CN114318416A - Method for producing electrodeposited cobalt - Google Patents
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Abstract
The invention relates to a method for producing electrodeposited cobalt, which comprises the following steps: leaching and deironing: crushing and ball milling cobalt material and using H2SO4And SO2Leaching to obtain CoSO4Leaching liquor, and removing iron from the leaching liquor to obtain iron-removed liquor; and (3) extraction: removing impurity elements from the iron-removed solution by a P204 impurity extraction process, introducing the impurity-removed raffinate into a P507 cobalt extraction process, and performing back extraction by using sulfuric acid or the electrodeposition solution to obtain pure CoSO4A solution; deep purification: further removal of CoSO by extraction or ion exchange4Small amount of impurities in solution, and to CoSO4Deeply removing oil from the solution; preparing electrolyte: deeply purified CoSO4Adding an additive into the solution to obtain a solution before electrodeposition; electrodeposition: and carrying out electrodeposition operation on the pre-electrodeposition solution to obtain a cobalt electrodeposit product and a post-electrodeposition solution. The invention does not generate Cl in the electrodeposition process2Greatly improves the operating environment and reduces the corrosion resistance to the equipmentAnd (4) requiring.
Description
Technical Field
The invention relates to the technical field of hydrometallurgy, in particular to a method for producing electrodeposited cobalt.
Background
At present, the production of the electro-deposited cobalt is mainly based on a chlorination system, and a large amount of Cl is generated in the electro-deposition process2May cause Cl in case of carelessness2Leakage, not only can cause serious pollution to the environment, but also can seriously affect the health of production personnel, and can also shorten the equipment for producing the electrodeposited cobaltThe service life of (2). Compared with the production of the electrodeposited cobalt by a chlorination system, the method adopts the electrodeposited CoSO4The method for producing the electrodeposited cobalt does not generate Cl2But the defects of poor quality of the cobalt plate and low current efficiency exist.
Wherein, patent CN101532095 discloses a method for producing electrodeposited cobalt by non-hydrochloric acid electrolyte, CoCl prepared by the patent2The electrolyte is obtained after the solution is subjected to extraction transformation, dechlorination and oil removal, and the defects of long working procedure and high production cost exist;
patent CN102206761 discloses a method for producing high-purity cobalt, which removes Fe and Ni in electrolyte by ion exchange before electrodeposition, and obtains cobalt ingots by a vacuum melting method of cobalt plates obtained by electrodeposition, wherein the method has the defects of long working procedure, complex equipment and high production cost;
patent CN103436913 discloses a device for electrodeposition of nickel or cobalt, which is provided with a cathode frame and an anode frame in an electrodeposition tank, and a permeable membrane is arranged between the cathode frame and the anode frame, the cathode frame occupies a certain space, and the effective volume of the electrodeposition tank is reduced, thereby reducing the productivity; in addition, the permeable membrane disclosed in the patent is made of polyester staple fiber, and has certain limitations.
Disclosure of Invention
Based on the problems and the defects in the prior art, the invention provides a method for producing electrodeposited cobalt, which is used for improving the operating environment, reducing the corrosion to equipment, reducing the consumption of raw materials, improving the current efficiency and the like.
The specific technical scheme is as follows:
a method for producing electrodeposited cobalt, comprising the steps of:
s1, leaching and removing iron: crushing and ball milling cobalt material and using H2SO4And SO2Leaching to obtain CoSO4Leaching liquor, and removing iron from the leaching liquor to obtain iron-removed liquor; the Fe concentration in the iron-removed liquid is less than 1mg/L so as to reduce the burden of the extraction process.
S2, extraction: removing impurity elements from the iron-removed liquid by a P204 impurity extraction process, and introducing the impurity-removed raffinate into P507Cobalt extraction process, back extraction with sulfuric acid or the solution after electrodeposition to obtain pure CoSO4Solution of said CoSO4The concentration of cobalt ions in the solution is 60-100 g/L, the higher the concentration of cobalt ions in the electrolyte is, the more compact cathode sediment is generated, the hydrogen ion discharge is reduced, and the current density is improved, but the too high concentration of cobalt ions can obtain dark spongy cathode sediment, the concentration of cobalt ions in the electrolyte in industry is generally 60-100 g/L, and the concentration is easy to obtain high-quality electrodeposited cobalt products.
