CN112442596B - Method for separating and recovering nickel, cobalt and manganese in battery intermediate feed liquid by carboxylic acid extracting agent - Google Patents
Method for separating and recovering nickel, cobalt and manganese in battery intermediate feed liquid by carboxylic acid extracting agent Download PDFInfo
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- CN112442596B CN112442596B CN202011131786.2A CN202011131786A CN112442596B CN 112442596 B CN112442596 B CN 112442596B CN 202011131786 A CN202011131786 A CN 202011131786A CN 112442596 B CN112442596 B CN 112442596B
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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
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
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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
- C22B23/00—Obtaining nickel or cobalt
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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
- C22B47/00—Obtaining manganese
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to a method for separating nickel, cobalt and manganese from a battery intermediate feed liquid containing nickel, cobalt and manganese, which comprises the following steps: (1) Carrying out chemical impurity removal on the feed liquid to obtain a water phase 1 and iron-containing aluminum slag; (2) Performing manganese extraction on the water phase 1 obtained in the step (1) by using an extractant A to obtain a manganese loaded organic phase and a water phase 2; (3) Carrying out nickel extraction on the water phase 2 obtained in the step (2) by using an extractant B to obtain a nickel loaded organic phase and a water phase 3; (4) Carrying out cobalt extraction on the water phase 3 obtained in the step (3) by using an extractant C to obtain a cobalt loaded organic phase and a water phase 4; (5) And (3) enriching and separating sodium sulfate crystals in the water phase 4 obtained in the step (4) to obtain a sodium sulfate product, and treating the wastewater to reach the standard and discharging, wherein the extracting agent B used in the nickel extraction comprises a carboxylic acid extracting agent. The method provided by the invention can separate, extract and recover nickel, cobalt and manganese in the battery intermediate feed liquid containing nickel, cobalt and manganese, and the extracting agent B has high efficiency for extracting nickel, low acid and alkali consumption and low operation cost.
Description
Technical Field
The invention relates to the field of resource recovery, in particular to a method for separating nickel, cobalt and manganese from a battery intermediate feed liquid containing nickel, cobalt and manganese.
Background
The nickel-cobalt-manganese ternary cathode material has good cycle performance, stable structure and high cost performance, is a novel lithium ion battery cathode material, is widely applied to the new energy automobile industry, and the required scale of the lithium ion battery is continuously enlarged, so that the quantity of the waste lithium ion batteries is increased day by day. If the waste lithium battery is discarded at will, the environment is seriously polluted, and valuable metal resources are wasted in a large amount, and the best way for solving the problem is to realize recycling of nickel, cobalt, manganese and lithium, so that the recycling of the waste lithium battery has double effects of environmental effect and market effect.
Hydrometallurgy is a scientific technology for dissolving valuable metal components in ores, concentrates, waste battery anode materials and other materials in a solution or separating out the valuable metal components in a new solid phase by using a leaching agent to separate, enrich and extract metals, has the characteristics of low energy consumption, small pollution, high resource utilization rate and the like, and is continuously concerned and developed by a plurality of researchers all the time.
CN110066925A discloses a method for recovering valuable metals from waste nickel-cobalt-manganese ternary lithium batteries, which comprises the steps of extracting and purifying a battery feed liquid by using P204, performing back extraction to obtain a back extraction liquid containing manganese sulfate and a raffinate containing Co, ni and Li ions, removing Cu from the back extraction liquid, and performing evaporation concentration and crystallization to obtain manganese sulfate; extracting Co in the raffinate by using saponified P507, and obtaining a cobalt sulfate solution after back extraction; removing Mg in the raffinate by using C272, extracting Ni in the raffinate by using P507, and performing back extraction to obtain a nickel sulfate solution; the method for removing Fe, al, ca and Mg in the leachate comprises the steps of detecting the concentration of divalent Fe in the leachate, adding an oxidant to oxidize the divalent Fe into trivalent Fe, adding sodium carbonate to adjust the pH value of the leachate to be = 4.5-5.0, and removing Fe and Al precipitates; detecting the content of Ca and Mg, adding sodium fluoride or potassium fluoride to precipitate Ca and Mg, and filtering. The process flow is complex, the separation cost for respectively recovering nickel, cobalt and manganese elements is high, impurity metal ions such as Ca, mg and the like are removed by adopting a precipitation method, and valuable metal entrainment loss is easily caused.
Disclosure of Invention
In view of the problems in the prior art, the invention discloses a method for separating nickel, cobalt and manganese from a battery intermediate feed liquid containing nickel, cobalt and manganese, wherein a carboxylic acid extracting agent B adopted by the method can efficiently extract and extract nickel, and has good separation effect with impurity ions; the environmental effect is good; the organic phase can be recycled, the operation cost is low, and the economic benefit is good.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention aims to provide a method for separating nickel, cobalt and manganese from a battery intermediate feed liquid containing nickel, cobalt and manganese, which comprises the following steps:
(1) Carrying out chemical impurity removal on the feed liquid to obtain a water phase 1 and iron-containing aluminum slag;
(2) Performing manganese extraction on the water phase 1 obtained in the step (1) by using an extractant A to obtain a manganese loaded organic phase and a water phase 2;
(3) Carrying out nickel extraction on the water phase 2 obtained in the step (2) by using an extracting agent B to obtain a nickel loaded organic phase and a water phase 3;
(4) Carrying out cobalt extraction on the water phase 3 obtained in the step (3) by using an extracting agent C to obtain a cobalt loaded organic phase and a water phase 4;
(5) Sodium sulfate crystal enrichment and separation are carried out on the water phase 4 obtained in the step (4) to obtain a sodium sulfate product, the wastewater is treated and then discharged after reaching the standard,
wherein the extractant B used in the method comprises a carboxylic acid extractant; the carboxylic acid extractant has a structural formula shown in formula I and is named as CPH88:
wherein-C 8 H 17 Are all straight chain alkyl groups.
