CN114561541A - Method for synchronously recycling nickel, cobalt and manganese from battery positive plate leachate - Google Patents

Method for synchronously recycling nickel, cobalt and manganese from battery positive plate leachate Download PDF

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CN114561541A
CN114561541A CN202011360148.8A CN202011360148A CN114561541A CN 114561541 A CN114561541 A CN 114561541A CN 202011360148 A CN202011360148 A CN 202011360148A CN 114561541 A CN114561541 A CN 114561541A
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extraction
cobalt
extractant
manganese
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王雪
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Beijing Bocui Recycling Technology Co ltd
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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
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0086—Treating solutions by physical methods
    • 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
    • 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
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Abstract

The invention provides a method for synchronously recovering nickel, cobalt and manganese from a battery positive plate leachate, which comprises the following steps: (1) carrying out first-step extraction on the positive plate leaching solution by using an extractant A to obtain a loaded organic phase 1 and an extracted water phase 1; (2) extracting the raffinate water phase 1 obtained in the step (1) by using a carboxylic acid extracting agent to obtain a loaded organic phase 2 and a raffinate water phase 2; (3) washing and back-extracting the loaded organic phase 2 obtained in the step (2) to obtain a nickel-cobalt-manganese solution; according to the invention, the carboxylic acid extractant is added in the step (2), so that the method has the advantages of good selectivity of extracted ions, low water solubility, environmental friendliness and the like. The method for recovering nickel, cobalt and manganese from the mixed solution containing nickel, cobalt and manganese has the advantages of short flow, low energy consumption, small pollution and high economic benefit.

Description

Method for synchronously recycling nickel, cobalt and manganese from battery positive plate leachate
Technical Field
The invention belongs to the field of non-ferrous metal hydrometallurgy and resource recovery, and relates to a method for synchronously recovering nickel, cobalt and manganese from a battery positive plate leachate.
Background
In recent years, with the continuous development of electronic technologies such as informatization automation and 5G, industries such as artificial intelligence, intelligent manufacturing, new energy automobiles and the like become new engines for economic growth in China, and are also important driving forces for realizing high-quality development of economy. The core driving the development of the battery system is the battery system, the related raw materials are inevitably in more and more shortage along with the continuous expansion of the demand of the battery, and the problem of green and efficient recovery of valuable metals in the scrapped battery becomes a problem to be solved in the development process of the world.
The method for recycling valuable metals in waste lithium ion batteries by utilizing a hydrometallurgical technology is the most effective method at present, but is limited by the hydrometallurgical technology and raw materials, the recycling process basically adopts the traditional ore smelting technology, and the technology is long in process, large in pollution and not the best recycling process for recycling batteries.
CN105483382A discloses a method for separating and recovering a leachate of waste battery materials containing nickel, cobalt and manganese, which uses trialkyl hydroximic acid as a first extractant to extract nickel and cobalt in the leachate of batteries containing nickel, cobalt, manganese and lithium into an organic phase, so as to achieve the purpose of separating manganese and lithium; carrying out back extraction on the organic phase by using sulfuric acid or hydrochloric acid to obtain a nickel-cobalt solution, extracting the solution containing nickel and cobalt by using a second extracting agent, and extracting cobalt into the organic phase to separate nickel and cobalt; and extracting the solution containing manganese and lithium by using a third extracting agent to extract manganese into an organic phase so as to achieve the aim of separating manganese from lithium. And separating nickel, cobalt and manganese from lithium, separating nickel from cobalt and separating manganese from lithium respectively by three times of extraction. The process is complex, multiple extraction operations are adopted, and the extraction performance is influenced by mutual dissolution of the extractants due to the use of multiple different extractants.
CN107653378A discloses a method for recovering valuable metals in waste nickel-cobalt-manganese-lithium ion batteries, which comprises the steps of dismantling the waste lithium ion batteries, soaking the waste lithium ion batteries in an acid solution to obtain a leaching solution containing the valuable metals such as nickel-cobalt-manganese-lithium and copper-aluminum, then replacing the copper with iron, removing the iron and the aluminum with water to obtain a nickel-cobalt-manganese-lithium solution, adding the deficient elements according to the required proportion of a precursor to enable the total metal concentration of the solution to be about 70-100 g/L, and then adding alkali and ammonia water into the solution to synthesize a nickel-cobalt-manganese precursor. The method comprises the steps of removing impurities such as iron and copper by adopting a precipitation method, adding nickel, cobalt and manganese according to a ratio to enable the content of nickel, cobalt and manganese in a solution to meet the requirement of a precursor, and then performing alkaline precipitation to obtain a nickel, cobalt and manganese precursor. The recovery method of the method has the disadvantages of low recovery rate of valuable ions, incomplete removal of partial impurities, insufficient purity of the obtained precursor and the like, and various filter residues generated in the process are troublesome to post-treat and do not accord with green chemical characteristics.