S3, deep purification: further removal of CoSO by extraction or ion exchange4Small amount of impurities in solution, and to CoSO4The solution is deeply degreased, deep purification is not thorough, and the impurity content in the corresponding electrodeposited cobalt is increased, so that the quality of the electrodeposited cobalt is influenced. CoSO obtained after deep purification4The concentration of each metal impurity ion in the solution reaches the standard of the electrolyte, and the content of organic matters is less than 10 ppm. The organic matters are mainly organic phase carried in the extraction process, mainly sulfonated kerosene, and a small amount of extracting agents P204 and P507.
S4, preparation of electrolyte: deeply purified CoSO4Adding an additive into the solution to obtain a solution before electrodeposition; the additive is at least one of boric acid, sodium dodecyl sulfate and guar gum.
The addition of suitable additives is one of the effective measures for obtaining an electrodeposition product with compact structure, smooth surface and low impurity content.
When the cobalt is electrodeposited, a certain amount of boric acid is added to improve the quality of the cobalt, because in the electrodeposition process, the precipitation of cathode hydrogen is inevitable, the pH value of electrolyte on the surface of a cathode is increased, metal ions are hydrolyzed, and basic salt precipitates are formed and adsorbed on the surface of the cathode to influence the product quality. When boric acid is added to the electrolyte, because it is a weak acid, there is an ionization equilibrium in the solution, which ionizes H if the pH of the solution increases+So as to maintain the stability of the pH value of the electrolyte.
The electro-deposited cobalt production practice shows that when the concentration of the boric acid is lower than 2g/L, the buffering effect is weak, and when the content of the boric acid reaches 2g/L, the buffering effect is obvious, so that the concentration of the boric acid is controlled within the range of 2-20 g/L. Because the solubility of the boric acid is 40g/L at normal temperature, when the content of the boric acid is too high, the cathode current efficiency is reduced, and the boric acid is easy to crystallize and precipitate at low temperature, so that the surface of the electrodeposited cobalt plate is rough, burrs and the waste of raw materials are caused. In the process of electrodeposition, boric acid not only plays a role in stabilizing pH value and buffering, but also can expand the range of cathode bright current density so as to use higher current density, and make the cobalt plate have fine crystals and difficult scorching. In addition, the dissociation of boric acid is favorable for inhibiting the hydrolysis of cobalt sulfate, so that the electrodeposition reaction can be smoothly carried out.
Sodium dodecyl sulfate is a hydrophilic surface active substance, can be easily dissociated into sulfonate ions and sodium ions in water, and the sulfonate ions are easily mixed with Co2+Complex ions are formed, the cathode polarization value is increased due to the fact that the discharging speed is reduced, the crystal lattice growth is reduced, the phenomenon that the polar plate is loose and porous can be effectively improved and restrained, protruding particles are reduced, the surface of the electric cobalt is smooth, the physical performance is good, and meanwhile the iron content in the electric cobalt can be reduced. When the adding amount is too much, the surface of the cobalt electrolyte is often powdery and is easy to fall off, and the surface quality is deteriorated. When the concentration of the sodium dodecyl sulfate is too low, the improvement on the physical properties of the cobaltite is not obvious; when the concentration is too high, the surface of the cobalt electrolyte is often powdery and is easy to fall off, and the surface quality is poor.