By the method, nickel, cobalt and manganese in the intermediate feed liquid of the nickel-cobalt-manganese-containing battery are separated, extracted and recycled, and a byproduct sodium sulfate is concentrated and recycled, so that the nickel extraction process is not influenced by impurity metal ions such as calcium, magnesium and the like, the extraction pH value is low, the alkali consumption can be reduced, the whole process is simple to operate and stable in operation, and meanwhile, the extraction rate of the carboxylic acid extracting agent on Ni is more than 99.5%, and the back extraction rate of sulfuric acid is more than 99.9%.
In the present invention, the concentration of the solution of sodium sulfate and/or sodium carbonate used for the chemical removal of impurities in step (1) is 10 to 100g/L, for example, 10g/L, 15g/L, 20g/L, 23g/L, 27g/L, 30g/L, 33g/L, 45g/L, 50g/L, 65g/L, 70g/L, 80g/L, 90g/L, or 99g/L, but is not limited to the values listed above, and other values not listed in this range are also applicable.
In the present invention, the equilibrium pH of the raffinate aqueous phase in the manganese extraction in step (2) is 1 to 4, and may be, for example, 1, 1.2, 1.5, 1.9, 2.0, 2.5, 2.8, 3.0, 3.1, 3.6, 3.7 or 3.9, but is not limited to the values listed, and other values not listed in this range are also applicable.
In the present invention, the volume fraction of the high-purity extractant in the extractant a for manganese extraction in the step (2) is 5 to 30%, and may be, for example, 5%, 10%, 15%, 20%, 25%, or 30%, but is not limited to the recited values, and other values not recited in the range are also applicable.
In the present invention, the flow ratio of the extractant a for manganese extraction to the feed liquid in step (2) is (0.1 to 10) 1, and may be, for example, 0.1.
In the present invention, the stirring speed for manganese extraction in step (2) is 100 to 800r/min, and may be, for example, 100r/min, 200r/min, 220r/min, 300r/min, 350r/min, 380r/min, 400r/min, 500r/min, 600r/min, 700r/min, 780r/min or 790r/min, but is not limited to the values listed, and other values not listed in the range are also applicable.
In the present invention, the mixing time for manganese extraction in step (2) is 5 to 30min, and may be, for example, 5min, 7min, 8min, 10min, 13min, 15min, 16min, 18min, 21min, 22min, 25min, 28min or 29min, but is not limited to the values listed above, and other values not listed above in this range are also applicable.
In the present invention, the number of stages of the multistage countercurrent fractional extraction for manganese extraction in the step (2) is 2 to 30 stages, and may be, for example, 2, 3, 5, 7, 9, 10, 11, 13, 15, 17, 18, 20, 22, 24, 26, 28 or 29, etc., but is not limited to the values listed, and other values not listed in this range are also applicable.
As a preferred technical solution of the present invention, the extractant a used in the impurity removal extraction in the step (2) includes 1 or a combination of at least 2 of a phosphorus-type extractant, a carboxylic acid-type extractant, or an oxime-type extractant.
In the present invention, the phosphorus-based extractant includes 1 or a combination of at least 2 of P204, P507, or C272.
In the present invention, the carboxylic acid extractant includes 1 or a combination of at least 2 of BC191, BC192, BC194, or BC 196.
In the present invention, the oxime type extractant includes any 1 or a combination of at least 2 of Mextral 984H, lix63, or CP 50.
In the invention, if the feed liquid contains copper ions, oxime extractant is preferably selected to remove copper in the feed liquid in impurity removal and extraction.
In the invention, the manganese-loaded organic phase in the step (2) is subjected to multi-stage countercurrent washing and then is subjected to back extraction to obtain a manganese-containing metal ion solution and a regenerated organic phase.
Preferably, the regenerated organic phase is returned to use as extractant.
In the present invention, the pH of the aqueous phase 2 obtained by nickel extraction in step (3) is 1.9 to 5, and may be, for example, 1.9, 2.0, 2.1, 2.3, 2.4, 2.7, 3.0, 3.1, 3.4, 3.6, 3.8, 4.0, 4.2, 4.6, 4.8 or 4.9, but is not limited to the values listed, and other values not listed in this range are also applicable, and preferably 2.0 to 3.5.
As a preferable technical scheme of the invention, the metal elements in the feed liquid comprise 1-60 g/L of Ni, 1-50 g/L of Co, 1-50 g/L of Mn, less than or equal to 10g/L of Fe, less than or equal to 1g/L of Al, less than or equal to 10g/L of Cu, less than or equal to 5g/L of Zn, about 0.1-0.5 g/L of Ca and 0.1-50 g/L of Mg.
In the present invention, the concentration of Ni in the feed liquid is 1 to 60g/L, and may be, for example, 1g/L, 10g/L, 20g/L, 30g/L, 40g/L, 41g/L, 42g/L, 43g/L, 44g/L, 45g/L, 46g/L, 47g/L, 48g/L, 49g/L, 50g/L, 52g/L, 55g/L, 58g/L or 59g/L, but is not limited to the values listed, and other values not listed in the range are also applicable.
In the present invention, the concentration of Co in the feed liquid is 1 to 50g/L, and may be, for example, 1g/L, 5g/L, 15g/L, 16g/L, 17g/L, 18g/L, 19g/L, 20g/L, 21g/L, 32g/L, 35g/L, 37g/L, 40g/L, 43/L, 45g/L, 47g/L or 49g/L, but is not limited to the values listed, and other values not listed in the range are also applicable.
In the present invention, the concentration of Mn in the feed liquid is 1 to 50g/L, and may be, for example, 1g/L, 5g/L, 15g/L, 16g/L, 17g/L, 18g/L, 20g/L, 23g/L, 27g/L, 32g/L, 35g/L, 37g/L, 40g/L, 43/L, 45g/L, 47g/L or 49g/L, but is not limited to the values listed, and other values not listed in the range are also applicable.
