CN110983054B - Method for separating and recovering cobalt and nickel from manganese sulfate solution - Google Patents
Method for separating and recovering cobalt and nickel from manganese sulfate solution Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C22B23/00—Obtaining nickel or cobalt
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- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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Abstract
The invention discloses a method for separating and recovering cobalt and nickel from a manganese sulfate solution, which comprises the following steps: adding a mixed solution of ferrous sulfate and 30% of hydrogen peroxide aqueous solution in a molar ratio of 1:0.8-1.2 into a manganese sulfate solution, removing phosphorus and iron, then removing calcium and magnesium by using sodium fluoride, adding sodium dimethyl sulfamate to enable cobalt and nickel and other impurities to form a precipitate together, processing the precipitate by using ion exchange resin, enriching the cobalt and nickel, and finally performing oxidation reaction on the precipitate by using sodium nitrate to finally obtain the separated and recovered cobalt and nickel. The method can improve the leaching recovery rate of cobalt and nickel, the leaching recovery rate of cobalt is as high as 98.23%, and the leaching recovery rate of nickel is as high as 98.88%.
Description
Technical Field
The invention relates to the technical field of chemical materials, in particular to a method for separating and recovering cobalt and nickel from a manganese sulfate solution.
Background
The electrolytic process is one of the processes for obtaining manganese metal, and the basic steps are that firstly, manganese ore is used as raw material, after being crushed, sulfuric acid is added to prepare manganese-containing leaching solution, namely manganese sulfate solution, and then the manganese sulfate solution is subjected to impurity removal treatment and is used as electrolyte to be electrolyzed to obtain manganese metal. In the production of electrolytic manganese metal, cobalt and nickel contained in the raw material manganese ore have great influence on the production process of electrolytic manganese and are harmful elements which must be removed in the production process of electrolytic manganese. At present, in the electrolytic manganese industry, a flocculation precipitation method is mostly adopted for removing cobalt and nickel impurities, namely, a flocculating agent is added into a manganese sulfate solution to flocculate and precipitate the impurities in the solution, but the method is only suitable for primary purification of the solution containing a large amount of impurity ions, the purification effect is not thorough, and the cobalt and nickel cannot be well separated and recovered.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for separating and recovering cobalt and nickel from a manganese sulfate solution, which can effectively solve the problem of poor effect of separating and recovering cobalt and nickel in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:
a method for separating and recovering cobalt and nickel from a manganese sulfate solution comprises the following steps:
(1) adding a mixed solution of ferrous sulfate and 30% of hydrogen peroxide aqueous solution in a molar ratio of 1:0.8-1.2 into a manganese sulfate solution, reacting at room temperature for 10-20min, adding concentrated ammonia water under stirring to adjust the pH value of the solution to 4-5, stirring at room temperature until no precipitate is generated, standing, and filtering to obtain a first filtrate; wherein the molar ratio of iron ions in the ferrous sulfate to phosphorus in the manganese sulfate solution is 1-1.5: 1;
(2) adjusting the pH value of the first filtrate to 5-5.5, adding sodium fluoride to make the concentration of the first filtrate to be 4-6g/L, reacting at 90-100 ℃ until no precipitate is generated, and filtering to obtain a second filtrate;
(3) adding sodium dimethyl sulfamate into the filtrate II until no precipitate is generated, and filtering to obtain filter residue;
(4) dissolving the filter residue obtained in the step (3) in dilute sulfuric acid to enable the pH value of the solution to be 3-3.5, then entering an ion exchanger filled with WP-2 cation acidic resin for ion exchange reaction, controlling the sample injection amount to be 22-25 times/h of the volume of the resin, stopping sample injection after the exchange reaction time is 4-5h, eluting the resin with water, then regenerating with 5-8 wt% sulfuric acid, and regenerating nickel and cobalt under the condition that the pH value is 1-1.2 for 3-5h to obtain cobalt-nickel enrichment solution;
(5) adding sodium nitrate into the cobalt-nickel enrichment solution, stirring and reacting for 1-2h at 40-50 ℃, and filtering to obtain cobalt-nickel slag; wherein the weight ratio of the cobalt-nickel enrichment solution to the sodium nitrate is 1:0.5-0.8, and the stirring speed is 280-320 r/min.
Further, the molar ratio of the ferrous sulfate to the 30% hydrogen peroxide solution in the step (1) is 1: 1.2.