The addition of guar gum can increase the polarization potential of the cathode so as to make the surface of the electrodeposited cobalt smooth and flat. The action mechanism may be: guar gum molecules are dissociated into colloid roots with positive charges in the electrolyte, the colloid roots are close to a cathode under the action of current and are adsorbed on the surface of the cathode, and a glue film with poor conductivity is formed to enable the polarization potential of the cathode to be increased; guar gum and cobalt ions form complex cations in the electrolyte, the complex ions are firstly decomposed in the cathode active area to release free cobalt ions, and then the electrolytic cobalt is separated out on the cathode, so that the discharge speed of the cobalt ions on the cathode is delayed. The concentration of the guar gum is 2-10 mg/L. When the concentration of the guar gum is higher, the cathode polarization can be increased, and cobalt ions are difficult to discharge at the cathode, so that the aim of reducing the electro-cobalt deposition speed is fulfilled. When the guar gum concentration is too low, a colloidal film with poor conductivity is not formed enough, and when the guar gum concentration is too high, a growth center of sulfide is generated, the surface of a deposit is rough, stripes appear, a layering phenomenon is generated, and the quality of the electrocobalt is deteriorated.
S5, electrodeposition: and (3) carrying out electrodeposition operation on the pre-electrodeposition liquid to obtain an electrodeposited cobalt product and a post-electrodeposition liquid, washing and inspecting the electrodeposited cobalt, and warehousing the electrodeposited cobalt, wherein the post-electrodeposition liquid is reused for the extraction process for back-extracting the cobalt or for the leaching process for leaching the cobalt.
The electrodeposition process conditions are as follows: the electro-deposition liquid has the cobalt ion concentration of 60-100 g/L, the initial pH of 4.0-4.5, the electro-deposition temperature of 50-60 ℃ and the current density of 180-300A/m2And the same polar distance: 100-.
The acidity of the electrolyte affects not only the current efficiency but also the structure of the cobalt deposit. The more the acidity of the electrolyte (the lower the pH), the more hydrogen ions are precipitated at the cathode, and the lower the current efficiency. When the pH value of the electrolyte is higher, hydroxide of cobalt is easily generated on the cathode, and the produced cathode cobalt has high hardness, poor elasticity and is easy to delaminate.
The temperature is increased to promote the diffusion of cobalt ions, reduce concentration polarization, reduce cell voltage and improve current efficiency, and meanwhile, the temperature is increased to accelerate the growth rate of cathode sediment grains and make cathode cobalt crystal particles larger. However, the temperature is too high, so that on one hand, more energy is needed, on the other hand, the overpotential of hydrogen is reduced, the precipitation of hydrogen is increased, and the current efficiency is reduced. When the temperature is too low, the cathode cobalt is blackened, cracks and the like occur, the temperature of the electrolyte is controlled to be 50-60 ℃, the process temperature is required to be stable, and the cathode cobalt is curled or forms a net structure due to temperature fluctuation.
The greater the current density, the greater the current intensity passed, and the greater the yield. However, as the current density increases, the cell voltage increases, the current efficiency decreases, and the cathode cobalt obtained at a high current density has a rough surface and is liable to adsorb impurity particles. The current density of the invention is controlled to be 180-300A/m2。
The adoption of the same polar distance as small as possible is not only beneficial to reducing the cell voltage and improving the current efficiency, but also increases the production capacity of the electrolytic cell. However, the homopolar distance is too small, which easily causes short circuit due to increased contact in the groove, and brings great difficulty to the operation and management of the groove surface, but reduces the current efficiency. The same polar distance of the invention is controlled at 100-160 mm.
When the liquid before electrodeposition is electrodeposited, the adopted anode plate is one of a Pb plate, a Pb-Ag alloy plate and a Ti plate, and the cathode plate is a cobalt starting sheet and has the thickness of 0.3-1.0 mm.
The Pb plate, the Pb-Ag alloy plate and the Ti plate have low cost, good conductivity and good corrosion resistance, can prevent anode corrosion from entering cathode cobalt, and do not need to strip a cobalt sheet when the cobalt starting sheet is used as a cathode, thereby reducing the labor intensity.
The negative plate is also sleeved with a diaphragm bag, the diaphragm bag is a diaphragm which is made of at least one or any multiple of terylene, polypropylene fiber, chinlon and vinylon and has a filtering function, the diaphragm bag maintains a certain liquid level difference between the solution inside and outside the diaphragm bag, and H is reduced2So as to ensure that the pH value of the catholyte is 1.5-4.0. The liquid level difference between the liquid level in the diaphragm bag and the anode liquid is 15-30mm, so that H is reduced2So as to ensure that the pH value of the catholyte is 1.5-4.0.
