CN111392777A - Calcium removing method for manganese sulfate solution - Google Patents
Calcium removing method for manganese sulfate solution Download PDFInfo
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- CN111392777A CN111392777A CN202010144995.4A CN202010144995A CN111392777A CN 111392777 A CN111392777 A CN 111392777A CN 202010144995 A CN202010144995 A CN 202010144995A CN 111392777 A CN111392777 A CN 111392777A
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Abstract
The invention provides a calcium removal method for a manganese sulfate solution. The manganese sulfate solution contains impurity calcium ions, wherein the method comprises the following steps: adjusting the pH value of the manganese sulfate solution to 0.5-3; mixing an extracting agent P204 and sulfonated kerosene to obtain an extracted organic phase, wherein the volume concentration of the extracting agent P204 is 5-30%; extracting the manganese sulfate solution by using an extraction organic phase to obtain a manganese sulfate calcium-removed raffinate and a calcium-manganese-rich organic phase; performing multi-stage back extraction on the calcium-manganese-rich organic phase to obtain a back extraction aqueous phase and a back extraction organic phase; and (4) evaporating and crystallizing the back extraction water phase to obtain a manganese sulfate solid. The process provided by the invention is used for removing calcium from the manganese sulfate solution, and has the advantages of environmental friendliness, low cost and high calcium ion removal rate, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of metal salt impurity removal, in particular to a calcium removal method for a manganese sulfate solution.
Background
In recent years, the demand of manganese and its compound products in the market has increased dramatically. The high-purity manganese sulfate is mainly used for smelting high-grade ferromanganese alloy and electrolytic manganese metal of manganese-copper alloy; the manganese borate, the manganese nitrate, the manganese chloride and the like are produced by taking high-purity manganese sulfate as a basic raw material; the manganese dioxide is used for providing raw materials for electrolytic or chemical manganese dioxide for high-grade batteries, high-purity manganese carbonate and trimanganese tetroxide for soft magnetic ferrite materials. Among a plurality of functions, the high-purity manganese sulfate is applied to the synthesis of a lithium nickel cobalt manganese oxide ternary positive electrode material and a lithium manganate positive electrode material, and is a research hotspot of the domestic manganese industry in recent years.
The impurity components in manganese ores in China are complex, when manganese ions are leached from the manganese ores, impurity ions such as iron, copper, lead, cobalt, aluminum, nickel, zinc, calcium and magnesium also enter the leachate, and most impurity metal ions are separated out along with manganese sulfate crystallization, so that the quality of manganese sulfate products is directly influenced. Of the impurity ions, the removal of calcium ions is the most difficult, and the research and preparation of the electronic-grade manganese sulfate mainly aims at removing the impurity calcium ions. However, the removal of calcium in manganese sulfate solution is a great problem in the world, and the extraction method is generally adopted in the current main calcium removal method, but the extraction rate of calcium ions is low in the current process, so that the calcium removal effect is not ideal.
Chinese patent 201710552066.5 discloses a method for preparing battery-grade manganese sulfate, which comprises removing calcium, magnesium and ions by chemical precipitation of manganese sulfate solution with fluoride, and then extracting with alkaline extractant. However, the method uses a large amount of chemical precipitator, adds excessive fluoride ions, corrodes equipment and pollutes the environment. Chinese patent CN104445424A discloses a method for preparing high-purity manganese sulfate from manganese-containing waste liquid, which is to prepare high-purity manganese sulfate by removing heavy metals from sulfides and extracting manganese from Cyanex 272. Chinese patent 201810313444.9 discloses a method for reducing calcium and magnesium ions in qualified electrolytic manganese liquor, which is to extract manganese sulfate containing impurities with manganese soap organic matter to obtain calcium and magnesium loaded organic phase and qualified electrolytic manganese liquor, however, the extracting agents adopted in the method are P507 and Cyanex272, which have high cost and poor reproducibility.
Therefore, there is a need to provide a process for removing calcium from manganese sulfate solution, which is environment-friendly, low in cost and good in calcium ion removal effect.
Disclosure of Invention
The invention mainly aims to provide a method for removing calcium from a manganese sulfate solution, and aims to solve the problem that the prior art cannot consider environment-friendly property, low cost and calcium ion removal rate when the calcium of the manganese sulfate solution is removed.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for removing calcium from a manganese sulfate solution containing calcium ions as an impurity, wherein the method comprises the steps of: adjusting the pH value of the manganese sulfate solution to 0.5-3; mixing an extracting agent P204 and sulfonated kerosene to obtain an extracted organic phase, wherein the volume concentration of the extracting agent P204 is 5-30%; extracting the manganese sulfate solution by using an extraction organic phase to obtain a manganese sulfate calcium-removed raffinate and a calcium-manganese-rich organic phase; performing multi-stage back extraction on the calcium-manganese-rich organic phase to obtain a back extraction aqueous phase and a back extraction organic phase; and (4) evaporating and crystallizing the back extraction water phase to obtain a manganese sulfate solid.
Further, in the step of extracting the manganese sulfate solution by adopting the extraction organic phase, the O/A ratio of the extraction organic phase to the manganese sulfate solution is (1-3): 1.
Further, in the step of extracting the manganese sulfate solution by adopting the extraction organic phase, a 10-30 grade countercurrent extraction mode is adopted.
