EP0156721B1 - Verfahren zur Herstellung von feinen und ultrafeinen Zinkpulvern durch Elektrolyse in basischem Medium - Google Patents

Verfahren zur Herstellung von feinen und ultrafeinen Zinkpulvern durch Elektrolyse in basischem Medium Download PDF

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Publication number
EP0156721B1
EP0156721B1 EP85400470A EP85400470A EP0156721B1 EP 0156721 B1 EP0156721 B1 EP 0156721B1 EP 85400470 A EP85400470 A EP 85400470A EP 85400470 A EP85400470 A EP 85400470A EP 0156721 B1 EP0156721 B1 EP 0156721B1
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EP
European Patent Office
Prior art keywords
zinc
electrolysis
concentration
fine
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
EP85400470A
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English (en)
French (fr)
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EP0156721A1 (de
Inventor
Jean-Michel Castillo
Christian Jankowski
Serge Ferlay
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.)
Promotion Des Procedes Hydro-Metallurgiques SA Ste
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Promotion Des Procedes Hydro-Metallurgiques SA Ste
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Publication of EP0156721A1 publication Critical patent/EP0156721A1/de
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions

Definitions

  • the present invention relates to a process for the production of fine and ultrafine zinc powders by electrolysis in basic medium.
  • the zinc powders currently sold are obtained thermally, by melting and vaporization under vacuum of zinc ingots. They provide a fairly wide range of production, from coarse zinc powder to fine and ultra-fine zinc dust.
  • the powders obtained by alkaline electrolysis must be ground to approach the particle size standards of the powders obtained by thermal process.
  • the size of the grains obtained essentially depends on the speed ratio of these two processes. If the nucleation rate is higher than the growth rate of the crystal, the deposit will be fine and vice versa. The crystals will grow quickly and will therefore be coarse, if the metal-ions arriving at the solid-liquid interface are numerous. On the other hand, the nucleation centers will be abundant and the crystals will grow slowly and will therefore be fine, if the metal ions arriving at the solid-liquid interface are rare.
  • electrolysis involves relationships between the current, the electrolyte and the electrodes.
  • the study of the cathode has always been seen from the angle of corrosion and it focused on the search for a material resistant to corrosion.
  • the mechanical resistance and the appearance of this film is variable according to the metal constituting the cathode and according to the appearance of the surface of this cathode.
  • this process for the production of fine and ultrafine zinc powders by electrolysis in basic medium is characterized in that a cathode coated with a film of varnish or silicone obtained from an aerosol.
  • the bath can be agitated, during electrolysis, by irradiating it by means of ultrasound preferably having an emission frequency of 40 kHz.
  • the initial concentration of zinc in the bath is preferably limited to around 30 g / l.
  • the process according to the invention makes it possible to obtain, by alkaline electrolysis, fine and ultra fine powders and this directly, without requiring additional grinding.
  • the varnish or silicon used must have chemical resistance to attack by caustic solutions.
  • varnish or silicone must be as regular as possible, which supposes an appropriate solvent dosage. Indeed, a too viscous varnish, during its projection, forms granules which solidify without spreading and recreate by the same, by attenuating, a heterogeneity of surface. Likewise, a varnishing with a brush leads to poor results. It therefore appears essential that the solvent is sufficiently dosed to allow spreading by gravity flow of the varnish or of silicone. This condition being fulfilled, the surface can be considered very regular.
  • cathodes thus treated must be free of dust and traces of fatty substance, or of any other element, preventing a close link between metal and varnish.
  • the process according to the invention can possibly be improved by playing on the control of other parameters, namely the zinc electrolysis concentration and the agitation of the bath.
  • the solid lines of FIG. 2 show the influence of the initial zinc concentration Ci (between 10 and 45 g / 1), indicated on the ordinate, on the d 50 and the d 90 of the powder obtained, in the absence of any agitation of the bath, the particle size D in microns of the powder being plotted on the ordinate.
  • the electrolysis is controlled by the diffusion of the metal ions in the NERNST layer and the nucleation rate is higher than the growth rate of the crystals, and conversely in the strongly decreasing part.
  • the methods usually used reside in the pressure injection of the electrolyte in well chosen places or in a mechanical agitation.
  • the varnishing of the electrode according to the invention obviously introduces a faradyc loss of efficiency by adding an additional ohmic resistance to the cell. This loss is in fact very low (1 to 2%) of the order of the total uncertainty on the measurements, and it is obvious that the efficiency brought to the particle size control is without common measure with this reduction in yield.
  • the very regular character of deposit no warts or buttons creating short circuits that the varnishing induced, makes it possible to reduce the anode-cathode distance and to largely compensate for this resistance resistance.
  • the faradyque yield decreases to reach 30% at 0.5 g / 1 as indicated by the curve in Figure 3.