In the present invention, the concentration of Fe in the feed liquid is not more than 10g/L, and may be, for example, 10g/L, 9g/L, 8g/L, 7g/L, 6g/L, 5g/L, 4g/L or 3g/L, etc., but is not limited to the values listed above, and other values not listed above within the range are also applicable.
In the present invention, the concentration of Al in the feed liquid is not more than 1g/L, and may be, for example, 1g/L, 0.8g/L, 0.6g/L, 0.4g/L or 0.2g/L, but is not limited to the values listed above, and other values not listed in the range are also applicable.
In the present invention, the Cu concentration in the feed liquid is 10g/L or less, and may be, for example, 10g/L, 9.5g/L, 8.7g/L, 7.4g/L, 6.6g/L, 5.6g/L, 4.3g/L or 3g/L, etc., but is not limited to the values listed, and other values not listed in the range are also applicable.
In the present invention, the Zn concentration in the feed liquid is not more than 5g/L, and may be, for example, 5g/L, 4.3g/L, 3.5g/L, 2g/L or 1g/L, etc., but is not limited to the values listed above, and other values not listed above within the range are also applicable.
In the present invention, the Ca concentration in the feed liquid is 0.1 to 0.5g/L, for example, 0.1g/L, 0.2g/L, 0.33g/L, 0.45g/L or 0.5g/L, but is not limited to the values listed, and other values not listed in this range are also applicable.
In the present invention, the concentration of Mg in the feed liquid is 0.1 to 50g/L, and may be, for example, 0.1g/L, 10g/L, 20g/L, 30g/L, 40g/L or 50g/L, but is not limited to the values listed above, and other values not listed above in this range are also applicable.
In the invention, the nickel-nickel extractant in the step (3) is a carboxylic acid extractant, and the structural formula of the carboxylic acid extractant is as shown in formula I:
wherein-C 8 H 17 All are straight chain alkyl.
In the present invention, the volume fraction of carboxylic acid in the extractant B in the step (3) is 5 to 30%, for example, 5%, 10%, 15%, 20%, 25%, or 30%, but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the diluent of the extractant B comprises 1 or a combination of at least 2 of kerosene, escaid110, mineral spirits, dodecane.
In the present invention, the solvent may be mineral spirit No. 200 and/or mineral spirit No. 260.
In the present invention, the dodecane may be n-dodecane or the like.
Preferably, the extractant B is saponified before use.
Preferably, the saponification is performed using 6 to 14mol/L of an alkaline saponifier, and may be, for example, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L, 12mol/L, 13mol/L or 14mol/L, but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the alkaline saponifier comprises 1 or a combination of at least 2 of sodium hydroxide solution, magnesium oxide, potassium hydroxide solution or ammonia water.
The combination may be a combination of a sodium hydroxide solution and a potassium hydroxide solution, a combination of a potassium hydroxide solution and aqueous ammonia, or the like, but is not limited to the listed combinations, and other combinations not listed within the scope are also applicable.
Preferably, the nickel extraction in step (3) is a multi-stage countercurrent fractional extraction, the number of stages of the multi-stage countercurrent fractional extraction is 2 to 30, for example, 2, 3, 5, 10, 15, 20, 25 or 30, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, in the nickel extraction in step (3), the flow ratio of the extractant B to the aqueous phase 1 is (0.1 to 20): 1, which can be, for example, 0.1.
Preferably, the stirring speed in the nickel extraction in step (3) is 100-800 r/min, such as 100r/min, 150r/min, 220r/min, 300r/min, 350r/min, 370r/min, 400r/min, 500r/min, 600r/min, 700r/min, 780r/min or 790r/min, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the mixing time for nickel extraction in step (3) is 5-30 min, such as 5min, 10min, 15min, 20min, 25min or 30min, but not limited to the recited values, and other values not recited in this range are also applicable.
As a preferable technical scheme of the invention, the nickel-loaded organic phase in the step (3) is subjected to multi-stage countercurrent washing and then is subjected to back extraction to obtain a solution containing metal ions and a regenerated organic phase.
As a preferred technical scheme of the invention, the washing in the step (3) is multi-stage countercurrent washing.
Preferably, the number of washing stages is 2 to 20, and may be, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 13, 15, 16, 18 or 19, etc., but is not limited to the recited values, and other values not recited within this range are also applicable.
Preferably, the regenerated organic phase is returned to use as extractant.
In the invention, the washing of the nickel-loaded organic phase is carried out by adopting inorganic acid and/or acidified water and nickel sulfate solution; the ratio of the nickel-loaded organic phase to the washing stream is (0.1 to 10): 1, and may be, for example, 0.1.
In the present invention, the pH of the inorganic acid and/or acidified water is 0.1 to 2, and may be, for example, 0.1, 0.2, 0.4, 0.5, 0.7, 0.9, 1.0, 1.2, 1.5, 1.7, 1.8 or 1.9, but is not limited to the above-mentioned values, and other values not mentioned in the above range are also applicable.
In the present invention, the nickel sulfate solution may be 0.5 to 20g/L, for example, 0.5g/L, 1g/L, 1.5g/L, 5g/L, 6g/L, 7g/L, 10g/L, 12g/L, 13g/L, 15g/L, 17g/L, 18g/L, 19g/L or 20g/L, etc., but is not limited to the values listed, and other values not listed in the range are also applicable.
In the present invention, after the nickel-loaded organic phase is washed by a detergent in a multi-stage countercurrent manner, the nickel-cobalt-manganese-loaded organic phase is stripped by an acid solution, and the flow ratio of the nickel-cobalt-manganese-loaded organic phase to the acid in stripping is (0.1 to 10): 1, 0.5.
In the present invention, the concentration of the inorganic acid in the stripping agent is 0.5 to 4mol/L, for example, 0.5 mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L or 4mol/L, etc., but is not limited to the values listed, and other values not listed in the range are also applicable, and it is more preferable that the concentration of the stripping agent is 2mol/L.