Further, the molar ratio of iron ions in the ferrous sulfate to phosphorus in the manganese sulfate solution in the step (1) is 1.3: 1.
Further, in the step (2), the pH value of the filtrate I is adjusted to 5, then sodium fluoride is added to make the concentration of the filtrate I to be 5g/L, and then the reaction is carried out at 95 ℃ until no precipitate is formed.
Furthermore, in the step (4), the sample injection amount is controlled to be 25 times/h of the volume of the resin, and the sample injection is stopped after the exchange reaction time is 4 h.
Further, in the step (4), 6 wt% of sulfuric acid is used for regeneration, and the regeneration time is 4 h.
Further, the weight ratio of the cobalt-nickel enrichment solution to the sodium nitrate in the step (5) is 1: 0.6.
Further, in the step (5), the reaction condition is 40 ℃, the stirring reaction is carried out for 1.5h, and the stirring speed is 300 r/min.
The method for separating and recovering cobalt and nickel from the manganese sulfate solution has the following beneficial effects:
according to the method, a mixed solution composed of ferrous sulfite and hydrogen peroxide is added into a manganese sulfate solution for oxidation reaction, ferrous iron in the mixed solution is oxidized into ferric iron, then concentrated ammonia water is added to adjust the pH value of the solution, so that the unoxidized ferrous iron and phosphate form insoluble phosphate precipitate, and iron and phosphorus can be effectively removed through filtration.
And after removing iron and phosphorus, adding sodium fluoride, wherein the sodium fluoride can chemically react with calcium and magnesium in the filtrate I to generate insoluble calcium fluoride and magnesium fluoride. When the pH value is 5-5.5, the reaction temperature is 90-100 ℃ and the addition amount of sodium fluoride is 4-6g/L in the reaction process, the sodium fluoride can effectively combine calcium and magnesium to form precipitates, the formation of the precipitates by cobalt and nickel in the filtrate I is not influenced, the dissolution of the sodium fluoride is facilitated at the reaction temperature, the reaction rate is accelerated, the reaction time is shortened, and if the reaction temperature is too high, nickel sulfate crystallization precipitates and partial sodium fluoride is separated out due to large evaporation amount in the reaction process, so that the reaction result is influenced.
The content of cobalt and nickel in the filtrate after calcium and magnesium removal is lower, the invention adopts ion exchange resin to further enrich cobalt and nickel, the process can further enrich the solution with lower content of cobalt and nickel in the manganese sulfate solution, 5-8 wt% of dilute sulfuric acid is adopted as a desorbent in the process, particularly, when the concentration of the dilute sulfuric acid is 6 wt%, nickel can be regenerated, the content of cobalt reaches the highest, and the recycling value of cobalt and nickel is further improved.
After cobalt and nickel are enriched, the content of cobalt and nickel in the solution is improved, and at the moment, sulfide is added to leach cobalt and nickel in the filtrate, so that cobalt and nickel can be more easily precipitated, therefore, sodium nitrate is added at the moment, sodium nitrate is used as an oxidant, cobalt and nickel are further purified in a sulfuric acid medium, when the weight ratio of the cobalt and nickel enriched solution to the sodium nitrate is 1:0.5-0.8, cobalt and nickel with high purity can be further obtained after reaction for 1-2 hours at the reaction temperature of 40-50 ℃, and the leaching rate of cobalt and nickel is higher under the condition.
Detailed Description
The manganese sulfate solution is obtained by sulfating roasting and acid leaching of cobalt-manganese ore in Sichuan, and contains 32.21-36.85mg/L of manganese, 8.79-12.16mg/L of cobalt, 16.34-21.15mg/L of nickel, 68.65-76.78mg/L of iron, 29.42-35.17mg/L of phosphorus, 57.13-63.21mg/L of calcium, 12.36-16.78mg/L of magnesium and has the pH value of 5.5-6.5. Now, the cobalt and nickel in the manganese sulfate solution are separated and recovered, and the specific process is shown in the following examples.
