JPH1021969A - Method of recovering valuable substance from disposed ni-mh secondary battery, and ni-mh secondary battery waste electrode plate - Google Patents
Method of recovering valuable substance from disposed ni-mh secondary battery, and ni-mh secondary battery waste electrode plateInfo
- Publication number
- JPH1021969A JPH1021969A JP17343396A JP17343396A JPH1021969A JP H1021969 A JPH1021969 A JP H1021969A JP 17343396 A JP17343396 A JP 17343396A JP 17343396 A JP17343396 A JP 17343396A JP H1021969 A JPH1021969 A JP H1021969A
- Authority
- JP
- Japan
- Prior art keywords
- secondary battery
- slurry
- recovering valuable
- dispersant
- waste
- 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
Classifications
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、負極に水素吸蔵合
金を配したニッケル−水素二次電池（本明細書では以下
Ｎｉ−ＭＨ二次電池と略記する）が使用済み等のために
廃棄された際に、この廃棄されたＮｉ−ＭＨ二次電池及
びＮｉ−ＭＨ二次電池廃極板から有価物を回収する方法
に関する。BACKGROUND OF THE INVENTION The present invention relates to a nickel-hydrogen secondary battery (hereinafter abbreviated as Ni-MH secondary battery) in which a hydrogen storage alloy is disposed on a negative electrode because the battery has been used and the like. The present invention relates to a method of recovering valuable resources from the discarded Ni-MH secondary battery and the waste Ni-MH secondary battery electrode plate.
【０００２】[0002]
【従来の技術】Ｎｉ−ＭＨ二次電池は多孔質ニッケルま
たは繊維状金属ニッケルに水酸化ニッケルを充填した正
極と、ニッケルメッキした鉄のパンチプレートや多孔質
金属ニッケル等に水素吸蔵合金粉末を導電剤、結着剤と
ともに固着した負極と、ポリプレン等で形成されたセパ
レーター等を有し、これらは電解液とともに鋼製容器に
収納されて構成されている。2. Description of the Related Art A Ni-MH secondary battery has a positive electrode in which porous nickel or fibrous metal nickel is filled with nickel hydroxide, and a hydrogen-absorbing alloy powder that is passed through a nickel-plated iron punch plate or porous metal nickel. It has a negative electrode fixed together with an agent and a binder, a separator formed of polypropylene or the like, and these are housed in a steel container together with an electrolytic solution.
【０００３】このＮｉ−ＭＨ二次電池は有害なカドミウ
ムを部材として使用していないために、ニッケル−カド
ミウム電池とは異なり、廃棄しても深刻な公害を発生さ
せることがない。しかしニッケルや水素吸蔵合金は貴重
な資源であるために、廃棄されたＮｉ−ＭＨ二次電池及
びＮｉ−ＭＨ二次電池廃極板からこれらの有価物を回収
することは資源活用の観点から極めて重要である。Since this Ni-MH secondary battery does not use harmful cadmium as a member, unlike a nickel-cadmium battery, it does not cause serious pollution even when disposed. However, since nickel and hydrogen storage alloys are valuable resources, it is extremely difficult to recover these valuable materials from discarded Ni-MH secondary batteries and waste plates of Ni-MH secondary batteries from the viewpoint of resource utilization. is important.
【０００４】特開平８−２０８２５号で、本発明者ら
は、ニッケル基板、水酸化ニッケル、水素吸蔵合金、セ
パレーター、合成樹脂フィルム、鋼製容器などの、物理
的・化学的特性が異なる多種類の部材で構成されている
Ｎｉ−ＭＨ二次電池の廃棄物から簡易な方法で高い価値
を有する有価物を回収する方法について提案している。[0004] In Japanese Patent Application Laid-Open No. 8-20825, the inventors of the present invention disclosed various types of nickel substrates, nickel hydroxide, hydrogen storage alloys, separators, synthetic resin films, steel containers, and the like having different physical and chemical properties. The present invention proposes a method for recovering valuable materials having high value from waste of Ni-MH secondary batteries composed of the above members by a simple method.
