CN113120969A - Method for preparing cobalt chloride by using high-pressure crystallization method - Google Patents
Method for preparing cobalt chloride by using high-pressure crystallization method Download PDFInfo
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- CN113120969A CN113120969A CN201911406587.5A CN201911406587A CN113120969A CN 113120969 A CN113120969 A CN 113120969A CN 201911406587 A CN201911406587 A CN 201911406587A CN 113120969 A CN113120969 A CN 113120969A
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Abstract
The invention belongs to the technical field of battery material production, and discloses a method for preparing cobalt chloride by using a high-pressure crystallization method, which comprises the following steps: s1, primarily purifying the cobalt-manganese solution to obtain a purified solution; s2, carrying out hydrothermal reaction on the purified solution under the condition of pressurization, and controlling the temperature to be 200-220 ℃ to obtain a crude manganese sulfate crystal and a supernatant; s3, removing impurities from the supernatant by a P204 extraction line to obtain a P204 raffinate and a P204 strip liquor; evaporating and concentrating the P204 strip liquor to obtain a concentrate; mixing a concentrated solution into the purified solution in the S1, continuing the S2; s4, carrying out P507 extraction on the P204 raffinate to obtain a cobalt chloride solution. According to the invention, manganese in the cobalt-manganese solution is separated before P204 extraction and impurity removal, so that smooth operation of a P204 extraction line in the later period can be ensured, the productivity is further improved, and the production cost is reduced.
Description
Technical Field
The invention belongs to the technical field of battery material production, and particularly relates to a method for preparing cobalt chloride by using a high-pressure crystallization method.
Background
In the production process of battery materials, the cobalt and manganese are inevitably required to be separated, and the currently applied cobalt and manganese separation method mainly comprises a precipitation method and a solvent extraction method; the precipitation method mainly comprises a hydroxide precipitation method, a sulfide precipitation method, an ammonia/carbonate precipitation method and an oxidation precipitation method.
However, the existing methods have more or less problems, for example, cobalt-containing precipitation slag obtained by a hydroxide precipitation method and a sulfide precipitation method needs to be re-dissolved, wherein the sulfide precipitation slag needs to be leached under an oxidizing condition, so that the working procedures are increased; the oxidation precipitation method is more suitable for treating low-manganese solution, and the treatment cost is high for high-manganese solution.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing cobalt chloride by using a high pressure crystallization method, which aims at solving the problem of high treatment cost of the existing cobalt-manganese separation method.
The method is realized by adopting the following technical scheme: a method for preparing cobalt chloride by using a high-pressure crystallization method comprises the following steps:
s1, primarily purifying the cobalt-manganese solution to obtain a purified solution;
s1, primarily purifying the cobalt-manganese solution to obtain a purified solution;
s2, carrying out hydrothermal reaction on the purified solution under the condition of pressurization, and controlling the temperature to be 200-220 ℃ to obtain a crude manganese sulfate crystal and a supernatant;
s3, removing impurities from the supernatant by a P204 extraction line to obtain a P204 raffinate and a P204 strip liquor; evaporating and concentrating the P204 strip liquor to obtain concentrated liquor; mixing the concentrated solution into the purified solution in the S1, continuing the S2;
s4, carrying out P507 extraction on the P204 raffinate to obtain a cobalt chloride solution.
Preferably, the concentration of manganese in the cobalt-manganese solution in S1 is more than 30g/L, and the concentration of cobalt is 40 g/L-60 g/L.
Preferably, the temperature of the decontamination solution is between 20 ℃ and 35 ℃.
Preferably, the specific steps in S1 are: and adding sodium hydroxide into the cobalt-manganese solution, and filtering to obtain a purified solution.
Preferably, the specific process of S2 is:
carrying out hydrothermal reaction on the purified solution at the pressure of 0.1-0.3 Mpa and the temperature of 200-220 ℃; and after the hydrothermal reaction is finished, obtaining rough manganese sulfate crystals and a supernatant.
Preferably, in S3, the temperature for evaporation and concentration is 80-90 ℃, and the concentration is carried out until the density of the concentrated solution is 1.2-1.3 g/mL.
