CN113737000A - Method for cleanly recovering valuable metals in ternary battery material in short process - Google Patents

Method for cleanly recovering valuable metals in ternary battery material in short process Download PDF

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CN113737000A
CN113737000A CN202111070437.9A CN202111070437A CN113737000A CN 113737000 A CN113737000 A CN 113737000A CN 202111070437 A CN202111070437 A CN 202111070437A CN 113737000 A CN113737000 A CN 113737000A
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extraction
solution
value
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precipitation
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孟龙
魏广叶
沈晓博
余志辉
曲景奎
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Institute of Process Engineering of CAS
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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
    • 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
    • C22B21/00—Obtaining aluminium
    • C22B21/0015—Obtaining aluminium by wet processes
    • C22B21/0023—Obtaining aluminium by wet processes from waste materials
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
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    • Y02W30/84—Recycling of batteries or fuel cells

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Abstract

The invention provides a short-process clean recovery method of valuable metals in a ternary battery material, which comprises the following steps: extracting and back-extracting the waste ternary battery material after lithium extraction to obtain copper salt and back-extraction solution, precipitating and separating the back-extraction solution to obtain filtrate, and performing synergistic extraction and back-extraction separation on the filtrate to obtain the nickel-cobalt-manganese solution. The invention adopts a novel extraction system and a novel separation process to realize the directional short-range recovery of valuable components in waste battery materials and the efficient enrichment and selective separation and recovery of a multi-component solution system.

Description

Method for cleanly recovering valuable metals in ternary battery material in short process
Technical Field
The invention belongs to the technical field of battery material recovery, and relates to a short-process clean recovery method of valuable metals in a ternary battery material.
Background
With the vigorous popularization of the application range of the ternary battery, the demand of the whole new energy industry on related materials is gradually increased, and particularly the demand on metals such as nickel and cobalt is gradually increased. According to statistics, the external dependence of the nickel and cobalt resources in China exceeds 85% and 90% respectively. With the increase of economy, the consumption of lithium, nickel and cobalt is rapidly increased, and China has leaped the position of the first major consumer countries of lithium, nickel and cobalt in the world. In recent years, the ternary battery in the field of power lithium batteries is widely applied due to excellent performance, the waste amount of the ternary battery is increased year by year, and the amount of the retired lithium ion power battery in China reaches 36.23 million tons by 2022 years according to the estimation of the research center of automobile technology in China. The waste lithium battery contains various valuable metal resources, which account for 26-76% of the total content of the waste battery, wherein copper and aluminum account for about 20%, lithium accounts for 1-15%, cobalt accounts for 2-30%, and the balance is nickel, manganese, iron and the like, so that the waste lithium battery has a huge recovery prospect.
Related researches on battery material recovery technologies are carried out at home and abroad, wherein the resource recovery process mainly adopts wet extraction, namely valuable metals in the positive electrode waste are leached into a solution in an acidic or alkaline solution, and then selective separation and recovery of different types of metal ions are realized by means of chemical precipitation, solvent extraction, adsorption, ion exchange, electrodeposition and the like.
CN105591171A discloses a method for recovering waste and old materials without using any extractant and other organic solventsMethods for making various valuable metals for lithium batteries. Adjusting pH of the solution with alkaline solution by chemical precipitation to recover aluminum (Al (OH)3) (ii) a Adding acid to dissolve insoluble substances, adjusting the pH value of the solution to be alkaline, and recovering to obtain Lithium (LiOH); dissolving the precipitate insoluble substance with acid, complexing with ammonia water, adjusting pH of the solution to alkaline, adding soluble carbonate to form precipitate, and recovering to obtain manganese (MnCO)3) (ii) a Adding soluble carbonate into the filtrate, adjusting the pH of the solution to 3.0-3.5, adding hypochlorite to adjust the pH to 2.0-3.0, precipitating to obtain cobalt salt, and separating nickel and cobalt.
