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EP0058537B1 - Cellule d'électrodéposition - Google Patents

Cellule d'électrodéposition Download PDF

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Publication number
EP0058537B1
EP0058537B1 EP82300710A EP82300710A EP0058537B1 EP 0058537 B1 EP0058537 B1 EP 0058537B1 EP 82300710 A EP82300710 A EP 82300710A EP 82300710 A EP82300710 A EP 82300710A EP 0058537 B1 EP0058537 B1 EP 0058537B1
Authority
EP
European Patent Office
Prior art keywords
electrode
scraper
electrodeposit
axial extent
cathode
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
Application number
EP82300710A
Other languages
German (de)
English (en)
Other versions
EP0058537A1 (fr
Inventor
Frank Stanley Holland
Francis Charles Walsh
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
National Research Development Corp UK
Original Assignee
National Research Development Corp UK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by National Research Development Corp UK filed Critical National Research Development Corp UK
Publication of EP0058537A1 publication Critical patent/EP0058537A1/fr
Application granted granted Critical
Publication of EP0058537B1 publication Critical patent/EP0058537B1/fr
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/007—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells comprising at least a movable electrode

Definitions

  • This invention relates to an electrodeposition cell having a rotating cylindrical deposition electrode and to a method of removing deposit from such an electrode.
  • Rotating cylindrical cathodes for recovering metals from dilute salt solutions in electrodeposition cells are known, for example from GB Patent Specification No. 1505736.
  • the metal may deposit as a loosely adherent deposit which is washed off the cathode.
  • the current that can be passed through a freshly washed cathode is much less (e.g. six to sixty times less) than can be passed through a cathode bearing a rough deposit, at comparable current efficiencies.
  • GB-A-1505736 advocates pre-roughening the cathode.
  • GB-A-1505736 also suggests that a reciprocating scraper extending over part only of the length of the cathode may be provided, but states no special technical advantage.
  • US-A-3619389 discloses a static cathode which however is continuously roughened by an abrasive continuous activating belt, which also maintains, by entrainment, a high rate of supply of electrolyte to the cathode and removes the electrodeposit. This arrangement is cumbersome and complicated, and would require very careful control of the exact positions of the anode and cathode on opposite sides of the belt.
  • US-A-1535577 discloses apparatus for the electrolytic deposition of metals, comprising a rotating cathode and a scraper operating on the cathode to remove metal which has been electrodeposited on it.
  • the scraper is fixed in operation but is ajustable radially of the cathode to regulate the thickness of the metal allowed to grow on the cathode.
  • the scraper is the same height as the cylindrical cathode and therefore operates on the whole cylindrical area every revolution.
  • the invention is an electrodeposition cell. having a rotating cylindrical deposition electrode and a scraper engaging the electrodeposit and breaking away its outer portion for removing deposit from that electrode, such that, in operation, the electrode retains a substantially rough electrodeposit, characterised in that the axial extent of the engaging part of the scraper does not exceed half the axial extent of the electrode, the engaging part being axially movable so that, with the electrode rotating, the scraper can engage any point on the electrodeposit.
  • the engaging part may be arranged to be axially movable by making the scraper axially movable, or the scraper may comprise a rotatable helical blade whose axis is parallel to the cylinder axis; rotation of the scraper about its own axis will thus cause the contact area to traverse the electrode axially.
  • the axial extent of the part of the scraper at any instant engaging the electrode preferably does not exceed 0.1 of the axial extent of the electrode, more preferably does not exceed 0.01 thereof, most preferably does not exceed 0.002.
  • the invention is also a method of removing deposit from a rotating cylindrical deposition electrode in an electrodeposition cell during electrodeposition, such that the electrode retains a substantially rough electrodeposit, comprising applying to the electrodeposit, such that it will not bare the electrode, a scraper breaking away the outer portion of the electrodeposit, characterised in that the scraper scrapes not more than 0.1 of the cylindrical area of the electrode in one revolution thereof.
  • the electrodeposit stays at least microscopically rough even the instant after some has been removed.