Has the advantages that:
the method uses CoSO4The solution is electrolyte, and Cl is not generated in the electrodeposition process2Greatly improving the operation environment and reducing the corrosion prevention requirement on equipment.
The method improves the quality of the cobalt plate by adding the additive into the electrolyte, and the cobalt plate has compact crystal, smooth surface, less dendritic or round-head nodules and low impurity content.
In the method, a diaphragm bag is sleeved on a cathode plate in the electrodeposition process, a certain liquid level difference between the inside and the outside of the diaphragm bag is maintained by controlling the flow of circulating liquid, and the pH value of catholyte is controlled to be 1.5-4.0, so that H is reduced2The current efficiency is improved, and the current efficiency is increased to more than 80 percent from about 60 percent when the diaphragm bag is not sleeved.
Compared with the traditional method for neutralizing the solution after electrodeposition by using alkali, the method saves sulfuric acid, saves the alkali for neutralizing the solution after electrodeposition and greatly reduces the consumption of raw materials.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart of the method of the present invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
as shown in fig. 1, a method for producing electrodeposited cobalt, comprising the steps of:
s1, leaching and removing iron: crushing and ball milling the cobalt concentrate, and adding H2SO4And SO2Reduction leaching is carried out to obtain CoSO4Leaching liquor, and removing iron from the leaching liquor to obtain iron-removed liquor [ Fe]＝0.0008g/L；
S2, extraction: removing impurity elements such as Al, Cu, Mn, Zn, Ca and the like in the solution after iron removal by a P204 extraction processThe raffinate after impurity removal enters a P507 cobalt extraction process, and is back-extracted by sulfuric acid or the solution after electrodeposition to obtain pure CoSO4Solution, [ Co ]2+]＝80g/L；
S3, deep purification: further removal of CoSO by extraction4Small amount of impurities in solution, and to CoSO4Deeply deoiling the solution to obtain CoSO4The concentration of each impurity ion in the solution reaches the standard of electrolyte, and the content of organic matters is 5 ppm;
s4, preparation of electrolyte: to CoSO4Adding boric acid and sodium dodecyl sulfate as additives into the solution, wherein the concentration of the boric acid is 5g/L, and the concentration of the sodium dodecyl sulfate is 0.1mg/L to obtain a solution before electrodeposition;
s5, electrodeposition: and (3) carrying out electrodeposition operation on the pre-electrodeposition liquid to obtain an electrodeposited cobalt product and a post-electrodeposition liquid, washing and inspecting the electrodeposited cobalt, and warehousing the electrodeposited cobalt, wherein the post-electrodeposition liquid is recycled for the extraction process for back extraction of cobalt.
In the electrodeposition operation, the anode was a Pb plate, the cathode was a cobalt starting sheet with a thickness of 0.5mm, the cathode was covered with a polyester fabric diaphragm bag, the pre-electrodeposition solution flowed into the diaphragm bag, and the circulating flow rate was controlled so as to maintain the difference between the liquid level in the diaphragm bag and the liquid level of the anode at 20mm, at which time the pH of the catholyte was about 2.0, and the pre-electrodeposition solution [ Co ] was added2+]80g/L, pH 4.0-4.5, electrodeposition temperature 55 deg.C, current density 200A/m2And the same polar distance: 120mm, cell voltage 3.8V, post-electrodeposition liquid [ Co ]2+]60 g/L. In this embodiment, the cathode and the anode are separated by the cathode diaphragm bag, pure electrolyte flows into the cathode diaphragm bag without interruption, the liquid level in the diaphragm bag and the liquid level of the anolyte maintain a certain liquid level difference, and the filtering speed of the catholyte through the diaphragm bag is greater than the moving speed of impurity ions such as copper, iron and the like from the anode to the cathode under the action of current under the action of the liquid level difference, so that impurities are not added in the cathode chamber, the stability of the pH value of the catholyte is maintained, and the quality of the electrolytic cobalt and higher current efficiency are ensured.