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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)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Claims (4)

1. Verfahren zur Herstellung von feinen und ultrafeinen Zinkpulvern durch Elektrolyse in basischem Medium, dadurch gekennzeichnet, dass man eine Kathode benutzt, welche von einem Film aus Firnis oder Silikon überzogen ist, der aus einem Aerosol erhalten wird.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass man das Bad während der Elektrolyse durch Einwirkung von Ultraschall aufrührt.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass man das Elektrolysebad der Einwirkung von Ultraschall mit einer Emissionsfrequenz der Grössenordnung von 40 kHz aussetzt.
4. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass man die anfängliche Zinkkonzentration im Bad auf die Grössenordnung von 30 g/I beschränkt.
EP85400470A 1984-03-16 1985-03-12 Verfahren zur Herstellung von feinen und ultrafeinen Zinkpulvern durch Elektrolyse in basischem Medium Expired EP0156721B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8404091 1984-03-16
FR8404091A FR2561265B1 (fr) 1984-03-16 1984-03-16 Procede de production de poudres fines et ultrafines de zinc par electrolyse en milieu basique

Publications (2)

Publication Number Publication Date
EP0156721A1 EP0156721A1 (de) 1985-10-02
EP0156721B1 true EP0156721B1 (de) 1987-09-16

Family

ID=9302114

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85400470A Expired EP0156721B1 (de) 1984-03-16 1985-03-12 Verfahren zur Herstellung von feinen und ultrafeinen Zinkpulvern durch Elektrolyse in basischem Medium

Country Status (8)

Country Link
US (1) US4676877A (de)
EP (1) EP0156721B1 (de)
JP (1) JPS61501998A (de)
AU (1) AU572638B2 (de)
BR (1) BR8506051A (de)
DE (1) DE3560640D1 (de)
FR (1) FR2561265B1 (de)
WO (1) WO1985004195A1 (de)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1041757C (zh) * 1991-08-02 1999-01-20 北京矿冶研究总院 一种浸出电解法从含锌物料中生产锌粉的方法
DE4220849C1 (de) * 1992-06-25 1993-03-18 Schott Glaswerke, 6500 Mainz, De
BE1008304A6 (fr) * 1994-06-03 1996-04-02 Univ Bruxelles Dispositif pour la production de poudres ultrafines.
DE19840842A1 (de) * 1998-09-07 2000-03-09 Henkel Kgaa Elektrochemische Herstellung amorpher oder kristalliner Metalloxide mit Teilchengrößen im Nanometerbereich
CA2347308A1 (en) * 2001-02-02 2002-08-02 Clariant Finance (Bvi) Limited Electrochemical process for preparation of zinc powder
US6569311B2 (en) 2001-02-02 2003-05-27 Clariant Finance (Bvi) Limited Continuous electrochemical process for preparation of zinc powder
TW557596B (en) * 2002-06-03 2003-10-11 Ming Chi Inst Of Technology The method of preparing the solid-state polymer Zn-air battery
US7273537B2 (en) * 2002-09-12 2007-09-25 Teck Cominco Metals, Ltd. Method of production of metal particles through electrolysis
US7166203B2 (en) * 2002-09-12 2007-01-23 Teck Cominco Metals Ltd. Controlled concentration electrolysis system
US7470351B2 (en) * 2002-09-12 2008-12-30 Teck Cominco Metals Ltd. Discrete particle electrolyzer cathode and method of making same
US20040140222A1 (en) * 2002-09-12 2004-07-22 Smedley Stuart I. Method for operating a metal particle electrolyzer
US6811625B2 (en) * 2002-10-17 2004-11-02 General Motors Corporation Method for processing of continuously cast aluminum sheet
CN101942678B (zh) * 2010-09-19 2012-02-15 西南科技大学 一种高纯活性锌粉的制备方法
DE102011106564A1 (de) * 2011-07-05 2013-01-10 Mahle International Gmbh Verfahren zur Herstellung einer Zylinderlauffläche sowie Zylinderlaufbuchse
US11306405B2 (en) 2016-09-23 2022-04-19 Zinc8 Energy Solutions, Inc. Apparatus, systems and methods for high efficiency metal particle regeneration
RU2663918C1 (ru) * 2017-09-01 2018-08-13 Публичное акционерное общество "Челябинский цинковый завод" Способ получения цинкового порошка из цинксодержащих отходов
RU2743567C1 (ru) * 2020-02-03 2021-02-19 Негосударственное частное образовательное учреждение высшего образования "Технический университет УГМК" Способ получения цинкового порошка из цинксодержащих отходов

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1397008A (en) * 1918-09-16 1921-11-15 Mcgall Albert Method of preparing finely-divided metals
US1846697A (en) * 1929-09-18 1932-02-23 Copper Deoxidation Corp Method of making brittle cathodes
US2285762A (en) * 1938-02-04 1942-06-09 Phelps Dodge Corp Electrodeposition of copper powder
US3208920A (en) * 1962-08-09 1965-09-28 Gen Electric Process for electrolytically depositing metallic material
NL302152A (de) * 1963-01-05
US3326783A (en) * 1963-08-21 1967-06-20 Tennessee Corp Process for the production of electrolytic zinc powder
GB1057625A (en) * 1963-11-25 1967-02-01 Ici Ltd Electro deposition process
JPS5018358A (de) * 1973-06-11 1975-02-26
AU502514B2 (en) * 1975-07-21 1979-07-26 Compagnie Generale Oielectricite Sa Zinc regenerating method. and device
FR2372906A2 (fr) * 1976-12-03 1978-06-30 Comp Generale Electricite Procede et dispositif de regeneration de zinc
JPS5618358A (en) * 1979-07-20 1981-02-21 Jeol Ltd Field mover for electron microscope
JPS57192283A (en) * 1981-05-21 1982-11-26 Saito Yuri Manufactre of ultrafine metal particle

Also Published As

Publication number Publication date
JPS61501998A (ja) 1986-09-11
FR2561265B1 (fr) 1986-09-26
US4676877A (en) 1987-06-30
EP0156721A1 (de) 1985-10-02
DE3560640D1 (en) 1987-10-22
AU572638B2 (en) 1988-05-12
FR2561265A1 (fr) 1985-09-20
BR8506051A (pt) 1986-03-25
WO1985004195A1 (fr) 1985-09-26
AU4064685A (en) 1985-10-11

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