  • the scraper scrapes not more than 0.01, most preferably not more than 0.002 of the cylindrical area of the electrode in one revolution thereof.
  • the scraper may comprise a helical blade (as described above) or may comprise a full-axial-extent blade brought into contact with the electrode for only a fraction of a revolution or may comprise a part-axial-extent blade mounted on an axially-moving carrier so that, as the electrode rotates, the scraping follows a helical path (like a screw thread) over the area of the electrode.
  • the carrier may spring back to its starting point after the whole electrode is scraped or may move backwards at the same rate as forwards.
  • the scraper may contact the electrodeposit continuously, or may contact it intermittently. The degree of contact is such as to scrape off the outer portion only of the deposit.
  • a cathode 1 of an electrodeposition cell (which, being otherwise standard, is not further shown or described) is of cylindrical form, diameter 60 mm and height 63 mm, and is driven at 360 revolutions per minute (peripheral velocity: 1.13 m/s) by a motor 2.
  • An upright carrier 4, reciprocated by a pneumatic actuator 5, carries a scraper point 4a contacting the cathode 1 at an area whose height (parallel to the cylinder axis) is 1 mm. It is enlarged on the drawing for clarity.
  • the cathode 1 is in an aqueous electrolyte of 1.5 M sulphuric acid H 2 S0 4 plus 0.014 M copper sulphate CuS0 4 at 22°C.
  • the Reynolds number at its surface is about 59000.
  • a stop (not shown) holds the scraper point 4a clear of the cathode 1 and a voltage of approximately 2.5 V is applied.
  • Current starts to flow at 0.8 A, in good accordance with theory, and after about 20 minutes the copper depositing on the cathode begins perceptibly to roughen it.
  • the current starts to rise, after 1 hour reaching 3 A (the maximum possible at that current efficiency with a knurled cylinder having a peak-to-valley roughness of 1 mm, according to Kappesser et al, J. Electrochem Soc 118 (1971) p. 1957). Contrary to the Kappesser teaching, however, the current continues to rise, tending to level off at about 6A after 21--3 hours.
  • the stop is withdrawn, and the scraper point 4a contacts the electrodeposit on the cathode 1.
  • This electrodeposit is rough. Copper powder is scraped off by a dendrite-fracturing action and is collected, as schematically indicated at 6.
  • the actuator 5 pulls the carrier 4 downwards slowly at such a rate (3 mm/minute) that the point 4a leaves a helical trail on the cathode 1, the trail taking about 20 minutes to cover every part of the cylindrical area of the cathode 1.
  • the trail having been formed by a fracturing action, it is rough even when newly formed, and can maintain a current density substantially higher than that predicted by Kappesser, recovering to its maximum after about 1 minute.
  • the point 4a Immediately the point 4a has scraped an element of the cathode 1, electrodeposition resumes and the trail eventually disappears (as shown oversimplified in Figure 1), and there are 20 minutes' worth of electrodeposition to be scraped off when the point (or rather the leading edge of the point) 4a returns to that element.
  • the carrier 4 preferably flies back to its starting point or may move upwards and downwards (20 minutes each) at the same speed. Even while scraping is proceeding, the current is maintained at substantially 5.7 A; a smooth cathode could pass only 0.8 A at that voltage.
  • a cathode is shown identical to that in Figure 1, but the scraper differs.
  • the scraper 14 is in the form of a helical blade making just one rotation in the height of the cathode and driven by a slow-speed motor 15 at one revolution per 20 minutes.
  • a part-height or helical scraper fractures off the dendritic electrolytic deposits, leaving a beneficial underlying microroughness; a full-length scraper might bare the cathode and even burnish it, whereby the current density would regress to that described in relation to a brand new cathode.
  • This fracturing action also has the advantage of yielding a powder product reasonably consistent in size and type.
  • the electrodeposit becomes excessively rough and the energy required to rotate the rough cathode becomes correspondingly excessive.
  • this excessive roughness takes the form of spindly dendrites which can drop off randomly and which are of inconsistent quality. they can drop off in such a way as to lead to a 'peeling'of the electrodeposit; in catastrophic cases, up to 10% of the burden can be shed in this way, unbalancing the cathode to the detriment of its driving mechanism.
  • the spindly dendrites may also damage any nearby diaphragm or membrane.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electroplating Methods And Accessories (AREA)

Claims (7)