Compared with the prior art, the invention adopting the scheme has the beneficial effects that:
the method comprises the steps of firstly, preliminarily purifying the cobalt-manganese solution to preliminarily remove iron contained in the cobalt-manganese solution to obtain a purified solution, so that the phenomenon that a large amount of iron ions are crystallized during later crystallization to cause more impurities contained in manganese sulfate crystals is avoided;
because the high-concentration manganese is not beneficial to the operation of the P204 extraction line, sulfuric acid is added into the purified solution, hydrothermal reaction is carried out by regulating and controlling pressure and temperature, and then the purified solution is stood at high temperature and high pressure for crystallization, so that manganese sulfate in the purified solution is fully crystallized, the manganese is preliminarily separated out, the smooth operation of the P204 extraction line in the later period is ensured, the productivity is improved, and the production cost is reduced;
then, carrying out evaporation concentration on the P204 strip liquor to obtain a concentrated solution; mixing the concentrated solution into the purified solution in S1, and continuing to S2, so that manganese ions can be sufficiently crystallized and separated; and finally, performing P507 extraction on the P204 raffinate to obtain a cobalt chloride solution containing less impurities.
In summary, the invention separates manganese in the cobalt-manganese solution before the P204 extraction and impurity removal, which can ensure the smooth operation of the P204 extraction line in the later period, thereby improving the productivity and reducing the production cost.
Drawings
FIG. 1 is a flow chart of a method for preparing cobalt chloride by high pressure crystallization.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the production process of battery materials, if the cobalt-manganese solution flowing out of a wet workshop is directly discharged, not only is the environmental pollution caused, but also the waste of raw materials is caused, so that the cobalt and manganese are required to be separated in the actual production process, and the cobalt and manganese are recycled.
The invention provides a method for preparing cobalt chloride by using a high-pressure crystallization method, which comprises the following steps:
s1, primarily purifying the cobalt-manganese solution to obtain a purified solution;
s2, carrying out hydrothermal reaction on the purified solution under the condition of pressurization, and controlling the temperature to be 200-220 ℃ to obtain a crude manganese sulfate crystal and a supernatant;
s3, removing impurities from the supernatant by a P204 extraction line to obtain P204 raffinate and P204 strip liquor; evaporating and concentrating the P204 strip liquor to obtain concentrated liquor; mixing the concentrated solution into the purified solution in S1, and continuing S2;
s4, carrying out P507 extraction on the P204 raffinate to obtain a cobalt chloride solution.
It should be noted that, experimentally, the solubility of manganese sulfate increases with increasing temperature below 27 ℃ and gradually decreases with increasing temperature above 27 ℃, especially sharply decreases above 100 ℃. Therefore, by utilizing the characteristic of manganese sulfate, the solution with lower manganese concentration can be crystallized to obtain the manganese sulfate.
The method of the present invention will be described in detail with reference to specific examples.
Example 1
In the cobalt-manganese solution of the present embodiment, the cobalt concentration is 40g/L, and the manganese concentration is 35g/L, and the cobalt-manganese separation is specifically performed by the following method:
s1, adding sodium hydroxide (namely liquid caustic soda) into the cobalt-manganese solution to remove iron ions in the cobalt-manganese solution, and then filtering to obtain a purified solution, wherein the temperature of the purified solution is 20 ℃;
s2, adding the purified solution into a closed reaction kettle, adding sulfuric acid, stirring and mixing uniformly, standing, introducing steam into the reaction kettle for heating the purified solution, increasing the pressure in the closed reaction kettle, and ensuring that the temperature in the reaction kettle is maintained at about 200 ℃; the pressure in the reaction kettle is maintained at about 0.1Mpa, and hydrothermal reaction is carried out in the environment; after the hydrothermal reaction is finished, obtaining rough manganese sulfate crystals and supernatant;
s3, passing the supernatant in the S2 through a P204 extraction line to remove impurities, and obtaining P204 raffinate and P204 strip liquor; evaporating and concentrating the P204 strip liquor at 80 ℃ until the density of the concentrated liquor is 1.2 g/mL; subsequently, the concentrated solution was mixed into the purified solution in S1, and S2 was continued;
s4, carrying out P507 extraction on the P204 raffinate to obtain a cobalt chloride solution.
In this embodiment, on the premise of ensuring that the recovery rate of cobalt and manganese at least reaches 99%, the flow rate of the supernatant can be maintained at 158L/h to 163L/h while passing through the P204 extraction line, which results in higher productivity of the whole process.
