JPS6338434B2 - - Google Patents
Info
- Publication number
- JPS6338434B2 JPS6338434B2 JP22547784A JP22547784A JPS6338434B2 JP S6338434 B2 JPS6338434 B2 JP S6338434B2 JP 22547784 A JP22547784 A JP 22547784A JP 22547784 A JP22547784 A JP 22547784A JP S6338434 B2 JPS6338434 B2 JP S6338434B2
- Authority
- JP
- Japan
- Prior art keywords
- metal
- electrode
- liquid
- metal ions
- deposited
- 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.)
- Expired
Links
- 239000002184 metal Substances 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 26
- 229910021645 metal ion Inorganic materials 0.000 claims description 20
- 238000011084 recovery Methods 0.000 claims description 16
- 238000003795 desorption Methods 0.000 claims description 11
- 239000002699 waste material Substances 0.000 claims description 6
- 239000002738 chelating agent Substances 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 3
- 239000013522 chelant Substances 0.000 description 11
- 239000002351 wastewater Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- 239000011324 bead Substances 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
- C02F1/4678—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction of metals
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Electrolytic Production Of Metals (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
〔産業上の利用分野〕
本発明は、廃液中に含まれる金属イオンを金属
粉体として回収する金属回収装置に関する。
〔従来技術およびその問題点〕
従来、工場等から排出される廃液又は、廃水は
その内に含まれる金属イオンを中和し、沈澱さ
せ、濾過後、スラツジを形成し、この金属を含む
スラツジは、埋立又は海洋投棄されるだけで、再
利用等の有効利用されていない。
また、上記方法による処理は、処理場として大
きな設置場所が必要なうえ、多額の薬品代を必要
とする欠点がある。
この欠点を改良した回収装置として本発明者等
は、特願昭58―184864号（特開昭60―77937号）
で出願しており、この回収装置は、廃液中の金属
イオンをキレート剤によつて濃縮し、この濃縮さ
れた金属イオンを脱離液で脱離させて金属イオン
の高濃度液を生成する濃縮手段と、電極および絶
縁ビーズを収納し、前記高濃度液を電解して、前
記電極面に金属を析出させる電解槽とからなり、
前記絶縁ビーズを撹拌しながら金属を回収する装
置である。
この装置は、金属イオンをスラツジとして回収
する装置と比較して、はるかに小さい装置で効率
よく高純度の金属を安価に回収できる利点があつ
た。
上記装置により回収される金属は高純度ではあ
るが、回収される状態が、電極に密着したまま
で、しかも板状等の固体で回収されるため、再利
用の際、手間や費用がかかる欠点があつた。ま
た、前記の状態で回収されるため回収毎に新しい
電極を用意しなければならなかつた。さらに、金
属を回収する時、絶縁ビーズを撹拌しながら行な
うので、電極に絶縁ビーズが付着するおそれがあ
つた。
〔解決しようとする問題点〕
特願昭58―184864号に示した金属回収装置にお
いて高濃度液から電解により回収する金属を電極
上に付着することなく、しかも粉体の状態で回収
する金属回収装置を得ることである。
〔問題点を解決するための手段〕
廃液中の金属イオンをキレート剤によつて濃縮
し、この濃縮された金属イオンを脱離液で脱離さ
せて金属イオンの高濃度液を生成するキレート塔
を有する濃縮部から導いた高濃度液を電解する電
解槽からなり、該電解槽が下部から金属を回収す
る構造の槽内に陰極または陽極のいずれかで円筒
状の内電極と該内電極の周囲に逆の極からなる外
電極を設け、金属が析出する電解の表面に接触す
るか近接した状態に回収板を設け、かつ金属の析
出する電極表面に超音波を照射できる位置に超音
波発振器を配置し、前記金属が析出する電極と該
電極の金属析出面に接する回収板の少なくとも一
方が回転する金属回収装置である。
〔作 用〕
金属が析出する電極の析出面に超音波発振器か
ら発せられた超音波が照射されるので、金属は電
極は付着せず、粉体または粒体の状態で回収でき
る。
また、金属が析出する電極と該電極の金属析出
面に接するように設けた回収板の少なくとも一方
が回転可能に設けたので、電極付近に析出する金
属を電極に付着させることなく回収できる。
〔実施例〕
以下、本発明の一実施例を図面に基づいて説明
する。
第１図は、本発明の金属回収装置を利用して工
場廃水を処理する工程を示すフローチヤートであ
る。
図中１は廃水貯槽を示し、ここから金属イオン
を含有する廃水はPH調整槽２へ送られ、ここで金
属イオンへ後述するキレート剤に選択吸着させる
のに好ましいPH値に硫酸又は水酸化ナトリウム等
を用いて調整する。PH調整された廃水は濾過塔３
へ送られ、ここで浮遊物質が除去された後、キレ
ート塔４へ送られる。キレート塔４において、廃
水中の金属イオンは、キレートに吸着、濃縮され
る。
金属イオンを除去された廃水は、PH調整槽５へ
送られ、ここで排水基準のPH値（PH＝７前後）に
調整された後放流される。キレート塔４内のキレ
ート剤に吸着された金属イオンは、脱離液槽８か
ら供給された脱離液に接触して脱離し、金属液イ
オン含有液を生成する。例えば回収すべき金属が
Cu、Niの場合には、H2SO4等が脱離液として利
用され、したがつてCuSO4、NiSO4が生成する。
キレート塔４において、脱離開始時と終了時に
金属イオン濃度の薄い液が生成するが、この薄い
液は脱離廃液槽７へ送られて貯蔵され、さらにこ
こから再濃縮のために廃水貯槽１へ送られる。脱
離開始時と脱離終了時の間の一定時間内において
金属イオン濃度の濃い液が生成するが、この高濃
度液は回収液槽６へ送られて貯蔵される。なお、
キレート塔４は処理すべき廃水の量が多い場合や
安全性を考慮して、通常２塔設置され、一方のキ
レート塔で脱離が実施されている間に、他方のキ
レート塔で吸着が続行される。
キレート塔４に用いられるキレート樹脂は、所
望の金属を選択的に吸着するものを用いるのが、
本発明により回収される金属の純度が上昇するの
で都合が良い。例えば、下記の表は、選択的に吸
着した金属イオンに対応するキレート樹脂（商品
名）のほんの一例を示す。