Example 1
A method for separating and recovering cobalt and nickel from a manganese sulfate solution comprises the following steps:
(1) adding a mixed solution of ferrous sulfate and 30% of hydrogen peroxide aqueous solution in a molar ratio of 1:0.8 into a manganese sulfate solution, reacting for 20min at room temperature, adding strong ammonia water under stirring to adjust the pH value of the solution to 4, stirring at room temperature until no precipitate is generated, standing, and filtering to obtain a first filtrate; wherein the molar ratio of iron ions in the ferrous sulfate to phosphorus in the manganese sulfate solution is 1: 1;
(2) adjusting the pH value of the first filtrate to 5, then adding sodium fluoride to make the concentration of the first filtrate to be 4g/L, then reacting at 90 ℃ until no precipitate is generated, and filtering to obtain a second filtrate;
(3) adding sodium dimethyl sulfamate into the filtrate II until no precipitate is generated, and filtering to obtain filter residue;
(4) dissolving the filter residue obtained in the step (3) in dilute sulfuric acid to enable the pH value of the solution to be 3, then entering an ion exchanger filled with WP-2 cation acidic resin for ion exchange reaction, controlling the sample introduction amount to be 25 times/h of the volume of the resin, stopping sample introduction after the exchange reaction time is 4h, eluting the resin with water, then regenerating with 5 wt% sulfuric acid, and regenerating nickel and cobalt under the condition that the pH value is 1 for 5h to obtain cobalt-nickel enrichment solution;
(5) adding sodium nitrate into the cobalt-nickel enrichment solution, stirring and reacting for 2 hours at the temperature of 40 ℃, and filtering to obtain cobalt-nickel slag; wherein the weight ratio of the cobalt-nickel enrichment solution to the sodium nitrate is 1:0.5, and the stirring speed is 280 r/min.
Example 2
A method for separating and recovering cobalt and nickel from a manganese sulfate solution comprises the following steps:
(1) adding a mixed solution of ferrous sulfate and 30% of hydrogen peroxide aqueous solution in a molar ratio of 1:0.9 into a manganese sulfate solution, reacting for 12min at room temperature, adding strong ammonia water under stirring to adjust the pH value of the solution to 4.2, stirring at room temperature until no precipitate is generated, standing, and filtering to obtain a first filtrate; wherein the molar ratio of iron ions in the ferrous sulfate to phosphorus in the manganese sulfate solution is 1.2: 1;
(2) adjusting the pH value of the first filtrate to 5.5, then adding sodium fluoride to make the concentration of the first filtrate to be 4.5g/L, then reacting at 92 ℃ until no precipitate is generated, and filtering to obtain a second filtrate;
(3) adding sodium dimethyl sulfamate into the filtrate II until no precipitate is generated, and filtering to obtain filter residue;
(4) dissolving the filter residue obtained in the step (3) in dilute sulfuric acid to enable the pH value of the solution to be 3, then entering an ion exchanger filled with WP-2 cation acidic resin for ion exchange reaction, controlling the sample introduction amount to be 23 times/h of the volume of the resin, stopping sample introduction after the exchange reaction time is 4.2h, eluting the resin with water, then regenerating with 6 wt% sulfuric acid, and regenerating nickel and cobalt under the condition that the pH value is 1.2 for 3.5h to obtain cobalt-nickel enrichment solution;
(5) adding sodium nitrate into the cobalt-nickel enrichment solution, stirring and reacting for 1.2h at 42 ℃, and filtering to obtain cobalt-nickel slag; wherein the weight ratio of the cobalt-nickel enrichment solution to the sodium nitrate is 1:0.6, and the stirring speed is 290 r/min.
Example 3
A method for separating and recovering cobalt and nickel from a manganese sulfate solution comprises the following steps:
(1) adding a mixed solution of ferrous sulfate and 30% of hydrogen peroxide aqueous solution in a molar ratio of 1:1.2 into a manganese sulfate solution, reacting for 12min at room temperature, adding strong ammonia water under stirring to adjust the pH value of the solution to 4.2, stirring at room temperature until no precipitate is generated, standing, and filtering to obtain a first filtrate; wherein the molar ratio of iron ions in the ferrous sulfate to phosphorus in the manganese sulfate solution is 1.3: 1;
(2) adjusting the pH value of the first filtrate to 5, then adding sodium fluoride to make the concentration of the first filtrate to be 5g/L, then reacting at 95 ℃ until no precipitate is generated, and filtering to obtain a second filtrate;
(3) adding sodium dimethyl sulfamate into the filtrate II until no precipitate is generated, and filtering to obtain filter residue;
(4) dissolving the filter residue obtained in the step (3) in dilute sulfuric acid to enable the pH value of the solution to be 3, then entering an ion exchanger filled with WP-2 cation acidic resin for ion exchange reaction, controlling the sample introduction amount to be 25 times/h of the volume of the resin, stopping sample introduction after the exchange reaction time is 4h, eluting the resin with water, then regenerating with 6 wt% sulfuric acid, and regenerating nickel and cobalt under the condition that the pH value is 1.2 for 4h to obtain cobalt-nickel enrichment solution;
(5) adding sodium nitrate into the cobalt-nickel enrichment solution, stirring and reacting for 1.5h at the temperature of 40 ℃, and filtering to obtain cobalt-nickel slag; wherein the weight ratio of the cobalt-nickel enrichment solution to the sodium nitrate is 1:0.6, and the stirring speed is 300 r/min.