In the present invention, the number of the stripping stages is 3 to 10, and may be, for example, 3, 4, 5, 6, 7, 8 or 9, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In the invention, in the step (4), the aqueous phase 3 obtained in the step (3) is subjected to cobalt extraction by using an extracting agent C, wherein the extracting agent C can be a phosphine extracting agent and a carboxylic acid extracting agent.
In the invention, the phosphine extractant is P507, and the carboxylic acid extractant is BC191, BC193, BC196 and the like.
In the present invention, the volume fraction of the extractant C is 5 to 30%, and may be, for example, 5%, 10%, 15%, 20%, 25%, or 30%, but is not limited to the values listed, and other values not listed in the range are also applicable.
In the present invention, the cobalt extraction in the step (4) may be performed using, for example, a phosphine extraction in which the aqueous phase equilibrium pH is 3 to 5, and may be, for example, 3.1, 3.4, 3.5, 3.7, 4.0, 4.3, 4.6, 4.8 or 4.9, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In the present invention, the cobalt extraction in the step (4) may be performed using a carboxylic acid extraction in which the aqueous phase equilibrium pH is 5 to 7.8, for example, 5.1, 5.4, 5.5, 5.7, 6.0, 6.3, 7.0, 7.4, or 7.8, but is not limited to the above-mentioned values, and other values not listed in the above range are also applicable.
In the present invention, the extractant C is saponified before use, and the saponifying agent includes 1 or at least 2 combinations of sodium hydroxide solution, magnesium oxide, potassium hydroxide solution, and aqueous ammonia, and the combinations may be a combination of sodium hydroxide solution and potassium hydroxide solution, or a combination of potassium hydroxide solution and aqueous ammonia, but are not limited to the combinations listed, and other combinations not listed within the scope are also applicable.
Preferably, the saponification is carried out using 6 to 14mol/L of an alkaline saponifier, and may be, for example, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L, 12mol/L, 13mol/L or 14mol/L, but is not limited to the values listed, and other values not listed in this range are also applicable.
In the present invention, the cobalt extraction in the step (4) is a multi-stage countercurrent fractional distillation, the number of stages of the multi-stage countercurrent extraction is 2 to 30, and may be, for example, 2, 3, 5, 10, 15, 20, 25 or 30, etc., but the present invention is not limited to the above-mentioned values, and other values not listed in the range are also applicable.
In the present invention, the flow ratio of the extractant C to the aqueous phase 3 in the nickel extraction in step (4) is (0.1 to 20): 1, and may be, for example, 0.1.
In the present invention, the stirring speed in the cobalt extraction in the step (4) is 100 to 800r/min, and may be, for example, 100r/min, 150r/min, 220r/min, 300r/min, 350r/min, 370r/min, 400r/min, 500r/min, 600r/min, 700r/min, 780r/min or 790r/min, but is not limited to the values listed, and other values not listed in the range are also applicable.
In the present invention, the mixing time for cobalt extraction in step (4) is 5 to 30min, and may be, for example, 5min, 10min, 15min, 20min, 25min or 30min, but is not limited to the above-mentioned values, and other values not shown in the above range are also applicable.
As a preferable technical scheme of the invention, the cobalt-loaded organic phase in the step (4) is subjected to multi-stage countercurrent washing and then is subjected to back extraction to obtain a metal ion-containing solution and a regenerated organic phase.
As a preferred technical scheme of the invention, the washing in the step (4) is multi-stage countercurrent washing.
Preferably, the number of washing steps is 2 to 20, and may be, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 13, 15, 16, 18 or 19, but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the regenerated organic phase is returned to use as extractant.
In the invention, the washing of the cobalt-loaded organic phase is carried out by adopting inorganic acid and/or acidified water and cobalt sulfate solution; the ratio of the nickel-loaded organic phase to the washing stream is (0.1 to 10): 1, and can be, for example, 0.1.
In the present invention, the pH of the inorganic acid and/or acidified water is 0.1 to 2, and may be, for example, 0.1, 0.2, 0.4, 0.5, 0.7, 0.9, 1.0, 1.2, 1.5, 1.7, 1.8 or 1.9, but is not limited to the above-mentioned values, and other values not mentioned in the above range are also applicable.
In the present invention, the cobalt sulfate solution is 0.5 to 20g/L, for example, 0.5g/L, 1g/L, 1.5g/L, 5g/L, 6g/L, 7g/L, 10g/L, 12g/L, 13g/L, 15g/L, 17g/L, 18g/L, 19g/L or 20g/L, etc., but is not limited to the values listed, and other values not listed in the range are also applicable.
In the present invention, the nickel-bearing organic phase is subjected to multistage counter-current washing with a detergent, and then subjected to back extraction with an acid solution, wherein the flow ratio of the cobalt-bearing organic phase to the acid in the back extraction is (0.1 to 10): 1, 0.5.
In the present invention, the concentration of the inorganic acid in the stripping agent is 0.5 to 4mol/L, and may be, for example, 0.5 mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L or 4mol/L, but is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned range are also applicable, and it is more preferable that the concentration of the stripping agent is 2mol/L.
In the present invention, the number of the stripping stages is 3 to 10, and may be, for example, 3, 4, 5, 6, 7, 8 or 9, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
As the preferred technical scheme of the invention, the reaction equipment for manganese extraction, nickel extraction and cobalt extraction is a mixer-settler.
As a preferable technical scheme of the invention, the water phase 4 in the step (5) is subjected to oil removal and crystallization sequentially to obtain sodium sulfate crystals.
Preferably, the crystallization is by MVR evaporation.
In the invention, the oil removal is realized by adopting a conventional oil removal method in the prior art, and the oil-water separation is realized.