[Industrial Application Field] The present invention relates to a metal recovery device that recovers metal ions contained in waste liquid as metal powder. [Prior art and its problems] Conventionally, waste fluids or wastewater discharged from factories, etc. neutralize metal ions contained therein, precipitate them, and form sludge after filtration, and this sludge containing metals is , they are simply landfilled or dumped into the ocean, and are not put to effective use such as reuse. Moreover, the treatment according to the above method requires a large installation space as a treatment plant, and has the drawback of requiring a large amount of chemical costs. The inventors of the present invention developed a recovery device that improved this drawback, as disclosed in Japanese Patent Application No. 184864-1983 (Japanese Patent Application No. 77937-1987).
This recovery device concentrates the metal ions in the waste liquid using a chelating agent, and desorbs the concentrated metal ions using a desorption liquid to produce a highly concentrated liquid of metal ions. and an electrolytic tank that houses electrodes and insulating beads and electrolyzes the highly concentrated liquid to deposit metal on the electrode surface,
This device collects metal while stirring the insulating beads. This device had the advantage of being able to efficiently recover high-purity metals at low cost with a much smaller device compared to devices that recover metal ions in the form of sludge. Although the metal recovered by the above device is of high purity, the recovered state remains in close contact with the electrode and is recovered in the form of a solid such as a plate, which is a disadvantage in that it requires time and money when reusing. It was hot. Furthermore, since the electrodes are collected in the above-mentioned state, new electrodes had to be prepared each time they are collected. Furthermore, since the metal is recovered while stirring the insulating beads, there is a risk that the insulating beads may adhere to the electrodes. [Problem to be solved] Metal recovery in which the metal recovered from a highly concentrated liquid by electrolysis in the metal recovery device shown in Japanese Patent Application No. 184864/1986 does not adhere to the electrode and is recovered in the form of powder. is to get the equipment. [Means for solving the problem] A chelating tower that concentrates the metal ions in the waste liquid using a chelating agent and removes the concentrated metal ions using a desorption liquid to produce a highly concentrated liquid of metal ions. It consists of an electrolytic cell that electrolyzes a highly concentrated liquid led from a concentrating section with An outer electrode with opposite polarity is provided around the periphery, a collection plate is provided in contact with or close to the electrolytic surface where metal is deposited, and an ultrasonic oscillator is placed at a position where ultrasonic waves can be irradiated to the electrode surface where metal is deposited. This is a metal recovery device in which at least one of an electrode on which the metal is deposited and a recovery plate in contact with the metal deposition surface of the electrode rotate. [Operation] Since the deposition surface of the electrode on which metal is deposited is irradiated with ultrasonic waves emitted from an ultrasonic oscillator, the metal does not adhere to the electrode and can be recovered in the form of powder or granules. Furthermore, since at least one of the electrode on which the metal is deposited and the collection plate provided in contact with the metal deposition surface of the electrode is rotatably provided, the metal deposited near the electrode can be collected without adhering to the electrode. [Example] Hereinafter, an example of the present invention will be described based on the drawings. FIG. 1 is a flowchart showing the process of treating factory wastewater using the metal recovery device of the present invention. 1 in the figure indicates a wastewater storage tank, from which wastewater containing metal ions is sent to PH adjustment tank 2, where it is adjusted to a pH value suitable for selectively adsorbing metal ions to a chelating agent (described later) using sulfuric acid or sodium hydroxide. etc. to adjust. PH-adjusted wastewater is sent to filtration tower 3