Example 4
A method for separating and recovering cobalt and nickel from a manganese sulfate solution comprises the following steps:
(1) adding a mixed solution of ferrous sulfate and 30% of hydrogen peroxide aqueous solution in a molar ratio of 1:1 into a manganese sulfate solution, reacting at room temperature for 18min, adding concentrated ammonia water under stirring to adjust the pH value of the solution to 4.6, stirring at room temperature until no precipitate is generated, standing, and filtering to obtain a first filtrate; wherein the molar ratio of iron ions in the ferrous sulfate to phosphorus in the manganese sulfate solution is 1.4: 1;
(2) adjusting the pH value of the first filtrate to 5.5, then adding sodium fluoride to make the concentration of the first filtrate to be 5.5g/L, then reacting at 98 ℃ until no precipitate is generated, and filtering to obtain a second filtrate;
(3) adding sodium dimethyl sulfamate into the filtrate II until no precipitate is generated, and filtering to obtain filter residue;
(4) dissolving the filter residue obtained in the step (3) in dilute sulfuric acid to enable the pH value of the solution to be 3.5, then entering an ion exchanger filled with WP-2 cation acidic resin for ion exchange reaction, controlling the sample introduction amount to be 24 times/h of the volume of the resin, stopping sample introduction after the exchange reaction time is 4.6h, eluting the resin with water, then regenerating with 7 wt% sulfuric acid, and regenerating nickel and cobalt under the condition that the pH value is 1.1 for 4.5h to obtain cobalt-nickel enrichment solution;
(5) adding sodium nitrate into the cobalt-nickel enrichment solution, stirring and reacting for 1.2h at 46 ℃, and filtering to obtain cobalt-nickel slag; wherein the weight ratio of the cobalt-nickel enrichment solution to the sodium nitrate is 1:0.7, and the stirring speed is 310 r/min.
Example 5
A method for separating and recovering cobalt and nickel from a manganese sulfate solution comprises the following steps:
(1) adding a mixed solution of ferrous sulfate and 30% of hydrogen peroxide aqueous solution in a molar ratio of 1:1.2 into a manganese sulfate solution, reacting for 10min at room temperature, adding strong ammonia water under stirring to adjust the pH value of the solution to 5, stirring at room temperature until no precipitate is generated, standing, and filtering to obtain a first filtrate; wherein the molar ratio of iron ions in the ferrous sulfate to phosphorus in the manganese sulfate solution is 1.5: 1;
(2) adjusting the pH value of the first filtrate to 5.5, then adding sodium fluoride to make the concentration of the first filtrate to be 6g/L, then reacting at 100 ℃ until no precipitate is generated, and filtering to obtain a second filtrate;
(3) adding sodium dimethyl sulfamate into the filtrate II until no precipitate is generated, and filtering to obtain filter residue;
(4) dissolving the filter residue obtained in the step (3) in dilute sulfuric acid to enable the pH value of the solution to be 3.5, then, entering an ion exchanger filled with WP-2 cation acidic resin for ion exchange reaction, controlling the sample introduction amount to be 22 times/h of the volume of the resin, stopping sample introduction after the exchange reaction time is 5h, eluting the resin with water, then, regenerating with 8 wt% sulfuric acid, and regenerating nickel and cobalt under the condition that the pH value is 1.2 for 3h to obtain cobalt-nickel enrichment solution;
(5) adding sodium nitrate into the cobalt-nickel enrichment solution, stirring and reacting for 1h at the temperature of 50 ℃, and filtering to obtain cobalt-nickel slag; wherein the weight ratio of the cobalt-nickel enrichment solution to the sodium nitrate is 1:0.8, and the stirring speed is 320 r/min.