Further, in the step of extracting the manganese sulfate solution by adopting an extraction organic phase, the extraction temperature is 25-45 ℃.
Further, in the step of carrying out multistage back extraction on the calcium-manganese-rich organic phase, the adopted back extractant is a sulfuric acid solution with the pH value of 0.5-2.
Further, in the step of carrying out multistage back extraction on the calcium-manganese-rich organic phase, the number of back extraction stages is 1-3.
Further, in the step of adjusting the pH value of the manganese sulfate solution, sulfuric acid is used as a pH adjusting agent.
Further, before the pH value of the manganese sulfate solution is adjusted, the method further comprises the step of adjusting the content of manganese ions in the manganese sulfate solution to 80-150 g/L.
Further, the step of subjecting the strip aqueous phase to evaporative crystallization comprises: carrying out primary evaporative crystallization on the back extraction water phase at the temperature of 60-100 ℃, and concentrating the volume of the back extraction water phase to 40-60% of the volume of the back extraction water phase to obtain primary concentrated solution; and carrying out secondary evaporative crystallization on the primary concentrated solution at the temperature of 40-60 ℃, concentrating the primary concentrated solution to 50-80% of the volume of the primary concentrated solution to obtain a secondary concentrated solution, filtering the secondary concentrated solution under a heat preservation state, and crystallizing to obtain a manganese sulfate solid.
Further, after obtaining the stripping organic phase, the method further comprises: the back extraction organic phase is used as part or all of the extraction organic phase for recycling.
The method for removing calcium from the manganese sulfate solution provided by the invention is characterized in that the pH value of the manganese sulfate solution is adjusted to 0.5-3, and an extracting agent P204 and sulfonated kerosene are mixed to obtain an extracted organic phase with a specific volume concentration. By adopting the extraction organic phase to extract the manganese sulfate solution, calcium ions and a part of manganese ions are extracted and loaded in the organic phase, and the rest part of manganese sulfate is remained in raffinate, and the purity of the part of manganese sulfate is higher. Secondly, after the calcium-manganese-rich organic phase is obtained, the method carries out multi-stage back extraction on the calcium-manganese-rich organic phase, so that calcium and manganese in the organic phase are further separated, calcium is left in the organic phase, and manganese enters a back extraction water phase. Finally, the invention further processes the back extraction water phase through evaporative crystallization, and finally separates calcium and manganese to obtain manganese sulfate solid with higher purity.
Because the invention adopts the extraction organic phase formed by the extractant P204 and the sulfonated kerosene, the P204 extractant is cheap and can be recycled, the production process is green and environment-friendly, has no pollution, low production and operation cost, and is easy to realize large-scale production. And the invention has better extraction and separation effects on impurity calcium ions in the extraction process by adjusting the process conditions of the proportion of the extractant P204 and the pH value of the manganese sulfate solution. And calcium ions are further removed by combining stripping and evaporative crystallization, so that the manganese sulfate solid with higher purity is obtained. In a word, the process provided by the invention is used for removing calcium from the manganese sulfate solution, and has the advantages of environmental friendliness, low cost and high calcium ion removal rate, and has wide application prospect. Meanwhile, the method can recover manganese sulfate as completely as possible, and the loss of manganese sulfate is small or even zero.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
Unless otherwise specified, the solutions in the present invention are all aqueous solutions.
As described in the background art, the prior art cannot consider the aspects of environmental friendliness, low cost, calcium ion removal rate and the like when removing calcium from a manganese sulfate solution.
In order to solve the problems, the invention provides a calcium removal method of a manganese sulfate solution, wherein the manganese sulfate solution contains impurity calcium ions, and the method comprises the following steps: adjusting the pH value of the manganese sulfate solution to 0.5-3; mixing an extracting agent P204 and sulfonated kerosene to obtain an extracted organic phase, wherein the volume concentration of the extracting agent P204 is 5-30%; extracting the manganese sulfate solution by using an extraction organic phase to obtain a manganese sulfate calcium-removed raffinate and a calcium-manganese-rich organic phase; performing multi-stage back extraction on the calcium-manganese-rich organic phase to obtain a back extraction aqueous phase and a back extraction organic phase; and (4) evaporating and crystallizing the back extraction water phase to obtain a manganese sulfate solid.
The method for removing calcium from the manganese sulfate solution provided by the invention is characterized in that the pH value of the manganese sulfate solution is adjusted to 0.5-3, and an extracting agent P204 and sulfonated kerosene are mixed to obtain an extracted organic phase with a specific volume concentration. By adopting the extraction organic phase to extract the manganese sulfate solution, calcium ions and a part of manganese ions are extracted and loaded in the organic phase, and the rest part of manganese sulfate is remained in raffinate, and the purity of the part of manganese sulfate is higher. Secondly, after the calcium-manganese-rich organic phase is obtained, the method carries out multi-stage back extraction on the calcium-manganese-rich organic phase, so that calcium and manganese in the organic phase are further separated, calcium is left in the organic phase, and manganese enters a back extraction water phase. Finally, the invention further processes the back extraction water phase through evaporative crystallization, and finally separates calcium and manganese to obtain manganese sulfate solid with higher purity.
