CN112342387A - Method for separating nickel and magnesium and application thereof - Google Patents
Method for separating nickel and magnesium and application thereof Download PDFInfo
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- CN112342387A CN112342387A CN202011131789.6A CN202011131789A CN112342387A CN 112342387 A CN112342387 A CN 112342387A CN 202011131789 A CN202011131789 A CN 202011131789A CN 112342387 A CN112342387 A CN 112342387A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
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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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
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- C22B3/362—Heterocyclic compounds of a single type
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The invention provides a nickel and magnesium separation method and application thereof, wherein the separation method comprises the following steps: (1) preparing a high-purity extracting agent and a diluting agent into an extracted organic phase with a certain volume fraction, and then performing saponification reaction on the extracted organic phase and an alkaline compound to obtain a saponified organic phase; the extracting agent contains specific carboxylic acid compounds; (2) mixing, extracting and layering the saponified organic phase-to-nickel-magnesium feed liquid obtained in the step (1) to obtain a loaded organic phase and an extracted water phase; (3) washing the loaded organic phase by using a detergent to remove extracted or carried magnesium ions as impurities to obtain a washed loaded organic phase and a washed residual liquid; (4) carrying out back extraction on the washed loaded organic phase obtained in the step (3) by using a back extractant to obtain a metal ion enrichment solution and a regenerated organic phase; the whole separation process is simple and convenient to operate, low in acid consumption, fast in phase splitting and environment-friendly; the separation method has good nickel and magnesium separation effect and high separation coefficient, and the used extraction reagent has low and stable water solubility, can be recycled after regeneration, is favorable for reducing the separation cost, and is suitable for large-scale application.
Description
Technical Field
The invention belongs to the technical field of metal ion separation and purification, and particularly relates to a nickel and magnesium separation method and application thereof.
Background
At present, new energy automobiles obtain a lot of achievements in the aspect of improving urban pollution, carbon emission can be effectively reduced in the aspect of environmental protection, the development of electric automobiles is rapidly returned to the updating and upgrading of power battery technology, nickel metal elements are used as essential metal materials for power battery production, the utilization technology of the nickel metal is improved, the power battery is about to come into new revolution, a part of the nickel metal elements are from laterite nickel ore and nickel sulfide ore, and a part of the nickel metal elements are from the recovery of waste lithium batteries. Meanwhile, heavy metals such as nickel, cobalt, manganese and the like contained in the waste batteries have serious harm to the environment, so that the precious metals contained in the waste lithium batteries are recycled, resources can be recycled, the environment can be protected, and the environment-friendly lithium battery has better environment and market prospects.
The main methods for recovering noble metals such as nickel and the like from waste lithium ion batteries are an active method metallurgy method and a wet method metallurgy method. The application of pyrometallurgy is limited due to the problems of poor operating conditions, high operating temperature, high energy consumption, serious air pollution, complex driving and parking and the like; the hydrometallurgy method can be directly made into products, has the characteristics of low cost, high automation and the like, and has optimistic application prospect. The hydrometallurgical methods mainly include chemical precipitation, membrane separation, ion exchange, adsorption, and solvent extraction.
CN102814058A discloses a method for separating, enriching and purifying nickel and magnesium by using an adsorption material experiment, wherein a solution to be treated containing nickel ions and magnesium ions is adjusted to pH value of 1.0-5.5 to obtain a pickle liquor, the pickle liquor is contacted and mixed with a heavy metal adsorption material of an adsorption column, the heavy metal adsorption material can adsorb the nickel ions in the pickle liquor, the magnesium ions are remained in the pickle liquor, and the heavy metal adsorption material is washed by 5-30% sulfuric acid solution to carry out desorption operation to obtain a nickel-containing desorption liquor and an analyzed heavy metal adsorption material. And (3) carrying out electrodeposition operation by using the nickel-containing desorption solution to obtain nickel metal or nickel metal powder, wherein the desorbed heavy metal adsorption material can be recycled. The method has the advantages of convenience in operation and simplicity in equipment, but the production process of the heavy metal adsorption material is complex, the capacity and the adsorption efficiency of the heavy metal adsorption material are reduced after the heavy metal adsorption material is used for multiple times, the heavy metal adsorption material is easily affected by insoluble substances and impurities in a system, and the heavy metal adsorption material needs to be replaced and needs to be further treated after being replaced.
