CN105887137B - One kind reduces the brittle method of electrolytic cobalt - Google Patents
One kind reduces the brittle method of electrolytic cobalt Download PDFInfo
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- CN105887137B CN105887137B CN201610473779.8A CN201610473779A CN105887137B CN 105887137 B CN105887137 B CN 105887137B CN 201610473779 A CN201610473779 A CN 201610473779A CN 105887137 B CN105887137 B CN 105887137B
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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
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
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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
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
Abstract
The invention belongs to field of hydrometallurgy, is specially a kind of reduction brittle method of electrolytic cobalt, comprises the following steps：1) waterless cobaltous chloride is dissolved in buffer system, the cobalt chloride solution for 60~100g/L that pH is 3.5 4.0 is made；2) cobalt chloride solution exchanges purification by filtering, resin adsorption and extraction, goes the removal of impurity；3) when monitoring solution concentration of cobalt ions ＜ 60g/L, a certain amount of waterless cobaltous chloride is added, dissolving Posterior circle is well mixed, to stablize the concentration of cobalt ions in cobalt chloride solution system as 60~100g/L；4) obtained solution is put into progress low temperature direct electrolysis in electrolytic cell, prepares electrolytic cobalt；5) electrolyte dynamic circulation.The cathode cobalt product consistency that this method electrolytic preparation obtains is high, and fragility is little, is easy to follow-up shearing.The fragility of electrolytic cobalt is reduced, is advantageous to improve the availability of electrolytic cobalt product, and substantially reduces production cost.
Description
Technical field
The invention belongs to field of hydrometallurgy, it is related to the preparation method of high-purity cobalt, and in particular to it is crisp that one kind reduces electrolytic cobalt
The method of property.
Background technology
Electrolytic cobalt is the glossiness steel grey metal of tool, hard and crisp.Because its special property, hydrometallurgy electrolytic cobalt are normal
Often there is phenomena such as fragility is big, and minus plate ruptures, and product cobalt plate can not completely strip with titanium starting sheet, fragility causes in cutting process
Burst, cause electrolytic cobalt product availability there was only for 50% the problems such as so that electrolytic cobalt product is wasted seriously, and increase is produced into
This.
Zhou Ronghua, Lv Jingwen are in the text of production practices one for improving starting sheet qualification rate, for existing in starting sheet quality
Long particle, rotten corner, became uneven, embrittlement the problems such as, carried out process modification, mainly from concentration of electrolyte, electrolysis liquid temperature
In terms of degree and flow, and adjustment and the dosage of control ox glue and casein additive, the starting sheet qualification rate after adjusting process
Raising by a relatively large margin is obtained, but the electrolysis temperature of this technique is higher than 60 DEG C, adds the volatilization of electrolyte, causes production existing
Field bad environments, while the addition of additive must strictly control its content in electrolytic process, be unfavorable for human users, Yi Jike
The quality fluctuation that product can be produced causes quality unstable.
Ma Meiyan is in patent is a kind of method using ionic liquid low-temperature electro-deposition cobalt, using Fixanol, alkane
Base quaternary phosphonium salt plasma liquid electrolyte, it is 25~60 DEG C in electrolysis temperature, so as to raw on negative electrode in a manner of DC electrodeposition
Output cobalt, the temperature of this method is relatively low, less energy consumption, but does not refer to the brittleness problems of cathode cobalt plate, meanwhile, in electrolyte
The addition of organic active agent, it will increase Organic Pollution electro-deposition cobalt plate, increase the risk of bubble or hydrogen embrittlement on pole plate.
Therefore, the brittle method of electrolytic cobalt can be reduced by being badly in need of one kind, to improve the yield rate of product.
The content of the invention
It is an object of the invention to for the deficiencies in the prior art, there is provided one kind reduces the brittle side of electrolytic cobalt
Method, this method can maintain main body Co iso-ionias in solution, be not required to add any surfactant, you can obtain high densification
Degree, low brittle electrolytic cobalt, without heater, energy consumption is small, and solution evaporation is few, and working environment can substantially improve, and reduces surface
The risk that activating agent influences on product pattern and hydrogen embrittlement, electrolytic cobalt product can be promoted to carry out environment-friendly, inexpensive, efficient
Mass production.