The cobalt plate produced by the embodiment has compact crystallization, smooth surface and silver gray luster, only a small amount of grains exist, the cobalt content is 99.99 percent, the quality standard of Co9998 is met, and the current efficiency is up to 89 percent. And (4) washing and inspecting the electrodeposited cobalt, and warehousing, wherein the liquid after electrodeposition is recycled in the extraction process for back extraction of cobalt.
Example 2:
a method for producing electrodeposited cobalt comprising the steps of:
s1, leaching and removing iron: crushing and ball milling the rough cobalt hydroxide, and adding H2SO4And SO2Reduction leaching is carried out to obtain CoSO4Leaching solution, iron-removed solution [ Fe ] obtained by iron removal of leaching solution]＝0.0009g/L；
S2, extraction: removing impurity elements such as Al, Cu, Mn, Zn, Ca and the like in the iron-removed solution through a P204 impurity extraction process, introducing the impurity-removed raffinate into a P507 cobalt extraction process, and performing back extraction on the solution after electrodeposition to obtain pure CoSO4Solution, [ Co ]2+]＝70g/L；
S3, deep purification: further removal of CoSO by ion exchange4Small amount of impurities in solution, and to CoSO4Deeply deoiling the solution to obtain CoSO4The concentration of each impurity ion of the solution reaches the standard of electrolyte, and the content of organic matters is 3 ppm;
s4, preparation of electrolyte: to CoSO4Adding boric acid as an additive into the solution, wherein the concentration of the boric acid is 8g/L, and obtaining a liquid before electrodeposition;
s5, electrodeposition: and (3) carrying out electrodeposition operation on the pre-electrodeposition liquid to obtain an electrodeposited cobalt product and a post-electrodeposition liquid, washing and inspecting the electrodeposited cobalt, and warehousing the electrodeposited cobalt, wherein the post-electrodeposition liquid is reused for the leaching process to leach the cobalt.
In this example, the anode was a Ti plate, the cathode was a 0.6mm thick cobalt starting sheet, the cathode was a polypropylene fabric diaphragm bag, the pre-electrodeposition solution flowed into the diaphragm bag, and the appropriate circulation flow rate was controlled to maintain the difference between the liquid level in the diaphragm bag and the anode liquid level at 25mm, at which time the pH of the catholyte was about 2.5.
In addition, during electrodeposition, the solution [ Co ] before electrodeposition2+]70g/L, pH 4.0-4.5, 60 deg.C, and 250A/m2And the same polar distance: 140mm, cell voltage 4.0V, post-electrodeposition liquid [ Co ]2+]＝55g/L。
The produced cobalt plate has compact crystallization, smooth surface with silver gray luster, only a small amount of grains, 99.99 percent of cobalt content, reaching the quality standard of Co9998 and high current efficiency of 85 percent. And (4) washing and inspecting the electrodeposited cobalt, and warehousing, wherein the liquid after electrodeposition is recycled for the leaching process to leach the cobalt.
Example 3:
a method for producing electrodeposited cobalt comprising the steps of:
s1, leaching and removing iron: crushing and ball-milling the lithium battery waste, and adding H2SO4And SO2Reduction leaching is carried out to obtain CoSO4Leaching solution, iron-removed solution [ Fe ] obtained by iron removal of leaching solution]＝0.0006g/L；
S2, extraction: removing impurity elements such as Al, Cu, Mn, Zn, Ca and the like in the iron-removed solution through a P204 impurity extraction process, introducing the impurity-removed raffinate into a P507 cobalt extraction process, and performing back extraction on the solution after electrodeposition to obtain pure CoSO4Solution, [ Co ]2+]＝60g/L；
S3, deep purification: further removal of CoSO by extraction4Small amount of impurities in solution, and to CoSO4Deeply deoiling the solution to obtain CoSO4The concentration of each impurity ion of the solution reaches the standard of electrolyte, and the content of organic matters is 3 ppm;
s4, preparation of electrolyte: to CoSO4Adding boric acid and guar gum as additives into the solution, wherein the concentration of the boric acid is 20g/L, and the concentration of the guar gum is 2mg/L to obtain a solution before electrodeposition;
s5, electrodeposition: and (3) carrying out electrodeposition operation on the pre-electrodeposition liquid to obtain an electrodeposited cobalt product and a post-electrodeposition liquid, washing and inspecting the electrodeposited cobalt, and warehousing the electrodeposited cobalt, wherein the post-electrodeposition liquid is recycled for the extraction process for back extraction of cobalt.