The invention patent of CN102676827B discloses a method for recovering valuable metals from nickel cobalt manganese lithium batteries, which comprises the steps of leaching raw materials by using a mixed solution of hydrogen peroxide and sulfuric acid, adjusting the pH value of filtrate to 6.5-7.5 by using alkali liquor to precipitate aluminum ions, copper ions and iron ions, then adding carbonate into the filtrate to precipitate nickel cobalt manganese and obtain a lithium-containing solution.
CN104577248A discloses a method for recovering a lithium battery anode material, wherein aluminum hydroxide and lithium cobaltate powder can be obtained from a lithium battery normal material soaked in an alkali liquor, the lithium cobaltate powder is obtained by hydrolysis, then the lithium cobaltate powder is placed in an atmosphere furnace, and hydrogen is introduced to heat the lithium cobaltate powder to 580-780 ℃ at high temperature to obtain lithium cobaltate; and (3) hydrolyzing the hydrogenated lithium cobaltate, heating soda ash to obtain lithium carbonate, performing solid-liquid separation and drying to obtain cobalt oxide, and using the cobalt oxide to prepare a battery material.
Current recovery schemes typically attempt to separate and recover each of the metallic elements in the positive electrode material in order to achieve higher recovery rates. However, in the leaching link, almost all metal elements in the positive electrode material are simultaneously leached, so that the components of the leachate are very complex, and the operations of chemical precipitation, extraction, ion adsorption and the like are required for multiple times to realize effective separation of different components in the leachate. The process is complex in process, long in recovery process and high in production cost, entrainment loss of other metal elements can be caused almost every step of operation, and in addition, the composition and the structure of the anode material are more complex and changeable along with continuous development of anode material doping and coating preparation technology, so that the existing recovery mode is more complicated. Aiming at the problems existing at present, the invention greatly shortens the process flow, reduces the production cost, realizes short-range, clean and efficient selective separation and recovery of valuable components in the waste batteries and improves the comprehensive utilization of waste resources by means of solution chemical regulation and synergistic extraction strengthening.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for cleanly recovering valuable metals in a ternary battery material in a short flow.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a short-flow clean recovery method for valuable metals in ternary battery materials, which comprises the following steps:
extracting and back-extracting the waste ternary battery material after lithium extraction to obtain copper salt and back-extraction solution, precipitating and separating the back-extraction solution to obtain filtrate, and performing synergistic extraction and back-extraction separation on the filtrate to obtain the nickel-cobalt-manganese solution.
The invention adopts a novel extraction system and a novel separation process to realize the directional short-range recovery of valuable components in waste battery materials and the efficient enrichment and selective separation and recovery of a multi-component solution system.
As a preferred technical solution of the present invention, the extracting agent used in the extracting process includes any one of LIX63, LIX984, or LIX841, or a combination of at least two thereof.
Preferably, the volume concentration of the extractant is 5-40 vol%, for example, 5 vol%, 10 vol%, 15 vol%, 20 vol%, 25 vol%, 30 vol%, 35 vol% or 40 vol%, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
In a preferred embodiment of the present invention, the pH value of the reaction equilibrium in the extraction process is 2.0 to 5.5, for example, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0 or 5.5, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the extraction process has an O/a ratio of 0.5 to 7, for example 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5 or 7, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the extraction time is 1-30 min, such as 1min, 5min, 10min, 15min, 20min, 25min or 30min, but not limited to the values listed, and other values not listed in the range of values are also applicable.
In a preferred embodiment of the present invention, the precipitant used in the precipitation separation process includes any one or a combination of at least two of sodium hydroxide, potassium hydroxide, and ammonia water.
Preferably, the concentration of the precipitant is 1 to 50 wt%, and may be, for example, 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, or 50 wt%, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
In a preferred embodiment of the present invention, the time for separating the precipitate is 0.5 to 3 hours, for example, 0.5 hour, 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the precipitation separation temperature is 25 ~ 100 ℃, for example can be 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃, but not limited to the number, in the range of other values are also applicable.
As a preferable technical scheme of the invention, the precipitate obtained after the precipitation separation comprises ferric hydroxide and aluminum hydroxide.
Preferably, different precipitates are obtained by precipitation through adjusting the pH value of the stripping solution in the precipitation separation process.