CN108569723A discloses a method for treating nickel-containing electroplating wastewater by a chemical precipitation method, wherein the nickel-containing electroplating wastewater enters a reactor, sodium sulfide and calcium hydroxide are added into the reactor at the same time, the full reaction is carried out under the stirring condition, the stirring is stopped after 20 minutes, after 5 days of precipitation in the reactor, the supernatant is discharged into the next reactor, after the calcium hydroxide is added again for full reaction, and after 1 day of standing, the supernatant is discharged by a drain valve. The method removes nickel in a precipitation form, simultaneously the removal rate of nickel can reach 99%, the recovery of nickel is improved on the basis of effective treatment of sewage, and the method has the advantages of simple process method and low operation cost, but the method needs huge equipment, limited treatment capacity and longer treatment time, the separation effect is poor due to impurity ions carried by nickel precipitation, and meanwhile, the nickel precipitation sludge needs to be matched with working sections such as dehydration, retreatment and the like. Otherwise, secondary pollution is easily caused.
The solvent extraction method has the characteristics of high-efficiency extraction, fine separation, energy conservation, low carbon, continuous automatic operation, easy industrialization and the like, and becomes a research hotspot for recovering noble metals such as nickel and the like from waste batteries at present.
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, carrying out back extraction to obtain a back extraction solution containing manganese sulfate and a raffinate containing Co, Ni and Li ions, removing Cu from the back extraction solution, and then carrying out 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; 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, 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.
Therefore, it is important to develop a method for separating nickel and magnesium with low acid consumption, high extraction efficiency and low cost to improve the separation efficiency and recovery rate of nickel and magnesium.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a nickel and magnesium separation method and application thereof, the separation method utilizes a carboxylic acid compound CPH88 with a specific structure as an extracting agent, and successfully separates nickel and magnesium in a nickel-magnesium feed liquid through the combination of means such as extraction and the like, and the whole separation process has the advantages of simplicity in operation, environmental friendliness, low cost and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for separating nickel and magnesium, the method comprising the steps of:
(1) performing saponification reaction on the extracted organic phase and an alkaline compound to obtain a saponified organic phase, wherein the saponified organic phase can control the water phase balance pH value of an extraction system to be in a proper range so as to better separate nickel and magnesium metal ions;
the extracted organic phase contains carboxylic acid compound CPH88 with the structure shown in formula I:
wherein, C8H17All are straight chain branched chain-containing alkane groups;
(2) performing mixed extraction on the saponified organic phase nickel-magnesium material obtained in the step (1), clarifying and layering to obtain a loaded organic phase and an extracted water phase; the raffinate water phase contains magnesium ions, and the step separates nickel from magnesium;
(3) washing the loaded organic phase by using a detergent, washing out extracted or carried magnesium ions as impurities to obtain a washed loaded organic phase and a washed residual liquid, and removing the magnesium ions carried and extracted in the extraction process to obtain a nickel ion solution with higher purity in a back extraction section;
(4) and (3) carrying out back extraction on the washed loaded organic phase obtained in the step (3) by using a back extractant to obtain a metal ion enriched solution and a regenerated organic phase, so that the metal ion enriched solution containing nickel ions is obtained on one hand, and the organic phase is regenerated on the other hand, thereby being beneficial to recycling and reducing the cost. The whole separation process has low acid consumption, simple operation, low cost and good nickel and magnesium separation effect.
Preferably, the organic phase further comprises a diluent.
