CN112662878A - Method for preparing high-purity cobalt sulfate from electrolytic manganese sulfide slag - Google Patents
Method for preparing high-purity cobalt sulfate from electrolytic manganese sulfide slag Download PDFInfo
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Abstract
The invention discloses a method for preparing high-purity cobalt sulfate from electrolytic manganese sulfide slag, which comprises the following steps: (1) crushing and sieving; (2) oxidizing and leaching; (3) removing calcium; (4) removing manganese; (5) synchronously extracting cobalt and nickel; (6) and (3) recovering cobalt: taking the cobalt-nickel-rich organic phase, adding dilute sulfuric acid for back extraction to obtain a cobalt-nickel sulfuric acid solution and a neodecanoic acid organic phase; separating cobalt-nickel sulfuric acid solution, adding a fourth organic extracting agent formed by mixing saponified P507-Cyanex301 and sulfonated kerosene for extraction to obtain a cobalt-rich organic phase and a nickel sulfate solution; separating out a cobalt-rich organic phase, adding sulfuric acid for back extraction to obtain a high-purity cobalt sulfate-rich solution and a P507-Cyanex301 organic phase; (7) and (3) preparing high-purity cobalt sulfate. The method has the advantages of simplicity, feasibility, realization of cobalt sulfate leaching, avoidance of generation of hydrogen sulfide gas, use of an iron precipitation process and a method for removing calcium and magnesium ions by fluoride ion precipitation.
Description
Technical Field
The invention belongs to the field of wet metallurgy and clean metallurgy, and particularly relates to a method for preparing high-purity cobalt sulfate from electrolytic manganese sulfide slag.
Background
Cobalt is an important industrial raw material, and the electrolytic method is a common method for producing manganese, and comprises the following basic steps: leaching manganese ore to obtain manganese-containing leachate, then neutralizing and deironing, removing heavy metals by using a vulcanizing agent, finally electrolyzing to obtain electrolytic manganese, and precipitating a large amount of cobalt in the form of cobalt sulfide in the heavy metals removal by using the vulcanizing agent to cause cobalt loss, so that the recovery of the cobalt in the electrolytic manganese is of great significance. At present, sulfuric acid is adopted to directly leach electrolytic manganese sulfide slag, toxic hydrogen sulfide gas is easily generated, a leached liquid is subjected to iron removal by a neutralization iron precipitation method, the process operation flow is increased, calcium and magnesium ions are removed by a fluoride ion precipitation method after iron removal, a site is needed for depositing and accumulating fluoride, and secondary pollution is easily caused to the fluoride. We have now found patents relating to the preparation of cobalt sulphate from waste residues, including the following:
1. application No.: 201710213431.X, invention name: the method for enriching and recovering nickel and cobalt from manganese-containing waste comprises the following steps: pulping manganese-containing waste sulfide slag, adding acid liquor into the sulfide slag for stirring and filtering, repulping the obtained acid-washed waste slag, adding an oxidant and the acid liquor, controlling the reaction temperature and the reaction pH value, carrying out a first stirring reaction, adding alkali liquor to increase the pH value after the reaction is completed, carrying out a second stirring reaction, filtering, adjusting the pH value to acidity in the obtained nickel-cobalt mixed solution, adding sulfide for precipitation again, and filtering to obtain nickel-cobalt-containing enriched slag and a supernatant which can be returned to a manganese sulfate production line. The method has the advantages of effective utilization of waste resources, low cost, good impurity removal effect, small environmental risk and the like. The invention has the following disadvantages: after a complex process flow is adopted, only cobalt-nickel-containing enriched slag is obtained, and a leaching-extraction process is further adopted for utilizing the cobalt-nickel-containing enriched slag, so that the process is complicated.
2. Application No.: 201610737450.8, title of the invention: the method comprises the steps of removing iron and aluminum in a leaching solution by an oxidation precipitation method, extracting copper, extracting zinc, and finally synchronously extracting nickel, cobalt and manganese by tributyl phosphate and saponified neodecanoic acid. The invention has the following disadvantages: after the manganese-cobalt-nickel-containing waste residue is leached, an oxidation precipitation method is further adopted to remove impurities from iron and aluminum.
Disclosure of Invention
The invention aims to solve the technical problems and provide a simple and feasible method for preparing high-purity cobalt sulfate from electrolytic manganese sulfide slag, which can realize leaching of cobalt sulfate, avoid generation of hydrogen sulfide gas, use of an iron precipitation process and use of a method for removing calcium and magnesium ions by fluoride ion precipitation.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for preparing high-purity cobalt sulfate from electrolytic manganese sulfide slag comprises the following steps:
(1) crushing and sieving: crushing and sieving pyrolusite and electrolytic manganese sulfide slag;
(2) oxidizing and leaching: uniformly mixing the sieved pyrolusite and electrolytic manganese sulfide slag according to a certain slag ratio, adding dilute sulfuric acid, stirring and heating, introducing oxygen, leaching for a certain time, and filtering to obtain filter residue and leachate; the leachate contains calcium, magnesium, manganese, cobalt and nickel;
(3) calcium removal: adding a first organic extracting agent formed by mixing saponified P204 and sulfonated kerosene into the leachate for extraction to obtain a calcium-loaded organic phase and a manganese-rich cobalt-nickel-magnesium solution;
(4) removing manganese: adding a second organic extracting agent formed by mixing saponified P204 and sulfonated kerosene into the manganese-rich cobalt-nickel-magnesium solution for extraction to obtain a manganese-loaded organic phase and a cobalt-nickel-magnesium-rich solution;
(5) synchronous extraction of cobalt and nickel: adding a third organic extracting agent formed by mixing saponified neodecanoic acid and sulfonated kerosene into the cobalt-nickel-rich magnesium solution for extraction to obtain a cobalt-nickel-rich organic phase and a magnesium-containing water phase;
(6) and (3) recovering cobalt: taking the cobalt-nickel-rich organic phase, adding dilute sulfuric acid for back extraction to obtain a cobalt-nickel sulfuric acid solution and a neodecanoic acid organic phase; separating cobalt-nickel sulfuric acid solution, adding a fourth organic extracting agent formed by mixing saponified P507-Cyanex301 and sulfonated kerosene for extraction to obtain a cobalt-rich organic phase and a nickel sulfate solution; separating out a cobalt-rich organic phase, adding sulfuric acid for back extraction to obtain a high-purity cobalt sulfate-rich solution and a P507-Cyanex301 organic phase;
(7) preparing high-purity cobalt sulfate: separating out high-purity cobalt sulfate-rich solution, evaporating, concentrating, crystallizing and centrifuging to obtain the high-purity cobalt sulfate.