CN109207727A discloses a method for recovering and preparing metal materials from waste nickel-cobalt-copper ternary lithium ion batteries, which comprises the steps of disassembling and leaching waste lithium ion batteries to obtain leachate containing copper, lithium, nickel and cobalt, removing impurities from the leachate to obtain an impurity-removed solution, performing fractional extraction with an extraction system to obtain an organic phase and a nickel-rich raffinate, performing back extraction on the organic phase with hydrochloric acid to obtain a cobalt-containing back extract, adding an alkaline substance into the cobalt-lithium back extract to separate cobalt and lithium, performing back extraction on the cobalt-back extracted organic phase with sulfuric acid to obtain a copper-containing back extract, performing nickel extraction on the nickel-rich raffinate to obtain a nickel-rich organic phase, performing back extraction on the nickel-rich organic phase, and recovering nickel. The process comprises the steps of removing impurities, extracting cobalt and lithium, performing two-step back extraction to obtain cobalt and copper, extracting enriched nickel, and finally recovering nickel, cobalt, lithium and copper. The process route is long and complex, and the economic benefit is low.
The technical scheme has the problems of complex process flow, low recovery rate or low purity of the obtained precursor and the like, so that the development of the method for synchronously recovering the nickel, the cobalt and the manganese in the leachate of the battery positive plate, which has the advantages of simple process flow, low cost and high recovery rate, is necessary.
Disclosure of Invention
The invention aims to provide a method for synchronously recycling nickel, cobalt and manganese from a battery positive plate leachate, wherein the method can synchronously extract nickel, cobalt and manganese by adopting a BC194 extractant in the second step of extraction, and has high extraction rate and good separation effect with impurity ions; the water solubility is low, the environment is friendly, the loss is less in the actual use process, and the concentration component is not changed greatly; the back extraction rate is high, and the high-efficiency recovery of nickel, cobalt and manganese can be achieved; the organic phase after back extraction can be recycled, the operation cost is low, and the economic benefit is high.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for synchronously recovering nickel, cobalt and manganese from a battery positive plate leachate, which comprises the following steps:
(1) carrying out first-step extraction on the positive plate leaching solution by using an extractant A to obtain a loaded organic phase 1 and an extracted water phase 1;
(2) performing second-step extraction on the raffinate water phase 1 obtained in the step (1) by using a carboxylic acid extractant B to obtain a loaded organic phase 2 and a raffinate water phase 2;
(3) washing and back-extracting the loaded organic phase 2 obtained in the step (2) to obtain a nickel, cobalt and manganese-rich solution;
wherein the carboxylic acid extractant B in the step (2) is a BC194 extractant, and the BC194 extractant has the following structural formula:
Figure BDA0002803744120000031
according to the method provided by the invention, nickel, cobalt and manganese in the nickel, cobalt and manganese containing positive plate leaching solution are synchronously recovered, the method is not influenced by impurity metal ions such as calcium and magnesium, the operation is simple, the process operation is stable, and the separation cost for respectively recovering nickel, cobalt and manganese and the purification cost for extracting and removing impurities are reduced. Meanwhile, the invention realizes the impurity removal rate and the extraction rates of Ni, Co and Mn of more than 99.0 percent by adopting the specific carboxylic acid extractant in the step (2), and the sulfuric acid back extraction rate is more than 99.5 percent.
The concentration of Li in the leaching solution is 1-20 g/L, for example: 1g/L, 5g/L, 8g/L, 9g/L, 10g/L, 11g/L, 12g/L, 15g/L, 18g/L, 19g/L, 20g/L, and the like.
The concentration of Ni in the leachate is 1-60 g/L, for example: 1g/L, 10g/L, 20g/L, 30g/L, 40g/L, 41g/L, 42g/L, 43g/L, 44g/L, 45g/L, 46g/L, 50g/L, 55g/L, 60g/L, and the like.
The concentration of Co in the leachate is 1-25 g/L, for example: 1g/L, 5g/L, 15g/L, 16g/L, 17g/L, 18g/L, 19g/L, 20g/L, 21g/L, 22g/L, 23g/L, 24g/L, 25g/L, or the like.
The concentration of Mn in the leachate is 1-20 g/L, for example: 1g/L, 5g/L, 10g/L, or 20g/L, etc., but are not limited to the recited values, and other values not recited within the range are also applicable.
The Fe concentration in the leachate is less than or equal to 5g/L, for example: 0.1g/L, 0.5g/L, 1g/L, 3g/L, 4g/L, or 5g/L, etc.
The Al concentration in the leachate is less than or equal to 1g/L, for example: 0.2g/L, 0.4g/L, 0.6g/L, 0.8g/L, 1g/L, etc.
The Cu concentration in the leachate is less than or equal to 10g/L, for example: 1g/L, 3g/L, 5g/L, 6g/L, 7g/L, 8g/L, 9g/L, or 10g/L, etc.
The Zn concentration in the leaching solution is less than or equal to 5g/L, for example: 0.1g/L, 0.5g/L, 1g/L, 3g/L, 4g/L, or 5g/L, etc.
The concentration of Ca in the leaching solution is 0.1-0.5 g/L, for example: 0.1g/L, 0.2g/L, 0.3g/L, 0.4g/L, or 0.5g/L, etc.
The Mg concentration in the leachate is 0.1-50 g/L, for example: 0.1g/L, 10g/L, 20g/L, 30g/L, 40g/L, or 50g/L, etc.