In this example, the anode was a Pb-Ag plate, the cathode was a 0.3mm thick cobalt starting sheet, the cathode plate was made of polypropylene fabric diaphragm bag, the pre-electrodeposition solution flowed into the diaphragm bag, and the appropriate circulation flow rate was controlled to maintain the difference between the liquid level in the diaphragm bag and the anode liquid level at 15mm, at which time the pH of the catholyte was about 1.5.
In addition, during electrodeposition, the solution [ Co ] before electrodeposition2+]60g/L, pH 4.0-4.5, electrodeposition temperature 50 deg.C, and current density180A/m2And the same polar distance: 100mm, cell voltage 3.6V, post-electrodeposition liquid [ Co ]2+]＝48g/L。
The produced cobalt plate has compact crystallization, smooth surface with silver gray luster, only a small amount of grains, 99.98 percent of cobalt content, reaching the quality standard of Co9998 and high current efficiency of 86 percent. And (4) washing and inspecting the electrodeposited cobalt, and warehousing, wherein the liquid after electrodeposition is recycled in the extraction process for back extraction of cobalt.
Example 4:
a method for producing electrodeposited cobalt comprising the steps of:
s1, leaching and removing iron: crushing and ball milling the cobalt concentrate, and adding H2SO4And SO2Reduction leaching is carried out to obtain CoSO4Leaching solution, iron-removed solution [ Fe ] obtained by iron removal of leaching solution]＝0.0008g/L；
S2, extraction: removing impurity elements such as Al, Cu, Mn, Zn, Ca and the like in the iron-removed solution through a P204 impurity extraction process, introducing the impurity-removed raffinate into a P507 cobalt extraction process, and performing back extraction on the solution after electrodeposition to obtain pure CoSO4Solution, [ Co ]2+]＝100g/L；
S3, deep purification: further removal of CoSO by extraction4Small amount of impurities in solution, and to CoSO4Deeply deoiling the solution to obtain CoSO4The concentration of each metal impurity ion in the solution reaches the standard of electrolyte, and the content of organic matters is 9 ppm;
s4, preparation of electrolyte: to CoSO4Adding guar gum as an additive into the solution, wherein the concentration of the guar gum is 10mg/L, and obtaining a pre-electrodeposition solution;
s5, electrodeposition: and (3) carrying out electrodeposition operation on the pre-electrodeposition liquid to obtain an electrodeposited cobalt product and a post-electrodeposition liquid, washing and inspecting the electrodeposited cobalt, and warehousing the electrodeposited cobalt, wherein the post-electrodeposition liquid is reused for the leaching process to leach the cobalt.
In this example, the anode was a Pb-Ag plate, the cathode was a 1.0mm thick cobalt starting sheet, a polyamide diaphragm bag was used for the cathode plate, the pre-electrodeposition solution flowed from the diaphragm bag, and the appropriate circulation flow rate was controlled to maintain the difference between the liquid level in the diaphragm bag and the anode liquid level at 30mm, at which time the pH of the catholyte was about 4.0.
In addition, during electrodeposition, the solution [ Co ] before electrodeposition2+]100g/L, pH 4.5, 60 deg.C, current density 300A/m2And the same polar distance: 160mm, cell voltage 4.1V, post-electrodeposition liquid [ Co ]2+]＝100g/L。
The produced cobalt plate has compact crystallization, smooth surface, silver gray luster and only a small amount of grains, the cobalt content is 99.99 percent, the cobalt plate reaches the quality standard of Co9998, and the current efficiency is as high as 88 percent. And (4) washing and inspecting the electrodeposited cobalt, and warehousing, wherein the liquid after electrodeposition is recycled for the leaching process to leach the cobalt.