As a further technical scheme, the crushing and sieving are carried out, and the number of sample separation meshes is 200-400 meshes.
As a further technical scheme, in the step (2), the mass ratio of the pyrolusite to the electrolytic sulfide slag is 1.0: 1-2.0: 1, the mass concentration of the dilute sulfuric acid is 50 g/L-200 g/L, the liquid-solid ratio of the reaction is 5: 1-10: 1, the leaching temperature is 50-90 ℃, the oxygen pressure is 0.1-1 MPa, the leaching time is 60-180 min, and the end point pH of the leaching is 3.0-4.0.
As a further technical scheme, in the step (3), before the first organic extracting agent is added for extraction, the pH of the leaching solution is adjusted to 0.5-2.0; the first organic extracting agent is prepared by mixing P204 and sulfonated kerosene according to the volume fraction of P204 being 10-30%, then adding sodium hydroxide for saponification, wherein the saponification rate is 10-50%, and the O/A ratio of an organic phase to a water phase is 1: 1-3: 1.
As a further technical scheme, in the step (4), before the second organic extracting agent is added for extraction, the pH value of the manganese-cobalt-nickel-magnesium-rich solution is adjusted to 2.5-4.5; the second organic extracting agent is prepared by mixing P204 and sulfonated kerosene according to the volume fraction of P204 being 10-40%, then saponifying with sodium hydroxide, wherein the saponification rate is 10-50%, and the O/A ratio of an organic phase to a water phase is 1: 1-3: 1.
As a further technical scheme, in the step (5), before the third organic extracting agent is added for extraction, the pH value of the cobalt-nickel-magnesium-rich solution is adjusted to 2.0-5.0; the third organic extracting agent is prepared by mixing neodecanoic acid and sulfonated kerosene according to the volume fraction of the neodecanoic acid being 10-40%, then saponifying with sodium hydroxide, wherein the saponification rate is 10-50%, and the ratio of organic phase to aqueous phase is 1: 1-3: 1.
As a further technical scheme, the pH of the separated cobalt-nickel sulfuric acid solution is adjusted to 3.0-4.5; the fourth organic extracting agent is prepared by mixing a P507-Cyanex301 synergistic extraction system with sulfonated kerosene according to the volume fraction of 10-40%, wherein the mass ratio of P507 to Cyanex301 is 1: 4-2: 1, then saponifying with sodium hydroxide, the saponification rate is 10-50%, and the O/A ratio of an organic phase to a water phase is 1: 1-3: 1.
As a further technical scheme, the calcium-loaded organic phase is subjected to back extraction by using sulfuric acid with the concentration of 100 g/L-200 g/L, the O/A ratio of the organic phase to the water phase is 1: 5-1: 10, a P204 organic phase is obtained, and the organic phase is returned to the step (3) for recycling.
As a further technical scheme, the manganese-loaded organic phase is subjected to back extraction by using sulfuric acid with the concentration of 100 g/L-200 g/L, the ratio of O/A of the organic phase to the aqueous phase is 1: 5-1: 10, a P204 organic phase and a manganese sulfate solution are obtained, and the P204 organic phase is returned to the step (4) for recycling.
As a further technical scheme, the organic phase of the neodecanoic acid is returned to the step (5) for cyclic utilization; and (3) separating a cobalt-rich organic phase, adding sulfuric acid into the cobalt-rich organic phase for back extraction, wherein the concentration of the sulfuric acid is 100 g/L-200 g/L, the ratio of the organic phase to the aqueous phase is 1: 5-1: 10, and returning the P507-Cyanex301 organic phase to the step (6) for recycling the cobalt-nickel sulfuric acid solution.
Compared with the prior art, the invention has the beneficial effects that:
1. the method has simple and feasible process, realizes the leaching of the cobalt sulfide, and has the basic principle of oxidative leaching as follows:
4MnO2+2CoS+4O2+4H2SO4＝4MnSO4+2CoSO4+4H2O；
4MnO2+2NiS+4O2+4H2SO4＝4MnSO4+2NiSO4+4H2O；
4MnO2+2MnS+2O2+4H2SO4＝6MnSO4+4H2O；
in the step, the negative divalent sulfur is oxidized into sulfate radicals, so that the generation of hydrogen sulfide is avoided, and the safety is improved.
2. The method adopts dilute sulfuric acid as a leaching agent, oxygen is introduced to reduce the acid dosage and improve the leaching rate, the end point pH value is 3.0-4.0 by controlling the acid dosage, a small amount of leached iron is oxidized to form ferric hydroxide to be directly precipitated, and the subsequent complex iron precipitation process is avoided. The invention adopts the oxidation leaching end point control to ensure that the iron is directly precipitated in the leaching process, thereby simplifying the process flow
3. The invention adopts the first organic extractant formed by mixing the saponified P204 and the sulfonated kerosene to extract and remove calcium, thereby avoiding secondary pollution of fluoride caused by a fluoride ion precipitation method, and the extractant can be recycled, thereby reducing the production cost.
4. The invention adopts a P507-Cyanex301 synergistic extraction system to separate cobalt and nickel, thereby improving the separation effect and reducing the extraction stages.
Drawings
FIG. 1 is a process flow diagram of a method for preparing high-purity cobalt sulfate from electrolytic manganese sulfide slag according to the invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited to the scope of the examples.
The materials involved in the examples are all available from the factory or on the market.
A method for preparing high-purity cobalt sulfate from electrolytic manganese sulfide slag comprises the following steps:
(1) crushing and sieving: crushing and sieving pyrolusite and electrolytic manganese sulfide slag; crushing and sieving, wherein the adopted sample separation sieve mesh number is 200-400 meshes.