Preferably, when the pH of the stripping solution is adjusted to 1.0 to 3.0, the ferric hydroxide is precipitated, and may be, for example, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8 or 3.0, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the aluminum hydroxide is precipitated when the pH of the stripping solution is adjusted to 3.0 to 5.0, and may be, for example, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8 or 5.0, 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 synergistic extraction agent used in the synergistic extraction process includes any one or a combination of at least two of LIX984, P507, LIX63, P204, LIX841, Versatic10, Cyanex272, and alkylated bipyridine amine.
Preferably, the volume concentration of the synergistic extractant is 5 to 40 vol%, for example, 5 vol%, 10 vol%, 15 vol%, 20 vol%, 25 vol%, 30 vol%, 35 vol% or 40 vol%, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
In a preferred embodiment of the present invention, the reaction equilibrium pH of the synergistic extraction is 2.0 to 6.0, for example, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5 or 6.0, but is not limited to the values listed above, and other values not listed above are also applicable within this range.
Preferably, the co-extraction has an O/a ratio of 0.5 to 7, for example 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5 or 7, but not limited to the values listed, and other values not listed within this range are equally applicable.
Preferably, the synergistic extraction time is 1-30 min, such as 1min, 5min, 10min, 15min, 20min, 25min or 30min, but not limited to the recited values, and other values not recited in the range of values are also applicable.
As a preferred technical solution of the present invention, the stripping agent used in the stripping process includes a sulfuric acid solution.
Preferably, the concentration of the stripping agent is 1-100 g/L, for example, 1g/L, 10g/L, 20g/L, 30g/L, 40g/L, 50g/L, 60g/L, 70g/L, 80g/L, 90g/L or 100g/L, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the stripping process has an O/a of 0.5 to 10, for example, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, but not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the stripping time is 1-30 min, such as 1min, 2min, 4min, 6min, 8min, 10min, 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min, 28min or 30min, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the reaction equilibrium of the stripping process has a pH of 0.5 to 6, for example, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5 or 6, but not limited to the recited values, and other values not recited in the range of values are also applicable.
As a preferred technical solution of the present invention, the method specifically comprises the following steps:
extracting the waste ternary battery material subjected to lithium extraction for 1-30 min by adopting 5-40 vol% of extracting agent to obtain an organic phase solution, wherein the extracting agent comprises any one or combination of at least two of LIX63, LIX984 or LIX841, the pH value of reaction balance in the extraction process is 2.0-5.5, and the O/A ratio in the extraction process is 0.5-7;
(II) carrying out back extraction on the organic phase solution obtained in the step (I) for 1-30 min by adopting 1-100 g/L sulfuric acid solution to obtain a back extraction solution, wherein the O/A in the back extraction process is 0.5-10, and the pH value of the reaction balance in the back extraction process is 0.5-6;
(III) adding 1-50 wt% of precipitator into the stripping solution obtained in the step (II) to perform precipitation separation for 0.5-3 h at 25-100 ℃ to obtain filtrate, wherein the precipitator comprises any one or combination of at least two of sodium hydroxide, potassium hydroxide or ammonia water, different precipitates are obtained through precipitation by adjusting the pH value of the stripping solution in the precipitation separation process, ferric hydroxide is obtained through precipitation when the pH value of the stripping solution is adjusted to 1.0-3.0, and aluminum hydroxide is obtained through precipitation when the pH value of the stripping solution is adjusted to 3.0-5.0;
(IV) carrying out synergistic extraction on the filtrate obtained in the step (III) for 1-30 min by adopting 5-40 vol% of a synergistic extraction agent to obtain an extraction liquid, wherein the synergistic extraction agent comprises any one or a combination of at least two of LIX984, P507, LIX63, P204, LIX841, Versatic10, Cyanex272 or alkylated bipyridine amine, the reaction equilibrium pH value of the synergistic extraction is 2.0-6.0, and the O/A ratio of the synergistic extraction is 0.5-7;
and (V) carrying out back extraction on the extraction liquid obtained in the step (IV) for 1-30 min by adopting 1-100 g/L sulfuric acid solution to obtain a nickel-cobalt-manganese solution, wherein the O/A in the back extraction process is 0.5-10, and the pH value of the reaction balance in the back extraction process is 0.5-6.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts a novel extraction system and a novel separation process to realize the directional short-range recovery of valuable components in waste battery materials and the efficient enrichment and selective separation and recovery of a multi-component solution system.
