JPH0313313B2 - - Google Patents
Info
- Publication number
- JPH0313313B2 JPH0313313B2 JP63053565A JP5356588A JPH0313313B2 JP H0313313 B2 JPH0313313 B2 JP H0313313B2 JP 63053565 A JP63053565 A JP 63053565A JP 5356588 A JP5356588 A JP 5356588A JP H0313313 B2 JPH0313313 B2 JP H0313313B2
- Authority
- JP
- Japan
- Prior art keywords
- anode
- conductive medium
- medium particles
- plate
- packed bed
- 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 - Lifetime
Links
- 239000002245 particle Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 10
- 239000004917 carbon fiber Substances 0.000 claims description 10
- 238000005363 electrowinning Methods 0.000 claims description 8
- 238000012856 packing Methods 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
- 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)
Description
〔産業上の利用分野〕
本発明は有価金属又は有害金属を含有する溶液
から、これら金属を採取する電解採取装置に関す
る。
〔従来の技術〕
メツキ廃水等に含まれる有価金属の回収や有害
金属の除去に用いられる装置として、第１図に示
すような充填床式の電解採取装置が知られてい
る。この装置は垂直に設けられた板状アノード２
と、該アノードに対置された板状カソード３を備
え、アノードとカソードとの間に導電性媒体粒子
５として、例えばグラフアイト粒子等を充填した
もので、処理すべき溶液を両電極間を流すことに
より含まれている金属を電解により前記グラフア
イト粒子等の表面に析出させ、回収するものであ
る。該装置においては、導電性媒体粒子はカソー
ドと接触して稼動時にはカソードの一部として機
能するものであるため、アノードとは接触により
短絡が起きないように間隙を保つておく必要があ
る。そのため、アノードの近傍に、通常、格子
状、スパイラル状等のスペーサ６を介してアノー
ド表面から離隔して隔膜４が設けられ、該隔膜に
よつて導電性媒体粒子がアノードと接触すること
を防止している。しかしながら上記装置では、導
電性媒体粒子のアノードに近い側ほど金属の析出
が著しく、該導電性媒体粒子の内部層や板状カソ
ードに近い部分では、まだ金属析出能力が十分に
残つているにもかかわらず、有効な電解析出状態
を維持できず、充填されている導電性媒体粒子を
早いサイクルで新品と交換したり、再生に行う必
要があるなどの不都合があつた。特に処理すべき
溶液の電気伝導度が低い場合に一層、上記不都合
が顕著であつた。
〔発明が解決しようとする課題〕
そこで、本発明の目的は、上記問題点を解消
し、処理すべき溶液の電気伝導度が低い場合にお
いても初期の電解採取効率を長期間維持させるこ
とができる金属電解採取装置を提供することにあ
る。
〔課題を解決するための手段〕
上記問題点を解消するために板状アノードと該
アノードに対向して設置された板状アノードと、
前記アノードの表面近傍にかつ該表面から離隔し
て設けられた透液性隔膜と、前記カソードと前記
透液性隔膜との間に設けられた導電性媒体粒子充
填床とを備えた充填床式電解採取装置において、
前記導電性媒体粒子として嵩密度0.01〜0.035
ｇ／cm3の炭素繊維を用い、前記充填床へ充填密度
0.02〜0.05ｇ／cm3で充填した点に特徴がある。
〔作用〕
該炭素繊維の形態はフエルト、マツト、チヨ
プ、ミルド、ヤーン等が挙げられ、フエルト、マ
ツトが好適である。このような繊維を一種類又は
二種類以上を混合して使用することができる。該
炭素繊維の嵩密度は0.01〜0.035ｇ／cm3が良く、
更に望ましくは0.020〜0.031ｇ／cm3である。もし
も0.01ｇ／cm3未満であると、該炭素繊維の電極と
しての有効面積が少くなり、逆に0.035ｇ／cm3を
越えると、電解時に発生する水素ガスのガス抜け
が不良となりそのため有効な電解が進行しなくな
り不都合である。該炭素繊維を該充填床へ充填す
るに当り、充填密度が0.02〜0.05ｇ／cm3、更に望
ましくは0.026〜0.047ｇ／cm3とすることが重要で
ある。もしも、0.02ｇ／cm3未満であると有効な電
解面積が小さくなり、逆に0.05ｇ／cm3を越えると
該ガス抜けが不良となり良くない。
〔実施例〕
横幅６cm、奥行４cm、高さ10cm（内寸）の塩化
ビニール製の電解槽で、板状アノードと隔膜との
面間距離を0.3cmとし、板状カソードと隔膜との
面間距離を３cmとなるようにし、板状アノードと
しては5.5×12.0×0.2cmの酸化ルテニウム（TDK
製）を用い、板状カソードとしては６×12.0×５
cmのグラフアイト板（東洋カーボン製）を使用し
た。充填床に直径12〜13μｍ体積固有抵抗率1.5〜
1.6×10-2Ω・cm、嵩密度0.020、0.026、0.031ｇ／
cm3のフエルト状炭素繊維（大阪ガス製）を高さ８
cmのところまで、充填密度0.042ｇ／cm3で順番に
充填し、試験に用いた。処理水溶液としてはCu、
500ｇ／のピロリン酸銅溶液を電気伝導度が
7.8mS／cmとなるように調整し、上記電解装置に
0.29／Ｈで供給し、陰極板に対する電流密度
2.0A／ｄm2、室温20℃で電解を行つた。金属の
回収率目標を95％として、処理時間を求めた。こ
の結果を第１表に示す。
実施例 ２
嵩密度0.020ｇ／cm3のフエルト状炭素繊維を充
填密度0.026、0.039、0.047ｇ／cm3とした以外は実
施例１と同じ処理水溶液および電解条件で実験を
した。この結果を第１表に示す。
〔比較例〕
フエルト状炭素繊維を嵩密度0.015および、
0.047ｇ／cm3、充填密度0.042ｇ／cm3とした場合、
フエルト状炭素繊維を嵩密度0.020ｇ／cm3、充填
密度0.020および0.057ｇ／cm3とした場合、更に−
７〜＋９メツシユ（JIS規格）のグラフアイト粒
子を、それぞれ導電性媒体粒子として用いた以外
は実施例１と同じ処理水溶液および電解条件で実
験した。これらの結果を第１表に示す。
第１表から明らかなように、本発明による実施
例では、処理時間が約33時間となり、充填床の寿
命が延びていることがわかる。
[Industrial Application Field] The present invention relates to an electrowinning apparatus for extracting valuable metals or toxic metals from a solution containing these metals. [Prior Art] A packed bed type electrowinning apparatus as shown in FIG. 1 is known as an apparatus used for recovering valuable metals and removing harmful metals contained in waste water and the like. This device consists of a plate-shaped anode 2 installed vertically.