Preferably, the extractant a of the first extraction in step (1) comprises any one or a combination of at least two of phosphine extractant, oxime extractant and carboxylic acid extractant, preferably carboxylic acid extractant.
Preferably, the carboxylic acid extractant has the following structural formula:
Figure BDA0002803744120000051
wherein m + n is more than or equal to 10 and less than or equal to 22.
Preferably, said CnH2n+1Is a linear or branched alkyl group having 1 to 21 carbon atoms (e.g., 1, 3, 5, 7, 9, 14, 16, 18, 21, etc.).
Preferably, said CmH2m+1Is a linear or branched alkyl group having 1 to 21 carbon atoms (e.g., 1, 3, 5, 7, 9, 14, 16, 18, 21, etc.).
The phosphine extractant of the invention comprises any one or the combination of at least two of P204, P507 or C272.
In the present invention, if the leachate contains copper ions, the first extraction is preferably performed by using an oxime-type extractant to remove copper from the leachate.
The oxime extractant of the invention comprises any one or the combination of at least two of Mextral984H, Lix984N, Lix63 or CP 50.
Preferably, the volume ratio of the extracting agent A to the leaching solution is (0.1-10): 1, for example: 0.1: 1. 0.5:1, 1: 1. 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1, etc.
Preferably, the extractant A in the step (1) further comprises a diluent.
Preferably, the diluent comprises any one of sulfonated kerosene, dodecane, kerosene, escoid 110, hexane or heptane, or a combination of at least two thereof.
Preferably, the extractant A in the step (1) is further required to be subjected to saponification treatment before extraction.
Preferably, the saponifying agent is an alkaline solution.
Preferably, the alkaline solution comprises any one of sodium hydroxide, potassium hydroxide or ammonia or a combination of at least two of them.
Preferably, the concentration of the alkaline solution is 6-14 mol/L, such as: 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L, 12mol/L, 13mol/L or 14mol/L, etc.
Preferably, the method of the first step of extraction in step (1) comprises single-stage extraction and/or multi-stage countercurrent extraction, preferably multi-stage countercurrent extraction.
Preferably, the stirring speed in the first extraction step is 100-300 r/min, for example: 100r/min, 120r/min, 140r/min, 160r/min, 180r/min, 200r/min, 210r/min, 230r/min, 250r/min, 270r/min, 300r/min, etc.
Preferably, the mixing time in the first extraction step is 3-30 min, for example: 3min, 6min, 9min, 10min, 15min, 18min, 20min, 22min, 26min, 27min or 30min and the like.
Preferably, the time for standing and phase separation in the first-step extraction is 5-60 min, for example: 5min, 10min, 15min, 20min, 30min, 40min, 50min or 60min and the like.
Preferably, the extraction stages of the multistage countercurrent extraction are 2-30 stages, such as: 2, 5, 10, 15, 20, 25, 30, etc.
Preferably, the loaded organic phase 1 obtained after the first extraction in step (1) needs to be subjected to washing treatment and back extraction treatment to obtain iron, aluminum, copper and zinc ion-containing solution and a blank organic phase 1.
Preferably, the number of washing treatments is 2 to 20, for example: 2, 4, 6, 10, 15, 18, or 20 stages, etc.
Preferably, the washing agent used in the washing treatment is an acid solution.
Preferably, the acid solution comprises a dilute sulfuric acid and/or hydrochloric acid solution.
Preferably, the pH value of the acid solution is 0.1-4, such as: 0.1, 0.5, 1, 2, 3, or 4, etc.
Preferably, the number of stages of the stripping treatment is 1-6, for example: stage 1, stage 2, stage 3, stage 4, stage 5, or stage 6.
Preferably, the stripping agent used in the stripping treatment is an acid solution.
Preferably, the acid solution comprises a dilute sulfuric acid and/or hydrochloric acid solution.
Preferably, H of the acid solution+The concentration is 4-8M, for example: 4M, 5M, 6M, 7M or 8M, etc.
Preferably, the blank organic phase 1 is reused as extractant.
In the invention, the operation pH value of the first extraction has different pH value operation intervals due to different extracting agents, the invention is not particularly limited, and the selection can be carried out by referring to impurity ions removed in the first extraction in the prior art, for example, when P204 is adopted, the pH value of the first extraction is 2.5-3.5, and when an oxime extracting agent is adopted, the pH value of the first extraction is 2-2.5.
Preferably, the volume fraction of the BC194 extractant in the organic phase of the extraction in the step (2) is 5-30%, for example: 5%, 8%, 10%, 15%, 20%, 25%, 30%, or the like.
Preferably, the BC194 extractant further comprises a diluent.
Preferably, the diluent comprises any one of sulfonated kerosene, dodecane, hexane, heptane or Escaid110 or a combination of at least two thereof.
Preferably, the BC194 extractant is saponified prior to use.
Preferably, the saponifying agent is an alkaline solution.
Preferably, the alkaline solution comprises any one of sodium hydroxide, potassium hydroxide or ammonia or a combination of at least two of them.
Preferably, the concentration of the alkaline solution is 6-14 mol/L, such as: 6mol/L, 8mol/L, 10mol/L, 11mol/L, 12mol/L, 13mol/L or 14mol/L, etc.