Drawings
Fig. 1 is a flowchart of a method provided in embodiment 1 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a short-flow clean recovery ternary batteryMethod for preparing valuable metal in material, waste ternary battery material comprises 29.73g/L of Ni2+50.86g/L of Co2+Mn of 24.17g/L2+0.29g/L of Ca2+0.42g/L of Mg2+5.72g/L Fe2+7.23g/L of Al3+5.51g/L of Cu2+(ii) a The method is shown in fig. 1, and specifically comprises the following steps:
(I) extracting the waste ternary battery material after lithium extraction for 5min by adopting 20 vol% of LIX984 extracting agent to obtain CuSO4The pH value of the reaction balance in the extraction process of the organic phase solution is 2.0, and the O/A ratio in the extraction process is 1;
(II) carrying out back extraction on the organic phase solution obtained in the step (I) for 5min by adopting 5g/L sulfuric acid solution to obtain a back extraction solution, wherein the O/A in the back extraction process is 3, the pH value of the reaction balance in the back extraction process is 6, and the single extraction recovery rate of copper is 97.10%;
(III) adding 10 wt% of sodium hydroxide solution into the stripping solution obtained in the step (II), precipitating and separating for 0.5h at 30 ℃ to obtain filtrate, precipitating to obtain ferric hydroxide when the pH value of the stripping solution is adjusted to 2.8, precipitating to obtain aluminum hydroxide when the pH value of the stripping solution is adjusted to 4.2, and precipitating to obtain aluminum hydroxide, wherein the precipitation rates of the iron and the aluminum are 99.9% and 85.6% respectively;
(IV) carrying out synergistic extraction on the filtrate obtained in the step (III) for 5min by adopting a mixed extracting agent consisting of Versatic10 and alkylated bipyridine amine (the concentration of the mixed extracting agent is 20 vol%, and the concentrations of Versatic10 and the alkylated bipyridine amine are the same) to obtain an extract liquor, wherein the reaction equilibrium pH value of the synergistic extraction is 5.3, and the O/A ratio of the synergistic extraction is 10;
and (V) carrying out back extraction on the extract liquor obtained in the step (IV) for 5min by adopting 80g/L sulfuric acid solution to obtain a nickel-cobalt-manganese solution, wherein the O/A in the back extraction process is 1, the reaction balance pH value in the back extraction process is 3, the nickel-cobalt-manganese solution is obtained after 3-stage cascade back extraction and organic phase washing impurity removal, the nickel-cobalt-manganese solution meets the requirement of preparing a ternary precursor, and the extraction recovery rates of nickel, cobalt and manganese are 99.55%, 99.89% and 99.10% respectively.