【０００５】[0005]
【発明が解決しようとする課題】負極に粉末状水素吸蔵
合金を配した、廃棄されたＮｉ−ＭＨ二次電池及びＮｉ
−ＭＨ二次電池廃極板から有価物を回収するに際し、該
Ｎｉ−ＭＨ二次電池を砕断し砕断片を水中で処理して粉
末部をスラリーとし、ついでスラリー化しない部分とス
ラリーとに分離し、スラリーから比重分離及びまたは浮
遊分離により有価物を回収する工程において、有価物と
導電剤や結着剤の分散性が悪く、水素吸蔵合金の分離効
率が小さいなどの問題点があった。本発明は、スラリー
から効率的に有価物を回収する方法の提供を課題として
いる。DISCLOSURE OF THE INVENTION Disposal of Ni-MH secondary battery in which a powdery hydrogen storage alloy is disposed on the negative electrode and Ni
-When recovering valuable materials from the waste electrode plate of the MH secondary battery, the Ni-MH secondary battery is crushed, and the crushed pieces are treated in water to turn the powder portion into a slurry, and then to the non-slurried portion and the slurry. In the process of separating and recovering valuable materials from the slurry by specific gravity separation and / or floating separation, there were problems such as poor dispersibility of the valuable materials and the conductive agent and the binder, and low separation efficiency of the hydrogen storage alloy. . An object of the present invention is to provide a method for efficiently recovering valuable resources from a slurry.
【０００６】[0006]
【課題を解決するための手段及び作用】本発明は、
（１）負極に粉末状水素吸蔵合金を配した、廃棄された
Ｎｉ−ＭＨ二次電池から有価物を回収するに際し、該二
次電池を砕断し砕断片を水中で処理してスラリー化しな
い部分とスラリーとに分離し、スラリーから比重分離及
びまたは浮遊分離により有価物を回収する工程におい
て、砕断片を水中で処理してスラリー化しない部分とス
ラリーとに分離する際に分散剤を含有させることを特徴
とする、廃棄されたＮｉ−ＭＨ二次電池及びＮｉ−ＭＨ
二次電池廃極板から有価物を回収する方法である。SUMMARY OF THE INVENTION The present invention provides:
(1) When recovering valuable resources from a discarded Ni-MH secondary battery having a powdered hydrogen storage alloy disposed on the negative electrode, the secondary battery is crushed, and the crushed pieces are treated in water so as not to be slurried. In the step of separating valuable parts from the slurry and recovering valuable resources from the slurry by specific gravity separation and / or suspension separation, a dispersant is contained when the crushed fragments are treated in water to separate them into a slurry-free part and a slurry. Disposal of Ni-MH secondary battery and Ni-MH
This is a method of recovering valuable resources from waste electrode plates of secondary batteries.
【０００７】また（２）スラリーから比重分離及びまた
は浮遊分離により有価物を回収する工程において、スラ
リーに分散剤を添加することを特徴とする、前記（１）
に記載の廃棄されたＮｉ−ＭＨ二次電池及びＮｉ−ＭＨ
二次電池廃極板から有価物を回収する方法である。(2) In the step of recovering valuable resources from the slurry by specific gravity separation and / or suspension separation, a dispersant is added to the slurry.
Ni-MH secondary battery and Ni-MH
This is a method of recovering valuable resources from waste electrode plates of secondary batteries.
【０００８】また（３）分散剤が、アニオン系分散剤及
び又はノニオン系分散剤であることを特徴とする、前記
（１）または（２）に記載の廃棄されたＮｉ−ＭＨ二次
電池及びＮｉ−ＭＨ二次電池廃極板から有価物を回収す
る方法である。(3) The Ni-MH secondary battery according to (1) or (2), wherein the dispersant is an anionic dispersant and / or a nonionic dispersant. This is a method of recovering valuable resources from waste Ni-MH secondary battery plates.