(2) Oxidizing and leaching: uniformly mixing the sieved pyrolusite and electrolytic manganese sulfide slag according to a certain slag ratio, adding dilute sulfuric acid, stirring and heating, introducing oxygen, leaching for a certain time, and filtering to obtain filter residue and leachate; the mass ratio of the pyrolusite to the electrolytic sulfide slag is 1.0: 1-2.0: 1, the mass concentration of the dilute sulfuric acid is 50-200 g/L, the liquid-solid ratio of the reaction is 5: 1-10: 1, the leaching temperature is 50-90 ℃, the oxygen pressure is 0.1-1 MPa, the leaching time is 60-180 min, and the end point pH of the leaching is 3.0-4.0.
(3) Calcium removal: adjusting the pH value of the leachate to 0.5-2.0, and then adding a first organic extracting agent formed by mixing saponified P204 and sulfonated kerosene into the leachate for extraction to obtain a calcium-loaded organic phase and a manganese-rich cobalt-nickel-magnesium solution; the first organic extracting agent is prepared by mixing P204 and sulfonated kerosene according to the volume fraction of P204 being 10-30%, then adding sodium hydroxide for saponification, wherein the saponification rate is 10-50%, and the O/A ratio of an organic phase to a water phase is 1: 1-3: 1; and (3) carrying out back extraction on the calcium-loaded organic phase by adopting sulfuric acid with the concentration of 100 g/L-200 g/L, comparing the organic phase with the water phase by the ratio of O/A (1: 5-1: 10) to obtain a P204 organic phase, and returning to the step (3) for recycling.
(4) Removing manganese: taking the manganese-cobalt-nickel-magnesium-rich solution, and adjusting the pH value to 2.5-4.5; adding a second organic extracting agent formed by mixing saponified P204 and sulfonated kerosene for extraction to obtain a manganese-loaded organic phase and a cobalt-nickel-magnesium-rich solution; the second organic extracting agent is prepared by mixing P204 and sulfonated kerosene according to the volume fraction of P204 being 10-40%, then saponifying with sodium hydroxide, wherein the saponification rate is 10-50%, and the O/A ratio of an organic phase to a water phase is 1: 1-3: 1; and (3) carrying out back extraction on the manganese-loaded organic phase by adopting sulfuric acid with the concentration of 100-200 g/L, comparing the organic phase with the water phase by the ratio of O/A (1: 5-1: 10) to obtain a P204 organic phase and a manganese sulfate solution, and returning the P204 organic phase to the step (4) for recycling.
(5) Synchronous extraction of cobalt and nickel: taking the cobalt-nickel-magnesium-rich solution, and adjusting the pH value to 2.0-5.0; adding a third organic extracting agent formed by mixing saponified neodecanoic acid and sulfonated kerosene for extraction to obtain a cobalt-nickel-rich organic phase and a magnesium-containing aqueous phase; the third organic extracting agent is prepared by mixing neodecanoic acid and sulfonated kerosene according to the volume fraction of the neodecanoic acid being 10-40%, then saponifying with sodium hydroxide, wherein the saponification rate is 10-50%, and the O/A ratio of the organic phase to the aqueous phase is 1: 1-3: 1.
(6) And (3) recovering cobalt: taking the cobalt-nickel-rich organic phase, adding dilute sulfuric acid for back extraction to obtain a cobalt-nickel sulfuric acid solution and a neodecanoic acid organic phase; separating a cobalt-nickel sulfuric acid solution, adjusting the pH value of the cobalt-nickel sulfuric acid solution to 3.0-4.5, adding a fourth organic extracting agent formed by mixing saponified P507-Cyanex301 and sulfonated kerosene for extraction, and obtaining a cobalt-rich organic phase and a nickel sulfate solution; the fourth organic extractant is formed by mixing a P507-Cyanex301 synergistic extraction system with sulfonated kerosene according to the volume fraction of 10-40%, wherein the mass ratio of P507 to Cyanex301 is 1: 4-2: 1, then saponifying with sodium hydroxide, the saponification rate is 10-50%, and the O/A ratio of an organic phase to a water phase is 1: 1-3: 1. Separating out a cobalt-rich organic phase, adding sulfuric acid for back extraction to obtain a high-purity cobalt sulfate-rich solution and a P507-Cyanex301 organic phase;
(7) preparing high-purity cobalt sulfate: separating out high-purity cobalt sulfate-rich solution, evaporating, concentrating, crystallizing and centrifuging to obtain the high-purity cobalt sulfate.
The component detection of the electrolytic manganese sulfide slag adopted by the invention is shown in the table 1:
TABLE 1
| wMn/％ | wCo/％ | wNi/％ | wCa/％ | wMg/％ | wFe/％ |
| 11.71 | 1.21 | 0.97 | 1.92 | 1.26 | 1.28 |
The following examples were carried out in accordance with the above procedure for preparing high purity cobalt sulfate.
Example 1:
crushing and sieving 10g of electrolytic manganese sulfide slag and 17g of pyrolusite to 200 meshes, uniformly mixing, adding 90g/L sulfuric acid solution according to a liquid-solid ratio of 10:1, introducing oxygen of 0.1Mpa, heating to 90 ℃, mechanically stirring, leaching for 180min, measuring the end point pH of 3.0, filtering, adjusting the pH of the leachate to 0.5 by using dilute sulfuric acid, removing calcium by using 30% of P204+ 70% of sulfonated kerosene according to a ratio of O/A to 1:1, wherein the saponification rate of an extracting agent is 20%, extracting for 10min, separating in a separating funnel to obtain a calcium-removed rich manganese cobalt nickel magnesium solution, adjusting the pH of the calcium-rich manganese cobalt nickel magnesium solution to 3.5 by using sodium hydroxide, removing manganese from the manganese-rich cobalt nickel magnesium solution by using 30% of P204+ 70% of sulfonated kerosene according to a ratio of O/A to 2:1, extracting for 10min to obtain a manganese-loaded organic phase, and back extracting the manganese-loaded organic phase by using 200g/L of sulfuric acid according to a ratio of O/A to 10:1, obtaining a high-purity manganese sulfate solution, and then concentrating, crystallizing and centrifuging the manganese sulfate solution to obtain high-purity manganese sulfate crystals; adjusting the pH of the cobalt-nickel-magnesium-rich solution to 2.0 by using dilute sulfuric acid, synchronously extracting nickel by using 30% neodecanoic acid and 70% sulfonated kerosene according to a ratio of O/A to 2:1, wherein the saponification rate of an extracting agent is 30%, extracting for 10min, separating in a separating funnel to obtain a cobalt-nickel-rich organic phase and a magnesium-containing aqueous phase, performing back extraction on the cobalt-nickel-rich organic phase by using 200g/L sulfuric acid according to a ratio of O/A to 1:10 to obtain a cobalt-nickel sulfuric acid solution, adjusting the pH of the cobalt-nickel sulfuric acid solution to 4.0 by using sodium hydroxide, performing extraction on the cobalt-nickel sulfuric acid solution by using 30% (P507+ Cyanex301) and 70% sulfonated kerosene according to a ratio of O/A to 2:1 to obtain a cobalt-nickel sulfuric acid solution, wherein the ratio of P507 to Cyanex301 is 1:2, the saponification rate of the extracting agent is 30%, extracting for 10min to obtain a cobalt-rich organic phase and a nickel sulfate solution, performing back extraction on the cobalt-rich organic phase by using 200g/L sulfuric acid according to a ratio of, obtaining high-purity cobalt sulfate solution, concentrating, crystallizing and centrifuging the cobalt sulfate solution to obtain high-purity cobalt sulfate crystal. The measured recovery rate of manganese is 91.2 percent, and the purity of high-purity manganese sulfate is 99.95 percent; the recovery rate of cobalt is 90.2%, and the purity of high-purity cobalt sulfate is 99.15%.