Preferably, the diluent comprises any one of diluent Escaid110, mineral spirit, toluene, hexane, heptane, dodecane or kerosene, or a combination of at least two thereof; more preferably Escaid110 and/or dodecane.
Preferably, the dodecane is n-dodecane.
Preferably, the high purity extractant is present in an amount of 5 to 30% by volume of the organic phase to be extracted, for example 5%, 6%, 8%, 10%, 12%, 15%, 18%, 20%, 21%, 23%, 25%, 27% or 30%, and the specific values therebetween, including for brevity and clarity, are not exhaustive of the invention.
Preferably, the basic compound of step (1) comprises an inorganic base.
Preferably, the inorganic base comprises any one of sodium hydroxide, magnesium oxide, potassium hydroxide or ammonia water or a combination of at least two of the foregoing.
Preferably, the volume ratio of the saponified organic phase in the step (2) to the nickel-magnesium feed liquid is 1 (0.1-10), such as 1:0.1, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, or 1: 9.5.
As a preferred technical scheme, the volume ratio of the saponified organic phase to the nickel-magnesium feed liquid in the step (2) is 1 (0.1-10), and the overlarge volume ratio causes the volume proportion of the nickel-magnesium feed liquid to be too small, so that magnesium-containing extract liquid is entrained or extracted by magnesium ions, and the later-stage metal enrichment concentration is influenced; too small a volume ratio results in insufficient extraction capacity of the extracted organic phase, resulting in incomplete extraction of metallic nickel ions and difficulty in uniform mixing.
Preferably, the pH of the raffinate water phase in step (2) is 5.0 to 7.8, for example 5.0, 5.8, 6.0, 6.4, 6.7, 7.0, 7.1, 7.2 or 7.7, and the specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not intended to be limited to the specific values included in the ranges.
As a preferred technical scheme of the invention, the pH value of the raffinate water phase is 5.0-7.8, the pH value is too small, and the nickel extraction rate is low; the pH value is too large, magnesium extracted to an organic phase in the nickel-magnesium feed liquid is increased, and the washing cost is increased.
Preferably, the extraction of step (2) is carried out under stirring conditions.
Preferably, the stirring speed in step (2) is 800rpm/min, such as 120rpm/min, 140rpm/min, 150rpm/min, 300rpm/min, 500rpm/min, 600rpm/min, 700rpm/min or 790rpm/min, and the specific values therebetween are not exhaustive for the purpose of brevity and conciseness.
Preferably, the stirring and mixing time is 3-30 min, such as 3min, 5min, 8min, 10min, 12min, 15min, 18 min, 20min, 22min, 25min or 29min, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive of the specific values included in the range.
Preferably, the extraction in step (2) is a multi-stage countercurrent fractional extraction.
Preferably, the extraction stages of the multi-stage countercurrent fractional extraction are 2-30 stages, such as 3 stages, 4 stages, 5 stages, 6 stages, 7 stages, 8 stages, 9 stages, 12 stages, 15 stages, 17 stages, 18 stages, 19 stages, 22 stages, 25 stages, 27 stages or 29 stages, and specific point values between the above point values are limited in space and for the sake of brevity, and the invention is not exhaustive of the specific point values included in the range.
Preferably, the layering time in step (2) is 2-50 min, such as 10min, 15min, 20min, 25min, 30min, 35min, 40min or 45min, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the loaded organic phase obtained in the step (3) is subjected to a washing step to remove magnesium ions as impurities;
preferably, the number of washing stages is 2 to 20, such as 3, 4, 5, 6, 7, 10, 12, 14, 16, 18 or 19 stages;
preferably, the washing comprises inorganic acid and/or acidified water, ultrapure water and nickel sulfate solution washing;
preferably, the pH of the mineral acid and/or acidified water is between 0.1 and 2, such as 0.1, 0.5, 0.7, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8 or 1.9, and the specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not intended to be limited to the specific values encompassed by the scope.
