。
結晶粒微細化剤を添加すると、析出するＣｕの結晶粒が微細になり、析出するＣｕの表面が平滑になるので、Ｓｎスラッジの巻き込みが少なくなり、高品位のＣｕを回収することができる。また界面活性剤を添加するとＣｕの表面がさらに平滑になり、Ｓｎスラッジの巻き込みと硫酸の含有をさらに防止することができる。 The electrolytic extraction of Cu includes at least one grain refiner selected from the group consisting of aromatic sulfonic acid, aromatic sulfonate, aromatic carboxylic acid, aromatic carboxylate, alkylbenzene sulfonic acid, alkylbenzene sulfone. It is preferable to add at least one surfactant selected from the group consisting of acid salts to the stripping waste liquid.
When the crystal grain refining agent is added, the crystal grains of the precipitated Cu become finer and the surface of the precipitated Cu becomes smooth, so that Sn sludge is less involved and high quality Cu can be recovered. Further, when a surfactant is added, the surface of Cu becomes smoother, and Sn sludge entrainment and sulfuric acid content can be further prevented.

〔凝集処理〕
酸化処理した剥離廃液のｐＨを０.５〜２.５、好ましくはｐＨ１〜２に調整（中和）した後に凝集剤を添加してＳｎスラッジを凝集させる。ｐＨ０.５未満では凝集剤が十分に作用し難くなるため、大量の凝集剤が必要となり、凝集剤に巻き込まれたＣｕイオンや、凝集剤由来の有機物成分がＳｎスラッジに混入し、高品位のＳｎの回収が困難になる。一方、ｐＨ３を上回ると、Ｃｕ水酸化物の沈殿が生じ、ＳｎスラッジにＣｕ水酸化物が混入するようになるので、Ｓｎの品位が低下する。上記ｐＨ域に調整してＳｎスラッジを凝集させることによって、高品位のＳｎを回収することができる。剥離廃液のｐＨを上記範囲に調整するには、例えば、剥離廃液に水を加えて希釈すれば良い。 [Aggregation treatment]
After adjusting (neutralizing) the pH of the oxidized stripping waste liquid to 0.5 to 2.5, preferably pH 1 to 2, a flocculant is added to agglomerate Sn sludge. If the pH is less than 0.5, the flocculant is not sufficiently effective, so a large amount of flocculant is required, and Cu ions entrained in the flocculant and organic substances derived from the flocculant are mixed into the Sn sludge. It becomes difficult to collect Sn. On the other hand, if it exceeds pH 3, precipitation of Cu hydroxide occurs, and Cu hydroxide is mixed into Sn sludge, so that the quality of Sn decreases. High-grade Sn can be recovered by aggregating Sn sludge by adjusting to the above pH range. In order to adjust the pH of the stripping waste liquid to the above range, for example, water may be added to the stripping waste liquid and diluted.

ｐＨ調整した後に凝集剤を添加してＳｎスラッジを凝集させる。凝集剤としてはハイモ社のＡＰ１０７（商品名）、ＳＳ−５００（商品名）などを用いることができる。Ｓｎスラッジ凝集物は固液分離して回収する。 After adjusting the pH, a flocculant is added to agglomerate Sn sludge. As the aggregating agent, AP107 (trade name), SS-500 (trade name) manufactured by Hymo Co., Ltd. can be used. Sn sludge aggregates are recovered by solid-liquid separation.

本発明の方法によれば、剥離廃液に酸化剤を添加し、液中のＳｎ(II)イオンを十分に酸化してＳｎスラッジを生成させて凝集するので、Ｓｎの回収率を高めることができる。また剥離廃液を酸化処理することによって液中のＣｕ粉が溶解するので、Ｓｎ凝集体にＣｕ粉が混入せず、Ｃｕ分が概ね３wt％以下の高品位Ｓｎを回収することができる。 According to the method of the present invention, an oxidizing agent is added to the stripping waste liquid, Sn (II) ions in the liquid are sufficiently oxidized to produce Sn sludge and agglomerate, so that the Sn recovery rate can be increased. . Moreover, since the Cu powder in the liquid is dissolved by oxidizing the stripping waste liquid, the Cu powder is not mixed into the Sn aggregate, and high-grade Sn having a Cu content of approximately 3 wt% or less can be recovered.