Because the invention adopts the extraction organic phase formed by the extractant P204 and the sulfonated kerosene, the P204 extractant is cheap and can be recycled, the production process is green and environment-friendly, has no pollution, low production and operation cost, and is easy to realize large-scale production. And the invention has better extraction and separation effects on impurity calcium ions in the extraction process by adjusting the process conditions of the proportion of the extractant P204 and the pH value of the manganese sulfate solution. And calcium ions are further removed by combining stripping and evaporative crystallization, so that the manganese sulfate solid with higher purity is obtained. In a word, the process provided by the invention is used for removing calcium from the manganese sulfate solution, and has the advantages of environmental friendliness, low cost and high calcium ion removal rate, and has wide application prospect. Meanwhile, the method can recover manganese sulfate as completely as possible, and the loss of manganese sulfate is small or even zero.
By using the method, the calcium-removed raffinate of the manganese sulfate with high purity obtained in the extraction process and the manganese sulfate solid obtained after evaporation and crystallization can be used as high-purity manganese sulfate products, and liquid preparation or drying can be carried out according to the requirements of subsequent processes.
In a preferred embodiment, the volume concentration of P204 in the organic phase is 10-20%. This has a better effect when extracted with a manganese sulphate solution at the above mentioned pH.
In order to further improve the extraction separation effect on calcium ions and obtain high-purity manganese sulfate calcium-removed raffinate, in a preferred embodiment, in the step of extracting the manganese sulfate solution by using the extraction organic phase, the O/A ratio of the extraction organic phase to the manganese sulfate solution is (1-3): 1. More preferably, in the step of extracting the manganese sulfate solution by using the extraction organic phase, a 10-30-grade countercurrent extraction mode is adopted. Further preferably, in the step of extracting the manganese sulfate solution by adopting the extraction organic phase, the extraction temperature is 25-45 ℃.
After extraction, impurity calcium ions and part of manganese enter an extraction organic phase together, and in order to more fully separate calcium and manganese in the organic phase, in a preferred embodiment, a stripping agent is a sulfuric acid solution with the pH value of 0.5-2. More preferably, in the step of carrying out multistage back extraction on the calcium-manganese-rich organic phase, the number of back extraction stages is 1-3. So that the separation of calcium and manganese is more complete.
In order to avoid introducing other impurities, in a preferred embodiment, sulfuric acid is used as a pH regulator in the step of adjusting the pH value of the manganese sulfate solution, and more preferably, the method further comprises the step of adjusting the content of manganese ions in the manganese sulfate solution to 80-150 g/L before the pH value of the manganese sulfate solution is adjusted.
The purpose of the evaporative crystallization is to further separate and remove trace calcium ions in the manganese-rich strip aqueous phase, and in a preferred embodiment, the step of subjecting the strip aqueous phase to evaporative crystallization comprises: carrying out primary evaporative crystallization on the back extraction water phase at the temperature of 60-100 ℃, and concentrating the volume of the back extraction water phase to 40-60% of the volume of the back extraction water phase to obtain primary concentrated solution; and carrying out secondary evaporative crystallization on the primary concentrated solution at the temperature of 40-60 ℃, concentrating the primary concentrated solution to 50-80% of the volume of the primary concentrated solution to obtain a secondary concentrated solution, and filtering the secondary concentrated solution under the heat preservation state to obtain a manganese sulfate solid. By carrying out evaporation crystallization under the process, impurity calcium ions can be removed more slightly, and high-purity manganese sulfate solid is obtained.
In a preferred embodiment, after obtaining the stripping organic phase, the method further comprises: the back extraction organic phase is used as part or all of the extraction organic phase for recycling. This is favorable to further reduce the cost and improve the resource utilization rate.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
(1) And determining the actual content of each ion in the manganese sulfate solution through atomic absorption, wherein the content of manganese ions in the manganese sulfate solution is Mn80 g/L, the content of calcium ions in the manganese sulfate solution is 0.45 g/L, and the pH value of the manganese sulfate solution is adjusted to 2 by adopting sulfuric acid with the mass concentration of 93%.
(2) Preparing an extraction organic phase, wherein the extraction organic phase consists of an extractant P204 and sulfonated kerosene, and the volume fraction of P204 is 10%.
(3) And (3) mixing the manganese sulfate solution with the pH value adjusted in the step (1) with the extraction organic phase in the step (2) for multi-stage extraction, wherein the O/A ratio of the extraction organic phase to the manganese sulfate solution is 1.5:1, performing 30-stage countercurrent extraction at the extraction temperature of 30 ℃, and allowing calcium and a small amount of manganese in the manganese sulfate solution to enter the extraction organic phase to form a calcium-manganese-rich organic phase, wherein manganese ions can be retained in raffinate to obtain high-purity manganese sulfate calcium-removed raffinate, and the detection shows that the manganese sulfate in the raffinate is about 56 g/L, the content of calcium ions is 6ppm, and the content of calcium is lower than 1.5% (relative to the concentration of calcium ions in the original solution).
(4) And (3) carrying out back extraction on the calcium-manganese-rich organic phase in the step (3) by adopting sulfuric acid, wherein the pH of the back extraction sulfuric acid is 2, the O/A ratio of the calcium-manganese-rich organic phase to the sulfuric acid is 1:1, the number of the back extraction stages is 2, so that a back extraction water phase and a regenerated organic phase for reducing calcium are obtained, and the regenerated organic phase can be recycled to the step (2) for continuous use.