【０００９】また（４）アニオン系分散剤が、低重合ア
クリル酸ソーダ、オレイン酸ソーダの何れかあるいは双
方よりなることを特徴とする、前記（３）に記載の廃棄
されたＮｉ−ＭＨ二次電池及びＮｉ−ＭＨ二次電池廃極
板から有価物を回収する方法である。(4) The secondary Ni-MH secondary material according to (3), wherein the anionic dispersant comprises one or both of low-polymer sodium acrylate and sodium oleate. This is a method of recovering valuable resources from batteries and waste plates of Ni-MH secondary batteries.
【００１０】また（５）ノニオン系分散剤が、ポリオキ
シエチレンソルビタンオレエート、ポリオキシエチレン
ソルビタンステアレートの何れかあるいは双方であるこ
とを特徴とする、前記（３）に記載の廃棄されたＮｉ−
ＭＨ二次電池及びＮｉ−ＭＨ二次電池廃極板から有価物
を回収する方法である。(5) The discarded Ni as described in (3) above, wherein the nonionic dispersant is one or both of polyoxyethylene sorbitan oleate and polyoxyethylene sorbitan stearate. −
This is a method for recovering valuable resources from MH secondary batteries and Ni-MH secondary battery waste electrode plates.
【００１１】本発明において、負極に粉末状水素吸蔵合
金を配した、廃棄されたＮｉ−ＭＨ二次電池及びＮｉ−
ＭＨ二次電池廃極板から有価物を回収するに際し、該二
次電池を砕断する。なお、本発明において水素吸蔵合金
を配した廃極板があらかじめ解体されている場合、この
負極板ないしは電池製造工程で発生する廃電極の大きさ
（幅）が小さい場合には砕断せずに用いることができる
事は勿論であり、また危険防止のためにはこの砕断は水
をかけながらあるいは水中で行う砕断でもよい事は云う
までもない。In the present invention, a discarded Ni-MH secondary battery in which a powdery hydrogen storage alloy is disposed on a negative electrode, and a Ni-MH secondary battery.
When recovering valuable resources from the MH secondary battery waste electrode plate, the secondary battery is crushed. In the present invention, when the waste electrode plate provided with the hydrogen storage alloy has been dismantled in advance, if the size (width) of the negative electrode plate or the waste electrode generated in the battery manufacturing process is small, the electrode is not cut. Of course, it can be used, and it goes without saying that this crushing may be performed with or without water to prevent danger.
【００１２】本発明において、この極板から有価物を分
離する。この分離処理は例えば前記破断された廃極板を
ボールミルやセメントミキサー等中に装入し水が不足し
ている場合は水を加え、内容物を撹拌混合する事が好ま
しく、含まれている水素吸蔵合金、Ｎｉ(ＯＨ)2、Ｃ等
の内容物を、容器、極板等の破断片から分離してスラリ
ー化する。本発明ではこの時に分散剤を添加する。これ
が本発明の特徴である。なお分散剤の量としては、スラ
リー量に対して０．１〜１０％が好ましい。In the present invention, valuables are separated from the electrode plate. For this separation treatment, for example, it is preferable to charge the broken waste electrode plate into a ball mill or a cement mixer or the like, add water if water is insufficient, and stir and mix the contents. The contents of the storage alloy, Ni (OH) 2 , C and the like are separated from broken pieces such as containers and electrode plates to form a slurry. In the present invention, a dispersant is added at this time. This is a feature of the present invention. The amount of the dispersant is preferably 0.1 to 10% based on the amount of the slurry.