以下、本発明の実施例を比較例と共に示す。実施例および比較例において、Ｓｎ(II)イオン濃度１０ｇ/L、Ｃｕ(II)イオン濃度５０ｇ/L、ＳｎＯ2スラッジ濃度３０ｇ/L、Ｃｕ粉濃度５ｇ/L、硫酸濃度３０ｇ/LのＳｎめっき剥離廃液を用いた。Ｓｎ濃度はＩＣＰ−ＡＥＳによって測定した。 Examples of the present invention are shown below together with comparative examples. In Examples and Comparative Examples, Sn plating with Sn (II) ion concentration 10 g / L, Cu (II) ion concentration 50 g / L, SnO 2 sludge concentration 30 g / L, Cu powder concentration 5 g / L, and sulfuric acid concentration 30 g / L. A stripping waste liquid was used. Sn concentration was measured by ICP-AES.

〔実施例１〕
上記Ｓｎめっき剥離廃液に、液中のＳｎ(II)イオンとＣｕ粉の合計量(mol量)に対して各々０.５倍、１倍、２.５倍のmol量になる過酸化水素を添加し、３５℃にて２４時間、酸化処理した。その後、該剥離廃液に水を加えてｐＨ１に調整し、凝集剤（ハイモ社製品SS-500）を１００ppm添加してフロックを形成した。該フロックを遠心分離機により回収し、乾燥して品位を分析した。この結果を表１に示す。 [Example 1]
Hydrogen peroxide that is 0.5 times, 1 time, and 2.5 times the mol amount of the total amount (mol amount) of Sn (II) ions and Cu powder in the solution is added to the Sn plating stripping waste liquid. The mixture was added and oxidized at 35 ° C. for 24 hours. Thereafter, water was added to the stripping waste liquid to adjust the pH to 1, and 100 ppm of a flocculant (product of Hymo Co., Ltd., SS-500) was added to form floc. The floc was collected by a centrifuge, dried and analyzed for quality. The results are shown in Table 1.

〔実施例２〕
過酸化水素に代えて硝酸、ペルオキソ二硫酸ナトリウムを用いて剥離廃液を酸化処理した後に、実施例１と同様にしてフロックを形成し、該フロックを遠心分離機により回収し、乾燥してＳｎの品位を分析した。この結果を表１に示す。 [Example 2]
After oxidizing the stripping waste liquid using nitric acid and sodium peroxodisulfate instead of hydrogen peroxide, flocs were formed in the same manner as in Example 1, and the flocs were collected by a centrifuge and dried to produce Sn. The quality was analyzed. The results are shown in Table 1.

〔実施例３〕
表１のNo.２の試料について、酸化処理の後に該剥離廃液に水を加えてｐＨ０.１、ｐＨ０.５、ｐＨ２.５、ｐＨ５に調整した以外は実施例１と同様にして、凝集剤を添加してフロックを形成した。該フロックを遠心分離機により回収し、乾燥して品位を分析した。この結果を表２に示す。 Example 3
For the sample No. 2 in Table 1, the flocculant was prepared in the same manner as in Example 1 except that water was added to the stripping waste liquid after the oxidation treatment to adjust the pH to 0.1, pH 0.5, pH 2.5, and pH 5. Was added to form a floc. The floc was collected by a centrifuge, dried and analyzed for quality. The results are shown in Table 2.

〔実施例４〕
実施例１と同様に剥離廃液を酸化処理した後に、この剥離廃液にＳＵＳ３１６をカソードとし、酸化イリジウムコートチタン板をアノードとして、浴温３５℃、電流密度２Ａ/dm2にて４８時間、Ｃｕの電解採取を行った。電解採取後の剥離廃液のＣｕ(II)イオン濃度は５ｇ/Lであった。電解採取後に、実施例１と同様にしてフロックを形成し、該フロックを遠心分離機により回収し、乾燥してＳｎの品位を分析したところ、ＳｎＯ2含有率９５.３wt％、Ｃｕ含有率１.２％であった。 Example 4
After oxidizing the stripping waste liquid in the same manner as in Example 1, the stripping waste liquid was treated with SUS316 as a cathode and iridium oxide-coated titanium plate as an anode at a bath temperature of 35 ° C. and a current density of 2 A / dm 2 for 48 hours. Electrolytic collection was performed. The Cu (II) ion concentration in the stripping waste liquid after electrolytic collection was 5 g / L. After electrolytic collection, flocs were formed in the same manner as in Example 1. The flocs were collected by a centrifuge, dried, and analyzed for Sn quality. As a result, the SnO 2 content was 95.3 wt%, the Cu content was 1 It was 2%.