(5) And (4) carrying out two-stage concentration and evaporation on the back extraction water phase in the step (4): firstly, carrying out primary concentration at the temperature of 90 ℃, wherein the concentration is 50% of the volume of a back extraction water phase; then placing the mixture in a water bath kettle at 60 ℃ for secondary concentration, wherein the concentration is 60% of the volume of the primary concentrated solution. And then filtering the concentrated solution under the heat preservation state, and crystallizing to obtain the refined manganese sulfate. And then measuring the content of calcium in the manganese sulfate solution and the manganese sulfate solid treated by the previous step by adopting atomic absorption, and knowing that the removal rate of calcium ions reaches more than 98%.
Example 2
(1) The actual content of each ion in the manganese sulfate solution is determined through atomic absorption, the content of the manganese ions in the manganese sulfate solution is Mn80 g/L, the content of the calcium ions in the manganese sulfate solution is 0.45 g/L, and the pH value of the manganese sulfate solution is adjusted to 0.5 by adopting 93 percent sulfuric acid.
(2) Preparing an extraction organic phase, wherein the extraction organic phase consists of an extractant P204 and sulfonated kerosene, and the volume fraction of P204 is 30%.
(3) Mixing the manganese sulfate solution with the pH value adjusted in the step (1) with the extraction organic phase in the step (2) for multi-stage extraction, wherein the O/A ratio of the extraction organic phase to the manganese sulfate solution is 1.5:1, performing 30-stage countercurrent extraction at the extraction temperature of 30 ℃, and allowing calcium and a small amount of manganese in the manganese sulfate solution to enter the extraction organic phase to form a calcium-manganese-rich organic phase, while manganese ions are retained in raffinate to obtain high-purity manganese sulfate calcium-removed raffinate, wherein the calcium content in the raffinate is lower than 2% by detection.
(4) And (3) carrying out back extraction on the calcium-manganese-rich organic phase in the step (3) by adopting sulfuric acid, wherein the pH of the back extraction sulfuric acid is 2, the O/A ratio of the calcium-manganese-rich organic phase to the sulfuric acid is 1:1, the number of the back extraction stages is 2, so that a back extraction water phase and a regenerated organic phase for reducing calcium are obtained, and the regenerated organic phase can be recycled to the step (2) for continuous use.
(5) And (4) carrying out two-stage concentration and evaporation on the back extraction water phase in the step (4): firstly, carrying out primary concentration at the temperature of 90 ℃, wherein the concentration is 50% of the volume of a back extraction water phase; then placing the mixture in a water bath kettle at 60 ℃ for secondary concentration, wherein the concentration is 60% of the volume of the primary concentrated solution. And then filtering the concentrated solution under the heat preservation state, and crystallizing to obtain the refined manganese sulfate. And then measuring the content of calcium in the manganese sulfate solution and the manganese sulfate solid treated by the previous step by adopting atomic absorption, and knowing that the removal rate of calcium ions reaches more than 96%.
Example 3
(1) The actual content of each ion in the manganese sulfate solution is determined through atomic absorption, the content of the manganese ions in the manganese sulfate solution is Mn80 g/L, the content of the calcium ions in the manganese sulfate solution is 0.45 g/L, and the pH value of the manganese sulfate solution is adjusted to be 3 by adopting 93 percent sulfuric acid.
(2) Preparing an extraction organic phase, wherein the extraction organic phase consists of an extractant P204 and sulfonated kerosene, and the volume fraction of P204 is 5%.
(3) Mixing the manganese sulfate solution with the pH value adjusted in the step (1) with the extraction organic phase in the step (2) for multi-stage extraction, wherein the O/A ratio of the extraction organic phase to the manganese sulfate solution is 1.5:1, performing 30-stage countercurrent extraction at the extraction temperature of 30 ℃, and allowing calcium and a small amount of manganese in the manganese sulfate solution to enter the extraction organic phase to form a calcium-manganese-rich organic phase, while manganese ions are retained in raffinate to obtain high-purity manganese sulfate calcium-removed raffinate, wherein the calcium content in the raffinate is lower than 1.8% through detection.
(4) And (3) carrying out back extraction on the calcium-manganese-rich organic phase in the step (3) by adopting sulfuric acid, wherein the pH of the back extraction sulfuric acid is 2, the O/A ratio of the calcium-manganese-rich organic phase to the sulfuric acid is 1:1, the number of the back extraction stages is 2, so that a back extraction water phase and a regenerated organic phase for reducing calcium are obtained, and the regenerated organic phase can be recycled to the step (2) for continuous use.
(5) And (4) carrying out two-stage concentration and evaporation on the back extraction water phase in the step (4): firstly, carrying out primary concentration at the temperature of 90 ℃, wherein the concentration is 50% of the volume of a back extraction water phase; then placing the mixture in a water bath kettle at 60 ℃ for secondary concentration, wherein the concentration is 60% of the volume of the primary concentrated solution. And then filtering the concentrated solution under the heat preservation state, and crystallizing to obtain the refined manganese sulfate. And then measuring the content of calcium in the manganese sulfate solution and the manganese sulfate solid treated by the previous step by adopting atomic absorption, and knowing that the removal rate of calcium ions reaches more than 96.5 percent.