Example 2:
crushing and sieving 10g of electrolytic manganese sulfide slag and 17g of pyrolusite to 200 meshes, uniformly mixing, adding 90g/L sulfuric acid solution according to a liquid-solid ratio of 10:1, introducing oxygen of 0.2Mpa, heating to 90 ℃, mechanically stirring, leaching for 180min, measuring the end point pH to be 3.0, filtering, adjusting the pH of the leachate to be 1 by using dilute sulfuric acid, removing calcium by using 20% P204+ 80% sulfonated kerosene according to a ratio of O/A to 1:1, wherein the saponification rate of an extracting agent is 30%, extracting for 10min, separating liquid in a separating funnel to obtain a calcium-removed cobalt-nickel-magnesium-rich solution, adjusting the pH of a water phase to be 4.0 by using dilute sulfuric acid, removing manganese by using 30% P204+ 70% sulfonated kerosene according to a ratio of O/A to 2.5:1, wherein the saponification rate of the extracting agent is 30%, extracting for 10min to obtain a manganese-loaded organic phase, back extracting the manganese-loaded organic phase by using 150g/L sulfuric acid according to a ratio of O/A to be 1:8, obtaining a high-purity manganese sulfate solution, and then concentrating, crystallizing and centrifuging the manganese sulfate solution to obtain high-purity manganese sulfate crystals; adjusting the pH of the cobalt-nickel-magnesium-rich solution to 2.5 by using dilute sulfuric acid, synchronously extracting nickel by using 35% neodecanoic acid and 65% sulfonated kerosene according to a ratio of O/A to 2:1, wherein the saponification rate of an extracting agent is 30%, extracting for 10min, separating in a separating funnel to obtain a cobalt-nickel-rich organic phase and a magnesium-containing aqueous phase, performing back extraction on the cobalt-nickel-rich organic phase by using 200g/L sulfuric acid according to a ratio of O/A to 1:10 to obtain a cobalt-nickel sulfuric acid solution, adjusting the pH of the cobalt-nickel sulfuric acid solution to 4.0 by using sodium hydroxide, performing extraction on the cobalt-nickel sulfuric acid solution by using 30% (P507+ Cyanex301) and 70% sulfonated kerosene according to a ratio of O/A to 2:1 to obtain a cobalt-nickel sulfuric acid solution, wherein the ratio of P507 to Cyanex301 is 1:2, the saponification rate of the extracting agent is 30%, extracting for 10min to obtain a cobalt-rich organic phase and a nickel sulfate solution, performing back extraction on the cobalt-rich organic phase by using 200g/L sulfuric acid according to a ratio of, obtaining high-purity cobalt sulfate solution, concentrating, crystallizing and centrifuging the cobalt sulfate solution to obtain high-purity cobalt sulfate crystal. The measured recovery rate of manganese is 92.2 percent, and the purity of high-purity manganese sulfate is 99.93 percent; the recovery rate of cobalt is 91.2%, and the purity of high-purity cobalt sulfate is 99.45%.
Example 3:
crushing and sieving 10g of electrolytic manganese sulfide slag and 15g of pyrolusite to 400 meshes, uniformly mixing, adding 90g/L sulfuric acid solution according to a liquid-solid ratio of 9:1, introducing oxygen of 0.4Mpa, heating to 90 ℃, mechanically stirring, leaching for 180min, measuring the end point pH value of 3.0, filtering, adjusting the pH value of the leachate to 1.5 by using dilute sulfuric acid, removing calcium by using 20% of P204+ 80% of sulfonated kerosene according to a ratio of O/A to 1:1, wherein the saponification rate of an extracting agent is 40%, extracting for 10min, separating liquid in a separating funnel to obtain a calcium-removed manganese-rich cobalt-nickel-magnesium solution, adjusting the pH value of a water phase to 3.0 by using dilute sulfuric acid, removing manganese by using 30% of P204+ 70% of sulfonated kerosene according to a ratio of O/A to 2.5:1, wherein the saponification rate of the extracting agent is 30%, extracting for 10min to obtain a manganese-loaded organic phase, then extracting the manganese-loaded organic phase by using 150g/L sulfuric acid according to a ratio of O/A to 1:8, obtaining high-purity manganese sulfate solution, and then concentrating, crystallizing and centrifuging the manganese sulfate solution to obtain high-purity manganese sulfate crystals. Adjusting the pH of the cobalt-nickel-magnesium-rich solution to 3.0 by using dilute sulfuric acid, synchronously extracting nickel by using 35% neodecanoic acid and 65% sulfonated kerosene according to a ratio of O/A to 2.5:1, wherein the saponification rate of an extracting agent is 35%, extracting for 10min, separating in a separating funnel to obtain a cobalt-nickel-rich organic phase and a magnesium-containing aqueous phase, performing back extraction on the cobalt-nickel-rich organic phase by using 200g/L sulfuric acid according to a ratio of O/A to 1:8 to obtain a cobalt-nickel sulfuric acid solution, adjusting the pH of the cobalt-nickel sulfuric acid solution to 3.5 by using sodium hydroxide, performing extraction on the cobalt-nickel sulfuric acid solution by using 20% (P507+ Cyanex301) and 80% sulfonated kerosene according to a ratio of O/A to 2.5:1 to obtain a cobalt-nickel sulfuric acid solution, wherein the ratio of P507 to Cyanex301 is 1:2, the saponification rate of the extracting agent is 40%, extracting for 10min to obtain a cobalt-nickel-rich organic phase and a nickel sulfate solution, and performing back extraction on the cobalt-rich organic phase by using 200g/L sulfuric acid, obtaining high-purity cobalt sulfate solution, concentrating, crystallizing and centrifuging the cobalt sulfate solution to obtain high-purity cobalt sulfate crystal. The measured recovery rate of manganese is 90.2 percent, and the purity of the high-purity manganese sulfate is 99.43 percent; the recovery rate of cobalt is 89.2%, and the purity of high-purity cobalt sulfate is 99.05%.