〔比較例〕
酸化処理を行わない以外は実施例１と同様にしてフロックを形成し、該フロックを遠心分離機により回収し、乾燥してＳｎの品位を分析した。この結果を表１に示す。 [Comparative Example]
A floc was formed in the same manner as in Example 1 except that the oxidation treatment was not performed. The floc was collected by a centrifuge, dried, and analyzed for Sn quality. The results are shown in Table 1.

Figure 2015001000
Figure 2015001000

Figure 2015001000
Figure 2015001000

Claims (3)

銅基錫めっき材の錫めっき剥離廃液に酸化剤を添加して液中のＳｎイオンを酸化してＳｎスラッジを生成させると共に液中のＣｕ粉を溶解し（酸化処理）、次いで該剥離廃液のｐＨを０.５〜２.５に中和した後に凝集剤を添加してＳｎスラッジを凝集させる（凝集処理）ことを特徴とする錫めっき剥離廃液からの錫の回収方法。
An oxidizing agent is added to the tin plating stripping waste liquid of the copper-based tin plating material to oxidize Sn ions in the liquid to produce Sn sludge and dissolve Cu powder in the liquid (oxidation treatment), and then the stripping waste liquid A method for recovering tin from a tin plating stripping waste liquid, characterized in that after the pH is neutralized to 0.5 to 2.5, a flocculant is added to agglomerate Sn sludge (aggregation treatment).
酸化剤の添加量が、液中のＳｎ(II)イオンとＣｕ粉の合計量(mol量)の０.５〜２.５倍量(mol量)である請求項１に記載する錫の回収方法。
The recovery of tin according to claim 1, wherein the addition amount of the oxidizing agent is 0.5 to 2.5 times (mol amount) the total amount (mol amount) of Sn (II) ions and Cu powder in the liquid. Method.
剥離廃液に酸化剤を添加して酸化処理した後に、該剥離廃液を電気分解してＣｕを析出させて回収し（電解処理）、次いで該剥離廃液のｐＨを０.５〜２．５に中和した後に凝集剤を添加してＳｎスラッジを凝集させる（凝集処理）請求項１または請求項２に記載する錫の回収方法。 After oxidizing the stripping waste liquid by adding an oxidizing agent, the stripping waste liquid is electrolyzed and Cu is deposited and recovered (electrolytic treatment), and then the pH of the stripping waste liquid is adjusted to 0.5 to 2.5. The method for recovering tin according to claim 1 or 2, wherein after the addition, a flocculant is added to agglomerate Sn sludge (aggregation treatment).
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JP2015047573A (en) * 2013-09-03 2015-03-16 株式会社高松メッキ METHOD OF PRODUCING Sn-BASED RECYCLE SLUDGE
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JP2015047573A (en) * 2013-09-03 2015-03-16 株式会社高松メッキ METHOD OF PRODUCING Sn-BASED RECYCLE SLUDGE
CN104986892A (en) * 2015-07-02 2015-10-21 清远市新绿环境技术有限公司 Tin stripping waste liquid treating method
CN108862530A (en) * 2018-06-26 2018-11-23 闫明光 A kind of tin stripper recovery process
CN110240305A (en) * 2019-05-20 2019-09-17 南京金陵化工厂有限责任公司 A kind of production wastewater treatment pond of stabilizer for plastics and its processing method
CN110512082B (en) * 2019-09-20 2020-11-03 常州工学院 Recovery method of waste metal sludge
CN110512082A (en) * 2019-09-20 2019-11-29 常州工学院 A kind of recovery method of discarded metal sludge
CN110607444A (en) * 2019-09-29 2019-12-24 湖南仁发材料科技有限公司 Novel treatment method for copper and tin slag removal
CN110607444B (en) * 2019-09-29 2021-07-02 湖南仁发材料科技有限公司 Novel treatment method for copper and tin slag removal
CN111995118A (en) * 2020-08-31 2020-11-27 武汉钢铁有限公司 Method for recycling water quenching of cold-rolling electrotinning unit
CN111995118B (en) * 2020-08-31 2022-05-17 武汉钢铁有限公司 Method for recycling water quenching of cold-rolling electrotinning unit
CN114232030A (en) * 2021-12-23 2022-03-25 广东鑫菱环境科技有限公司 PCB methanesulfonic acid tin stripping waste liquid recycling method and application thereof
CN114804458A (en) * 2022-04-22 2022-07-29 盛隆资源再生（无锡）有限公司 Recycling method of waste tin stripping liquid
CN114804458B (en) * 2022-04-22 2023-02-07 盛隆资源再生（无锡）有限公司 Recycling method of waste tin stripping liquid

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