Example 4
(1) The actual content of each ion in the manganese sulfate solution is determined through atomic absorption, the content of the manganese ions in the manganese sulfate solution is Mn80 g/L, the content of the calcium ions in the manganese sulfate solution is 0.45 g/L, and the pH value of the manganese sulfate solution is adjusted to 2 by adopting 93 percent sulfuric acid.
(2) Preparing an extraction organic phase, wherein the extraction organic phase consists of an extractant P204 and sulfonated kerosene, and the volume fraction of P204 is 10%.
(3) Mixing the manganese sulfate solution with the pH value adjusted in the step (1) with the extraction organic phase in the step (2) for multi-stage extraction, wherein the O/A ratio of the extraction organic phase to the manganese sulfate solution is 3:1, performing 30-stage countercurrent extraction at the extraction temperature of 25 ℃, and allowing calcium and a small amount of manganese in the manganese sulfate solution to enter the extraction organic phase to form a calcium-manganese-rich organic phase, while manganese ions are retained in raffinate to obtain high-purity manganese sulfate calcium-removed raffinate, wherein the calcium content in the raffinate is lower than 1% by detection.
(4) And (3) carrying out back extraction on the calcium-manganese-rich organic phase in the step (3) by adopting sulfuric acid, wherein the pH of the back extraction sulfuric acid is 2, the O/A ratio of the calcium-manganese-rich organic phase to the sulfuric acid is 1:1, the number of the back extraction stages is 2, so that a back extraction water phase and a regenerated organic phase for reducing calcium are obtained, and the regenerated organic phase can be recycled to the step (2) for continuous use.
(5) And (4) carrying out two-stage concentration and evaporation on the back extraction water phase in the step (4): firstly, carrying out primary concentration at the temperature of 90 ℃ to 50% of the volume of a back extraction water phase; then placing the mixture in a water bath kettle at 60 ℃ for secondary concentration, wherein the concentration is 60% of the volume of the primary concentrated solution. And then filtering the concentrated solution under the heat preservation state, and crystallizing to obtain the refined manganese sulfate. And then measuring the content of calcium in the manganese sulfate solution and the manganese sulfate solid treated by the previous step by adopting atomic absorption, and knowing that the removal rate of calcium ions reaches more than 99%.
Example 5
(1) The actual content of each ion in the manganese sulfate solution is determined through atomic absorption, the content of the manganese ions in the manganese sulfate solution is Mn80 g/L, the content of the calcium ions in the manganese sulfate solution is 0.45 g/L, and the pH value of the manganese sulfate solution is adjusted to 2 by adopting 93 percent sulfuric acid.
(2) Preparing an extraction organic phase, wherein the extraction organic phase consists of an extractant P204 and sulfonated kerosene, and the volume fraction of P204 is 10%.
(3) Mixing the manganese sulfate solution with the pH value adjusted in the step (1) with the extraction organic phase in the step (2) for multi-stage extraction, wherein the O/A ratio of the extraction organic phase to the manganese sulfate solution is 1:1, performing 10-stage countercurrent extraction at the extraction temperature of 45 ℃, and allowing calcium and a small amount of manganese in the manganese sulfate solution to enter the extraction organic phase to form a calcium-manganese-rich organic phase, while manganese ions are retained in raffinate to obtain high-purity manganese sulfate calcium-removed raffinate, wherein the calcium content in the raffinate is lower than 2% by detection.
(4) And (3) carrying out back extraction on the calcium-manganese-rich organic phase in the step (3) by adopting sulfuric acid, wherein the pH of the back extraction sulfuric acid is 2, the O/A ratio of the calcium-manganese-rich organic phase to the sulfuric acid is 1:1, the number of the back extraction stages is 2, so that a back extraction water phase and a regenerated organic phase for reducing calcium are obtained, and the regenerated organic phase can be recycled to the step (2) for continuous use.
(5) And (4) carrying out two-stage concentration and evaporation on the back extraction water phase in the step (4): firstly, carrying out primary concentration at the temperature of 100 ℃, wherein the concentration is 60% of the volume of a back extraction water phase; then placing the mixture in a water bath kettle at 40 ℃ for secondary concentration, wherein the concentration is 50% of the volume of the primary concentrated solution. And then filtering the concentrated solution under the heat preservation state, and crystallizing to obtain the refined manganese sulfate. And then measuring the content of calcium in the manganese sulfate solution and the manganese sulfate solid treated by the previous step by adopting atomic absorption, and knowing that the removal rate of calcium ions reaches more than 96%.
Example 6
(1) The actual content of each ion in the manganese sulfate solution is determined through atomic absorption, the content of the manganese ions in the manganese sulfate solution is Mn80 g/L, the content of the calcium ions in the manganese sulfate solution is 0.45 g/L, and the pH value of the manganese sulfate solution is adjusted to 2 by adopting 93 percent sulfuric acid.
(2) Preparing an extraction organic phase, wherein the extraction organic phase consists of an extractant P204 and sulfonated kerosene, and the volume fraction of P204 is 10%.