Preferably, the second-step extraction method in step (2) comprises single-stage extraction and/or multi-stage countercurrent extraction, preferably multi-stage countercurrent extraction.
In the present invention, the countercurrent extraction is one of the extraction and separation methods, and the water phase and the organic phase containing the extract flow into the extractor from both ends thereof, flow in opposite directions, and are continuously stirred in multiple stages to contact and separate layers, thereby achieving the purpose of separation.
Preferably, the stirring speed in the second extraction step is 100-300 r/min, for example: 100r/min, 120r/min, 140r/min, 160r/min, 180r/min, 200r/min, 210r/min, 230r/min, 250r/min, 270r/min, 300r/min, etc.
Preferably, the mixing time in the second extraction is 3-30 min, for example: 3min, 6min, 9min, 10min, 15min, 18min, 20min, 22min, 26min, 27min or 30min and the like.
Preferably, the time for standing and phase separation in the second-step extraction is 5-60 min, for example: 5min, 10min, 15min, 20min, 30min, 40min, 50min or 60min and the like.
Preferably, the extraction stages of the multistage countercurrent extraction are 2-30 stages, such as: 2, 5, 10, 15, 20, 25, 30, etc.
Preferably, the washing agent used in the washing treatment is an acid solution.
Preferably, the acid solution comprises a dilute sulfuric acid and/or hydrochloric acid solution.
Preferably, the pH value of the acid solution is 0.1-4, such as: 0.1, 0.5, 1, 2, 3, or 4, etc.
Preferably, the number of stages of the stripping treatment is 1-6, for example: stage 1, stage 2, stage 3, stage 4, stage 5, or stage 6.
Preferably, the stripping agent used in the stripping treatment is an acid solution.
Preferably, the acid solution comprises a dilute sulfuric acid and/or hydrochloric acid solution.
Preferably, H of the acid solution+The concentration is 4-8M, for example: 4M, 5M, 6M, 7M or 8M, etc.
In the present invention, the reaction equation of the relevant process is as follows:
saponification of carboxylic acid extractant: HA(org)+NaOH→NaA(org)+H2O
Extracting with carboxylic acid extractant: 2NaA(org)+MSO4→MA2(org)+Na2SO4
Sulfuric acid back extraction: MA (MA)2(org)+H2SO4→2HA(org)+MSO4
Wherein: m is Fe3+、Cu2+、Al3+、Zn2+、Ni2+、Co2+、Mn2+Any one or a combination of at least two of them.
As a preferable aspect of the present invention, the method comprises the steps of:
(1) diluting the extracting agent A by using a diluent, and then saponifying by using a saponifying agent of 6-14 mol/L;
(2) mixing the saponified extractant A obtained in the step (1) with the positive plate leaching solution at a speed of 100-300 r/min for 3-30 min, and standing for 5-60 min to obtain a loaded organic phase 1 and an extracted water phase 1;
(3) washing the loaded organic phase 1 obtained in the step (2) by using an acidic detergent with the pH value of 0.1-4, and then using H+Carrying out back extraction by using an acidic back extractant with the concentration of 4-8M to obtain a solution containing iron, aluminum, copper and zinc ions and a blank organic phase 1;
(4) preparing an extracted organic phase, wherein the volume fraction of the extracting agent BC194 in the extracted organic phase is 5-30%, and then performing saponification treatment by using a saponifying agent of 6-14 mol/L;
(5) mixing the raffinate water phase 1 obtained in the step (2) with the saponified BC194 in the step (4) at a speed of 100-300 r/min for 3-30 min, and standing for 5-60 min to obtain a loaded organic phase 2 and a raffinate water phase 2;
(6) washing the loaded organic phase 2 obtained in the step (5) by using an acidic detergent with the pH value of 0.1-4, and then using H+And (4) carrying out back extraction by using an acidic back extractant with the concentration of 4-8M to obtain a nickel, cobalt and manganese-rich solution.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method provided by the invention has good separation effect on metal ions, realizes synchronous extraction and recovery of nickel, cobalt and manganese in the nickel-cobalt-manganese battery leaching solution by utilizing the coupling effect between the extracting agent and the extraction pH value, is not influenced by impurity metal ions such as calcium, magnesium and the like, is simple to operate, reduces the separation cost for respectively recovering nickel, cobalt and manganese and the extraction and purification cost for impurity metal ions, and in addition, the adopted carboxylic acid extracting agent has small water solubility and can be recycled.
(2) The recovery method provided by the invention has the impurity removal rate of more than or equal to 99 percent, the extraction rate of nickel, cobalt and manganese of more than or equal to 99 percent and the sulfuric acid back extraction rate of more than or equal to 99.5 percent.
Drawings
FIG. 1 is a schematic view of a recovery flow in example 1 of the present invention.