Comparative example 1
A method for separating and recovering cobalt and nickel from a manganese sulfate solution comprises the following steps:
(1) adding sodium dimethyl sulfamate into the manganese sulfate solution until no precipitate is generated, and filtering to obtain filter residue;
(2) mixing sulfuric acid and sodium nitrate according to the molar ratio of 1.2:1 to obtain a mixed solution, then adding the mixed solution into the filter residue obtained in the step (1), stirring and reacting for 1.5 hours at the temperature of 40 ℃, and filtering to obtain cobalt-nickel residue; wherein the solid-liquid ratio of the filter residue to the mixed solution is 1:5g/mL, and the stirring speed is 300 r/min.
Comparative example 2
A method for separating and recovering cobalt and nickel from a manganese sulfate solution comprises the following steps:
a method for separating and recovering cobalt and nickel from a manganese sulfate solution comprises the following steps:
(1) adding a mixed solution of ferrous sulfate and 30% of hydrogen peroxide aqueous solution in a molar ratio of 1:1.2 into a manganese sulfate solution, reacting for 12min at room temperature, adding strong ammonia water under stirring to adjust the pH value of the solution to 4.2, stirring at room temperature until no precipitate is generated, standing, and filtering to obtain a first filtrate; wherein the molar ratio of iron ions in the ferrous sulfate to phosphorus in the manganese sulfate solution is 1.3: 1;
(2) adjusting the pH value of the first filtrate to 5, then adding sodium fluoride to make the concentration of the first filtrate to be 5g/L, then reacting at 95 ℃ until no precipitate is generated, and filtering to obtain a second filtrate;
(3) adding sodium dimethyl sulfamate into the filtrate II until no precipitate is generated, and filtering to obtain filter residue;
(4) mixing sulfuric acid and sodium nitrate according to the molar ratio of 1.2:1 to obtain a mixed solution, then adding the mixed solution into the filter residue obtained in the step (3), stirring and reacting for 1.5 hours at the temperature of 40 ℃, and filtering to obtain cobalt-nickel residue; wherein the solid-liquid ratio of the filter residue to the mixed solution is 1:5g/mL, and the stirring speed is 300 r/min.
Comparative example 3
A method for separating and recovering cobalt and nickel from a manganese sulfate solution comprises the following steps:
(1) adding a mixed solution of ferrous sulfate and 30% of hydrogen peroxide aqueous solution in a molar ratio of 1:1.2 into a manganese sulfate solution, reacting for 12min at room temperature, adding strong ammonia water under stirring to adjust the pH value of the solution to 4.2, stirring at room temperature until no precipitate is generated, standing, and filtering to obtain a first filtrate; wherein the molar ratio of iron ions in the ferrous sulfate to phosphorus in the manganese sulfate solution is 1.3: 1;
(2) adjusting the pH value of the first filtrate to 5, then adding sodium fluoride to make the concentration of the first filtrate to be 5g/L, then reacting at 95 ℃ until no precipitate is generated, and filtering to obtain a second filtrate;
(3) adding sodium dimethyl sulfamate into the filtrate II until no precipitate is generated, and filtering to obtain filter residue;
(4) dissolving the filter residue obtained in the step (3) in dilute sulfuric acid to enable the pH value of the solution to be 3, then entering an ion exchanger filled with WP-2 cation acidic resin for ion exchange reaction, controlling the sample introduction amount to be 25 times/h of the volume of the resin, stopping sample introduction after the exchange reaction time is 4h, eluting the resin with water, then regenerating with 6 wt% sulfuric acid, and regenerating nickel and cobalt under the condition that the pH value is 1.2 for 4h to obtain cobalt-nickel enrichment solution;
(5) and carrying out reduced pressure concentration on the obtained cobalt-nickel enriched liquid to obtain a cobalt-nickel solid.