【００１３】この水処理品を例えば１ｍｍの篩いで電極
等の破断片を分離除去し、更に２００メッシュの篩を用
いてスラリー化しない他の内容物を分離する（一次分
離）。なお２００メッシュ篩下のスラリーに分散剤を更
に添加し、有価物を次の回収工程に供することもでき
る。これ等の分散剤含有スラリーを、超音波処理し分散
性を向上させることは、有価物回収効率を高めるのに有
効である。有価物は、スラリーから比重分離または浮遊
分離によって回収するが、この比重分離または浮遊分離
による回収は例えばテーブル選鉱機や液体サイクロンを
用いる事によって行うことができる。The water-treated product is separated and removed with, for example, a 1-mm sieve to separate broken pieces of electrodes and the like, and further separated using a 200-mesh sieve to separate other contents that are not slurried (primary separation). It should be noted that a dispersant may be further added to the slurry below the 200-mesh sieve, and the valuable material may be subjected to the next recovery step. Improving the dispersibility of these dispersant-containing slurries by ultrasonic treatment is effective for increasing the valuable resource recovery efficiency. Valuables are recovered from the slurry by specific gravity separation or floating separation. The recovery by specific gravity separation or floating separation can be performed, for example, by using a table ore separator or a liquid cyclone.
【００１４】本発明者らは分散性を高めるために種々の
分散剤を実験し、特定のアニオン系分散剤、ノニオン系
分散剤が好ましい事を確認した。アニオン系分散剤とし
ては、好ましくは低重合アクリル酸ソーダ、オレイン酸
ソーダ等が、また、ノニオン系分散剤としては、好まし
くはポリオキシエチレンソルビタンオレエート、ポリオ
キシエチレンソルビタンステアレート等が効果が大きい
ことを実験を繰り返すことにより見出した。上記の分散
剤を用いると分散剤分子が粒子の表面を被覆し、アニオ
ン系分散剤ではその親水基の静電気反発力により、また
ノニオン系分散剤は吸着分子の立体反発力により、それ
ぞれ粒子同士の接近と再凝集が妨げられ、好ましい結果
が得られる。The present inventors have experimented with various dispersants to enhance dispersibility, and have confirmed that specific anionic dispersants and nonionic dispersants are preferable. As the anionic dispersant, preferably low-polymer sodium acrylate, sodium oleate and the like, and as the nonionic dispersant, preferably polyoxyethylene sorbitan oleate, polyoxyethylene sorbitan stearate and the like are effective. This was found by repeating the experiment. When the above dispersant is used, the dispersant molecules cover the surface of the particles, the anionic dispersant uses the electrostatic repulsion of the hydrophilic group, and the nonionic dispersant uses the steric repulsion of the adsorbed molecules to form particles. Access and reagglomeration are prevented, with favorable results.
【００１５】[0015]
【実施例】Ｎｉ−ＭＨ二次電池を低速破砕機で水をかけ
ながら砕断し、ついで、ボールミルに破断片を装入し、
分散剤を加えて水中で２０分間撹拌処理した。これを篩
い目が１ｍｍ、１００メッシュ、および２００メッシュ
の篩を三段に重ねた分離機にかけて、一次分離して２０
０メッシュ以下のスラリーを得、これを液体サイクロン
にて処理し、有価物の一つの水素吸蔵合金を回収した。
この際に用いた分散剤と添加量を表１に示す。EXAMPLE A Ni-MH rechargeable battery was broken by sprinkling water with a low-speed crusher, and then a fragment was charged into a ball mill.
The dispersant was added and the mixture was stirred in water for 20 minutes. This was firstly separated by a separator in which sieves having a sieve of 1 mm, 100 mesh, and 200 mesh were stacked in three stages to obtain a primary separation of 20 mm.
A slurry having a mesh size of 0 mesh or less was obtained, and the slurry was treated with a liquid cyclone to recover one of the valuable resources, a hydrogen storage alloy.
Table 1 shows the dispersant used and the amount added.
【００１６】なお、液体サイクロンのシンク品は、再度
液体サイクロンにかける繰り返しの処理を行ったが、こ
の際の処理回数と回収品のＣ分析値を表１に示す。The liquid cyclone sink product was subjected to a repetitive process of reapplying to the liquid cyclone. Table 1 shows the number of times of processing and the C analysis value of the recovered product.