FIG. 2 is a graph of the E-pH curve of the carboxylic acid-based extractant BC194 used in the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The BC194 extracting agent used in the embodiment of the invention is prepared by the following method:
Figure BDA0002803744120000101
into a 500mL round bottom flask was added 20g (0.12mol) of dipicolinic acid, and 200mL of thionyl chloride was slowly added dropwise with stirring at room temperature, and the reaction was confirmed by the temperature rise, and after completion of the addition, the reaction was refluxed for 30 minutes, and excess thionyl chloride was distilled off. Subsequently, 200mL of methylene chloride and 25g (0.25mol) of triethylamine were added to the flask, and 24.6g (0.12mol) of p-octylaniline was added dropwise to the flask, followed by reaction at room temperature for 1 hour, and then the reaction was stopped. After washing twice with hydrochloric acid at pH 1, then 1 time with water, drying over sodium sulfate and spin-drying the solvent, the desired product 32.1g was obtained in about 75% yield.
Characterization data:13C NMR(101MHz,CDCl3)δ168.1(s),142.3(s),139.2(s),135.1(s),127.7(s),125.6(s),128.3(m),121.6(m),51.6(m),32.5–31.1(m),29.7(m),27.4(m),24.7(m),14.3(d,J＝5.9Hz)；1H NMR(400MHz,CDCl3)δ9.86(1H)，8.81(1H)，8.75(1H)，8.52(1H),7.58(2H),7.15(1H)，2.52(2H),1.56(2H),1.27(10H),0.86(3H)；MS:354.2。
the E-pH curve diagram of the prepared extractant BC194 is shown in fig. 2, and it can be seen from fig. 2 that the selectivity of the BC194 extractant for extracting Ni, Co, and Mn is good, the extraction rate of Ni, Co, and Mn can reach over 90% when the extraction equilibrium pH is 6, and the extraction rate of Ca and Mg is less than 15%, so that the extractant BC194 has the advantage of being applied to the positive electrode sheet leachate for synchronously extracting nickel, cobalt, and manganese.
Example 1
The embodiment provides a method for recovering nickel, cobalt and manganese in a battery positive plate leachate containing nickel, cobalt and manganese, as shown in fig. 1.
The leachate in this example is a leachate of a battery positive plate containing nickel, cobalt and manganese, the pH of the leachate is 4.82, and the components are shown in table 1:
TABLE 1
Element(s) Fe Al Zn Cu Ni Co Mn Ca Mg Li
Content (g/L) 0.001 0.001 0.52 0.7 51 18 20 0.4 0.5 10
In the embodiment, before the first-step extraction, extraction is performed on copper in the leachate by using a saponified Mextral984H extractant (the volume fraction is 20%, the diluent is sulfonated kerosene, and the saponifier is a 10.2mol/L NaOH solution), the extraction level is 1, the volume ratio of an organic phase to the leachate is 0.5:1, the mixing time is 15min, the stirring speed is 150r/min, the standing is performed for 20min, the temperature is 25 ℃, the pH of a water phase is controlled to be 2.7, a copper-loaded organic phase and a leachate after copper removal are obtained after phase separation, a copper-loaded organic phase is subjected to 1-level countercurrent washing by using dilute sulfuric acid with the pH of 0.8, then back extraction is performed for 1 time by using 3.5mol/L sulfuric acid, and the volume ratio of the organic phase 1 to the washing solution or the back extraction solution is 10:1, so as to obtain a copper sulfate solution.
In the first extraction step of this example, P204 was used as an extractant, the volume fraction was 25%, and the diluent was Escaid110, and saponification was performed with 10.2mol/L NaOH solution.
Performing multi-stage countercurrent extraction on the leachate after copper removal by using saponified P204, wherein the extraction stage is 4, the volume ratio of an organic phase to the leachate after copper removal is 0.5:1, the mixing time is 15min, the stirring speed is 150r/min, the standing time is 20min, the temperature is 25 ℃ at room temperature, phase separation is performed to obtain a loaded organic phase 1 and an extracted water phase 1 with the pH value of 3.2, after 5-stage countercurrent washing is performed on the loaded organic phase 1 by using dilute sulfuric acid with the pH value of 0.8, back extraction is performed for 2 times by using 3.5mol/L sulfuric acid, the volume ratio of the loaded organic phase 1 to a washing solution or a back extraction solution is 10:1, so as to obtain a zinc sulfate solution, and the blank organic phase 1 is returned to the saponification process for recycling.
Carrying out multistage countercurrent extraction on the raffinate water phase 1 by using saponified BC194 (the volume fraction is 25%, the diluent is Escaid110, and the saponifier is 10.2mol/L NaOH solution), wherein the extraction stage number is 15, the volume ratio of an organic phase to the water phase 1 is 4:1, the mixing time is 15min, the stirring speed is 150r/min, standing is carried out for 20min, the temperature is 25 ℃ at room temperature, the load organic phase 2 and the raffinate water phase 2 with the pH value of 6.3 are respectively obtained, carrying out 8-stage countercurrent washing on the load organic phase 2 by using dilute sulfuric acid with the pH value of 0.8, carrying out back extraction for 3 times by using 3.5mol/L sulfuric acid, and the volume ratio of the load organic phase 2 to the washing solution or the back extraction solution is 8:1 to obtain the nickel, cobalt and manganese-rich solution.
In this example, the impurity removal rate was 99.5%, the extraction rates of Ni, Co, and Mn were 99.9%, 99.5%, and 99.2%, respectively, and the back extraction rates were 99.5%, 99.6%, and 99.6%, respectively.
