Basic cobaltous carbonates, process for preparing the same...

Details Basic cobaltous carbonates, process for preparing the same... Basic cobaltous carbonates, process for preparing the same...

1997-11-25

2001-02-06

Anthony, Joseph D. (Department: 1714)

Electrolysis: processes, compositions used therein, and methods

Electrolytic synthesis

Preparing inorganic compound

C205S480000, C205S509000, C205S587000, C423S419100, C423S594120, C252S182100

Reexamination Certificate

active

06183621

ABSTRACT:

The present invention relates to processes for the production of basic cobalt(II) carbonates corresponding to the general formula Co[(OH)
2
]
a
[CO
3
]
1−a
, cobalt(II) carbonates and cobalt(II) oxalate carbonates obtainable by the process and the use thereof.
Pure-phase cobalt(II) hydroxide is required for a number of industrial applications. For example, it can be used directly or after previous calcination to cobalt(II) oxide as a component in the positive electrode of modern heavy duty secondary batteries based on nickel/cadmium or nickel/metal hydride.
By means of cobaltates (II) which are formed as intermediaries and are soluble in the alkaline electrolytes of the battery (30% by weight of KOH), it is distributed uniformly in the electrode mass and deposited there by oxidation in the so-called forming cycles as electrically conductive CoO(OH) layer on the nickel hydroxide particles. Cobalt (III) contents present in the starting material do not form soluble cobaltates and are therefore unusable.
The use of cobalt compounds in alkaline secondary batteries based on nickel/cadmium or nickel/metal hydride is disclosed in EP-A 353837. Pure cobalt(II) oxides are also used as catalyst and in electronics.
Correspondingly pure basic cobalt(II) carbonates or hydroxides are used for the production of cobalt(II) salts of weak acids.
Cobalt(II) hydroxide can be produced by precipitation from aqueous cobalt(II) salt solutions with alkali liquors. The precipitates formed generally have a gel-like consistency and are difficult to filter and therefore difficult to wash free of neutral salts. Furthermore, they are very sensitive to oxidation in alkaline media, so filtration and washing processes have to be carried out while carefully excluding atmospheric oxygen.
Basic cobalt(II) carbonates are less sensitive to oxidation. They can be produced by precipitation from cobalt(II) salt solutions with alkali and/or ammonium carbonate solutions. Equimolar quantities of neutral salts are inevitably formed during precipitation. In order to wash the basic cobalt(II) carbonates obtained substantially free from neutral salts, it is necessary to use large quantities of washing water of up to 100 l per kg of cobalt.
Only impure cobalt raw materials of the type produced; for example, in the working up of cobalt-containing scrap are generally used for producing highly concentrated cobalt(II) salt solutions containing 100 to 200 g of Co/l, of the type used for the described precipitation processes. The comparatively low price of the cobalt in this scrap is in part lost again owing to the expensive cleaning processes.
High-purity cobalt raw materials of the type obtainable in an environmentally friendly and economical manner by electrolytic purification, for example in the form of cathodes, dissolve in highly concentrated hot mineral acids only with unsatisfactory space/time yields.
Anodic oxidation in an electrolysis process is possible for the production of cobalt hydroxides low in neutral salts. The discharge of these salts into the environment is minimized by circulation of the electrolyte solution containing the neutral salts.
Electrolysis processes of this type are described, for example, Gmelins Handbuch der Anorganischen Chemie, 8th edition (1961), Kobalt, Part A Supplement, pages 314-319. Cobalt(II) hydroxide produced in this way is very readily oxidized in the electrolytic cell to cobalt (III) hydroxide or cobalt (III) oxide hydroxide CoO(OH). Furthermore, these precipitates are difficult to filter and the neutral salt impurities in the product can be reduced only by the use of large amounts of washing water. However, the purities obtainable in this way generally remain unsatisfactory.