Preferably, the ultrapure water is reverse-osmosis-treated with primary water;
preferably, the nickel sulfate solution is 0.5-20 g/L; e.g., 0.5g/L, 1g/L, 3g/L, 5g/L, 12g/L, 13g/L, 15g/L, 17g/L, 18g/L, or 19g/L, and the specific values therebetween, are not intended to be limiting in space and for the sake of brevity and not to be exhaustive of the invention in any way including the specific values recited herein.
Preferably, the stripping agent of step (4) comprises an inorganic acid.
Preferably, the inorganic acid comprises any one of hydrochloric acid, nitric acid or sulfuric acid, or a combination of at least two thereof.
Preferably, the concentration of the inorganic acid in the stripping agent is 0.5-4 mol/L, such as 0.6mol/L, 0.9mol/L, 1.2mol/L, 1.5mol/L, 1.8mol/L, 2.1mol/L, 2.4mol/L, 2.7mol/L, 3mol/L, 3.3mol/L, 3.6mol/L or 3.9mol/L, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the back extraction in the step (4) has the number of stages of 1-10, such as 2, 3, 4, 5, 6, 8 or 9 stages.
Preferably, the volume ratio of the stripping agent to the loaded organic phase is 1 (0.1-15), such as 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, 1:11, 1:13, 1:14 or 1: 15.
Preferably, the reaction equipment is a mixer-settler, a packed extraction tower, a spray extraction tower, and more preferably the reaction equipment is a mixer-settler.
Preferably, the separation method specifically comprises the following steps:
(1) carrying out saponification reaction on the extracted organic phase and an alkaline compound to obtain a saponified organic phase; the extraction organic phase comprises a diluent and a carboxylic acid compound CPH88 with the structure shown in the formula I:
wherein, C8H17All of which are straight chain branched alkane-containing groups
(2) Extracting and layering the saponified organic phase-to-nickel-magnesium feed liquid obtained in the step (1) according to the volume ratio of 1 (0.1-10) to obtain a nickel ion-containing loaded organic phase and a magnesium ion-containing extraction water phase with the pH value of 5.0-7.8;
(3) washing the loaded organic phase obtained in the step (2) by using a detergent to obtain a washed loaded organic phase and a washed residual liquid;
(4) carrying out back extraction by using a back extractant to obtain a metal ion enriched solution containing nickel ions and a regenerated organic phase; the volume ratio of the stripping agent to the loaded organic phase is 1 (0.1-15).
In a second aspect, the present invention provides a use of the separation method according to the first aspect for separating nickel and magnesium from a battery recycle waste liquid.
Preferably, the battery is a ternary nickel-cobalt-manganese ion battery.
In a third aspect, the invention provides an application of an extraction reagent containing carboxylic acid compounds with the structure shown in formula I in separation of nickel and magnesium.
Compared with the prior art, the invention has the following beneficial effects:
the method for separating nickel and magnesium provided by the invention comprises the steps of firstly saponifying an extraction organic phase containing carboxylic acid compounds with specific structures to obtain a saponified organic phase, then extracting nickel-magnesium material liquid by utilizing the saponified organic phase to separate nickel and magnesium, and finally back-extracting the extracted organic phase containing nickel to obtain a regenerated organic phase and a metal ion enriched solution.
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.
Preparation example 1
A carboxylic acid compound has the following structure:
wherein, C8H17All of which are straight chain branched alkane-containing groups
The preparation method comprises the following steps:
20g of dipicolinic acid was added to a 500mL round-bottom flask, 200mL of thionyl chloride was slowly added dropwise with stirring at room temperature, the reaction was indicated 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 24g (about 2eq) of triethylamine were added to the flask, and 28.9g (1eq) of diisooctylamine 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 having a pH of 1, followed by washing 1 time with water, drying over sodium sulfate and spin-drying the solvent, 34.6g of the objective product was obtained.