Example 2
The embodiment provides a method for recovering nickel, cobalt and manganese from a leaching solution containing nickel, cobalt and manganese, the leaching solution in this embodiment is a battery leaching solution containing nickel, cobalt and manganese, the pH value of the leaching solution is 2.35, and the components are shown in table 2:
TABLE 2
Element(s) Fe Al Zn Cu Ni Co Mn Ca Mg Li
Content (g/L) 0.5 0.01 0.2 0.3 48 20 18 0.5 0.5 10
In the first extraction step of the present example, C272 was used as an extractant, the volume fraction was 25%, the diluent was sulfonated kerosene, and saponification was performed with 13mol/L NaOH solution.
Performing multistage countercurrent extraction on the leachate by using saponified C272, wherein the extraction stages are 4 stages, the volume ratio of an organic phase to the leachate is 0.4:1, the mixing time is 8min, the stirring speed is 200r/min, the experimental temperature is 25 ℃, the standing time is 10min, the phase separation is performed to obtain a loaded organic phase 1 and a raffinate aqueous phase 1 with the pH value of 3.3, 5-stage countercurrent washing is performed on the loaded organic phase 1 by using dilute sulfuric acid with the pH value of 1, then back extraction is performed for 3 times by using 2mol/L sulfuric acid, and the volume of the loaded organic phase 1 and a washing solution or a back extraction solution is 15:1, so that a mixed solution of ferric sulfate, copper sulfate, zinc sulfate, aluminum sulfate and the like is obtained.
Carrying out multistage countercurrent extraction on the raffinate water phase 1 by using saponified BC194 (the volume fraction is 25%, the diluent is Escaid110, and the saponifier is 10.2mol/L NaOH solution), wherein the extraction stage number is 11, the volume ratio of an organic phase to the raffinate water phase 1 is 4:1, the mixing time is 5min, the stirring speed is 200r/min, standing is 10min, the experimental temperature is 25 ℃, the loaded organic phase 2 and the raffinate water phase 2 with the pH value of 6.1 are respectively obtained, carrying out 8-stage countercurrent washing on the loaded organic phase 2 by using dilute sulfuric acid with the pH value of 1, and carrying out back extraction for 5 times by using 2mol/L sulfuric acid, and the volume ratio of the loaded organic phase 2 to the washing solution or the back extraction solution is 10:1, so as to obtain the nickel, cobalt and manganese-rich solution.
In this example, the impurity removal rate was 99.4%, the extraction rates of Ni, Co, and Mn were 99.8%, 99.6%, and 99.5%, respectively, and the back extraction rates were 99.7%, and 99.6%, respectively.
Example 3
The embodiment provides a method for recovering nickel, cobalt and manganese from a leaching solution containing nickel, cobalt and manganese, the leaching solution in this embodiment is a battery leaching solution containing nickel, cobalt and manganese, the pH value of the leaching solution is 4.3, and the components are shown in table 3:
TABLE 3
Figure BDA0002803744120000131
Figure BDA0002803744120000141
In the embodiment, before the first extraction, the saponified Lix984N extractant (the volume fraction is 25%, the diluent is sulfonated kerosene, and the saponifier is 11mol/L NaOH solution) is used for extracting copper in the leachate, the extraction stage number is 1, the ratio is 0.5:1, the mixing time is 3min, the stirring speed is 200r/min, the standing is 10min, the experimental temperature is 25 ℃, the pH of the water phase is controlled to be 2.6, the leachate after copper loading and copper removal is obtained after phase separation, the copper loading organic phase is subjected to 1-stage countercurrent washing by dilute sulfuric acid with the pH of 1, and then the back extraction is performed for 2 times by using 2mol/L sulfuric acid, and the volume of the organic phase 1 and the washing solution or the back extraction solution is 10:1, so that the copper sulfate solution is obtained.
In the first extraction, P507 is used as an extracting agent, the volume fraction is 20%, the diluent is sulfonated kerosene, and 11mol/L NaOH solution is used for saponification.
Carrying out 7-stage countercurrent extraction on the copper-removed leaching solution containing nickel, cobalt and manganese by using saponified P507, wherein the volume ratio of an extracting agent to the copper-removed leaching solution is 0.5:1, the mixing time is 3min, the stirring speed is 300r/min, the experimental temperature is 25 ℃, phase splitting is carried out to obtain a loaded organic phase 1 and a raffinate water phase 1 with the pH value of 2.5 respectively, carrying out 6-stage countercurrent washing on the loaded organic phase 1 by using hydrochloric acid with the pH value of 1, carrying out back extraction for 2 times by using 4mol/L hydrochloric acid, and the volume of the loaded organic phase 1 and a washing solution or a back extraction solution is 15:1, so that the obtained mixed solution organic phase of calcium chloride, zinc chloride and the like is returned to the saponification process for recycling.