After the suspended solids are removed there, it is sent to the chelate tower 4. In the chelate tower 4, metal ions in the wastewater are adsorbed to the chelate and concentrated. The wastewater from which metal ions have been removed is sent to the PH adjustment tank 5, where it is adjusted to the PH value of wastewater standards (PH = around 7) and then discharged. The metal ions adsorbed by the chelating agent in the chelate tower 4 come into contact with the desorption liquid supplied from the desorption liquid tank 8 and are desorbed, thereby producing a metal liquid ion-containing liquid. For example, if the metal to be recovered is
In the case of Cu and Ni, H 2 SO 4 or the like is used as a desorption liquid, thus producing CuSO 4 and NiSO 4 . In the chelate tower 4, a liquid with a low concentration of metal ions is produced at the start and end of desorption. sent to. A liquid with a high metal ion concentration is generated within a certain period of time between the start of desorption and the end of desorption, and this high concentration liquid is sent to the recovery liquid tank 6 and stored. In addition,
When the amount of wastewater to be treated is large or for safety reasons, two chelate towers 4 are usually installed, and while desorption is carried out in one chelate tower, adsorption continues in the other chelate tower. be done. The chelate resin used in the chelate tower 4 is one that selectively adsorbs the desired metal.
Advantageously, the present invention increases the purity of the metal recovered. For example, the table below shows just a few examples of chelating resins (trade names) that support selective adsorption of metal ions.
本発明の装置は、以上の構成からなるので、従
来のスラツジとして回収処理装置に比べて、本発
明は、はるかに小さい装置で、かつ低電圧低電流
で効率よく高純度（99.5％以上）の金属粉を安価
に回収できる。
また、回収される金属が、粉体または粒体で回
収できるので、再利用のとき、そのまま使用でき
従来のように再使用における分離等の煩雑な作業
を必要としない。
さらに、超音波の周波数を変えることにより、
回収する金属粉の粒径を変えることができ、所望
の金属粉を廃液から容易に得ることができる。
Since the apparatus of the present invention has the above-mentioned configuration, compared to conventional sludge recovery processing apparatuses, the present invention is much smaller and can efficiently produce high purity (99.5% or more) with low voltage and low current. Metal powder can be recovered at low cost. Furthermore, since the recovered metal can be recovered in the form of powder or granules, it can be used as is when reusing it, and there is no need for complicated operations such as separation during reuse as in the past. Furthermore, by changing the ultrasonic frequency,
The particle size of the recovered metal powder can be changed, and desired metal powder can be easily obtained from waste liquid.
第１図は、本発明の金属回収装置の一実施例を
廃水処理工程の中で説明するフローチヤート、第
２図は、本発明の装置の電解槽を示す説明図、第
３図は第２図の電極の配置例を示す説明図、第４
図は、他の電解槽の配置例を示す説明図、第５図
は、本発明の装置による銅の回収状態を示すグラ
フである。
４……キレート塔、６……回収液槽、８……脱
離液槽、９……循環槽、１０……電解槽、１１…
…槽、１３……陰極、１４……回収板、１５……
陽極、１６……超音波発振器。
FIG. 1 is a flowchart explaining one embodiment of the metal recovery device of the present invention in a wastewater treatment process, FIG. 2 is an explanatory diagram showing an electrolytic cell of the device of the present invention, and FIG. Explanatory diagram showing an example of the arrangement of the electrodes in Figure 4.