Example 2
The embodiment is providedProvides a method for cleanly recovering valuable metals in a ternary battery material in a short process, and the waste ternary battery material comprises 29.03g/L of Ni2+50.68g/L of Co2+Mn of 24.25g/L2+0.27g/L of Ca2+0.40g/L of Mg2+5.71g/L Fe2+7.33g/L of Al3+5.28g/L of Cu2+(ii) a The method is shown in fig. 1, and specifically comprises the following steps:
(I) extracting the waste ternary battery material after lithium extraction for 10min by adopting 15 vol% of LIX63 extractant to obtain CuSO4The pH value of the reaction balance in the extraction process of the organic phase solution is 2.8, and the O/A ratio in the extraction process is 2;
(II) carrying out back extraction on the organic phase solution obtained in the step (I) for 10min by adopting 3g/L sulfuric acid solution to obtain a back extraction solution, wherein the O/A in the back extraction process is 3, the pH value of the reaction balance in the back extraction process is 6, and the single extraction recovery rate of copper is 97.83%;
(III) adding 15 wt% of sodium hydroxide solution into the stripping solution obtained in the step (II) and precipitating and separating for 0.5h at 25 ℃ to obtain filtrate, wherein when the pH value of the stripping solution is adjusted to 2.7, ferric hydroxide is obtained through precipitation, when the pH value of the stripping solution is adjusted to 4.0, aluminum hydroxide is obtained through precipitation, and the precipitation rates of iron and aluminum are 99.95% and 86.9% respectively;
(IV) performing synergistic extraction on the filtrate obtained in the step (III) for 10min by adopting 15 vol% Versatic10 extractant to obtain extract liquor, wherein the reaction equilibrium pH value of the synergistic extraction is 5.1, and the O/A ratio of the synergistic extraction is 7;
and (V) carrying out back extraction on the extract liquor obtained in the step (IV) for 10min by adopting 100g/L sulfuric acid solution to obtain a nickel-cobalt-manganese solution, wherein the O/A in the back extraction process is 3, the reaction balance pH value in the back extraction process is 4, the nickel-cobalt-manganese solution is obtained after 3-stage cascade back extraction and organic phase washing impurity removal, the nickel-cobalt-manganese solution meets the requirement of preparing a ternary precursor, and the extraction recovery rates of nickel, cobalt and manganese are 99.15%, 99.18% and 99.07% respectively.
Example 3
The embodiment provides a method for cleanly recovering valuable metals in a ternary battery material in a short processThe method comprises the step of adding 28.84g/L of Ni into a waste ternary battery material2+51.68g/L of Co2+Mn of 24.27g/L2+0.26g/L of Ca2+0.41g/L of Mg2+5.57g/L Fe2+7.21g/L of Al3+5.37g/L of Cu2+(ii) a The method is shown in fig. 1, and specifically comprises the following steps:
(I) extracting the waste ternary battery material subjected to lithium extraction for 15min by adopting a mixed extractant (the total concentration of the mixed extractant is 25 vol%, and the concentrations of the LIX841 and the LIX984 are the same) consisting of LIX841 and LIX984 to obtain CuSO4The pH value of the reaction balance in the extraction process of the organic phase solution is 2.8, and the O/A ratio in the extraction process is 3;
(II) carrying out back extraction on the organic phase solution obtained in the step (I) for 10min by adopting a 5g/L sulfuric acid solution to obtain a back extraction solution, wherein the O/A in the back extraction process is 3, the pH value of the reaction balance in the back extraction process is 5.5, and the single extraction recovery rate of copper is 97.67%;
(III) adding 25 wt% of sodium hydroxide solution into the stripping solution obtained in the step (II), precipitating and separating for 0.5h at 35 ℃ to obtain filtrate, precipitating to obtain ferric hydroxide when the pH value of the stripping solution is adjusted to 2.9, and precipitating to obtain aluminum hydroxide when the pH value of the stripping solution is adjusted to 4.5, wherein the precipitation rates of the ferric hydroxide and the aluminum hydroxide are respectively 100% and 87.6%;
(IV) carrying out synergistic extraction on the filtrate obtained in the step (III) for 15min by adopting a mixed extractant consisting of LIX984 and P204 (the total concentration of the mixed extractant is 25 vol%, and the concentrations of the LIX984 and the P204 are the same) to obtain an extract liquor, wherein the reaction equilibrium pH value of the synergistic extraction is 5.5, and the O/A ratio of the synergistic extraction is 5;
and (V) performing back extraction on the extract liquor obtained in the step (IV) for 10min by adopting 90g/L sulfuric acid solution to obtain a nickel-cobalt-manganese solution, wherein the O/A in the back extraction process is 2, the reaction balance pH value in the back extraction process is 3.5, and the nickel-cobalt-manganese solution is obtained after 3-stage cascade back extraction and organic phase washing impurity removal, meets the requirement of preparing a ternary precursor, and the extraction recovery rates of nickel, cobalt and manganese are 99.85%, 99.36% and 99.42% respectively.