Performing secondary extraction on the raffinate water phase 1 by using saponified BC194 (the volume fraction is 30%, the diluent is Escaid110, and the saponifier is 11mol/L NaOH solution), performing 12-stage multistage countercurrent extraction on the extraction stages, wherein the volume ratio of the BC194 extractant to the raffinate water phase 1 is 3:1, the mixing time is 3min, the stirring speed is 300r/min, the experimental temperature is 25 ℃ at room temperature, obtaining a loaded organic phase 2 and a raffinate water phase 2 with the pH value of 7.1 respectively, performing 10-stage countercurrent washing on the loaded organic phase 2 by using sulfuric acid with the pH value of 1, and performing back extraction for 6 times by using 2mol/L sulfuric acid, wherein the volume of the loaded organic phase 2 and the washing solution or the back extraction solution is 9:1, so as to obtain the nickel, cobalt and manganese-rich solution.
In this example, the impurity removal rate was 99.3%, the extraction rates of Ni, Co, and Mn were 99.8%, 99.7%, and 99.6%, respectively, and the back extraction rates were 99.7%, 99.6%, and 99.5%, respectively.
Example 4
The difference between this example and example 1 is only that the pH of the raffinate aqueous phase 2 was controlled to 5.5, the impurity removal rate in this example was 99.3%, the extraction rates of Ni, Co and Mn were 99.2%, 99.0% and 99.2%, respectively, and the back-extraction rates were 99.7%, 99.6% and 99.6%, respectively, which reduced the washing process and the washing cost.
Comparative example 1
The comparative example differs from example 1 only in that the extractant BC194 in the second extraction step is replaced by the same amount of P507, and nickel, cobalt and manganese cannot be extracted simultaneously.
Comparative example 2
The comparative example only differs from example 1 in that the extractant BC194 in the second extraction step was replaced with the same amount of P204 and nickel cobalt manganese could not be extracted simultaneously.
Comparative example 3
The difference between the comparative example and the example 1 is only that the extractant BC194 in the second step of extraction is replaced by the carboxylic acid extractant Versatic 10, the extraction rates of Ni, Co and Mn are respectively 98.6%, 98.4% and 97.8%, the water solubility is high, the process is easy to be unstable, and the wastewater treatment cost is high.
According to the results of the examples 1 to 4 and the comparative examples 1 to 3, the method provided by the invention realizes synchronous extraction and recovery of nickel, cobalt and manganese in the leachate of the waste lithium ion battery positive plate by utilizing the coupling effect between the extracting agent and the extraction pH value, is not influenced by impurity metal ions such as calcium, magnesium and the like, is simple to operate, and reduces the separation cost for respectively recovering nickel, cobalt and manganese and the extraction and purification cost for the impurity metal ions. Meanwhile, the impurity removal rate of the carboxylic acid extractant is more than or equal to 99.0 percent, and the sulfuric acid back extraction rate is more than or equal to 99.5 percent.
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 synchronously recovering nickel, cobalt and manganese from a battery positive plate leachate is characterized by comprising the following steps:
(1) carrying out first-step extraction on the positive plate leaching solution by using an extractant A to obtain a loaded organic phase 1 and an extracted water phase 1;
(2) performing second-step extraction on the raffinate water phase 1 obtained in the step (1) by using a carboxylic acid extractant B to obtain a loaded organic phase 2 and a raffinate water phase 2;
(3) washing and back-extracting the loaded organic phase 2 obtained in the step (2) to obtain a nickel, cobalt and manganese-rich solution;
wherein the carboxylic acid extractant B in the step (2) is a BC194 extractant, and the structural formula of the BC194 extractant is as follows:
Figure FDA0002803744110000011
2. the method for synchronously recovering nickel, cobalt and manganese from the leachate of the battery positive plate according to claim 1, wherein the extractant A of the first extraction in the step (1) comprises any one or a combination of at least two of a phosphine extractant, an oxime extractant and a carboxylic acid extractant, and is preferably a carboxylic acid extractant;
preferably, the carboxylic acid extractant has the following structural formula:
Figure FDA0002803744110000012
wherein m + n is more than or equal to 10 and less than or equal to 22;
preferably, said CnH2n+1Is a linear or branched alkyl group having 1 to 21 carbon atoms;
preferably, said CmH2m+1Is a linear or branched alkyl group having 1 to 21 carbon atoms;
preferably, the volume ratio of the extracting agent A to the leaching solution is (0.1-10): 1.
3. The method for synchronously recovering nickel, cobalt and manganese from the leachate of the battery positive plate as claimed in claim 1 or 2, wherein the extracting agent A in the step (1) further comprises a diluent;
preferably, the diluent comprises any one of sulfonated kerosene, dodecane, kerosene, Escaid110, hexane or heptane, or a combination of at least two thereof;
preferably, the extractant A in the step (1) is further required to be subjected to saponification treatment before extraction;
preferably, the saponifying agent is an alkaline solution;
preferably, the alkaline solution comprises any one of sodium hydroxide, potassium hydroxide or ammonia water or a combination of at least two of the above;
preferably, the concentration of the alkaline solution is 6-14 mol/L.
4. A method for synchronously recovering nickel, cobalt and manganese from leachate of a battery positive plate as claimed in any one of claims 1 to 3, wherein the first extraction step in the step (1) comprises single-stage extraction and/or multi-stage countercurrent extraction, preferably multi-stage countercurrent extraction;
preferably, the stirring speed in the first-step extraction is 100-300 r/min;
preferably, the mixing time in the first-step extraction is 3-30 min;
preferably, the standing phase separation time in the first-step extraction is 5-60 min;
preferably, the extraction stages of the multistage countercurrent extraction are 2-30 stages.