and a plate-shaped cathode 3 placed opposite to the anode, and conductive medium particles 5 such as graphite particles are filled between the anode and the cathode, and the solution to be treated is caused to flow between the two electrodes. The metal contained therein is deposited on the surface of the graphite particles etc. by electrolysis and recovered. In this device, since the conductive medium particles come into contact with the cathode and function as part of the cathode during operation, it is necessary to maintain a gap from the anode to prevent a short circuit from occurring due to contact. Therefore, a diaphragm 4 is provided near the anode and separated from the anode surface via a spacer 6 in the form of a grid, spiral, etc., and the diaphragm prevents conductive medium particles from coming into contact with the anode. are doing. However, in the above-mentioned apparatus, metal precipitation is more pronounced on the side of the conductive medium particles closer to the anode, and even though the inner layer of the conductive medium particles and the portion closer to the plate-like cathode still have sufficient metal deposition ability. However, there are disadvantages in that an effective electrolytic deposition state cannot be maintained and the filled conductive medium particles must be replaced with new ones or regenerated at an early cycle. The above-mentioned disadvantages were particularly noticeable when the electrical conductivity of the solution to be treated was low. [Problems to be Solved by the Invention] Therefore, an object of the present invention is to solve the above problems and to maintain the initial electrowinning efficiency for a long period of time even when the electrical conductivity of the solution to be treated is low. An object of the present invention is to provide a metal electrowinning device. [Means for solving the problem] In order to solve the above problems, a plate-shaped anode and a plate-shaped anode installed opposite to the anode,
A packed bed type comprising a liquid permeable diaphragm provided near the surface of the anode and spaced apart from the surface, and a bed packed with conductive medium particles provided between the cathode and the liquid permeable diaphragm. In electrowinning equipment,
The bulk density of the conductive medium particles is 0.01~0.035
g/cm 3 of carbon fiber, and the packing density was increased to the packed bed.
It is characterized by being filled with 0.02 to 0.05 g/cm 3 . [Function] Examples of the form of the carbon fibers include felt, mat, yarn, milled, yarn, etc., with felt and mat being preferred. One type of such fibers or a mixture of two or more types can be used. The bulk density of the carbon fiber is preferably 0.01 to 0.035 g/ cm3 ,
More preferably, it is 0.020 to 0.031 g/cm 3 . If it is less than 0.01 g/cm 3 , the effective area of the carbon fiber as an electrode will be reduced, and if it exceeds 0.035 g/cm 3 , hydrogen gas generated during electrolysis will not be able to escape properly, so it will not be effective. This is inconvenient because electrolysis does not proceed. When filling the packed bed with the carbon fibers, it is important that the packing density is 0.02 to 0.05 g/cm 3 , more preferably 0.026 to 0.047 g/cm 3 . If it is less than 0.02 g/cm 3 , the effective electrolyzing area will be small, and if it exceeds 0.05 g/cm 3 , the gas release will be poor, which is not good. [Example] In a vinyl chloride electrolytic cell with a width of 6 cm, a depth of 4 cm, and a height of 10 cm (inner dimensions), the distance between the plate anode and the diaphragm was 0.3 cm, and the distance between the plate cathode and the diaphragm was 0.3 cm. The distance was set to 3 cm, and the plate anode was made of 5.5 x 12.0 x 0.2 cm of ruthenium oxide (TDK
6 x 12.0 x 5 as a plate cathode.