Example 4
The embodiment provides a short-process clean recovery method of valuable metals in ternary battery materials, wherein the waste ternary battery materials comprise 29.52g/L of Ni2+50.73g/L of Co2+Mn of 24.06g/L2+0.25g/L of Ca2+0.43g/L of Mg2+5.75g/L Fe2+7.18g/L of Al3+5.33g/L of Cu2+(ii) a The method is shown in fig. 1, and specifically comprises the following steps:
(I) extracting the waste ternary battery material after lithium extraction for 30min by adopting 5 vol% of LIX984 extracting agent to obtain CuSO4The pH value of the reaction balance in the extraction process of the organic phase solution is 2.0, and the O/A ratio in the extraction process is 0.5;
(II) carrying out back extraction on the organic phase solution obtained in the step (I) for 30min by adopting 1g/L sulfuric acid solution to obtain a back extraction solution, wherein the O/A in the back extraction process is 0.5, the pH value of the reaction balance in the back extraction process is 0.5, and the single extraction recovery rate of copper is 97.55%;
(III) adding 1 wt% of potassium hydroxide solution into the stripping solution obtained in the step (II) and precipitating and separating for 1h at 100 ℃ to obtain filtrate, wherein when the pH value of the stripping solution is adjusted to 1.0, ferric hydroxide is obtained through precipitation, when the pH value of the stripping solution is adjusted to 3.0, aluminum hydroxide is obtained through precipitation, and the precipitation rates of iron and aluminum are 99.98% and 85.5% respectively;
(IV) carrying out synergistic extraction on the filtrate obtained in the step (III) for 30min by adopting 5 vol% of P204 to obtain an extraction liquid, wherein the reaction equilibrium pH value of the synergistic extraction is 2.0, and the O/A ratio of the synergistic extraction is 0.5;
and (V) performing back extraction on the extract liquor obtained in the step (IV) for 30min by adopting 50g/L sulfuric acid solution to obtain a nickel-cobalt-manganese solution, wherein the O/A in the back extraction process is 0.5, the pH value of the reaction balance in the back extraction process is 0.5, the nickel-cobalt-manganese solution is obtained after 3-stage cascade back extraction and organic phase washing impurity removal, the nickel-cobalt-manganese solution meets the requirement of preparing a ternary precursor, and the extraction recovery rates of nickel, cobalt and manganese are respectively 99.63%, 99.56% and 99.35%.
Example 5
The embodiment provides a short-process clean recovery ternary battery materialMethod for preparing valuable metal in material, waste ternary battery material comprises 29.46g/L of Ni2+50.96g/L of Co2+Mn 24.34g/L2+0.30g/L of Ca2+0.35g/L of Mg2+5.80g/L Fe2+7.53g/L of Al3+5.42g/L of Cu2+(ii) a The method is shown in fig. 1, and specifically comprises the following steps:
(I) extracting the waste ternary battery material after lithium extraction for 15min by adopting a mixed extracting agent consisting of LIX63 and LIX984 (the concentration of the mixed extracting agent is 20 vol%, and the concentrations of LIX63 and LIX984 are the same) to obtain CuSO4The pH value of the reaction balance in the extraction process of the organic phase solution is 4.0, and the O/A ratio in the extraction process is 3;
(II) carrying out back extraction on the organic phase solution obtained in the step (I) for 15min by adopting 5g/L sulfuric acid solution to obtain a back extraction solution, wherein the O/A in the back extraction process is 5, the pH value of the reaction balance in the back extraction process is 3, and the single extraction recovery rate of copper is 97.48%;
(III) adding 20 wt% of ammonia water into the stripping solution obtained in the step (II) to perform precipitation separation for 2 hours at 60 ℃ to obtain filtrate, precipitating to obtain ferric hydroxide when the pH value of the stripping solution is adjusted to 2.0, precipitating to obtain aluminum hydroxide when the pH value of the stripping solution is adjusted to 4.0, and precipitating to obtain aluminum hydroxide, wherein the precipitation rates of the ferric hydroxide and the aluminum hydroxide are respectively 100% and 88.2%;
(IV) carrying out synergistic extraction on the filtrate obtained in the step (III) for 15min by adopting a mixed extracting agent consisting of P507 and P204 (the total concentration of the mixed extracting agent is 20 vol%, and the concentrations of P507 and P204 are the same) to obtain an extract liquor, wherein the reaction equilibrium pH value of the synergistic extraction is 4.0, and the O/A ratio of the synergistic extraction is 3;
and (V) carrying out back extraction on the extract liquor obtained in the step (IV) for 15min by adopting 60g/L sulfuric acid solution to obtain a nickel-cobalt-manganese solution, wherein the O/A in the back extraction process is 5, the reaction balance pH value in the back extraction process is 3, the nickel-cobalt-manganese solution is obtained after 3-stage cascade back extraction and organic phase washing impurity removal, the nickel-cobalt-manganese solution meets the requirement of preparing a ternary precursor, and the extraction recovery rates of nickel, cobalt and manganese are 99.78%, 99.65% and 99.21% respectively.