Characterization data:13C NMR(101MHz,CDCl3)δ167.1(s),149.3(s),144.2(s),140.7(s),127.6(m),51.5(m),32.31–31.38(m),29.37(m),27.2(m),24.3(m),14.1(d,J＝4.4Hz)；11.3(d,J＝5.9Hz)；1H NMR(400MHz,CDCl3)δ12.1(1H)，8.79(1H)，8.68(1H)，8.49(1H),2.72(4H),1.92(2H),1.27(16H),0.89(6H)，0.85(6H)；MS:390.3
preparation example 2
The preparation method comprises the following steps:
20g of dipicolinic acid was added to a 500mL round-bottom flask, 200mL of thionyl chloride was slowly added dropwise with stirring at room temperature, the reaction was indicated 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 24g (about 2eq) of triethylamine were added to the flask, and 28.9g (1eq) of diisooctylamine 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 having a pH of 1, followed by washing 1 time with water, drying over sodium sulfate and spin-drying the solvent, 36.6g of the objective product was obtained.
Characterization data:13C NMR(101MHz,CDCl3)δ168.1(s),150.3(s),146.2(s),126.6(m),140.7(s),45.5(m),32.31–31.38(m),29.37(m),27.2(m),22.3(d,J＝5.9Hz),14.02(d,J＝4.4Hz)；1H NMR(400MHz,CDCl3)δ12.1(1H)，8.81(1H)，8.70(1H)，8.51(1H),2.94(4H),1.52(4H),1.27(20H),0.85(6H)；MS:390.3
example 1
A method for separating nickel and magnesium comprises the following specific steps:
(1) dissolving the carboxylic acid compound obtained in the preparation example 1 in a diluent Escaid110 to enable the volume percentage content of a high-purity extracting agent in the Escaid110 to be 25%, adding a NaOH solution with the concentration of 10mol/L, and mixing to obtain a saponified organic phase with the saponification degree of 41%, wherein the saponified organic phase is used as an organic phase system;
(2) taking a nickel-magnesium feed liquid as an aqueous phase system (containing 2.0g/L of nickel, 18g/L of magnesium and having a pH value of 5.3, specifically derived from an intermediate material in the nickel purification of a waste lithium ion battery anode material leaching liquid), respectively flowing into a saponification organic phase obtained in the step (1) from two ends of a mixing clarification tank, wherein the flow ratio of the saponification organic phase to the nickel-magnesium feed liquid is 1:5, mixing at a stirring speed of 600rpm/min for 15min at a temperature of 25 ℃, performing multi-stage countercurrent fractional extraction, wherein the extraction stage number is 10 stages, standing for 22min, and layering to obtain a nickel ion-loaded organic phase and a magnesium ion-containing outlet aqueous phase (namely an extraction residual aqueous phase) having a pH value of 7;
(3) carrying out 12-stage countercurrent washing on the loaded organic phase obtained in the step (2) by using a sulfuric acid solution with the pH value of 1, and then carrying out back extraction by using sulfuric acid with the concentration of 2mol/L, wherein the number of the back extraction stages is 6; the flow ratio of the detergent sulfuric acid solution to the loaded organic phase is 1:0.2, and the flow ratio of the 2mol/L sulfuric acid to the loaded organic phase is 1:10, so that a metal ion enriched solution and a regenerated organic phase are obtained.