The cobalt-nickel leaching recovery rates in the above examples 1 to 5 and comparative documents 1 to 3 were calculated by the following formula: (cobalt or nickel content in the solid obtained after final separation and recovery/cobalt/nickel content in the original solution). times.100%, the specific results are as follows:
example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
Cobalt | 97.67% | 98.01% | 98.23% | 98.13% | 98.15% | 77.12% | 86.31% | 92.17% |
Nickel (II) | 97.89% | 98.35% | 98.88% | 98.56% | 98.42% | 75.35% | 86.42% | 92.78% |
As can be seen from the above table, as long as cobalt and nickel are recovered according to the separation and recovery method of the present invention, the leaching recovery rate of cobalt and nickel can be effectively improved within the parameter range of each step of the present invention, and the leaching recovery rate can be greatly affected due to the absence of the ion resin exchange step in the separation and recovery process, because when the concentration of cobalt and nickel in the solution is low, cobalt and nickel are difficult to separate and recover, and can be effectively recovered only by enriching the cobalt and nickel through the ion exchange resin; in the absence of the sodium nitrate oxidation process and the previous impurity removal process, although the weight of the obtained solid matter of the product is heavy, the content of cobalt and nickel in the solid matter is not high because some cobalt and nickel in the solution are not well separated and recovered and contain a large amount of impurities.
Claims (8)
1. A method for separating and recovering cobalt and nickel from a manganese sulfate solution is characterized by comprising the following steps:
(1) adding a mixed solution of ferrous sulfate and 30% of hydrogen peroxide aqueous solution in a molar ratio of 1:0.8-1.2 into a manganese sulfate solution, reacting at room temperature for 10-20min, adding concentrated ammonia water under stirring to adjust the pH value of the solution to 4-5, stirring at room temperature until no precipitate is generated, standing, and filtering to obtain a first filtrate; wherein the molar ratio of iron ions in the ferrous sulfate to phosphorus in the manganese sulfate solution is 1-1.5: 1;
(2) adjusting the pH value of the first filtrate to 5-5.5, adding sodium fluoride to make the concentration of the first filtrate to be 4-6g/L, reacting at 90-100 ℃ until no precipitate is generated, and filtering to obtain a second filtrate;
(3) adding sodium dimethyl sulfamate into the filtrate II until no precipitate is generated, and filtering to obtain filter residue;
(4) dissolving the filter residue obtained in the step (3) in dilute sulfuric acid to enable the pH value of the solution to be 3-3.5, then entering an ion exchanger filled with WP-2 cation acidic resin for ion exchange reaction, controlling the sample injection amount to be 22-25 times/h of the volume of the resin, stopping sample injection after the exchange reaction time is 4-5h, eluting the resin with water, then regenerating with 5-8 wt% sulfuric acid, and regenerating nickel and cobalt under the condition that the pH value is 1-1.2 for 3-5h to obtain cobalt-nickel enrichment solution;
(5) adding sulfide into the cobalt-nickel enrichment solution, adding sodium nitrate, stirring and reacting for 1-2h at 40-50 ℃, and filtering to obtain cobalt-nickel slag; wherein the weight ratio of the cobalt-nickel enrichment solution to the sodium nitrate is 1:0.5-0.8, and the stirring speed is 280-320 r/min.
2. The method for separating and recovering cobalt and nickel from a manganese sulfate solution as claimed in claim 1, wherein the molar ratio of the ferrous sulfate to the 30% aqueous hydrogen peroxide solution in terms of mass fraction in step (1) is 1: 1.2.
3. The method for separating and recovering cobalt and nickel from the manganese sulfate solution as claimed in claim 1, wherein the molar ratio of iron ions in ferrous sulfate to phosphorus in the manganese sulfate solution in the step (1) is 1.3: 1.
4. The method for separating and recovering cobalt and nickel from manganese sulfate solution as claimed in claim 1, wherein in the step (2), the pH value of the first filtrate is adjusted to 5, then sodium fluoride is added to make the concentration of the first filtrate to be 5g/L, and then the first filtrate is reacted at 95 ℃ until no precipitate is formed.
5. The method for separating and recovering cobalt and nickel from manganese sulfate solution as claimed in claim 1, wherein in the step (4), the sample injection amount is controlled to be 25 times/h of the volume of the resin, and the sample injection is stopped after the exchange reaction time is 4 h.
6. The method for separating and recovering cobalt and nickel from manganese sulfate solution as claimed in claim 1, wherein the regeneration with 6 wt% sulfuric acid in step (4) is carried out for 4 h.
7. The method for separating and recovering cobalt and nickel from a manganese sulfate solution as claimed in claim 1, wherein the weight ratio of the cobalt-nickel concentrated solution to sodium nitrate in the step (5) is 1: 0.6.
8. The method for separating and recovering cobalt and nickel from manganese sulfate solution as claimed in claim 1, wherein the reaction condition in step (5) is 40 ℃, the stirring reaction is carried out for 1.5h, and the stirring speed is 300 r/min.
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