As a preferred technical scheme of the invention, the method comprises the following steps:
the method is characterized by comprising the following steps:
(1) Chemically removing impurities from the feed liquid by using sodium sulfate and/or sodium carbonate to obtain a water phase 1 and iron-containing aluminum slag liquid, and performing filter pressing on the slag liquid to obtain iron-containing aluminum slag;
(2) Performing manganese extraction on the water phase 1 obtained in the step (1) by using an extractant A to obtain a manganese-loaded organic phase and a water phase 2, wherein the extractant A comprises 1 or at least 2 of phosphorus type extractants, carboxylic acid extractants or oxime extractants; the volume fraction of the extractant A is 5 to 30 percent; the manganese extraction comprises single-stage extraction or multi-stage countercurrent extraction; the flow ratio of an extracting agent A used in the manganese extraction to the feed liquid is (0.1-10) to 1; the stirring speed in the manganese extraction is 100-800 r/min; the mixing time in the manganese extraction is 5-30 min; the device for impurity removal and extraction is a mixer-settler; the manganese extraction is multi-stage countercurrent fractional extraction, the stage number is 2-30, the manganese-loaded organic is washed and then is back-extracted by a back-extractant, a manganese-rich solution and regenerated organic are obtained, the regenerated organic is recycled, and the cost is reduced.
(3) Carrying out nickel extraction on the water phase 2 obtained in the step (2) by using an extracting agent B to obtain a nickel loaded organic phase and a water phase 3, wherein the extracting agent B used in the nickel extraction process comprises a carboxylic acid extracting agent; the carboxylic acid extractant has a structural formula shown in a formula I, and is named as CPH88:
wherein-C 8 H 17 All are straight chain alkyl. The volume fraction of the extractant B is 5-30%, the diluent of the extractant B comprises 1 or at least 2 of solvent naphtha, kerosene, escaid110 and dodecane, the extractant B is saponified by using 6-14 mol/L alkaline saponifying agent comprising 1 or at least 2 of sodium hydroxide solution, magnesium oxide, potassium hydroxide solution or ammonia water before use, and the volume ratio of the extractant B to the aqueous phase 1 in the nickel extraction is (0.1-20): the method comprises the following steps of 1, stirring speed in nickel extraction is 100-800 r/min, mixing time in the nickel extraction in the step (3) is 5-30 min, extraction equipment used in the nickel extraction is a mixer-settler, the water phase equilibrium pH value of the nickel extraction is 1.9-5, the stages of the multistage countercurrent fractional extraction are 2-30 stages, 0.5-4 mol/L of inorganic acid is used in the back extraction and comprises any one or combination of at least two of hydrochloric acid, nitric acid or sulfuric acid, the stages of the back extraction are 3-10 stages, the volume ratio of a back extraction agent to a nickel loaded organic phase is 1 (0.1-10), a step of washing the nickel loaded organic phase obtained in the step (3) is further included before the back extraction, the stages of the washing are 2-20 stages, the washing comprises washing of the inorganic acid and/or acidified water and a nickel sulfate solution, and the nickel loaded organic phase is washed and then back extracted by using a back extraction agent to obtain a sulfuric acid solution and a regenerated organic phase, the regenerated organic phase is recycled, and the cost is reduced.
(4) And (2) performing cobalt extraction on the water phase 3 obtained in the step (3) by using an extractant C to obtain a cobalt-loaded organic phase and a water phase 4, wherein the extractant C used in the step (3) can be carboxylic acid extractants BC191, BC193 and BC196, and can also be a phosphorus extractant P507, the equipment used in the cobalt extraction is a mixed clarifying tank, before extraction, the extractant C is saponified by using an alkaline compound, the alkaline saponifying agent comprises 1 or at least 2 of sodium hydroxide solution, magnesium oxide, potassium hydroxide solution or ammonia water, the concentration range of the alkaline saponifying agent is 6-14 mol/L, the saponified organic phase and the water phase are contacted step by step, the volume ratio of the extractant C to the water phase 1 in the cobalt extraction is (0.1-20): 1, the stirring speed is controlled at 100-800 r/min, the cobalt extraction mixing time is 5-30 min, and after washing and back extraction are performed, a cobalt sulfate solution and an organic phase are obtained, the regenerated organic phase is recycled, and the cost is reduced.
In this step, the extractant C is different due to the water phase equilibrium pH required to be controlled by using different types of extractants, for example, cobalt extraction uses a water phase equilibrium pH in carboxylic acid extraction of 5-7.8 when a phosphine extractant is used, the water phase equilibrium pH is 3-5.
(5) And (4) sequentially removing oil and crystallizing the water phase 4 obtained in the step (4) to obtain sodium sulfate crystals, treating the wastewater, and discharging the wastewater after reaching the standard, wherein the crystallization mode is MVR evaporation.
In the present invention, the multi-stage countercurrent fractional extraction is one of the extraction separation methods, and the aqueous phase and the organic phase containing the extracted substance flow into the extractor from the two ends respectively and flow in opposite directions to perform continuous multi-stage stirring contact delamination to achieve the separation purpose.
In the present invention, the reaction equation of the relevant process is as follows:
saponification of carboxylic acid extractant: HA (org) +NaOH→NaA (org) +H 2 O
Extracting with carboxylic acid extractant: 2NaA (org) +MSO 4 →MA 2(org) +Na 2 SO 4
Sulfuric acid back extraction: MA (MA) 2(org) +H 2 SO 4 →2HA (org) +MSO 4
Wherein: m is Fe 3+ 、Cu 2+ 、Al 3+ 、Zn 2+ 、Ni 2+ 、Co 2+ 、Mn 2+ And the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the method provided by the invention, the carboxylic acid extractant CPH88 is utilized to carry out pre-extraction on the metal nickel, the extractant has a good nickel metal ion separation effect, the influence of impurity metal ions such as calcium and magnesium can be reduced, and the extraction is carried out at a low saponification rate, so that the acid-base consumption is reduced.
Drawings
FIG. 1 is a schematic diagram of the recovery process in example 1 of the present invention.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
This embodiment provides a method for recovering nickel, cobalt and manganese from a feed solution containing nickel, cobalt and manganese, as shown in fig. 1.