cm graphite plate (manufactured by Toyo Carbon) was used. Filled bed with a diameter of 12~13μm and a volume resistivity of 1.5~
1.6×10 -2 Ω・cm, bulk density 0.020, 0.026, 0.031g/
cm 3 felt-like carbon fiber (manufactured by Osaka Gas) with a height of 8
It was filled in order at a filling density of 0.042 g/cm 3 up to a point of 0.3 cm, and used for the test. Cu as a treatment aqueous solution,
Electric conductivity of 500g/copper pyrophosphate solution
Adjust it to 7.8mS/cm and apply it to the above electrolyzer.
Current density to the cathode plate is supplied at 0.29/H.
Electrolysis was carried out at 2.0 A/dm 2 and a room temperature of 20°C. The processing time was determined with a metal recovery target of 95%. The results are shown in Table 1. Example 2 An experiment was conducted using the same treated aqueous solution and electrolytic conditions as in Example 1 , except that felt carbon fibers with a bulk density of 0.020 g/cm 3 were used at packing densities of 0.026, 0.039, and 0.047 g/cm 3 . The results are shown in Table 1. [Comparative example] Felt-like carbon fibers with a bulk density of 0.015 and
When the filling density is 0.047g/cm 3 and 0.042g/cm 3 ,
When the felt carbon fiber has a bulk density of 0.020 g/cm 3 and a packing density of 0.020 and 0.057 g/cm 3 , -
Experiments were conducted using the same treated aqueous solution and electrolytic conditions as in Example 1, except that graphite particles of 7 to +9 mesh (JIS standard) were used as conductive medium particles. These results are shown in Table 1. As is clear from Table 1, in the example according to the present invention, the processing time was approximately 33 hours, indicating that the life of the packed bed was extended.
本発明によれば、低電気伝導度、希薄濃度の処
理液から金属を高回収率で回収し、充填床の寿命
を延ばすことができ、工業排水の処理に貢献する
ところ極めて大である。
According to the present invention, it is possible to recover metals at a high recovery rate from a treatment liquid with low electrical conductivity and dilute concentration, and the life of the packed bed can be extended, which greatly contributes to the treatment of industrial wastewater.
第１図は充填床式電解採取装置の縦断面を示
す。
１……電解槽、４……隔膜、５……導電性媒体
粒子、７……処理水入口、８……処理水出口。
FIG. 1 shows a longitudinal section of a packed bed type electrowinning device. 1... Electrolytic cell, 4... Diaphragm, 5... Conductive medium particles, 7... Treated water inlet, 8... Treated water outlet.
Claims (1)
れた板状カソードと、前記アノードの表面近傍に
かつ該表面から離隔して設けられた透液性隔膜
と、前記カソードと前記透液性隔膜との間に設け
られた導電性媒体粒子充填床とを備えた充填床式
電解採取装置において、前記導電性媒体粒子とし
て嵩密度0.01〜0.035ｇ／cm3の炭素繊維を用い、
前記充填床へ充填密度0.02〜0.05ｇ／cm3で充填し
た金属電解採取装置。1. A plate-shaped anode, a plate-shaped cathode installed opposite to the anode, a liquid-permeable diaphragm provided near the surface of the anode and spaced apart from the surface, and the cathode and the liquid-permeable diaphragm. In a packed bed type electrowinning apparatus equipped with a packed bed of conductive medium particles provided between the conductive medium particles, carbon fibers having a bulk density of 0.01 to 0.035 g/cm 3 are used as the conductive medium particles,
A metal electrowinning device in which the packed bed is filled with a packing density of 0.02 to 0.05 g/cm 3 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63053565A JPH01230791A (en) | 1988-03-09 | 1988-03-09 | Apparatus for electrowinning metal and electrowinning method using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63053565A JPH01230791A (en) | 1988-03-09 | 1988-03-09 | Apparatus for electrowinning metal and electrowinning method using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01230791A JPH01230791A (en) | 1989-09-14 |
| JPH0313313B2 true JPH0313313B2 (en) | 1991-02-22 |
Family
ID=12946345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63053565A Granted JPH01230791A (en) | 1988-03-09 | 1988-03-09 | Apparatus for electrowinning metal and electrowinning method using same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01230791A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02305987A (en) * | 1989-05-22 | 1990-12-19 | Kamioka Kogyo Kk | Single-electrode electrolytic cell and electrolytic method using the cell |
| JPH0387400A (en) * | 1989-08-30 | 1991-04-12 | Kamioka Kogyo Kk | Single-electrode electrolytic cell and electrolyzing method |
| CN111675284A (en) * | 2020-04-17 | 2020-09-18 | 生态环境部华南环境科学研究所 | Three-dimensional electrolysis device for treating waste copper waste liquid |
-
1988
- 1988-03-09 JP JP63053565A patent/JPH01230791A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01230791A (en) | 1989-09-14 |
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