Example 6
The embodiment provides a method for cleanly recovering valuable metals in a ternary battery material in a short process, wherein the waste ternary battery material comprises 29.33g/L of Ni2+50.58g/L of Co2+Mn of 24.45g/L2+0.32g/L of Ca2+0.44g/L Mg2+5.78g/L Fe2+7.35g/L of Al3+5.35g/L of Cu2+(ii) a The method is shown in fig. 1, and specifically comprises the following steps:
(I) extracting the waste ternary battery material after lithium extraction for 1min by adopting 40 vol% of LIX984 extracting agent to obtain CuSO4The pH value of the reaction balance in the extraction process of the organic phase solution is 5.5, and the O/A ratio in the extraction process is 7;
(II) carrying out back extraction on the organic phase solution obtained in the step (I) for 1min by adopting 10g/L sulfuric acid solution to obtain a back extraction solution, wherein the O/A in the back extraction process is 10, the pH value of the reaction balance in the back extraction process is 6, and the single extraction recovery rate of copper is 97.52%;
(III) adding 50 wt% of potassium hydroxide solution into the stripping solution obtained in the step (II) to perform precipitation separation for 3 hours at 25 ℃ to obtain filtrate, precipitating to obtain ferric hydroxide when the pH value of the stripping solution is adjusted to 3.0, and precipitating to obtain aluminum hydroxide when the pH value of the stripping solution is adjusted to 5.0, wherein the precipitation rates of the ferric hydroxide and the aluminum are 99.93% and 87.2% respectively;
(IV) carrying out synergistic extraction on the filtrate obtained in the step (III) for 1min by adopting 40 vol% of Cyanex272 synergistic extractant to obtain extract liquor, wherein the reaction equilibrium pH value of the synergistic extraction is 6.0, and the O/A ratio of the synergistic extraction is 7;
and (V) carrying out back extraction on the extract liquor obtained in the step (IV) for 1min by adopting 70g/L sulfuric acid solution to obtain a nickel-cobalt-manganese solution, wherein the O/A in the back extraction process is 10, the reaction balance pH value in the back extraction process is 6, the nickel-cobalt-manganese solution is obtained after 3-stage cascade back extraction and organic phase washing impurity removal, the nickel-cobalt-manganese solution meets the requirement of preparing a ternary precursor, and the extraction recovery rates of nickel, cobalt and manganese are 99.36%, 99.72% and 99.08% respectively.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. A method for clean recovery of valuable metals in ternary battery materials in a short process is characterized by comprising the following steps:
extracting and back-extracting the waste ternary battery material after lithium extraction to obtain copper salt and back-extraction solution, precipitating and separating the back-extraction solution to obtain filtrate, and performing synergistic extraction and back-extraction separation on the filtrate to obtain the nickel-cobalt-manganese solution.
2. The method of claim 1, wherein the extractant used in the extraction process comprises any one or a combination of at least two of LIX63, LIX984, or LIX 841;
preferably, the volume concentration of the extracting agent is 5-40 vol%.
3. The method according to claim 1 or 2, wherein the pH value of the reaction equilibrium of the extraction process is 2.0-5.5;
preferably, the O/A ratio of the extraction process is 0.5-7;
preferably, the extraction time is 1-30 min.