1. Cellule d'électrodéposition, comportant une électrode rotative cylindrique de déposition et un racleur venant au contact du dépôt électrolytique et en enlevant par rupture la partie externe pour enlever le dépôt de cette électrode de façon que, en service, l'électrode conserve un dépôt électrolytique essentiellement rugueux, cellule caractérisée en ce que l'étendue axiale de la patie en contact (4a, 14) du racleur n'excède pas la moitié de l'étendue axiale de l'électrode (1), la partie venant en contact étant axialement mobile de sorte que, avec l'électrode en rotation, le racleur peut venir au contact de n'importe quel point du dépôt électrolytique.
2. Cellule selon la revendication 1, caractérisée en ce que l'étendue axiale de la partie (4a, 14) du racleur venant en contact avec le dépôt n'excède pas 0,1 fois l'étendue axiale de l'électrode (1).
3. Cellule selon la revendication 1, caractérisée en ce que l'étendue axiale de la partie (4a, 14) du racleur venant au contact du dépôt n'excède pas 0,01 fois l'étendue axiale de l'électrode (1).
4. Cellule selon la revendication 1, caractérisée en ce que l'étendue axiale de la partie (4a, 14) du racleur venant au contact du dépôt n'excède pas 0,002 fois l'étendue axiale de l'électrode (1).
5. Cellule selon n'importe quelle revendication précédente, caractérisée en ce que le racleur (4) est mobile axialement.
6. Cellule selon l'une quelconque des revendications précédentes, caractérisée en ce que le racleur comprend une lame (14) hélicoïdale rotative dont l'axe est parallèle à l'axe du cylindre.
7. Procédé pour enlever un dépôt d'une électrode cylindrique rotative de dépôt dans une cellule d'électrodéposition pendant l'électrodéposition, de sorte que l'électrode conserve un dépôt électrolytique essentiellement rugueux, comprenant l'application, au dépôt électrolytique, de façon à ne pas dénuder l'électrode, d'un racleur qui enlève par rupture la partie externe du dépôt électrolytique, procédé caractérisé en ce que le racleur ne racle pas plus de 0,1 fois la surface cylindrique de l'électrode en un tour de celle-ci.
EP82300710A 1981-02-13 1982-02-12 Cellule d'électrodéposition Expired EP0058537B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8104624 1981-02-13
GB8104624 1981-02-13

Publications (2)

Publication Number Publication Date
EP0058537A1 EP0058537A1 (fr) 1982-08-25
EP0058537B1 true EP0058537B1 (fr) 1986-04-30

Family

ID=10519703

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82300710A Expired EP0058537B1 (fr) 1981-02-13 1982-02-12 Cellule d'électrodéposition

Country Status (4)

Country Link
EP (1) EP0058537B1 (fr)
JP (1) JPS57152482A (fr)
DE (1) DE3270833D1 (fr)
ES (1) ES8608060A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1188058A (fr) * 1981-06-30 1985-06-04 Robert D.H. Willians Methode et dispositif de decrassage d'electrodes
US4406753A (en) * 1982-01-19 1983-09-27 Ciba-Geigy Ag Electrolytic metal recovery cell and operation thereof
JPS61104096A (ja) * 1984-10-26 1986-05-22 Toppan Printing Co Ltd 金属回収装置
JPS61106788A (ja) * 1984-10-29 1986-05-24 Toppan Printing Co Ltd 金属回収方法およびその装置
EP0227689A1 (fr) * 1985-06-27 1987-07-08 Cheminor A/S Procede de production de metaux par electrolyse
DE3832674A1 (de) * 1988-09-27 1990-03-29 Kodak Ag Metallrueckgewinnungs-vorrichtung
NL1006340C2 (nl) * 1997-06-17 1998-12-21 Rafael Technologie En Manageme Werkwijze en inrichting voor het winnen van metalen.
CN105483759B (zh) * 2014-09-18 2018-01-12 有研亿金新材料有限公司 高温金属产品的刮除及收集装置
CN107130268A (zh) * 2017-06-08 2017-09-05 无锡中天固废处置有限公司 自动化剥桶装置
CN110306209A (zh) * 2019-08-09 2019-10-08 郑州金泉矿冶设备有限公司 电解法生产超细银粉的设备

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1505736A (en) * 1975-02-25 1978-03-30 Nat Res Dev Electrolytic production of metals

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1535577A (en) * 1923-01-04 1925-04-28 Cleave Arthur Harold Wyld Apparatus for the electrolytic deposition of metals
FR1264597A (fr) * 1960-05-12 1961-06-23 Procédé et dispositif pour la régénération par électrolyse de métaux sous forme divisée
US3619389A (en) * 1969-10-03 1971-11-09 Norton Co Electrodeposition system
JPS4941241A (fr) * 1972-08-28 1974-04-18
JPS51104592A (en) * 1975-03-13 1976-09-16 Inoue Japax Res Dodenzai mataha teikozairyoyokinzokuryushino seisakuhoho
DE7905205U1 (de) * 1979-02-24 1979-05-31 Dr. Eugen Duerrwaechter Doduco, 7530 Pforzheim Vorrichtung zum elektrolytischen rueckgewinnen von edelmetallen

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1505736A (en) * 1975-02-25 1978-03-30 Nat Res Dev Electrolytic production of metals

Also Published As

Publication number Publication date
ES509578A0 (es) 1986-06-01
EP0058537A1 (fr) 1982-08-25
JPS57152482A (en) 1982-09-20
ES8608060A1 (es) 1986-06-01
DE3270833D1 (en) 1986-06-05

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