Example 2
A method for separating nickel and magnesium comprises the following specific steps:
(1) dissolving the carboxylic acid compound obtained in preparation example 1 in Escaid110, wherein the volume percentage of CPH88 in the Escaid110 is 25%, adding 10mol/L NaOH solution, and mixing to obtain a saponified organic phase with the saponification degree of 30%, wherein the saponified organic phase is used as an organic phase system;
(2) taking a nickel-magnesium feed liquid as an aqueous phase system (containing 2.0g/L of nickel, 18g/L of magnesium and having a pH value of 5.3, specifically derived from an intermediate material in nickel purification of a waste lithium ion battery anode material leaching liquid), respectively flowing into the saponification organic phase in the step (1) from two ends of an extractor (the volume ratio of the saponification organic phase to the nickel-magnesium feed liquid is 1:4), mixing and keeping the stirring speed at 760rpm/min during mixing, the mixing time at 5min and the temperature at 25 ℃, carrying out multi-stage countercurrent fractional extraction, wherein the extraction stages are 12 stages, standing for 10min, and layering to obtain a nickel ion-loaded organic phase and a magnesium ion-containing raffinate aqueous phase with a pH value of 7.2-7.4;
(3) carrying out 18-stage countercurrent washing on the loaded organic phase obtained in the step (2) by using sulfuric acid with the pH value of 0.9, and then carrying out back extraction by using sulfuric acid with the concentration of 2mol/L, wherein the number of the back extraction stages is 6; the flow ratio of the washing sulfuric acid to the loaded organic phase is 1:0.25, and the flow ratio of the 2mol/L sulfuric acid to the loaded organic phase is 1:10, so that a metal ion enriched solution and a regenerated organic phase are obtained.
Example 3
A method for separating nickel and magnesium comprises the following specific steps:
(1) dissolving the carboxylic acid compound obtained in the preparation example 1 in dodecane, wherein the volume percentage of the carboxylic acid compound in the dodecane is 25%, adding an ammonia water solution with the concentration of 11mol/L, and mixing to obtain a saponified organic phase with the saponification degree of 30%, wherein the saponified organic phase is used as an organic phase system;
(2) taking a nickel-magnesium feed liquid as an aqueous phase system (containing 1.70g/L of nickel, 19g/L of magnesium and having a pH value of 5.20, specifically derived from an intermediate material in the nickel purification of a waste lithium ion battery anode material leaching solution), respectively flowing into the saponification organic phase from two ends of an extractor (the volume ratio of the saponification organic phase to the nickel-magnesium feed liquid is 1:4.5) in the step (1), mixing and keeping the stirring speed at 800rpm/min, the mixing time at 5min and the temperature at 25 ℃, carrying out multi-stage countercurrent fractional extraction, wherein the extraction stages are 6 stages, clarifying and layering for 10min to obtain a nickel ion-loaded organic phase and a magnesium ion-containing raffinate aqueous phase with a pH value of 6.8;
(3) carrying out 8-stage countercurrent washing on the loaded organic phase obtained in the step (2) by using sulfuric acid with the pH value of 1.0, and then carrying out back extraction by using sulfuric acid with the concentration of 2.5mol/L for 4 times; the flow ratio of the washing sulfuric acid to the loaded organic phase is 1:5, and the flow ratio of the 3mol/L sulfuric acid to the loaded organic phase is 1:10, so that the metal ion negative electrode solution and the regenerated organic phase are obtained.
Example 4
A method for separating nickel and magnesium, which differs from example 1 only in that: the sulfuric acid detergent in step (3) was replaced with 1.0g/L nickel sulfate solution, and the amounts of other components and experimental conditions were the same as in example 1.
Comparative example 1
A method for separating nickel and magnesium, which differs from example 1 only in that: the carboxylic acid compound in step (1) was replaced by the same amount of extractant P507 (2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester), and the amounts of other components and experimental conditions were the same as in example 1.
Comparative example 2
A method for separating nickel and magnesium, which differs from example 1 only in that: the carboxylic acid compound in step (1) was replaced with an equal amount of extractant C272 (bis- (2, 4, 4-trimethyl) pentylphosphonic acid), and the amounts of other components and experimental conditions were the same as in example 1.