Example 2
In the cobalt-manganese solution of the present embodiment, the cobalt concentration is 60g/L, and the manganese concentration is 50g/L, and the cobalt-manganese separation is specifically performed by the following method:
s1, adding sodium hydroxide (namely liquid caustic soda) into the cobalt-manganese solution to remove iron ions in the cobalt-manganese solution, and then filtering to obtain a purified solution, wherein the temperature of the purified solution is 35 ℃;
s2, adding the purified solution into a closed reaction kettle, adding sulfuric acid, stirring and mixing uniformly, standing, introducing steam into the reaction kettle for heating the purified solution, increasing the pressure in the closed reaction kettle, and ensuring that the temperature in the reaction kettle is maintained at about 220 ℃; the pressure in the reaction kettle is maintained at about 0.3Mpa, and hydrothermal reaction is carried out in the environment; obtaining rough manganese sulfate crystals and supernatant after the hydrothermal reaction is finished;
s3, passing the supernatant in the S2 through a P204 extraction line to remove impurities, and obtaining P204 raffinate and P204 strip liquor; evaporating and concentrating the P204 strip liquor at 90 ℃ until the density of the concentrated liquor is 1.3 g/mL; subsequently, the concentrated solution was mixed into the purified solution in S1, and S2 was continued;
s4, carrying out P507 extraction on the P204 raffinate to obtain a cobalt chloride solution.
In this embodiment, on the premise of ensuring that the recovery rate of cobalt and manganese at least reaches 99%, the flow rate of the supernatant can be maintained at 155L/h-161L/h when passing through the P204 extraction line, which makes the whole process have high productivity.
Example 3
In the cobalt-manganese solution of the present embodiment, the cobalt concentration is 50g/L, and the manganese concentration is 80g/L, and the cobalt-manganese separation is specifically performed by the following method:
s1, adding sodium hydroxide (namely liquid caustic soda) into the cobalt-manganese solution to remove iron ions in the cobalt-manganese solution, and then filtering to obtain a purified solution, wherein the temperature of the purified solution is 27 ℃;
s2, adding the purified solution into a closed reaction kettle, adding sulfuric acid, stirring and mixing uniformly, standing, introducing steam into the reaction kettle for heating the purified solution, increasing the pressure in the closed reaction kettle, and ensuring that the temperature in the reaction kettle is maintained at about 210 ℃; the pressure in the reaction kettle is maintained at about 0.2Mpa, and hydrothermal reaction is carried out in the environment; after the hydrothermal reaction is finished, obtaining rough manganese sulfate crystals and supernatant;
s3, passing the supernatant in the S2 through a P204 extraction line to remove impurities, and obtaining P204 raffinate and P204 strip liquor; evaporating and concentrating the P204 strip liquor at 85 ℃ until the density of the concentrated liquor is 1.25 g/mL; subsequently, the concentrated solution was mixed into the purified solution in S1, and S2 was continued;
s4, carrying out P507 extraction on the P204 raffinate to obtain a cobalt chloride solution.
In this embodiment, on the premise of ensuring that the recovery rate of cobalt and manganese at least reaches 99%, the flow rate of the supernatant can be maintained at 157L/h-165L/h when passing through the P204 extraction line, which results in higher productivity of the whole process.
The reaction parameters of the above examples 1 to 3 are specifically shown in Table 1.
Table 1 reaction parameters for examples 1-3
Comparative example 1
In the cobalt-manganese solution of the present embodiment, the cobalt concentration is 50g/L, and the manganese concentration is 80g/L, and the cobalt-manganese separation is specifically performed by the following method:
s1, adding sodium hydroxide (namely liquid caustic soda) into the cobalt-manganese solution to remove iron ions in the cobalt-manganese solution, and then filtering to obtain a purified solution, wherein the temperature of the purified solution is 27 ℃;
s2, removing impurities from the purified solution by passing through a P204 extraction line to obtain P204 raffinate and P204 strip liquor; evaporating and concentrating the P204 strip liquor at 85 ℃ until the density of the concentrated liquor is 1.25 g/mL; subsequently, the concentrated solution was mixed into the purified solution in S1, and S2 was continued;
s4, carrying out P507 extraction on the P204 raffinate to obtain a cobalt chloride solution.
The comparative example differs from the examples in that: whether to remove manganese from cobalt manganese solution before passing through P204 extraction line.
In the specific production process, no matter what production recovery process is adopted, the recovery rate of cobalt and manganese is ensured to reach 99%, so on this basis, how to improve the productivity becomes a core problem in industrial production.
