CN111363919A - Compound extracting agent for deep purification of lithium ore leaching solution and purification process - Google Patents
Compound extracting agent for deep purification of lithium ore leaching solution and purification process Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B3/40—Mixtures
- C22B3/409—Mixtures at least one compound being an organo-metallic compound
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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
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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Abstract
The invention belongs to the technical field of metal smelting, and particularly relates to a compound extracting agent for deep purification of lithium ore leaching solution and a purification process. The raw material of the compound extracting agent for deep purification of the lithium ore leaching solution comprises an acidic phosphorus extracting agent AD290, wherein the volume fraction of the acidic phosphorus extracting agent AD290 is 5-20%. The compound extractant for deep purification of the lithium ore leaching solution can simultaneously remove impurities such as iron, manganese, aluminum, calcium, magnesium and the like, so that the content of the impurities in the purified lithium ore leaching solution is reduced to below 1ppm, and the compound extractant can be directly used for preparing battery-grade lithium carbonate.
Description
Technical Field
The invention belongs to the technical field of metal smelting, and particularly relates to a compound extracting agent for deep purification of lithium ore leaching solution and a purification process.
Background
Lithium is an important source for manufacturing lithium batteries and can be obtained by smelting from lithium ore. Common methods include limestone roasting, sulfuric acid, sulfate, chloride roasting, and pressure cooking. The lithium ore leaching solution is a common intermediate product for smelting lithium from lithium ore, the lithium ore leaching solution contains lithium sulfate, and the lithium sulfate can be used for obtaining lithium carbonate through the processes of impurity removal, concentration, lithium precipitation, washing and the like. The battery-grade lithium carbonate is an important inorganic chemical product and is mainly used as a lithium source for preparing the anode material of the lithium ion battery. With the rapid development of the electronic and electric automobile industries, the usage amount of battery-grade lithium carbonate is rapidly increased. The quality standard of lithium carbonate is specified in the specification YS/T582-2013 of battery-grade lithium carbonate industry, and the lithium carbonate is required to have the content of more than or equal to 99.5 percent, the lead content of less than 0.0003 percent, the calcium content of less than 0.005 percent, the magnesium content of less than 0.008 percent, the aluminum content of less than 0.001 percent, the sodium content of less than 0.025 percent, the iron content of less than 0.001 percent, the silicon content of less than 0.003 percent, the chlorine content of less than 0.003 percent and the sulfate radical content of less than 0. Because the lithium ore leachate also contains various metal impurities besides lithium sulfate, and the impurities are concentrated along with the operations of concentration, lithium deposition and the like, the purity of the lithium carbonate can not meet the requirements of relevant standards. It is desirable to remove as much as possible the impurities in the lithium ore leachate in the impurity removal stage. The impurity removal effect of the lithium ore leaching solution has a remarkable influence on whether battery-grade lithium carbonate meeting the requirements of the industrial standard can be prepared.
At present, the impurity treatment method aiming at the lithium ore leaching solution generally adopts the working procedure of combining the traditional chemical precipitation method and the ion exchange method to purify and remove impurities. The above method has the following disadvantages: the addition of the reagent can introduce new impurities, the loss amount of lithium in the solution is large, the reaction period is long, the energy consumption is high, the generation amount of waste liquid is large, and the like. Also discloses a technical scheme for removing impurities from the lithium ore leaching solution by adopting an extraction method.
For example, CN 109097599a discloses a method for separating manganese from calcium and magnesium by co-extraction, which comprises performing counter-current extraction on saponified organic phase containing co-extractant and acidic manganese-containing solution containing calcium and magnesium impurities, wherein manganese is selectively extracted into the organic phase, and calcium and magnesium impurities are remained in raffinate. Because the impurities contained in the lithium ore leachate are more, the requirement on the impurity removal process is higher, and the method is not suitable for removing the impurities such as iron, aluminum and the like in the lithium ore leachate.
CN 1090975679a discloses a method for removing calcium and magnesium impurities in lithium ore leachate by using an extraction process, which comprises adding acidic phosphorus organic extraction agents P204 and P507 into the lithium ore leachate, and performing countercurrent extraction to remove calcium and magnesium impurities in the lithium ore leachate. However, because the lithium ore leachate also contains various impurities such as iron, manganese, aluminum and the like besides calcium and magnesium, the method has low impurity removal efficiency on the lithium ore leachate, and the method is adopted to remove the calcium and magnesium impurities in the lithium ore leachate and also needs to further remove other impurities, so that the process is complex.
CN 108517422a discloses a method for efficiently recovering lithium from a lithium-containing multi-metal mixed solution, which comprises adding at least one of organic phosphorus extractants P201, P507, P229, Cyanex272, Cyanex301, Cyanex471X, Cyanex921 and Cyanex923 into a lithium ore leachate to extract impurities (the extraction removal rates of calcium, magnesium, iron and aluminum are 99.2%, 98.8%, 99.8% and 97.9%, respectively), after obtaining a lithium-rich solution, deep oil removal treatment is required to be performed on the lithium-rich solution, then two-stage membrane electrodialysis is performed to realize one-step morphological conversion of lithium to obtain a lithium hydroxide solution, and evaporation concentration is performed to obtain a concentrated mother solution and an industrial-grade lithium hydroxide powder, wherein the recovery rate of Li is 98.1%. Although the method can simultaneously remove calcium, magnesium, iron and aluminum in the lithium ore leachate, the method cannot remove manganese in the lithium ore leachate, the residual oil phase content in the lithium-rich solution is high, the lithium-rich solution needs to be subjected to two-stage membrane electrodialysis treatment, and the process is complex.