Example 4:
crushing and sieving 10g of electrolytic manganese sulfide slag and 15g of pyrolusite to 400 meshes, uniformly mixing, adding 90g/L sulfuric acid solution according to a liquid-solid ratio of 9:1, introducing oxygen of 0.2Mpa, heating to 85 ℃, mechanically stirring, leaching for 180min, measuring the end point pH value of 3.0, filtering, adjusting the pH value of the leachate to 1.0 by using dilute sulfuric acid, removing calcium by using 20% P204+ 80% sulfonated kerosene according to a ratio of O/A to 1:1, wherein the saponification rate of an extracting agent is 40%, extracting for 10min, separating liquid in a separating funnel to obtain a calcium-removed manganese-rich cobalt-nickel-magnesium solution, adjusting the pH value of a water phase to 3.0 by using dilute sulfuric acid, removing manganese by using 30% P204+ 70% sulfonated kerosene according to a ratio of O/A to 2.0:1, wherein the saponification rate of the extracting agent is 30%, extracting for 10min to obtain a manganese-loaded organic phase, then extracting the manganese-loaded organic phase by using 150g/L sulfuric acid according to a ratio of O/A to 1:8, obtaining high-purity manganese sulfate solution, and then concentrating, crystallizing and centrifuging the manganese sulfate solution to obtain high-purity manganese sulfate crystals. Adjusting the pH of the cobalt-nickel-magnesium-rich solution to 3.0 by using dilute sulfuric acid, synchronously extracting nickel by using 35% neodecanoic acid and 65% sulfonated kerosene according to a ratio of O/A to 2.5:1, wherein the saponification rate of an extracting agent is 35%, extracting for 10min, separating in a separating funnel to obtain a cobalt-nickel-rich organic phase and a magnesium-containing aqueous phase, performing back extraction on the cobalt-nickel-rich organic phase by using 200g/L sulfuric acid according to a ratio of O/A to 1:7 to obtain a cobalt-nickel sulfuric acid solution, adjusting the pH of the cobalt-nickel sulfuric acid solution to 3.5 by using sodium hydroxide, performing extraction on the cobalt-nickel sulfuric acid solution by using 20% (P507+ Cyanex301) and 80% sulfonated kerosene according to a ratio of O/A to 2.5:1 to obtain a cobalt-nickel sulfuric acid solution, wherein the ratio of P507 to Cyanex301 is 1:3, the saponification rate of the extracting agent is 40%, extracting for 10min to obtain a cobalt-nickel-rich organic phase and a nickel sulfate solution, and performing back extraction on the cobalt-rich organic phase by using 200g/L sulfuric acid, obtaining high-purity cobalt sulfate solution, concentrating, crystallizing and centrifuging the cobalt sulfate solution to obtain high-purity cobalt sulfate crystal. The measured recovery rate of the manganese is 88.9 percent, and the purity of the high-purity manganese sulfate is 99.03 percent; the recovery rate of the cobalt is 89.5 percent, and the purity of the high-purity cobalt sulfate is 98.01 percent; the recovery rate of nickel is 85.06%, and the purity of high-purity nickel sulfate is 96.09%.
Example 5:
crushing and sieving 10g of electrolytic manganese sulfide slag and 15g of pyrolusite to 400 meshes, uniformly mixing, adding 90g/L sulfuric acid solution according to a liquid-solid ratio of 9:1, introducing oxygen of 0.3Mpa, heating to 85 ℃, mechanically stirring, leaching for 180min, measuring the end point pH value of 3.0, filtering, adjusting the pH value of the leachate to 1.0 by using dilute sulfuric acid, removing calcium by using 20% of P204+ 80% of sulfonated kerosene according to a ratio of O/A to 1:1, wherein the saponification rate of an extracting agent is 40%, extracting for 10min, separating liquid in a separating funnel to obtain a calcium-removed manganese-rich cobalt-nickel-magnesium solution, adjusting the pH value of a water phase to 3.5 by using dilute sulfuric acid, removing manganese by using 30% of P204+ 70% of sulfonated kerosene according to a ratio of O/A to 2.0:1, wherein the saponification rate of the extracting agent is 35%, extracting for 10min to obtain a manganese-loaded organic phase, extracting the manganese-loaded organic phase by using 150g/L sulfuric acid according to a ratio of O/A to 1:7, obtaining high-purity manganese sulfate solution, and then concentrating, crystallizing and centrifuging the manganese sulfate solution to obtain high-purity manganese sulfate crystals. Adjusting the pH of the cobalt-nickel-magnesium-rich solution to 3.0 by using dilute sulfuric acid, synchronously extracting nickel by using 35% neodecanoic acid and 65% sulfonated kerosene according to a ratio of O/A to 2.5:1, wherein the saponification rate of an extracting agent is 35%, extracting for 10min, separating in a separating funnel to obtain a cobalt-nickel-rich organic phase and a magnesium-containing aqueous phase, performing back extraction on the cobalt-nickel-rich organic phase by using 200g/L sulfuric acid according to a ratio of O/A to 1:7 to obtain a cobalt-nickel sulfuric acid solution, adjusting the pH of the cobalt-nickel sulfuric acid solution to 3.5 by using sodium hydroxide, performing extraction on the cobalt-nickel sulfuric acid solution by using 20% (P507+ Cyanex301) and 80% sulfonated kerosene according to a ratio of O/A to 2.0:1 to obtain a cobalt-nickel sulfuric acid solution, wherein the ratio of P507 to Cyanex301 is 1:1, the saponification rate of the extracting agent is 40%, extracting for 10min to obtain a cobalt-nickel-rich organic phase and a nickel sulfate solution, and performing back extraction on the cobalt-rich organic phase by using 200g/L sulfuric acid according, obtaining high-purity cobalt sulfate solution, concentrating, crystallizing and centrifuging the cobalt sulfate solution to obtain high-purity cobalt sulfate crystal. The recovery rate of the manganese is 89.1 percent, and the purity of the high-purity manganese sulfate is 97.01 percent; the recovery rate of cobalt is 89.6%, and the purity of high-purity cobalt sulfate is 98.17%.