The figure is an explanatory diagram showing another example of the arrangement of electrolytic cells, and FIG. 5 is a graph showing the state of copper recovery by the apparatus of the present invention. 4... Chelate tower, 6... Recovery liquid tank, 8... Desorption liquid tank, 9... Circulation tank, 10... Electrolytic tank, 11...
...tank, 13...cathode, 14...recovery plate, 15...
Anode, 16... Ultrasonic oscillator.
Claims (1)
縮し、この濃縮された金属イオンを脱離液で脱離
させて金属イオンの高濃度液を生成するキレート
塔を有する濃縮部と、高濃度液を電解する電解槽
からなり、該電解槽が槽内に陰極または陽極のい
ずれかで円筒状の内電極と該内電極の周囲に逆の
極からなる外電極を設け、金属が析出する電極の
表面に接触または近接した状態に回収板を設け、
かつ金属の析出する電極表面に超音波を照射でき
る位置に超音波発振器を配置し、前記金属が析出
する電極と該電極表面に接する回収板の少なくと
も一方が回転する金属回収装置。1. A concentration section having a chelating column that concentrates metal ions in the waste liquid using a chelating agent and desorbs the concentrated metal ions using a desorption liquid to generate a high concentration liquid of metal ions, and a high concentration liquid. The electrolytic cell is equipped with a cylindrical inner electrode as either a cathode or an anode, and an outer electrode with an opposite pole around the inner electrode, and the electrode on which the metal is deposited. A collection plate is provided in contact with or close to the surface,
and a metal recovery device in which an ultrasonic oscillator is arranged at a position where ultrasonic waves can be irradiated to the electrode surface on which metal is deposited, and at least one of the electrode on which the metal is deposited and a recovery plate in contact with the electrode surface rotates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59225477A JPS61104096A (en) | 1984-10-26 | 1984-10-26 | Apparatus for recovering metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59225477A JPS61104096A (en) | 1984-10-26 | 1984-10-26 | Apparatus for recovering metal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61104096A JPS61104096A (en) | 1986-05-22 |
| JPS6338434B2 true JPS6338434B2 (en) | 1988-07-29 |
Family
ID=16829928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59225477A Granted JPS61104096A (en) | 1984-10-26 | 1984-10-26 | Apparatus for recovering metal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61104096A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01195291A (en) * | 1988-01-29 | 1989-08-07 | Nec Corp | Recovering apparatus |
| JPH01234586A (en) * | 1988-03-14 | 1989-09-19 | Nittetsu Kakoki Kk | Separation of metal |
| WO2001051685A2 (en) * | 2000-01-10 | 2001-07-19 | Michael John Sole | Removal of metals from solution |
| JP4699105B2 (en) | 2005-06-24 | 2011-06-08 | アサヒプリテック株式会社 | Gold recovery method and apparatus |
| JP5485239B2 (en) * | 2010-09-17 | 2014-05-07 | 古河電気工業株式会社 | Method for producing copper fine particles |
| CN105329990B (en) * | 2015-10-28 | 2017-06-23 | 中海油天津化工研究设计院有限公司 | A kind of intensified by ultrasonic wave electrocatalytic oxidation processes the device and method of reverse osmosis concentrated water |
| JP7007620B1 (en) * | 2020-08-25 | 2022-01-24 | 株式会社ジージェーブイ | Metal ionized water production equipment and metal ionized water production method |
| WO2022085610A1 (en) | 2020-10-21 | 2022-04-28 | アサヒプリテック株式会社 | Condition monitoring system for metal recovery device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4925094A (en) * | 1972-05-26 | 1974-03-06 | ||
| JPS4941241A (en) * | 1972-08-28 | 1974-04-18 | ||
| JPS57152482A (en) * | 1981-02-13 | 1982-09-20 | Nat Res Dev | Electrodeposition cell |
-
1984
- 1984-10-26 JP JP59225477A patent/JPS61104096A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4925094A (en) * | 1972-05-26 | 1974-03-06 | ||
| JPS4941241A (en) * | 1972-08-28 | 1974-04-18 | ||
| JPS57152482A (en) * | 1981-02-13 | 1982-09-20 | Nat Res Dev | Electrodeposition cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61104096A (en) | 1986-05-22 |
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