【００１７】[0017]
【表１】 [Table 1]
【００１８】分散剤を添加すると表１にみられるよう
に、回収水素吸蔵合金中のＣ濃度は低下し、有価物の水
素吸蔵合金と導電剤、結着剤との分離が良好となる。な
お分散剤の添加量としては、３〜５％が最適であった。As shown in Table 1, when the dispersant is added, the C concentration in the recovered hydrogen storage alloy decreases, and the separation of the valuable hydrogen storage alloy from the conductive agent and the binder is improved. The optimum amount of the dispersant added was 3 to 5%.
【００１９】[0019]
【発明の効果】本発明によれば、廃棄されたＮｉ−ＭＨ
二次電池及びＮｉ−ＭＨ二次電池廃極板から有価物を効
率よく回収することができる。また回収された水素吸蔵
合金は、リサイクル使用が可能であり、また、電極ケー
ス、極板、水酸化ニッケル等他の有価物も、水素吸蔵合
金と同様、再利用することができる。According to the present invention, discarded Ni-MH
Valuables can be efficiently collected from the secondary battery and the waste electrode plate of the Ni-MH secondary battery. The recovered hydrogen storage alloy can be recycled, and other valuable materials such as an electrode case, an electrode plate, and nickel hydroxide can be reused similarly to the hydrogen storage alloy.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 笹井 興士 茨城県つくば市東光台５−９−６日本重化 学工業株式会社筑波研究所内 (72)発明者 中村 勝 茨城県つくば市東光台５−９−６日本重化 学工業株式会社筑波研究所内 (72)発明者 本多 次徳 東京都中央区日本橋小網町８番４号日本重 化学工業株式会社内 (72)発明者 釣 光廣 東京都中央区日本橋小網町８番４号日本重 化学工業株式会社内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Koji Sasai 5-9-6 Tokodai, Tsukuba, Ibaraki Pref., Japan Tsukuba Research Laboratory Co., Ltd. (72) Inventor Masaru Nakamura 5 Tokodai, Tsukuba, Ibaraki -9-6 Inside the Tsukuba Research Laboratories of Nippon Heavy Industries, Ltd. (72) Inventor Tsutsunori Honda 8-4 Nihonbashi Koamicho, Chuo-ku, Tokyo Inside Nippon Heavy Industries, Ltd. 8-4 Koamicho, Nihonbashi, Chuo-ku, Tokyo
Claims (5)
されたＮｉ−ＭＨ二次電池から有価物を回収するに際
し、該二次電池を砕断し砕断片を水中で処理してスラリ
ー化しない部分とスラリーとに分離し、スラリーから比
重分離及びまたは浮遊分離により有価物を回収する工程
において、砕断片を水中で処理してスラリー化しない部
分とスラリーとに分離する際に分散剤を含有させること
を特徴とする、廃棄されたＮｉ−ＭＨ二次電池及びＮｉ
−ＭＨ二次電池廃極板から有価物を回収する方法。In recovering valuable resources from a discarded Ni-MH secondary battery having a powdered hydrogen storage alloy disposed on a negative electrode, the secondary battery is crushed and crushed pieces are treated in water to obtain a slurry. In the process of separating valuable parts from the slurry by separating into a slurry and a slurry by specific gravity separation and / or floating separation from the slurry, a dispersing agent is used when the crushed fragments are treated in water to separate the slurry into the non-slurried part and the slurry. Ni-MH secondary battery and Ni discarded, characterized by containing
-A method of recovering valuable materials from MH secondary battery waste electrode plates.
により有価物を回収する工程において、スラリーに分散
剤を添加することを特徴とする、請求項１の廃棄された
Ｎｉ−ＭＨ二次電池及びＮｉ−ＭＨ二次電池廃極板から
有価物を回収する方法。2. A discarded Ni-MH secondary battery according to claim 1, wherein a dispersant is added to the slurry in the step of recovering valuable resources from the slurry by specific gravity separation and / or suspension separation. -A method of recovering valuable materials from MH secondary battery waste electrode plates.