4. The method according to any one of claims 1 to 3, wherein the precipitant used in the precipitation separation process comprises any one or a combination of at least two of sodium hydroxide, potassium hydroxide or ammonia water;
preferably, the concentration of the precipitant is 1-50 wt%.
5. The method according to any one of claims 1 to 4, wherein the precipitation separation time is 0.5 to 3 hours;
preferably, the temperature of the precipitation separation is 25-100 ℃.
6. The method according to any one of claims 1 to 5, wherein the precipitate obtained after the separation of the precipitate comprises iron hydroxide and aluminum hydroxide;
preferably, different precipitates are obtained by precipitation through adjusting the pH value of the stripping solution in the precipitation separation process;
preferably, when the pH value of the stripping solution is adjusted to 1.0-3.0, precipitating to obtain ferric hydroxide;
preferably, when the pH value of the stripping solution is adjusted to 3.0-5.0, aluminum hydroxide is obtained through precipitation.
7. The process of any one of claims 1 to 6, wherein the co-extractant used in the co-extraction process comprises any one or a combination of at least two of LIX984, P507, LIX63, P204, LIX841, Versatic10, Cyanex272 or an alkylated bipyridine amine;
preferably, the volume concentration of the synergistic extraction agent is 5-40 vol%.
8. The method according to any one of claims 1 to 7, wherein the reaction equilibrium pH of the synergistic extraction is 2.0 to 6.0;
preferably, the O/A ratio of the synergistic extraction is 0.5-7;
preferably, the synergistic extraction time is 1-30 min.
9. The method according to any one of claims 1 to 8, wherein the stripping process uses a stripping agent comprising a sulfuric acid solution;
preferably, the concentration of the stripping agent is 1-100 g/L;
preferably, the O/A in the back extraction process is 0.5-10;
preferably, the back extraction time is 1-30 min;
preferably, the pH value of the reaction balance in the back extraction process is 0.5-6.
10. The method according to any one of claims 1 to 9, characterized in that it comprises in particular the steps of:
extracting the waste ternary battery material subjected to lithium extraction for 1-30 min by adopting 5-40 vol% of extracting agent to obtain an organic phase solution, wherein the extracting agent comprises any one or combination of at least two of LIX63, LIX984 or LIX841, the pH value of reaction balance in the extraction process is 2.0-5.5, and the O/A ratio in the extraction process is 0.5-7;
(II) carrying out back extraction on the organic phase solution obtained in the step (I) for 1-30 min by adopting 1-100 g/L sulfuric acid solution to obtain a back extraction solution, wherein the O/A in the back extraction process is 0.5-10, and the pH value of the reaction balance in the back extraction process is 0.5-6;
(III) adding 1-50 wt% of precipitator into the stripping solution obtained in the step (II) to perform precipitation separation for 0.5-3 h at 25-100 ℃ to obtain filtrate, wherein the precipitator comprises any one or combination of at least two of sodium hydroxide, potassium hydroxide or ammonia water, different precipitates are obtained through precipitation by adjusting the pH value of the stripping solution in the precipitation separation process, ferric hydroxide is obtained through precipitation when the pH value of the stripping solution is adjusted to 1.0-3.0, and aluminum hydroxide is obtained through precipitation when the pH value of the stripping solution is adjusted to 3.0-5.0;
(IV) carrying out synergistic extraction on the filtrate obtained in the step (III) for 1-30 min by adopting 5-40 vol% of a synergistic extraction agent to obtain an extraction liquid, wherein the synergistic extraction agent comprises any one or a combination of at least two of LIX984, P507, LIX63, P204, LIX841, Versatic10, Cyanex272 or alkylated bipyridine amine, the reaction equilibrium pH value of the synergistic extraction is 2.0-6.0, and the O/A ratio of the synergistic extraction is 0.5-7;
and (V) carrying out back extraction on the extraction liquid obtained in the step (IV) for 1-30 min by adopting 1-100 g/L sulfuric acid solution to obtain a nickel-cobalt-manganese solution, wherein the O/A in the back extraction process is 0.5-10, and the pH value of the reaction balance in the back extraction process is 0.5-6.
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