The feed liquid in the embodiment is a battery intermediate feed liquid containing nickel, cobalt and manganese, the pH value of the feed liquid is 3.0, and the feed liquid comprises the following components:
| element(s) | Fe | Al | Zn | Cu | Ni | Co | Mn | Ca | Mg |
| Content (g/L) | 0.001 | 0.001 | 0.34 | 0.3 | 42 | 27 | 23 | 0.4 | 0.2 |
In this example, P204 was selected as the extractant for manganese extraction, the volume fraction was 25%, the diluent was sulfonated kerosene, 10mol/L NaOH solution was used for saponification, the degree of saponification was 42%, the flow ratio of the saponified organic phase to the aqueous phase was 2.5:1, reaction equipment uses a mixer-settler, the mixing time is 5min, the stirring speed is 200r/min, the designed extraction stage number is 10 stages, the washing stage number is 6 stages, metal elements such as nickel and cobalt carried by the metal elements are washed off, the washing residual liquid is merged into a water phase 2, the back extraction stage number is 4 stages, and the back extraction agent is 2.5mol/L sulfuric acid. Obtaining a manganese-rich solution and a regenerated organic phase, recycling the regenerated organic phase, and carrying out the next nickel extraction on the obtained water phase 2.
Performing nickel extraction on the aqueous phase 2, wherein in the embodiment, CPH88 is used as an extracting agent, the volume fraction of CPH88 is 25%, escaid110 is used as a diluent, 10mol/L NaOH solution is used for saponification, the saponification degree is 30%, and the flow ratio of a saponified organic phase to the aqueous phase 2 is 4: setting the mixing time of a mixing chamber to be 10min, setting the stirring speed to be 200r/min, using a mixer-settler as reaction equipment, designing the extraction stage number to be 5 stages, controlling the equilibrium pH value of an extraction water phase to be 2-4, washing the extraction water phase to be 6 stages, washing off metal elements such as cobalt, calcium, magnesium and the like carried in the extraction water phase, merging washing residual liquid into a water phase 3, performing back extraction on the extraction liquid to be 6 stages, and selecting 2.0mol/L sulfuric acid as a back extraction agent. Obtaining a nickel sulfate solution and a regenerated organic phase, recycling the regenerated organic phase, and carrying out cobalt extraction on the obtained water phase 3.
Cobalt extraction was performed on the aqueous phase 3, in this example, BC191 was used as the extractant, the BC191 volume fraction was 25%, escaid110 was used as the diluent, 10mol/L NaOH solution was used for saponification, the degree of saponification was 40%, the flow ratio of the saponified organic phase to the aqueous phase 2 was 2:1, setting the mixing time of a mixing chamber to be 8min, setting the stirring speed to be 200r/min, using a mixer-settler for reaction equipment, designing the extraction stage number to be 7, controlling the balance pH value of an extraction water phase to be 5-6.5, washing the extraction water phase to be 10 stages, washing off metal elements such as cobalt, calcium, magnesium and the like carried in the extraction water phase, merging washing residual liquid into a water phase 4, performing back extraction to be 6 stages, selecting 2.0mol/L sulfuric acid as a back extraction agent, and setting the volume of cobalt-loaded organic and washing liquid or back extraction liquid to be 10 to obtain a cobalt sulfate solution and a regenerated organic phase, recycling the regenerated organic phase, and performing next-step sodium sulfate precipitation on an obtained water phase 3.
After the aqueous phase 4 was degreased, it was crystallized by MVR evaporation.
In the embodiment, the contents of iron, aluminum, zinc and copper in the water phase after the manganese extraction are less than 0.001g/L, the extraction rates of Ni, co and Mn are respectively 99.8%, 99.7% and 99.6%, and the back extraction rates are respectively 99.8%, 99.8% and 99.6%.
Example 2
The feed liquid in the embodiment is a battery intermediate feed liquid containing nickel, cobalt and manganese, the pH value of the feed liquid is 2.0, and the feed liquid comprises the following components:
| element(s) | Fe | Al | Zn | Cu | Ni | Co | Mn | Ca | Mg |
| Content (g/L) | 1.2 | 1.0 | 0.20 | 0.01 | 48 | 22 | 27 | 0.36 | 0.48 |
In the embodiment, 20g/L of sodium carbonate is used for chemical impurity removal and iron and aluminum impurity removal, and the obtained water phase 1 is used for manganese extraction and iron and aluminum-containing slag.
In this example, P204 was selected as the extractant to perform manganese extraction on aqueous phase 1, the volume fraction was 25%, the diluent was sulfonated kerosene, 26% ammonia water solution was used for saponification, the degree of saponification was 30%, and the flow ratio of the saponified organic phase to the aqueous phase was 2:1, a reaction device uses a mixer-settler, the mixing time is 5min, the stirring speed is 300r/min, the designed extraction stage number is 8 stages, the washing stage number is 6 stages, metal elements such as nickel and cobalt carried by the metal elements are washed off, the washing residual liquid is merged into a water phase 2, the back extraction stage number is 4 stages, and the back extraction agent is 2.5mol/L sulfuric acid. And obtaining a manganese-rich solution and a regenerated organic phase, recycling the regenerated organic phase, and carrying out next nickel extraction on the obtained water phase 2.
Performing nickel extraction on the water phase 2, in the embodiment, using CPH88 as an extractant, the CPH88 volume fraction being 25%, using sulfonated kerosene as a diluent, using 26% ammonia water solution for saponification, the saponification degree being 45%, the flow ratio of the saponified organic phase to the water phase 2 being 5, setting the mixing time of the mixing chamber to be 10min, the stirring speed to be 300r/min, using a mixing and clarifying tank as reaction equipment, designing the extraction stage number to be 7, controlling the equilibrium pH value of the extraction water phase to be 2-4, washing 8 stages, washing off metal elements such as cobalt, calcium, magnesium and the like carried in the extraction water phase, merging the washing raffinate into the water phase 3, performing back extraction for 6 stages, and selecting 2.0mol/L sulfuric acid as the back extractant. Obtaining a nickel sulfate solution and a regenerated organic phase, recycling the regenerated organic phase, and carrying out cobalt extraction on the obtained water phase 3.