(3) Mixing the manganese sulfate solution with the pH value adjusted in the step (1) with the extraction organic phase in the step (2) for multi-stage extraction, wherein the O/A ratio of the extraction organic phase to the manganese sulfate solution is 0.5:1, adopting 8-stage countercurrent extraction, the extraction temperature is 20 ℃, calcium and a small amount of manganese in the manganese sulfate solution enter the extraction organic phase to form a calcium-manganese-rich organic phase, manganese ions can be remained in raffinate, high-purity manganese sulfate calcium-removed raffinate is obtained, and the calcium content in the raffinate is about 40% through detection.
(4) And (3) carrying out back extraction on the calcium-manganese-rich organic phase in the step (3) by adopting sulfuric acid, wherein the pH of the back extraction sulfuric acid is 2, the O/A ratio of the calcium-manganese-rich organic phase to the sulfuric acid is 1:1, the number of the back extraction stages is 2, so that a back extraction water phase and a regenerated organic phase for reducing calcium are obtained, and the regenerated organic phase can be recycled to the step (2) for continuous use.
(5) And (4) carrying out two-stage concentration and evaporation on the back extraction water phase in the step (4): firstly, carrying out primary concentration at the temperature of 90 ℃ to 50% of the volume of a back extraction water phase; then placing the mixture in a water bath kettle at 60 ℃ for secondary concentration, wherein the concentration is 60% of the volume of the primary concentrated solution. And then filtering the concentrated solution under the heat preservation state, and crystallizing to obtain the refined manganese sulfate. Then, the content of calcium in the manganese sulfate solution and the manganese sulfate solid treated by the above steps is measured by adopting atomic absorption, and the removal rate of calcium ions is about 82%.
Example 7
(1) The actual content of each ion in the manganese sulfate solution is determined through atomic absorption, the content of the manganese ions in the manganese sulfate solution is Mn80 g/L, the content of the calcium ions in the manganese sulfate solution is 0.45 g/L, and the pH value of the manganese sulfate solution is adjusted to 2 by adopting 93 percent sulfuric acid.
(2) Preparing an extraction organic phase, wherein the extraction organic phase consists of an extractant P204 and sulfonated kerosene, and the volume fraction of P204 is 10%.
(3) Mixing the manganese sulfate solution with the pH value adjusted in the step (1) with the extraction organic phase in the step (2) for multi-stage extraction, wherein the O/A ratio of the extraction organic phase to the manganese sulfate solution is 1.5:1, performing 30-stage countercurrent extraction at 25 ℃, and allowing calcium and a small amount of manganese in the manganese sulfate solution to enter the extraction organic phase to form a calcium-manganese-rich organic phase, while manganese ions are retained in raffinate to obtain high-purity manganese sulfate calcium-removed raffinate, wherein the calcium content in the raffinate is detected to be about 2%.
(4) And (3) carrying out back extraction on the calcium-manganese-rich organic phase in the step (3) by adopting sulfuric acid, wherein the pH of the back extraction sulfuric acid is 2, the O/A ratio of the calcium-manganese-rich organic phase to the sulfuric acid is 1:1, the number of the back extraction stages is 3, so that a back extraction water phase and a regenerated organic phase for reducing calcium are obtained, and the regenerated organic phase can be recycled to the step (2) for continuous use.
(5) And (4) carrying out two-stage concentration and evaporation on the back extraction water phase in the step (4): firstly, carrying out primary concentration at the temperature of 90 ℃ to 50% of the volume of a back extraction water phase; then placing the mixture in a water bath kettle at 60 ℃ for secondary concentration, wherein the concentration is 60% of the volume of the primary concentrated solution. And then filtering the concentrated solution under the heat preservation state, and crystallizing to obtain the refined manganese sulfate. Then measuring the content of calcium in the manganese sulfate solution and the manganese sulfate solid treated by the previous step by adopting atomic absorption, and knowing that the removal rate of calcium ions is about 98 percent
Example 8
(1) The actual content of each ion in the manganese sulfate solution is determined through atomic absorption, the content of the manganese ions in the manganese sulfate solution is Mn80 g/L, the content of the calcium ions in the manganese sulfate solution is 0.45 g/L, and the pH value of the manganese sulfate solution is adjusted to 2 by adopting 93 percent sulfuric acid.
(2) Preparing an extraction organic phase, wherein the extraction organic phase consists of an extractant P204 and sulfonated kerosene, and the volume fraction of P204 is 10%.
(3) Mixing the manganese sulfate solution with the pH value adjusted in the step (1) with the extraction organic phase in the step (2) for multi-stage extraction, wherein the O/A ratio of the extraction organic phase to the manganese sulfate solution is 0.5:1, adopting 8-stage countercurrent extraction, the extraction temperature is 20 ℃, calcium and a small amount of manganese in the manganese sulfate solution enter the extraction organic phase to form a calcium-manganese-rich organic phase, manganese ions can be remained in raffinate, high-purity manganese sulfate calcium-removed raffinate is obtained, and the calcium content in the raffinate is detected to be about 1.8%.