Example 6:
crushing and sieving 10g of electrolytic manganese sulfide slag and 10g of pyrolusite to 400 meshes, uniformly mixing, adding 200g/L sulfuric acid solution according to a liquid-solid ratio of 5:1, introducing oxygen gas under 1Mpa, heating to 50 ℃, mechanically stirring, leaching for 160min, measuring the end point pH value to be 4.0, filtering, adjusting the pH value of the leachate to be 2.0 by using dilute sulfuric acid, removing calcium by using 20% P204+ 80% sulfonated kerosene according to a ratio of O/A to 3:1, wherein the saponification rate of an extracting agent is 10%, extracting for 10min, separating liquid in a separating funnel to obtain a calcium-removed rich cobalt-nickel-magnesium solution, adjusting the pH value of a water phase to be 2.5 by using dilute sulfuric acid, recovering manganese by using 10% P204+ 90% sulfonated kerosene according to a ratio of O/A to 3:1, wherein the saponification rate of the extracting agent is 10%, extracting for 10min to obtain a manganese-loaded organic phase, then back extracting the manganese-loaded organic phase by using 100g/L sulfuric acid according to a ratio of O/A to be 1:5, obtaining high-purity manganese sulfate solution, and then concentrating, crystallizing and centrifuging the manganese sulfate solution to obtain high-purity manganese sulfate crystals. Adjusting the pH value of the cobalt-nickel-magnesium-rich solution to 5.0 by using sodium hydroxide, synchronously extracting nickel by using 10% neodecanoic acid and 90% sulfonated kerosene according to the ratio of O/A to 3:1, wherein the saponification rate of an extracting agent is 50%, extracting for 10min, separating liquid in a separating funnel to obtain a cobalt-nickel-rich organic phase and a magnesium-containing aqueous phase, performing back extraction on the cobalt-nickel-rich organic phase by using 200g/L sulfuric acid according to the ratio of O/A to 1:7 to obtain a cobalt-nickel sulfuric acid solution, adjusting the pH value of the cobalt-nickel sulfuric acid solution to 3.0 by using sodium hydroxide, performing extraction on the cobalt-nickel sulfuric acid solution by using 10% (P507+ Cyanex301) and 90% sulfonated kerosene according to the ratio of O/A to 3.0:1 to obtain a cobalt-nickel sulfuric acid solution, wherein the ratio of P507 to Cyanex301 is 1:4, the saponification rate of the extracting agent is 50%, extracting for 10min to obtain a cobalt-rich organic phase and a nickel sulfate solution, performing back extraction on the cobalt-nickel-rich organic phase by using 200g/L, obtaining high-purity cobalt sulfate solution, concentrating, crystallizing and centrifuging the cobalt sulfate solution to obtain high-purity cobalt sulfate crystal. The recovery rate of manganese is measured to be 85.1 percent, and the purity of the high-purity manganese sulfate is 97.82 percent; the recovery rate of cobalt is 88.3 percent, and the purity of the high-purity cobalt sulfate is 97.89 percent.
Example 7:
crushing and sieving 10g of electrolytic manganese sulfide slag and 20g of pyrolusite to 400 meshes, uniformly mixing, adding 50g/L of sulfuric acid solution according to a liquid-solid ratio of 10:1, introducing oxygen of 0.1Mpa, heating to 50 ℃, mechanically stirring, leaching for 60min, measuring the end point pH value to be 4.0, filtering, adjusting the pH value of the leaching solution to be 2.0 by using dilute sulfuric acid, removing calcium by using 20% P204+ 80% sulfonated kerosene according to a ratio of O/A to 1:1, wherein the saponification rate of an extracting agent is 50%, extracting for 10min, separating liquid in a separating funnel to obtain a calcium-removed manganese-rich cobalt-nickel-magnesium solution, adjusting the pH value of a water phase to be 4.5 by using dilute sulfuric acid, recovering manganese by using 30% P204+ 70% sulfonated kerosene according to a ratio of O/A to 1:1, wherein the saponification rate of the extracting agent is 50%, extracting for 10min to obtain a manganese-loaded organic phase, back extracting the manganese-loaded organic phase by using 100g/L of sulfuric acid according to a ratio of O/A to 1:5, obtaining high-purity manganese sulfate solution, and then concentrating, crystallizing and centrifuging the manganese sulfate solution to obtain high-purity manganese sulfate crystals. Adjusting the pH value of the cobalt-nickel-magnesium-rich solution to 5.0 by using sodium hydroxide, synchronously extracting nickel by using 40% neodecanoic acid and 60% sulfonated kerosene according to the ratio of O/A to 1:1, wherein the saponification rate of an extracting agent is 10%, extracting for 10min, separating liquid in a separating funnel to obtain a cobalt-nickel-rich organic phase and a magnesium-containing aqueous phase, performing back extraction on the cobalt-nickel-rich organic phase by using 200g/L sulfuric acid according to the ratio of O/A to 1:7 to obtain a cobalt-nickel sulfuric acid solution, adjusting the pH value of the cobalt-nickel sulfuric acid solution to 4.5 by using sodium hydroxide, performing extraction on the cobalt-nickel sulfuric acid solution by using 40% (P507+ Cyanex301) and 60% sulfonated kerosene according to the ratio of O/A to 1:1, wherein the ratio of P507 to Cyanex301 is 2:1, the saponification rate of the extracting agent is 10%, extracting for 10min to obtain a cobalt-nickel-rich organic phase and a nickel sulfate solution, performing back extraction on the cobalt-rich organic phase and the cobalt-nickel sulfate solution by using 200g/L sulfuric acid, obtaining high-purity cobalt sulfate solution, concentrating, crystallizing and centrifuging the cobalt sulfate solution to obtain high-purity cobalt sulfate crystal. The recovery rate of manganese is measured to be 84.2 percent, and the purity of the high-purity manganese sulfate is measured to be 98.16 percent; the recovery rate of cobalt is 84.21%, and the purity of high-purity cobalt sulfate is 95.24%.