When the method of the present comparative example is used, it is found that when the purified solution passes through the P204 extraction line, the flow rate of the purified solution is gradually reduced until stable as time goes on, and the flow rate after the stabilization can be maintained at 97L/h to 103L/h, which results in that the productivity of the method of comparative example 1 is lower, i.e., the productivity of the production method of example is 20% to 30% higher, compared to the productivity of comparative example 1 in the same production time as that of examples 1 to 3.
This is also demonstrated from another aspect that the method of the present embodiment has low treatment cost, and effectively solves the problem of high treatment cost of the existing cobalt-manganese separation method.
In the three embodiments, the cobalt-manganese solution is primarily purified, iron contained in the cobalt-manganese solution is primarily removed, and the purified solution is obtained, so that the phenomenon that a large amount of iron ions are crystallized during later crystallization, and more impurities are contained in manganese sulfate crystals is avoided;
because high concentrations of manganese are detrimental to the operation of the P204 extraction line; therefore, sulfuric acid is added into the purified solution, hydrothermal reaction is carried out by regulating and controlling pressure and temperature, and then the purified solution is stood at high temperature and high pressure for crystallization, so that manganese sulfate in the purified solution is fully crystallized, and thus, manganese is primarily separated out, the smooth operation of a P204 extraction line at the later stage is ensured, the productivity is further improved, and the production cost is reduced;
then, in order to sufficiently separate cobalt and manganese, the P204 strip liquor is evaporated and concentrated to obtain concentrated liquor; mixing the concentrated solution into the purified solution in S1, and continuing to S2, so that manganese ions can be sufficiently crystallized and separated;
and finally, performing P507 extraction on the P204 raffinate to obtain a cobalt chloride solution containing less impurities.
In summary, the invention separates manganese in the cobalt-manganese solution before the P204 extraction and impurity removal, which can ensure the smooth operation of the P204 extraction line in the later period, thereby improving the productivity and reducing the production cost.
The above description is only for the preferred 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 (6)
1. A method for preparing cobalt chloride by using a high-pressure crystallization method is characterized by comprising the following steps:
s1, primarily purifying the cobalt-manganese solution to obtain a purified solution;
s2, carrying out hydrothermal reaction on the purified solution under the condition of pressurization, and controlling the temperature to be 200-220 ℃ to obtain a crude manganese sulfate crystal and a supernatant;
s3, removing impurities from the supernatant by a P204 extraction line to obtain a P204 raffinate and a P204 strip liquor; evaporating and concentrating the P204 strip liquor to obtain concentrated liquor; mixing the concentrated solution into the purified solution in the S1, continuing the S2;
s4, carrying out P507 extraction on the P204 raffinate to obtain a cobalt chloride solution.
2. The method for preparing cobalt chloride by using a high pressure crystallization method according to claim 1, wherein the concentration of manganese in the cobalt-manganese solution in S1 is more than 30g/L, and the concentration of cobalt is 40-60 g/L.
3. The method for preparing cobalt chloride using high pressure crystallization according to claim 1, wherein the temperature of the purified solution is 20 ℃ to 35 ℃.
4. The method for preparing cobalt chloride by using a high pressure crystallization method according to claim 1, wherein the specific steps in S1 are as follows: and adding sodium hydroxide into the cobalt-manganese solution, and filtering to obtain a purified solution.
5. The method for preparing cobalt chloride by using high pressure crystallization method according to claim 1, wherein the specific process of S2 is as follows:
carrying out hydrothermal reaction on the purified solution at the pressure of 0.1-0.3 Mpa and the temperature of 200-220 ℃; and after the hydrothermal reaction is finished, obtaining rough manganese sulfate crystals and a supernatant.
6. The method for preparing cobalt chloride by high pressure crystallization according to any one of claims 1 to 5, wherein the temperature of the evaporation concentration in S3 is 80 ℃ to 90 ℃, and the concentration is carried out until the density of the concentrated solution is 1.2g/mL to 1.3 g/mL.
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| CN103496746A (en) * | 2013-08-27 | 2014-01-08 | 中南大学 | Method for preparing cell-grade high-purity manganese sulfate by low-grade manganese ore high-pressure crystallization |
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| CN103496746A (en) * | 2013-08-27 | 2014-01-08 | 中南大学 | Method for preparing cell-grade high-purity manganese sulfate by low-grade manganese ore high-pressure crystallization |
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| 张向宇编, 国防工业出版社 * |
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