Cobalt extraction was performed on the aqueous phase 3, in this example, BC196 was used as an extractant, the BC196 volume fraction was 25%, sulfonated kerosene was used as a diluent, and saponification was performed using a 26% aqueous ammonia solution, the saponification degree was 30%, and the flow ratio of the saponified organic phase to the aqueous phase 2 was 2:1, setting the mixing time of a mixing chamber to be 8min, setting the stirring speed to be 200r/min, using a mixer-settler for reaction equipment, designing the extraction stage number to be 7, controlling the balance pH value of an extraction water phase to be 6-7, washing by 10 stages, washing off metal elements such as cobalt, calcium, magnesium and the like carried in the extraction water phase, merging washing residual liquid into a water phase 4, performing back extraction by 6 stages, selecting 2.0mol/L sulfuric acid as a back extraction agent, obtaining a cobalt sulfate solution and a regenerated organic phase by using cobalt-loaded organic and washing liquid or back extraction liquid with the volume of 10, recycling the regenerated organic, and performing next step of sodium sulfate precipitation on an obtained water phase 3.
After the aqueous phase 4 was degreased, it was crystallized by MVR evaporation.
In the embodiment, the content of iron and aluminum in the water phase after chemical impurity removal is less than 0.3g/L, the content of iron, aluminum, zinc and copper in the water phase after manganese extraction is less than 0.001g/L, the extraction rates of Ni, co and Mn are respectively 99.6%, 99.7% and 99.9%, and the back extraction rates are respectively 99.8%, 99.8% and 99.9%.
Example 3
This embodiment provides a method for recovering nickel, cobalt, and manganese from a nickel, cobalt, and manganese-containing feed liquid, where the feed liquid in this embodiment is a nickel, cobalt, and manganese-containing battery intermediate feed liquid, and the pH of the feed liquid is 5.2, and the components are as follows:
| element(s) | Fe | Al | Zn | Cu | Ni | Co | Mn | Ca | Mg |
| Content (g/L) | 0.001 | 0.001 | 0.001 | 0.001 | 40 | 27 | 23 | 0.30 | 0.56 |
In this example, P204 was selected as the extractant to perform manganese extraction on aqueous phase 1, the volume fraction was 25%, the diluent was solvent oil No. 260, the slurry magnesium oxide solution was used to perform saponification, the degree of saponification was 34%, and the flow ratio of the saponified organic phase to the aqueous phase was 2:1, a reaction device uses a mixer-settler, the mixing time is 10min, the stirring speed is 500r/min, the designed extraction stage number is 10 stages, the washing stage is 12 stages, metal elements such as nickel, cobalt and the like carried by the metal elements are washed off, the washing residual liquid is merged into a water phase 2, the back extraction stage is 4 stages, and the back extraction agent is 2.0mol/L sulfuric acid. Obtaining a manganese-rich solution and a regenerated organic phase, recycling the regenerated organic phase, and carrying out the next nickel extraction on the obtained water phase 2.
Performing nickel extraction on the aqueous phase 2, in this embodiment, using CPH88 as an extractant, the CPH88 volume fraction being 25%, using number 260 solvent oil as a diluent, using a slurried magnesium oxide solution to perform saponification, the saponification degree being 30%, the flow ratio of a saponified organic phase to the aqueous phase 2 being 4, setting the mixing time of a mixing chamber to be 5min, the stirring speed to be 500r/min, using a mixing clarification tank as a reaction device, designing the number of extraction stages to be 10, controlling the equilibrium pH value of the extracted aqueous phase to be between 2 and 3, washing 12 stages, washing off metal elements such as cobalt, calcium, magnesium and the like carried in the extracted aqueous phase, merging the washing raffinate into the aqueous phase 3, performing back extraction on the stage 6, and selecting 2.0mol/L sulfuric acid as a back extractant. Obtaining a nickel sulfate solution and a regenerated organic phase, recycling the regenerated organic phase, and carrying out cobalt extraction on the obtained water phase 3.
Cobalt extraction was performed on aqueous phase 3, in this example, BC196 was used as the extractant, the BC196 volume fraction was 25%, no. 260 mineral spirit was used as the diluent, the slurry magnesium oxide solution was used for saponification, the degree of saponification was 25%, and the flow ratio of the saponified organic phase to aqueous phase 2 was 3:1, setting the mixing time of a mixing chamber to be 7min, setting the stirring speed to be 500r/min, using a mixer-settler for reaction equipment, designing the extraction stage number to be 10, controlling the balance pH value of an extraction water phase to be 6-7, washing 16 stages, washing off metal elements such as cobalt, calcium, magnesium and the like carried in the extraction water phase, merging washing residual liquid into a water phase 4, performing back extraction for 6 stages, selecting 2.0mol/L sulfuric acid as a back extraction agent, setting the volume of cobalt-loaded organic and washing liquid or back extraction liquid to be 10, obtaining a cobalt sulfate solution and a regenerated organic phase, recycling the regenerated organic phase, and performing next step of sodium sulfate precipitation on an obtained water phase 3.
After the aqueous phase 4 was degreased, it was crystallized by MVR evaporation.
In the embodiment, the content of iron, aluminum, zinc and copper in the water phase is about 0.001g/L, the purity of manganese extraction is more than 97%, the extraction rates of Ni, co and Mn are respectively 99.4%, 99.2% and 99.8%, and the back extraction rates are respectively 99.8%, 99.8% and 99.9%.
Example 4
The difference from the embodiment 2 is that the average pH of the water phase 3 is controlled to be 1.9, the extraction rates of Ni, co and Mn are respectively 99.9%, 99.7% and 99.9%, the back extraction rate is more than 99.5%, the extraction stages and the alkali consumption are reduced, and the advantage of efficiently extracting nickel by CPH88 at low pH is realized.
Example 5
The difference from the embodiment 1 is that the extraction agent for extracting manganese is changed from P204 to C272, the extraction rates of Ni, co and Mn are respectively 99.9%, 99.9% and 99.9%, and the back extraction rate is more than 99.5%.