The invention uses example 1 as an oxygen introduction comparative test:
example 1: crushing and sieving 10g of electrolytic manganese sulfide slag and 17g of pyrolusite to 200 meshes, uniformly mixing, adding 90g/L sulfuric acid solution according to the liquid-solid ratio of 10:1, introducing oxygen of 0.1Mpa, heating to 90 ℃, mechanically stirring, leaching for 180min, and measuring the end point pH to be 3.0.
Comparative example 1: crushing and sieving 10g of electrolytic manganese sulfide slag and 17g of pyrolusite to 200 meshes, uniformly mixing, adding 120g/L sulfuric acid solution according to the liquid-solid ratio of 10:1, heating to 90 ℃, mechanically stirring, and leaching for 180 min.
The results are shown in table 2:
TABLE 2
| Example 1 | Acidity (g/L) | Manganese leachingPercent ratio of | Cobalt leaching rate/%) | Nickel leaching rate/%) |
| 90 | 95.2 | 90.3 | 89.5 | |
| Comparative example 1 | Acidity (g/L) | Manganese leaching rate/% | Cobalt leaching rate/%) | Nickel leaching rate/%) |
| 120 | 83.1 | 79.1 | 78.4 |
As shown in Table 2, the acid dosage of example 1 is reduced by 30g/L, and the leaching rate of cobalt is improved by 11.2%, which shows that the acid dosage can be effectively reduced by introducing oxygen, and the leaching rate of cobalt can be improved.
The invention uses example 1 as a comparative test for the separation effect:
example 1: the method comprises the steps of preparing a cobalt-nickel sulfuric acid solution, adjusting the pH value of the cobalt-nickel sulfuric acid solution to be 4.0 by using sodium hydroxide, extracting the cobalt-nickel sulfuric acid solution by using 30% (P507+ Cyanex301) + 70% sulfonated kerosene according to the ratio of O/A to 2:1, wherein the ratio of P507 to Cyanex301 is 1:2, the saponification rate of an extracting agent is 30%, extracting for 10min to obtain a cobalt-rich organic phase and a nickel sulfate solution, performing back extraction on the cobalt-rich organic phase by using 200g/L sulfuric acid according to the ratio of O/A to 1:10 to obtain a high-purity cobalt sulfate solution, concentrating, crystallizing and centrifuging the cobalt sulfate solution to obtain the high-purity cobalt sulfate crystal. The recovery rate of cobalt is 90.2%, and the purity of high-purity cobalt sulfate is 99.15%. The extraction stage number is as follows: 2
Comparative example 2: taking the cobalt-nickel sulfuric acid solution in example 1, adjusting the pH of the cobalt-nickel sulfuric acid solution to 4.0 by using sodium hydroxide, extracting the cobalt-nickel sulfuric acid solution by using 30% of P507+ 70% of sulfonated kerosene according to the ratio of O/A to 2:1 with the saponification rate of an extracting agent of 30%, extracting for 10min to obtain a cobalt-rich organic phase and a nickel sulfate solution, then performing back extraction on the cobalt-rich organic phase by using 200g/L of sulfuric acid according to the ratio of O/A to 1:10 to obtain a high-purity cobalt sulfate solution, concentrating, crystallizing and centrifuging the cobalt sulfate solution to obtain high-purity cobalt sulfate crystals. The recovery rate of cobalt is 82.3 percent, the purity of high-purity cobalt sulfate is 85.2 percent, and the extraction stages are as follows: 4.
comparative example 3: the method comprises the steps of preparing a cobalt-nickel sulfuric acid solution, adjusting the pH value of the cobalt-nickel sulfuric acid solution to be 4.0 by using sodium hydroxide, extracting the cobalt-nickel sulfuric acid solution by using 30% Cyanex301 and 70% sulfonated kerosene according to the ratio of O/A to 2:1, extracting for 10min to obtain a cobalt-rich organic phase and a nickel sulfate solution, performing back extraction on the cobalt-rich organic phase by using 200g/L sulfuric acid according to the ratio of O/A to 1:10 to obtain a high-purity cobalt sulfate solution, concentrating, crystallizing and centrifuging the cobalt sulfate solution to obtain the high-purity cobalt sulfate crystal. The recovery rate of cobalt is 84.2%, the purity of high-purity cobalt sulfate is 90.34%, and the extraction grade number is as follows: 4.
by implementing the comparison invention, the P507-Cyanex301 synergistic extraction system has higher separation effect and fewer extraction stages.
The above-described embodiments are only specific examples for further explaining the object, technical solution and advantageous effects of the present invention in detail, and the present invention is not limited thereto. Any modification, equivalent replacement, improvement and the like made within the scope of the present disclosure are included in the protection scope of the present invention.