(4) And (3) carrying out back extraction on the calcium-manganese-rich organic phase in the step (3) by adopting sulfuric acid, wherein the pH of the back extraction sulfuric acid is 0.5, the O/A ratio of the calcium-manganese-rich organic phase to the sulfuric acid is 1.5:1, the number of the back extraction stages is 1, so that a back extraction water phase and a regenerated organic phase for reducing calcium are obtained, and the regenerated organic phase can be recycled to the step (2) for continuous use.
(5) And (4) carrying out two-stage concentration and evaporation on the back extraction water phase in the step (4): firstly, carrying out primary concentration at the temperature of 90 ℃ to 50% of the volume of a back extraction water phase; then placing the mixture in a water bath kettle at 60 ℃ for secondary concentration, wherein the concentration is 60% of the volume of the primary concentrated solution. And filtering the concentrated solution under the heat preservation state, and crystallizing to obtain the refined manganese sulfate. Then measuring the content of calcium in the manganese sulfate solution and the manganese sulfate solid treated by the previous step by adopting atomic absorption, and knowing that the removal rate of calcium ions is about 98 percent
Example 9
(1) The actual content of each ion in the manganese sulfate solution is determined through atomic absorption, the content of the manganese ions in the manganese sulfate solution is Mn120 g/L, the content of the calcium ions in the manganese sulfate solution is 0.4 g/L, and the pH value of the manganese sulfate solution is adjusted to 1.8 by adopting 93% sulfuric acid.
(2) Preparing an extraction organic phase, wherein the extraction organic phase consists of an extractant P204 and sulfonated kerosene, and the volume fraction of P204 is 10%.
(3) Mixing the manganese sulfate solution with the pH value adjusted in the step (1) with the extraction organic phase in the step (2) for multi-stage extraction, wherein the O/A ratio of the extraction organic phase to the manganese sulfate solution is 1.5:1, performing 30-stage countercurrent extraction at the extraction temperature of 30 ℃, and allowing calcium and a small amount of manganese in the manganese sulfate solution to enter the extraction organic phase to form a calcium-manganese-rich organic phase, while manganese ions are retained in raffinate to obtain high-purity manganese sulfate calcium-removed raffinate, wherein the calcium content in the raffinate is lower than 2% by detection.
(4) And (3) carrying out back extraction on the calcium-manganese-rich organic phase in the step (3) by adopting sulfuric acid, wherein the pH of the back extraction sulfuric acid is 1, the O/A ratio of the calcium-manganese-rich organic phase to the sulfuric acid is 1:1, the number of the back extraction stages is 3, so that a back extraction water phase and a regenerated organic phase for reducing calcium are obtained, and the regenerated organic phase can be recycled to the step (2) for continuous use.
(5) And (4) carrying out two-stage concentration and evaporation on the back extraction water phase in the step (4): firstly, carrying out primary concentration at the temperature of 90 ℃ to 50% of the volume of a back extraction water phase; then placing the mixture in a water bath kettle at 60 ℃ for secondary concentration, wherein the concentration is 60% of the volume of the primary concentrated solution. And then filtering the concentrated solution under the heat preservation state, and crystallizing to obtain the refined manganese sulfate. And then measuring the content of calcium in the manganese sulfate solution and the manganese sulfate solid treated by the previous step by adopting atomic absorption, and knowing that the removal rate of calcium ions reaches more than 98%.
Comparative example 1
(1) The actual content of each ion in the manganese sulfate solution is determined through atomic absorption, the content of the manganese ions in the manganese sulfate solution is Mn80 g/L, the content of the calcium ions in the manganese sulfate solution is 0.45 g/L, and the pH value of the manganese sulfate solution is adjusted to 3.5 by adopting 93 percent sulfuric acid.
(2) Preparing an extraction organic phase, wherein the extraction organic phase consists of an extractant P204 and sulfonated kerosene, and the volume fraction of P204 is 40%.
(3) Mixing the manganese sulfate solution with the pH value adjusted in the step (1) with the extraction organic phase in the step (2) for multi-stage extraction, wherein the O/A ratio of the extraction organic phase to the manganese sulfate solution is 1.5:1, performing 30-stage countercurrent extraction at the extraction temperature of 30 ℃, and allowing calcium and a small amount of manganese in the manganese sulfate solution to enter the extraction organic phase to form a calcium-manganese-rich organic phase, while manganese ions are retained in raffinate to obtain high-purity manganese sulfate calcium-removed raffinate, wherein the calcium content in the raffinate is about 46% by detection.
(4) And (3) carrying out back extraction on the calcium-manganese-rich organic phase in the step (3) by adopting sulfuric acid, wherein the pH of the back extraction sulfuric acid is 2, the O/A ratio of the calcium-manganese-rich organic phase to the sulfuric acid is 1:1, the number of the back extraction stages is 2, so that a back extraction water phase and a regenerated organic phase for reducing calcium are obtained, and the regenerated organic phase can be recycled to the step (2) for continuous use.
(5) And (4) carrying out two-stage concentration and evaporation on the back extraction water phase in the step (4): firstly, carrying out primary concentration at the temperature of 90 ℃, wherein the concentration degree is 50%; then placing the mixture in a water bath kettle at 60 ℃ for secondary concentration. And then filtering the concentrated solution under the heat preservation state, and crystallizing to obtain the refined manganese sulfate. Then, the content of calcium in the manganese sulfate solution and the manganese sulfate solid treated by the above steps is measured by adopting atomic absorption, and the removal rate of calcium ions is about 62 percent.