To achieve these goals, the present invention provides a kind of reduction brittle method of electrolytic cobalt, comprises the following steps：
1) liquid is matched somebody with somebody：Waterless cobaltous chloride is dissolved in special buffer system, it is 60~100g/L's that concentration of cobalt ions, which is made,
PH is 3.5-4.0 cobalt chloride solution；
2) purification and impurity removal：Cobalt chloride solution exchanges purification by filtering, resin adsorption and extraction, goes the removal of impurity；
3) the host ions liquid making such as：Solution concentration of cobalt ions is monitored, as concentration of cobalt ions ＜ 60g/L, is added a certain amount of
Waterless cobaltous chloride, dissolving Posterior circle be well mixed, to stablize the concentration of cobalt ions in cobalt chloride solution system as 60~100g/
L, the host ions electrolyte such as it is made；
4) it is electrolysed：Manufactured electrolyte in step 3) is put into progress low temperature direct electrolysis in electrolytic cell, prepares electrolytic cobalt,
Electrolyte is maintained constantly to circulate in electrolytic process；
5) electrolyte circulates：By the solution return to step 2 of step 4)) in, maintain electrolyte dynamic circulation.
Preferably, special buffer system described in step 1) is NaAc_HAc buffer solution or citric acid-sodium citrate
Cushioning liquid.
Preferably, the resin used during the purification and impurity removal described in step 2) is the two of resin 201,301, D311,711
Kind or two or more combinations to remove the metal impurities in solution.
Preferably, the temperature of electrolysis is 20 DEG C -25 DEG C in step 4).
Further illustrate, signified metal impurities are including Fe, Ni, Cu, Zn, Sb, Pb, Ag, Mn, Bi etc. in the present invention.
Further illustrate, described liquid making process is the concentration of cobalt ions in cobalt chloride solution before and after being purified by monitoring
Difference, the content of required cobalt is calculated, by adding waterless cobaltous chloride into existing electrolyte, complete Posterior circle is dissolved, stablizes molten
Concentration of cobalt ions in liquid, ensure enter electrolysis system in cobalt ions it is constant.
Solution after electrolytic cobalt is recycled in the present invention, raw material can be saved, reduces production cost.
Beneficial effects of the present invention are：
A kind of reduction brittle method of electrolytic cobalt provided by the invention, is not required to add any surfactant, electrolytic process
In be not required to heat, you can obtain high-compactness, low brittle electrolytic cobalt, the smooth compactness of cobalt product of preparation is high, electrolytic cobalt
Relative density is up to more than 99.20%, and availability is more than 99% after the shearing of electrolytic cobalt plate.This method energy consumption is small, and solution evaporation is few,
Working environment is good, and electrolytic cobalt product can be promoted to carry out environment-friendly, inexpensive, efficient industrial amplification production.
Brief description of the drawings
Fig. 1 is the process flow diagram of the reduction brittle method of electrolytic cobalt provided by the invention.
Embodiment
Technical scheme is further described with reference to Fig. 1.
With liquid：Waterless cobaltous chloride is dissolved in the cobalt chloride solution for being made that pH is 3.5-4.0 in special buffer system, wherein
Special buffer system is NaAc_HAc buffer solution or citric acid-sodium citrate buffer；
Purification and impurity removal：Cobalt chloride solution exchanges purification by filtering, resin adsorption and extraction, goes the removal of impurity, the tree used
Fat be resin 201,301, D311,711 two or more combination remove solution in metal impurities, including Fe, Ni, Cu,
Zn, Sb, Pb, Ag, Mn, Bi etc.；
Deng host ions liquid making：Solution concentration of cobalt ions is monitored, as concentration of cobalt ions ＜ 60g/L, is added a certain amount of
Waterless cobaltous chloride, dissolving Posterior circle is well mixed, to stablize the concentration of cobalt ions in cobalt chloride solution system as 60~100g/L,
The host ions electrolyte such as it is made；
Electrolysis：Manufactured electrolyte is put into electrolytic cell progress low temperature direct electrolysis, prepares electrolytic cobalt, and temperature is 20 DEG C-
25 DEG C, electrolyte is maintained constantly to circulate in electrolytic process；
Circulation and stress：The solution after electrolytic cobalt will be made to return in purifying step, maintain electrolyte dynamic circulation.
Embodiment 1
By waterless cobaltous chloride be dissolved in NaAc_HAc buffer solution prepare concentration of cobalt ions be 80g/L,
PH=3.5 cobalt chloride solution, solution is after resin 201, D311 purification and impurity removals, through analyzing in cobalt chloride solution
Concentration of cobalt ions ＜ 60g/L, for supplement waterless cobaltous chloride into electrolyte, dissolving is complete, concentration of cobalt ions is returned to 80g/L's
Electrolyte enters in electrolytic cell, is electrolysed under 20 DEG C of temperature conditionss, and the relative density for obtaining electrolytic cobalt plate is 99.33%, electrolysis
Solution afterwards returns to purifying step and carries out dynamic circulation.