Claims (10)
1. A method for preparing high-purity cobalt sulfate from electrolytic manganese sulfide slag is characterized by comprising the following steps:
(1) crushing and sieving: crushing and sieving pyrolusite and electrolytic manganese sulfide slag;
(2) oxidizing and leaching: uniformly mixing the sieved pyrolusite and electrolytic manganese sulfide slag according to a certain slag ratio, adding dilute sulfuric acid, stirring and heating, introducing oxygen, leaching for a certain time, and filtering to obtain filter residue and leachate;
(3) calcium removal: adding a first organic extracting agent formed by mixing saponified P204 and sulfonated kerosene into the leachate for extraction to obtain a calcium-loaded organic phase and a manganese-rich cobalt-nickel-magnesium solution;
(4) removing manganese: adding a second organic extracting agent formed by mixing saponified P204 and sulfonated kerosene into the manganese-rich cobalt-nickel-magnesium solution for extraction to obtain a manganese-loaded organic phase and a cobalt-nickel-magnesium-rich solution;
(5) synchronous extraction of cobalt and nickel: adding a third organic extracting agent formed by mixing saponified neodecanoic acid and sulfonated kerosene into the cobalt-nickel-rich magnesium solution for extraction to obtain a cobalt-nickel-rich organic phase and a magnesium-containing water phase;
(6) and (3) recovering cobalt: taking the cobalt-nickel-rich organic phase, adding dilute sulfuric acid for back extraction to obtain a cobalt-nickel sulfuric acid solution and a neodecanoic acid organic phase; separating cobalt-nickel sulfuric acid solution, adding a fourth organic extracting agent formed by mixing saponified P507-Cyanex301 and sulfonated kerosene for extraction to obtain a cobalt-rich organic phase and a nickel sulfate solution; separating out a cobalt-rich organic phase, adding sulfuric acid for back extraction to obtain a high-purity cobalt sulfate-rich solution and a P507-Cyanex301 organic phase;
(7) preparing high-purity cobalt sulfate: separating out high-purity cobalt sulfate-rich solution, evaporating, concentrating, crystallizing and centrifuging to obtain the high-purity cobalt sulfate.
2. The method for preparing high-purity cobalt sulfate from electrolytic manganese sulfide slag according to claim 1, wherein the method comprises the following steps: and (4) crushing and sieving, wherein the adopted sample separation sieve mesh number is 200-400 meshes.
3. The method for preparing high-purity cobalt sulfate from electrolytic manganese sulfide slag according to claim 1, wherein the method comprises the following steps: in the step (2), the mass ratio of the pyrolusite to the electrolytic sulfide slag is 1.0: 1-2.0: 1, the mass concentration of the dilute sulfuric acid is 50-200 g/L, the liquid-solid ratio of the reaction is 5: 1-10: 1, the leaching temperature is 50-90 ℃, the oxygen pressure is 0.1-1 MPa, the leaching time is 60-180 min, and the end point pH of the leaching is 3.0-4.0.
4. The method for preparing high-purity cobalt sulfate from electrolytic manganese sulfide slag according to claim 1, wherein the method comprises the following steps: in the step (3), before the first organic extractant is added for extraction, the pH of the leaching solution is adjusted to 0.5-2.0; the first organic extracting agent is prepared by mixing P204 and sulfonated kerosene according to the volume fraction of P204 being 10-30%, then adding sodium hydroxide for saponification, wherein the saponification rate is 10-50%, and the O/A ratio of an organic phase to a water phase is =1: 1-3: 1.
5. The method for preparing high-purity cobalt sulfate from electrolytic manganese sulfide slag according to claim 1, wherein the method comprises the following steps: in the step (4), before adding a second organic extracting agent for extraction, the pH value of the manganese-cobalt-nickel-magnesium-rich solution is adjusted to 2.5-4.5; the second organic extracting agent is prepared by mixing P204 and sulfonated kerosene according to the volume fraction of P204 being 10-40%, then saponifying with sodium hydroxide, wherein the saponification rate is 10-50%, and the organic phase and the aqueous phase are compared with each other in an O/A =1: 1-3: 1 ratio.
6. The method for preparing high-purity cobalt sulfate from electrolytic manganese sulfide slag according to claim 1, wherein the method comprises the following steps: in the step (5), before the third organic extractant is added for extraction, the pH value of the cobalt-nickel-magnesium-rich solution is adjusted to 2.0-5.0; the third organic extracting agent is prepared by mixing neodecanoic acid and sulfonated kerosene according to the volume fraction of the neodecanoic acid being 10-40%, saponifying with sodium hydroxide, wherein the saponification rate is 10-50%, and the organic phase and the aqueous phase are compared with each other in terms of O/A =1: 1-3: 1.
7. The method for preparing high-purity cobalt sulfate from electrolytic manganese sulfide slag according to claim 1, wherein the method comprises the following steps: adjusting the pH of the separated cobalt nickel sulfuric acid solution to 3.0-4.5; the fourth organic extracting agent is prepared by mixing a P507-Cyanex301 synergistic extraction system and sulfonated kerosene according to the volume fraction of 10-40%, wherein the mass ratio of P507 to Cyanex301 is 1: 4-2: 1, then saponifying with sodium hydroxide is carried out, the saponification rate is 10-50%, and the organic phase and the aqueous phase are compared with each other with O/A =1: 1-3: 1.
8. The method for preparing high-purity cobalt sulfate from electrolytic manganese sulfide slag according to claim 1, wherein the method comprises the following steps: and (3) carrying out back extraction on the calcium-loaded organic phase by adopting sulfuric acid with the concentration of 100-200 g/L, and returning the organic phase to the step (3) for recycling, wherein the ratio of the organic phase to the water phase is O/A =1: 5-1: 10 to obtain a P204 organic phase.
9. The method for preparing high-purity cobalt sulfate from electrolytic manganese sulfide slag according to claim 1, wherein the method comprises the following steps: and (3) carrying out back extraction on the manganese-loaded organic phase by adopting sulfuric acid with the concentration of 100-200 g/L, wherein the ratio of the organic phase to the water phase is O/A =1: 5-1: 10 to obtain a P204 organic phase and a manganese sulfate solution, and returning the P204 organic phase to the step (4) for recycling.
10. The method for preparing high-purity cobalt sulfate from electrolytic manganese sulfide slag according to claim 1, wherein the method comprises the following steps: the organic phase of the neodecanoic acid is returned to the step (5) for cyclic utilization; and (3) separating a cobalt-rich organic phase, adding sulfuric acid into the cobalt-rich organic phase for back extraction, wherein the concentration of the sulfuric acid is 100-200 g/L, the ratio of the organic phase to the water phase is O/A =1: 5-1: 10, and the P507-Cyanex301 organic phase is returned to the step (6) for recycling the cobalt-nickel sulfuric acid solution.
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| CN113388743A (en) * | 2021-06-18 | 2021-09-14 | 国家电投集团黄河上游水电开发有限责任公司 | Method for selectively extracting cobalt and nickel from nickel sulfide concentrate |
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