5. The method for synchronously recovering nickel, cobalt and manganese from the leachate of the battery positive plate as claimed in any one of claims 1 to 4, wherein the loaded organic phase 1 obtained after the first extraction in the step (1) is subjected to washing treatment and back extraction treatment to obtain iron, aluminum, copper and zinc ion solution and a blank organic phase 1;
preferably, the number of stages of the washing treatment is 2-20 stages;
preferably, the washing agent used in the washing treatment is an acid solution;
preferably, the acid solution comprises a dilute sulfuric acid and/or hydrochloric acid solution;
preferably, the pH value of the acid solution is 0.1-4;
preferably, the number of stages of the back extraction treatment is 1-6;
preferably, the stripping agent used in the stripping treatment is an acid solution;
preferably, the acid solution comprises a dilute sulfuric acid and/or hydrochloric acid solution;
preferably, H of the acid solution+The concentration is 4-8M;
preferably, the blank organic phase 1 is reused as extractant a.
6. The method for synchronously recovering nickel, cobalt and manganese from the leachate of the battery positive plate as claimed in any one of claims 1 to 5, wherein the BC194 extractant in the step (2) has a volume fraction of 5-30% in the organic phase;
preferably, the BC194 extractant further comprises a diluent;
preferably, the diluent comprises any one of sulfonated kerosene, dodecane, hexane, heptane or Escaid110 or a combination of at least two thereof;
preferably, the BC194 extractant is saponified before being used;
preferably, the saponifying agent is an alkaline solution;
preferably, the alkaline solution comprises any one of sodium hydroxide, potassium hydroxide or ammonia water or a combination of at least two of the above;
preferably, the concentration of the alkaline solution is 6-14 mol/L.
7. The method for synchronously recovering nickel, cobalt and manganese from the leachate of the positive electrode sheet of the battery as claimed in any one of claims 1 to 6, wherein the second extraction step in the step (2) comprises single-stage extraction and/or multi-stage countercurrent extraction, preferably multi-stage countercurrent extraction;
preferably, the stirring speed in the second-step extraction is 100-300 r/min;
preferably, the mixing time in the second-step extraction is 3-30 min;
preferably, the standing phase separation time in the second-step extraction is 5-60 min;
preferably, the extraction stages of the multistage countercurrent extraction are 2-30 stages.
8. The method for synchronously recycling nickel, cobalt and manganese from the leachate of the battery positive plate as claimed in any one of claims 1 to 7, wherein the washing treatment in the step (3) is performed in 2-20 stages;
preferably, the washing agent used in the washing treatment is an acid solution;
preferably, the acid solution comprises a dilute sulfuric acid and/or hydrochloric acid solution;
preferably, the pH value of the acid solution is 0.1-4.
9. The method for synchronously recycling nickel, cobalt and manganese from the leachate of the battery positive plate as claimed in any one of claims 1 to 8, wherein the stage number of the back extraction treatment in the step (3) is 1-6;
preferably, the stripping agent used in the stripping treatment is an acid solution;
preferably, the acid solution comprises a dilute sulfuric acid and/or hydrochloric acid solution;
preferably, H of the acid solution+The concentration is 4-8M.
10. The method for synchronously recovering nickel, cobalt and manganese from the leachate of the battery positive plate as claimed in any one of claims 1 to 9, wherein the method comprises the following steps:
(1) diluting the extracting agent A by using a diluent, and then saponifying by using a saponifying agent of 6-14 mol/L;
(2) mixing the saponified extractant A obtained in the step (1) with the positive plate leaching solution at a stirring speed of 100-300 r/min for 3-30 min, and standing for 5-60 min to obtain a loaded organic phase 1 and an extracted water phase 1;
(3) washing the loaded organic phase 1 obtained in the step (2) by using an acid solution with the pH value of 0.1-4, and then using H+Performing back extraction on an acid solution with the concentration of 4-8M to obtain a solution containing iron, aluminum, copper and zinc ions and a blank organic phase 1;
(4) preparing an extracted organic phase, wherein the volume fraction of the extracting agent BC194 in the extracted organic phase is 5-30%, and then performing saponification treatment by using a saponifying agent of 6-14 mol/L;
(5) mixing the raffinate water phase 1 obtained in the step (2) with the saponified BC194 extractant in the step (4) at a stirring speed of 100-300 r/min for 3-30 min for second-step extraction, and standing for 5-60 min to obtain a loaded organic phase 2 and a raffinate water phase 2;
(6) washing the loaded organic phase 2 obtained in the step (5) by using an acid solution with the pH value of 0.1-4, and then using H+And (4) carrying out back extraction on the acid solution with the concentration of 4-8M to obtain the nickel, cobalt and manganese-rich solution.
CN202011360148.8A 2020-11-27 2020-11-27 Method for synchronously recycling nickel, cobalt and manganese from battery positive plate leachate Pending CN114561541A (en)

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