Meanwhile, the method tests that no additive is added into the solution before electrodeposition, and the produced cobalt plate has a rough surface, more dendritic nodules and round-head nodules, the cobalt content is only 99.93 percent, the quality of the cobalt plate is poor, and the current efficiency is 82 percent.
Meanwhile, the application also tests that the cathode plate is not sleeved with a diaphragm bag, and the produced cobalt plate is not compact and is easy to delaminate, H2The precipitation amount is obviously increased, and the current efficiency is greatly reduced to 65 percent.
The above description is only for the specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A method for producing electrodeposited cobalt, comprising the steps of:
s1, leaching and removing iron: crushing and ball milling cobalt material and using H2SO4And SO2Leaching to obtain CoSO4Leaching liquor, and removing iron from the leaching liquor to obtain iron-removed liquor;
s2, extraction: removing impurity elements from the iron-removed solution by a P204 impurity extraction process, introducing the impurity-removed raffinate into a P507 cobalt extraction process, and performing back extraction by using sulfuric acid or the electrodeposition solution to obtain pure CoSO4A solution;
s3, deep purification: miningFurther removal of CoSO by extraction or ion exchange4Small amount of impurities in solution, and to CoSO4Deeply removing oil from the solution;
s4, preparation of electrolyte: deeply purified CoSO4Adding an additive into the solution to obtain a solution before electrodeposition;
s5, electrodeposition: and (3) carrying out electrodeposition operation on the pre-electrodeposition liquid to obtain an electrodeposited cobalt product and a post-electrodeposition liquid, washing and inspecting the electrodeposited cobalt, and warehousing the electrodeposited cobalt, wherein the post-electrodeposition liquid is reused for the extraction process for back-extracting the cobalt or for the leaching process for leaching the cobalt.
2. The method of claim 1, wherein: in step S1, the cobalt raw material includes one or more of cobalt concentrate, crude cobalt hydroxide, and lithium battery waste.
3. The method of claim 1, wherein: in step S1, the Fe concentration in the iron-removed liquid is less than 1 mg/L.
4. The method of claim 1, wherein: in step S2, the CoSO4The concentration of cobalt ions in the solution is 60-100 g/L.
5. The method of claim 1, wherein: in step S4, the additive is one or more of boric acid, sodium dodecyl sulfate, and guar gum.
6. The method of claim 5, wherein: the concentrations of the additives are respectively as follows: the concentration of boric acid is 2-20 g/L, the concentration of sodium dodecyl sulfate is 0.05-0.5 mg/L, and the concentration of guar gum is 2-10 mg/L.
7. The method of claim 1, wherein: in step S5, when performing electrodeposition on the pre-electrodeposition solution, it is further necessary to ensure that the initial pH of the electrodeposition solution is 4.0 to 4.5, the electrodeposition temperature is 50 to 60 ℃, and the current density is 180 to 300A/m2All are the same asPolar distance: 100-.
8. The method of claim 7, wherein: in step S5, when the pre-electrodeposition solution is subjected to electrodeposition, the anode plate is one of a Pb plate, a Pb-Ag alloy plate and a Ti plate, and the cathode plate is a cobalt starting sheet with a thickness of 0.3-1.0 mm.
9. The method of claim 8, wherein: the negative plate is also sleeved with a diaphragm bag, the diaphragm bag is a diaphragm which is made of at least one or any multiple of terylene, polypropylene fiber, chinlon and vinylon and has a filtering function, the diaphragm bag maintains a certain liquid level difference between the solution inside and outside the diaphragm bag, and H is reduced2So as to ensure that the pH value of the catholyte is 1.5-4.0.
10. The method of claim 9, wherein: the liquid level difference between the liquid level in the diaphragm bag and the anode liquid is 15-30 mm.
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| CN (1) | CN114318416A (en) |
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