And (3) performance testing:
the proportion of saponification refers to the alkali metal NH in the extractant+ 4And/or Na+The ratio of the original hydrogen ions, i.e., (V base XC base)/(V having XC) X100% (1)
In the formula (1), V is the volume mL of the added alkali aqueous solution, C is the concentration mol/L of the alkali in the added alkali aqueous solution, V is the volume mL of the organic phase, and C is the concentration mol/L of the extractant in the organic phase.
In the examples of the present invention, the content of metal ions in the aqueous phase was measured by inductively coupled plasma emission spectrometry (ICP-OES), and then the content of metal ions in the organic phase was determined by the subtraction method.
The extracted aqueous phase and the metal ion-enriched solution obtained in the step (2) of the extraction method described in examples 1 to 4 and comparative examples 1 to 2 were tested according to the above test methods, and the results are shown in table 1.
TABLE 1
| Purity of Back extraction Nickel sulfate (%) | Outlet water phase nickel content/mg/L | |
| Example 1 | 99.9 | 0.50 |
| Example 2 | 99.9 | 0.45 |
| Example 3 | 99.9 | 0.40 |
| Example 4 | 99.9 | 0.50 |
| Comparative example 1 | 98.7 | 4.0 |
| Comparative example 2 | 99.5 | 3.3 |
As can be seen from the data in Table 1, the method for separating nickel and magnesium provided by the invention has better separation effect compared with the prior art.
The applicant states that the present invention is illustrated by the above examples to a method for separating nickel and magnesium and its application, but the present invention is not limited to the above process steps, i.e. it is not meant that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. A method for separating nickel and magnesium, characterized in that the method comprises the following steps:
(1) preparing a high-purity extracting agent and a diluting agent into an extracted organic phase with a certain volume fraction, and then performing saponification reaction on the extracted organic phase and an alkaline compound to obtain a saponified organic phase;
the high-purity extractant is a carboxylic acid compound (CPH88) with a structure shown in a formula I:
wherein, C8H17All are straight chain branched chain-containing alkane groups;
(2) mixing the saponified organic phase obtained in the step (1) with a nickel-magnesium feed liquid, extracting, clarifying and splitting the phase to obtain a loaded organic phase and an extracted water phase, wherein the loaded organic phase contains metal nickel ions;
(3) washing the loaded organic phase by using a detergent, washing out extracted or entrained magnesium ions as impurities to obtain a washed loaded organic phase and a washed residual liquid, and merging the washed residual liquid into the extracted water phase;
(4) and (4) carrying out back extraction on the washed loaded organic phase obtained in the step (3) by using a back extractant to obtain a metal ion enrichment solution and a regenerated organic phase.
2. The method of claim 1, wherein the carboxylic acid compound having the structure of formula I is named CPH 88:
wherein, C8H17Are all straight chain branched chain alkane-containing groups.
3. The separation process of claim 1 or 2, wherein the extracted organic phase further comprises a diluent;
preferably, the diluent comprises any one of diluent Escaid110, mineral spirit, toluene, hexane, heptane, dodecane or kerosene, or a combination of at least two thereof; more preferably Escaid110 and/or dodecane;
preferably, dodecane is n-dodecane;
preferably, the high-purity extractant accounts for 5-30% of the volume percentage of the extracted organic phase.
4. The separation process according to any one of claims 1 to 3, wherein the basic compound of step (1) comprises an inorganic base;
preferably, the inorganic base comprises any one of sodium hydroxide, magnesium oxide, potassium hydroxide or ammonia water or a combination of at least two of the foregoing.
Preferably, the concentration of the alkaline compound is 2-14 mol/L.
5. The separation method according to any one of claims 1 to 4, wherein the volume ratio of the saponified organic phase to the nickel-magnesium feed liquid in the step (2) is 1 (0.1 to 10);
preferably, the equilibrium pH value of the raffinate water phase in the step (2) is 5.0-7.8;
preferably, the mixing of step (2) is carried out under stirring conditions;
preferably, the stirring speed is 100-800 rpm/min;
preferably, the mixing time is 3-30 min;
preferably, the extraction method in the step (2) is multi-stage countercurrent fractional extraction;
preferably, the extraction stages of the multistage countercurrent fractional extraction are 2-30 stages;
preferably, the extraction in the step (2) is carried out at the temperature of 10-50 ℃;
preferably, the time for clarifying and layering in the step (2) is 2-50 min;
preferably, the nickel magnesium system in the step (2) is a chloride system or a sulfate system, and a further preferred nickel magnesium system is a sulfate system.