An object of the present invention was accordingly to provide a process for the production of basic cobalt(II) carbonates and cobalt(II) hydroxide which does not have the described disadvantages of the prior art, in particular from the ecological point of view.
It has now surprisingly been found that the oxidation of cobalt to cobalt (III) during electrolytic conversion is prevented if the pH of the electrolyte solution is stabilized in the weakly acidic to alkaline range by buffering with the CO
3
2−
/HCO
3
−
/CO
2
system. Owing to the supply of hydrogen carbonate and carbonate anions in addition to hydroxide anions in the electrolyte solution, the anodically oxidized cobalt which is more stable to oxidation than cobalt(II) hydroxide forms basic carbonates corresponding to the general formula Co[(OH)
2
]
a
[CO
3
]
1−a
.
This invention accordingly relates to a process for the production of basic cobalt(II) carbonates corresponding to the general formula Co[(OH)
2
]
a
[CO
3
]
1−a
, wherein metallic cobalt is anodically oxidized in aqueous CO
2
-saturated electrolyte solutions and the basic cobalt(II) carbonate thus obtained is separated and washed.
By varying the composition of the electrolyte solution with respect to the supporting electrolytes, alkali metal chloride, alkali metal sulphate and alkali metal hydrogen carbonate or carbonate, it is possible substantially to optimize electrolysis with respect to electrolysis voltage and purity of the basic cobalt(II) carbonate produced. Anodic oxidation can be carried out under optimum conditions with current densities of up to 2000 A·m
−2
. Space/time yields of up to 50 kg Co(II)/h·m
3
are therefore readily obtainable. Such space/time yields cannot be achieved by chemical dissolution, in particular of high-purity cobalt metal.
The electrolyte solutions preferably contains, as supporting electrolyte, alkali metal chlorides in a concentration range of 0.1 to 5 mol/l, preferably 0.2 to 2 mol/l and/or alkali sulphates in a concentration range of 0 to 0.1 mol/l and/or cobalt(II) chloride up to a maximum of 0.1 mol/l.
The process according to the invention is also particulary efficient if a content of alkali metal carbonates and/or hydrogen carbonates in a concentration range of 0.02 to 2 mol/l, preferably 0.1 to 1 mol/l is maintained in the electrolyte solutions. In the process according to the invention, the electrolyte solutions preferably have temperatures in the range of 5 to 80° C., preferably 10 to 30° C. End products with a smaller content of impurities are obtainable at lower temperatures. The pH of the electrolyte solutions should be kept in a range of 5 and 11, preferably 6 and 9.5.
The purity of the electrolytically obtained basic cobalt(II) carbonate according to the invention is also influenced by the residence time in the electrolysis process. The residence time of 1 h selected in examples 1 to 5 ensures that the sodium and chloride impurities can be washed out well.
When assessing the quantities of washing water to be used, it must be borne in mind that about 7 to 10 l of electrolyte solution per kg of Co are removed from the electrolysis process in the form of adherent moisture with the basic cobalt(II) carbonate. This quantity is displaced from the solid material again during the washing process, flows back into the electrolysis circuit and does not affect the waste water balance.
The hot mashing carried out in the subsequent working up of the. filter cake causes a further reduction in the alkali and chloride values. Furthermore, CO
2
is liberated during heating of the basic cobalt(II) carbonates and can be recirculated directly into the electrolysis process for economic reasons. The separated basic cobalt(II) carbonate is therefore preferably mashed at temperatures between 50 and 100° C., filtered again and washed. Alkali liquors and/or ammonia can also advantageously be added during mashing. A further reduction in the chloride content can be achieved in this way. Substitution of the carbonate anion for hydroxide anions is also brought about in this way. Pure Co(OH)
2
can be obtained with an at least stoichiometric quantity of alkali liquors or ammonia.


REFERENCES:
patent: 4731454 (1988-03-01), Otake et al.
patent: 0 353 837 A1 (1990-07-01), None
patent: 4

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