Folded bent experiment is carried out to electrolytic cobalt plate, test specimen is placed on mould, under the drift for being 10mm with end radius
Pressure, 180 ° of experiment bending, sample has no crackle, illustrates to use the fragility of the electrolytic cobalt plate of technical solution of the present invention preparation little.
Embodiment 2
It is 100g/L, pH=that waterless cobaltous chloride, which is dissolved in citric acid-sodium citrate buffer to prepare concentration of cobalt ions,
4.0 cobalt chloride solution, solution analyze concentration of cobalt ions in cobalt chloride solution after resin 301, D311,711 purification and impurity removals
＜ 60g/L, for supplement waterless cobaltous chloride into electrolyte, dissolving is complete, and the electrolyte that concentration of cobalt ions returns to 100g/L enters
In electrolytic cell, it is electrolysed under 25 DEG C of temperature conditionss, the relative density of the electrolytic cobalt plate of acquisition is 99.48%, the solution after electrolysis
Return to purifying step and carry out dynamic circulation.
Electrolytic cobalt plate is subjected to folded bent experiment, test specimen is placed on mould, under the drift for being 5mm with end radius
Pressure, 180 ° of experiment bending, sample has no crackle, illustrates to use the fragility of the electrolytic cobalt plate of technical solution of the present invention preparation little.
From above-described embodiment as can be seen that the reduction brittle method of electrolytic cobalt provided by the invention, is not required to add any table
Face activating agent, it is not required to heat in electrolytic process, you can high-compactness, low brittle electrolytic cobalt are obtained, the cobalt product of preparation is smooth,
Compactness is high, and the relative density of electrolytic cobalt is up to more than 99.20%, and availability is more than 99% after the shearing of electrolytic cobalt plate.
Claims (2)
1. one kind reduces the brittle method of electrolytic cobalt, it is characterised in that comprises the following steps：
1) liquid is matched somebody with somebody：Waterless cobaltous chloride is dissolved in special buffer system, the pH that concentration of cobalt ions is 60~100g/L, which is made, is
3.5-4.0 cobalt chloride solution；
2) purification and impurity removal：Cobalt chloride solution exchanges purification by filtering, resin adsorption and extraction, goes the removal of impurity；
3) the host ions liquid making such as：Solution concentration of cobalt ions is monitored, as concentration of cobalt ions ＜ 60g/L, adds a certain amount of nothing
Water cobalt chloride, dissolving Posterior circle are well mixed, and using the concentration for stablizing cobalt ions in cobalt chloride solution system as 60~100g/L, are made
Into grade host ions electrolyte；
4) it is electrolysed：Manufactured electrolyte in step 3) is put into progress low temperature direct electrolysis in electrolytic cell, electrolytic cobalt is prepared, is electrolysed
During maintain electrolyte constantly circulate；
5) electrolyte circulates：By the solution return to step 2 of step 4)) in, maintain electrolyte dynamic circulation；
Wherein, special buffer system described in step 1) is that NaAc_HAc buffer solution or citric acid-sodium citrate buffering are molten
Liquid；Low temperature direct electrolysis temperature is 20 DEG C -25 DEG C in step 4).
2. the reduction brittle method of electrolytic cobalt according to claim 1, it is characterised in that the purification and impurity removal described in step 2)
During the resin that uses be two or more combination of resin 201,301, D311,711 to remove the metal in solution
Impurity.
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| CN201610473779.8A CN105887137B (en) | 2016-06-24 | 2016-06-24 | One kind reduces the brittle method of electrolytic cobalt |
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| CN101302585A (en) * | 2008-07-08 | 2008-11-12 | 金川集团有限公司 | Method for preparing high-purity cobalt |
| CN101538721A (en) * | 2009-03-19 | 2009-09-23 | 金川集团有限公司 | Method for preparing high-purity cobalt |
| CN102206761B (en) * | 2010-03-29 | 2013-05-22 | 苏州晶纯新材料有限公司 | Production method of high purity cobalt |
| CN101914784B (en) * | 2010-08-30 | 2013-01-09 | 江苏凯力克钴业股份有限公司 | Method for producing electrodeposited cobalt |
| CN103060842B (en) * | 2012-12-26 | 2016-06-08 | 浙江华友钴业股份有限公司 | A kind of method preparing electrodeposited cobalt under big flow |
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