オン系分散剤であることを特徴とする、請求項１または
請求項２に記載の廃棄されたＮｉ−ＭＨ二次電池及びＮ
ｉ−ＭＨ二次電池廃極板から有価物を回収する方法。3. The disposable Ni-MH secondary battery according to claim 1 or 2, wherein the dispersant is an anionic dispersant and / or a nonionic dispersant.
A method of recovering valuable resources from a waste electrode plate of an i-MH secondary battery.
ーダ、オレイン酸ソーダの何れかあるいは双方よりなる
ことを特徴とする、請求項３に記載の廃棄されたＮｉ−
ＭＨ二次電池及びＮｉ−ＭＨ二次電池廃極板から有価物
を回収する方法。4. The Ni-disposal according to claim 3, wherein the anionic dispersant comprises one or both of low-polymer sodium acrylate and sodium oleate.
A method of recovering valuable resources from MH secondary batteries and waste plates of Ni-MH secondary batteries.
ソルビタンオレエート、ポリオキシエチレンソルビタン
ステアレートの何れかあるいは双方よりなることを特徴
とする、請求項３に記載の廃棄されたＮｉ−ＭＨ二次電
池及びＮｉ−ＭＨ二次電池廃極板から有価物を回収する
方法。5. The discarded Ni-MH dichloride according to claim 3, wherein the nonionic dispersant comprises one or both of polyoxyethylene sorbitan oleate and polyoxyethylene sorbitan stearate. A method for recovering valuable resources from a secondary battery and a waste electrode plate of a Ni-MH secondary battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17343396A JP3605614B2 (en) | 1996-07-03 | 1996-07-03 | Discarded Ni-MH secondary battery and method for recovering valuable resources from waste Ni-MH secondary battery electrode plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17343396A JP3605614B2 (en) | 1996-07-03 | 1996-07-03 | Discarded Ni-MH secondary battery and method for recovering valuable resources from waste Ni-MH secondary battery electrode plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1021969A true JPH1021969A (en) | 1998-01-23 |
| JP3605614B2 JP3605614B2 (en) | 2004-12-22 |
Family
ID=15960378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17343396A Expired - Lifetime JP3605614B2 (en) | 1996-07-03 | 1996-07-03 | Discarded Ni-MH secondary battery and method for recovering valuable resources from waste Ni-MH secondary battery electrode plate |
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| Country | Link |
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| JP (1) | JP3605614B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002184471A (en) * | 2000-12-12 | 2002-06-28 | Sumitomo Metal Mining Co Ltd | Method of recovering valuable metal from used nickel- hydrogen secondary battery |
| JP2009144219A (en) * | 2007-12-17 | 2009-07-02 | Mitsubishi Materials Corp | Method for recovering metal from used solid oxide type fuel cell |
| JP2010253432A (en) * | 2009-04-28 | 2010-11-11 | Jfe Steel Corp | Method of recovering manganese oxide from dry cell |
-
1996
- 1996-07-03 JP JP17343396A patent/JP3605614B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002184471A (en) * | 2000-12-12 | 2002-06-28 | Sumitomo Metal Mining Co Ltd | Method of recovering valuable metal from used nickel- hydrogen secondary battery |
| JP4608773B2 (en) * | 2000-12-12 | 2011-01-12 | 住友金属鉱山株式会社 | Method of recovering valuable metals from used nickel metal hydride secondary batteries |
| JP2009144219A (en) * | 2007-12-17 | 2009-07-02 | Mitsubishi Materials Corp | Method for recovering metal from used solid oxide type fuel cell |
| JP2010253432A (en) * | 2009-04-28 | 2010-11-11 | Jfe Steel Corp | Method of recovering manganese oxide from dry cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3605614B2 (en) | 2004-12-22 |
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