Preferably, the nickel-magnesium ratio of the nickel-magnesium system in the step (2) is in the range of 1: (0.5-20), namely a high-magnesium low-nickel system;
preferably, the reaction equipment in the step (2) is a mixer-settler, a packed extraction tower, a spray extraction tower, and more preferably the reaction equipment is a mixer-settler.
6. The separation method according to any one of claims 1 to 5, wherein the loaded organic phase is washed by a detergent in the step (3) to remove extracted or entrained magnesium ions as impurities;
preferably, the washing stages are 2-20 stages;
preferably, the washing comprises inorganic acid and/or acidified water, ultrapure water and nickel sulfate solution washing;
preferably, the pH value of the inorganic acid and/or the acidified water is 0.1-2;
preferably, the nickel sulfate solution is 0.5-20 g/L;
preferably, the ultrapure water is obtained by reverse osmosis filtration of deionized water.
7. The separation process according to any one of claims 1 to 6, wherein the stripping agent comprises an inorganic acid;
preferably, the volume ratio of the stripping agent to the loaded organic phase is 1 (0.1-15);
preferably, the inorganic acid comprises any one of hydrochloric acid, nitric acid or sulfuric acid or a combination of at least two thereof;
preferably, the concentration of the inorganic acid in the stripping agent is 0.5-4 mol/L, and further preferably, the concentration of the stripping agent is 2 mol/L;
preferably, the number of the back extraction stages is 1-10.
8. The separation method according to any one of claims 1 to 7, characterized in that the separation method comprises in particular the steps of:
(1) carrying out saponification reaction on the extracted organic phase and an alkaline compound to obtain a saponified organic phase with a saponification degree of 1-50%; the extraction organic phase comprises a diluent and a carboxylic acid compound CPH88 with the structure shown in the formula I:
wherein, the branched chain C8H17Alkyl groups which are all straight chain;
(2) mixing and extracting the saponified organic phase obtained in the step (1) and a nickel-magnesium feed liquid with the pH value of 2-8 according to the volume ratio of 1 (0.1-10), and clarifying and phase-splitting to obtain a loaded organic phase containing nickel ions and an extracted water phase containing magnesium ions;
(3) washing the loaded organic phase by using a detergent, washing out extracted or carried magnesium ions as impurities to obtain a washed loaded organic phase and a washed residual liquid, and merging the washed residual liquid into the extracted residual liquid;
(4) and (4) carrying out back extraction on the washed loaded organic phase obtained in the step (3) by using a back extractant to obtain a metal ion enrichment solution and a regenerated organic phase.
9. Use of the separation method according to any one of claims 1 to 8 for separating nickel and magnesium from a battery nickel cobalt manganese metal recovery system;
preferably, the battery is a ternary nickel cobalt manganese battery.
10. The application of an extraction reagent containing carboxylic acid compounds with the structure shown in the formula I in separation of nickel and magnesium.
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| CN114015882A (en) * | 2021-10-29 | 2022-02-08 | 苏州博萃循环科技有限公司 | Method for recovering vanadium and nickel from POX carbon black |
| CN114085994A (en) * | 2021-11-09 | 2022-02-25 | 苏州博萃循环科技有限公司 | Method for recovering valuable metal from waste nickel-hydrogen battery |
| CN114134324A (en) * | 2021-10-29 | 2022-03-04 | 荆门市格林美新材料有限公司 | Method for extracting and purifying nickel-cobalt-manganese ternary solution |
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