Comparative example 2
(1) The actual content of each ion in the manganese sulfate solution is determined through atomic absorption, the content of the manganese ions in the manganese sulfate solution is Mn120 g/L, the content of calcium ions in the manganese sulfate solution is 0.4 g/L, and the pH value of the manganese sulfate solution is adjusted to 4 by adopting 60% sulfuric acid.
(2) Preparing an extraction organic phase, wherein the extraction organic phase consists of an extractant P204 and sulfonated kerosene, and the volume fraction of P204 is 35%.
(3) Mixing the manganese sulfate solution with the pH value adjusted in the step (1) with the extraction organic phase in the step (2) for multi-stage extraction, wherein the O/A ratio of the extraction organic phase to the manganese sulfate solution is 1:1, performing 20-stage countercurrent extraction at the extraction temperature of 20 ℃, and allowing calcium and a small amount of manganese in the manganese sulfate solution to enter the extraction organic phase to form a calcium-manganese-rich organic phase, while manganese ions are retained in raffinate to obtain high-purity manganese sulfate calcium-removed raffinate, wherein the calcium content in the raffinate is about 38% by detection.
(4) And (3) carrying out back extraction on the calcium-manganese-rich organic phase in the step (3) by adopting sulfuric acid, wherein the pH of the back extraction sulfuric acid is 2, the O/A ratio of the calcium-manganese-rich organic phase to the sulfuric acid is 1:1, the number of the back extraction stages is 2, so that a back extraction water phase and a regenerated organic phase for reducing calcium are obtained, and the regenerated organic phase can be recycled to the step (2) for continuous use.
(5) And (4) carrying out two-stage concentration and evaporation on the back extraction water phase in the step (4): firstly, carrying out primary concentration at the temperature of 90 ℃, wherein the concentration is 80% of the volume of a back extraction water phase; then placing the mixture in a water bath kettle at 60 ℃ for secondary concentration, wherein the concentration is 60% of the volume of the primary concentrated solution. And then filtering the concentrated solution under the heat preservation state, and crystallizing to obtain the refined manganese sulfate. Then, the content of calcium in the manganese sulfate solution and the manganese sulfate solid treated by the above steps is measured by adopting atomic absorption, and the removal rate of calcium ions is about 69 percent.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The method for removing calcium from a manganese sulfate solution, which contains impurity calcium ions, is characterized by comprising the following steps:
adjusting the pH value of the manganese sulfate solution to 0.5-3;
mixing an extracting agent P204 and sulfonated kerosene to obtain an extracted organic phase, wherein the volume concentration of the extracting agent P204 is 5-30%;
extracting the manganese sulfate solution by using the extraction organic phase to obtain a manganese sulfate calcium-removed raffinate and a calcium-manganese-rich organic phase;
performing multi-stage back extraction on the calcium-manganese-rich organic phase to obtain a back extraction aqueous phase and a back extraction organic phase;
and (4) evaporating and crystallizing the back extraction water phase to obtain a manganese sulfate solid.
2. The method as claimed in claim 1, wherein in the step of extracting the manganese sulfate solution with the organic extraction phase, the O/A ratio of the organic extraction phase to the manganese sulfate solution is (1-3): 1.
3. The method as claimed in claim 2, wherein in the step of extracting the manganese sulfate solution by using the extracted organic phase, a 10-30-stage countercurrent extraction mode is adopted.
4. The method as claimed in claim 2 or 3, wherein in the step of extracting the manganese sulfate solution by using the extracted organic phase, the extraction temperature is 25-45 ℃.
5. The method according to any one of claims 1 to 4, wherein in the step of performing multistage stripping on the calcium-manganese-rich organic phase, a stripping agent is adopted as a sulfuric acid solution with a pH value of 0.5-2.
6. The method according to claim 5, wherein the step of performing multistage stripping on the calcium-manganese-rich organic phase comprises 1-3 stages of stripping.
7. The method according to any one of claims 1 to 6, wherein in the step of adjusting the pH value of the manganese sulfate solution, sulfuric acid is used as a pH adjusting agent.
8. The method according to any one of claims 1 to 6, wherein the method further comprises the step of adjusting the manganese ion content of the manganese sulfate solution to 80-150 g/L before adjusting the pH value of the manganese sulfate solution.
9. The process according to any one of claims 1 to 6, wherein the step of subjecting the stripped aqueous phase to evaporative crystallization comprises:
carrying out primary evaporative crystallization on the back extraction water phase at the temperature of 60-100 ℃, and concentrating the volume of the back extraction water phase to 40-60% of the volume of the back extraction water phase to obtain primary concentrated solution;
and carrying out secondary evaporative crystallization on the primary concentrated solution at the temperature of 40-60 ℃, concentrating the primary concentrated solution to 50-80% of the volume of the primary concentrated solution to obtain a secondary concentrated solution, filtering the secondary concentrated solution under a heat preservation state, and crystallizing to obtain the manganese sulfate solid.
10. The process according to any one of claims 1 to 6, characterized in that after obtaining the stripped organic phase, the process further comprises: and recycling the back extraction organic phase as part or all of the extraction organic phase.
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