Comparative example 1
The only difference from example 1 is that the equilibrium pH of the aqueous phase of cobalt extraction was controlled to 7.6 and the impurity level of co was not standardized.
Comparative example 2
The only difference from example 3 is that the extractant CPH88 in the nickel extraction is replaced by an equal amount of P507, and the nickel cannot be separated by extraction.
From the results of the above examples and comparative examples, it can be seen that the method provided by the present invention can realize the effect of the prior high-efficiency separation of nickel and the extraction of impurity metal ions such as calcium and magnesium in the nickel extraction process by utilizing the advantage of the extraction of nickel with low acid by the extractant CPH88, and reduce the separation cost of separately recovering nickel, cobalt and manganese and the extraction and purification cost of impurity metal ions by using carboxylic acids to extract BC196, BC191 and the like in the cobalt extraction process.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are all within the protection scope of the present invention.
It should be noted that, in the above embodiments, the various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present invention does not separately describe various possible combinations.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A method for separating nickel, cobalt and manganese from a battery intermediate feed liquid containing nickel, cobalt and manganese is characterized by comprising the following steps:
(1) The metal elements in the feed liquid comprise: 1 to 60g/L of Ni, 1 to 50g/L of Co, 1 to 50g/L of Mn, less than or equal to 10g/L of Fe, less than or equal to 1g/L of Al, less than or equal to 10g/L of Cu, less than or equal to 5g/L of Zn, 0.1 to 0.5g/L of Ca and 0.1 to 50g/L of Mg; chemically removing impurities from the feed liquid by using sodium carbonate to obtain a water phase 1 and iron-containing aluminum slag liquid; carrying out filter pressing on the slag liquid to obtain iron-containing aluminum slag;
(2) Performing manganese extraction on the water phase 1 obtained in the step (1) by using an extractant A to obtain a manganese loaded organic phase and a water phase 2; wherein the extractant A is P204 or C272, and the volume fraction of the extractant A is 5 to 30 percent; saponifying the extractant A before use; the water phase equilibrium pH value of the manganese extraction is 1-4; the flow ratio of the extracting agent A to the feed liquid is (0.1-10) to 1, the manganese extraction mode is 2-30-stage multistage countercurrent fractional extraction, the stirring speed is 100-800 r/min, and the stirring and mixing time is 5-30 min; washing and back extracting the manganese-loaded organic to obtain a manganese-rich solution;
(3) Carrying out nickel extraction on the water phase 2 obtained in the step (2) by using an extractant B to obtain a nickel-loaded organic phase and a water phase 3, and washing and back-extracting the nickel-loaded organic phase to obtain a nickel sulfate solution;
wherein the extractant B comprises a carboxylic acid extractant; the carboxylic acid extractant has a structural formula shown in a formula I, and is named as CPH88:
wherein-C 8 H 17 Are all straight chain alkyl;
the volume fraction of the extractant B is 5-30%, the saponification degree of the extractant B is 5-60%, and the water phase equilibrium pH of nickel extraction is 1.9 or 2.0-3.5; the volume ratio of the extractant B to the water phase 2 is (0.1-20) to 1, the nickel extraction mode is 2-30 stages of multistage countercurrent fractional extraction, the stirring speed in the nickel extraction is 100-800 r/min, and the mixing time in the nickel extraction in the step (3) is 5-30 min;
(4) Carrying out cobalt extraction on the water phase 3 obtained in the step (3) by using an extractant C to obtain a cobalt loaded organic phase and a water phase 4; washing and back-extracting the cobalt-loaded organic phase to obtain a cobalt sulfate solution;
wherein the extractant C is P507, the volume concentration of the extractant C in an extracted organic phase is 5-30%, the saponification degree of the extractant C is 5-60%, and the water phase equilibrium pH of cobalt extraction is 3-5; the volume ratio of the extractant C to the water phase 3 is (0.1-20) to 1, the cobalt extraction mode is 2-30-stage multistage countercurrent fractional extraction, the stirring speed in the cobalt extraction is 100-800 r/min, and the mixing time in the cobalt extraction in the step (3) is 5-30 min;
(5) And (5) performing sodium sulfate crystal enrichment separation on the water phase 4 obtained in the step (4), wherein the sodium sulfate crystal enrichment separation comprises oil removal and MVR evaporation crystallization to obtain sodium sulfate crystals, and the wastewater is treated and then discharged after reaching the standard.
2. The method according to claim 1, wherein the concentration of sodium carbonate is between 10 and 100g/L.
3. The process of claim 1, wherein the diluent for extractant a, extractant B, extractant C comprises 1 or a combination of at least 2 of mineral spirits, sulfonated kerosene, escoid 110, hexane, heptane, dodecane.
4. The method of claim 1, wherein the saponifying of extractant a, extractant B, and extractant C is performed with 6 to 14mol/L of an alkaline saponifying agent.
5. The method of claim 4, wherein the alkaline saponifier comprises a combination of 1 or at least 2 of sodium hydroxide solution, magnesium oxide, potassium hydroxide solution, or ammonia water.
6. The method of claim 1, wherein the extraction equipment used in the manganese extraction in step (2), the nickel extraction in step (3), and the cobalt extraction in step (4) is a mixer settler.
7. The method according to claim 1, characterized in that the stripping agent used for the stripping of the loaded organic phase is sulfuric acid with a concentration of 2 mol/L; the back extraction stage number is 3-10; the flow ratio of the stripping agent to the loaded organic phase is 1 (0.1-15).
8. The method of claim 1, wherein the number of washing stages is 2 to 20; the washing comprises inorganic acid and/or acidified water, nickel sulfate and cobalt sulfate solution washing.
9. The method of claim 8, wherein the inorganic acid and/or acidified water has a pH of 0.1 to 2.
10. The method of claim 8, wherein the nickel sulfate and cobalt sulfate solution is 0.5-20 g/L.
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