Disclosure of Invention
The invention provides a compound extractant for deep purification of lithium ore leachate, which can simultaneously remove various impurities such as calcium, magnesium, iron, manganese, aluminum and the like in the lithium ore leachate, so as to solve the problem of low impurity removal efficiency of the lithium ore leachate in the prior art.
The specific technical scheme is as follows: a compound extracting agent for deep purification of a lithium ore leaching solution is prepared from an acidic phosphorus extracting agent AD290, wherein the volume fraction of the acidic phosphorus extracting agent AD290 is 5-20%, and the compound extracting agent is washed by alkali liquor and then used for deep purification of the lithium ore leaching solution. For example, the compound extractant may include a certain amount of diluent, such as common kerosene, aviation kerosene, sulfonated kerosene, xylene, No. 260 solvent oil, aliphatic hydrocarbon, aromatic hydrocarbon, D70 solvent oil or D80 solvent oil, etc., in addition to the acidic phosphorus extractant AD 290.
Preferably, the raw materials of the compound extracting agent also comprise tertiary carboxylic acid. In the prior art, the tertiary carboxylic acid is mostly used for separating nickel, cobalt and rare earth elements and extracting other divalent metals, and the compound extractant disclosed by the invention has a better extraction effect and a better separation effect of an organic phase and a water phase by adopting the tertiary carboxylic acid as a co-extractant.
Preferably, the volume ratio of the acidic phosphorus extractant AD209 to the tertiary carboxylic acid is (1-4): (2-4).
Preferably, the tertiary carboxylic acid is one or more of Versatic911, Versatic9 and Versatic 10.
Preferably, the raw materials of the compound extracting agent also comprise white oil. The white oil has the characteristics of no smell, low impurity content, low water solubility and the like, and the white oil can ensure that the phase separation effect of an organic phase and a water phase is better.
The invention also aims to provide a process for deeply purifying the lithium ore leaching solution. The specific technical scheme is as follows: a process for deeply purifying a lithium ore leaching solution comprises the following steps: (1) carrying out alkali liquor washing treatment on the compound extracting agent as defined in any one of claims 1 to 5, and separating to obtain the compound extracting agent after alkali liquor washing; (2) extracting and purifying the lithium ore leaching solution by using the compound extracting agent after alkali washing; (3) and separating the mixed solution of the lithium ore leaching solution and the compound extracting agent after alkali washing to obtain a loaded organic phase and the purified lithium ore leaching solution.
Preferably, the alkali liquor washing refers to 1-3-stage washing of the compound extracting agent by adopting 10-20% of alkali liquor by mass concentration, and the volume ratio of the compound extracting agent to the alkali liquor is (10-20): 1.
preferably, after the compound extracting agent after alkali washing is added into the lithium ore leaching solution, purifying the lithium ore leaching solution by adopting 4-8-level countercurrent extraction; the countercurrent extraction is carried out in a centrifugal extractor, and the ratio of O/A (1-3) to 1 in the mixed solution of the lithium ore leaching solution and the compound extracting agent after alkali washing is carried out.
Preferably, the method further comprises the step of recovering the loaded organic phase, and the method for recovering the loaded organic phase comprises the following steps: and carrying out back extraction on the loaded organic phase by using a hydrochloric acid solution, and washing the back-extracted organic phase by using pure water to remove chloride ions in the back-extracted organic phase.
Preferably, 2-4 levels of counter current back extraction are carried out on the loaded organic phase by adopting 4-6mol/L hydrochloric acid solution, and the volume ratio of the organic phase to the water phase in the back extraction is (5-10): 1; the pure water washes the organic phase after the back extraction at 1-3 stages, the volume ratio of the organic phase to the water phase is (10-15):1 when the pure water washes, and the back extraction and the pure water washing are both carried out in a centrifugal extractor.
The invention has the beneficial effects that: when the compound extracting agent is used for purifying metal impurities in the lithium ore leaching solution, various impurities such as calcium, magnesium, iron, manganese, aluminum and the like in the lithium ore leaching solution can be removed simultaneously, and the purifying efficiency is high.
The tertiary carboxylic acid in the compound extractant is used as the co-extractant, so that the compound extractant has better extraction effect, better separation effect of an organic phase and a water phase, no deep oil removal treatment on the purified lithium ore leachate is required, and the recovery rate of the compound extractant is higher.
The compound extracting agent can realize deep purification of the lithium ore leaching solution, so that the impurity content (iron, manganese, aluminum, calcium and magnesium) is lower than 1ppm (1mg/L), a high-purity lithium solution is obtained, and a battery-grade lithium carbonate product is obtained.
The compound extractant for deep purification of the lithium ore leaching solution is particularly suitable for the following lithium ore leaching solutions: lithium: 9-15 g/L, calcium: 0.2-0.8 g/L, magnesium: 0.2-1.0 g/L, iron: 0.2-0.9 g/L, manganese: 0.1-1.0 g/L, aluminum: 0.1-0.9 g/L, and a pH value of 3-6.5.
The deep purification process for the lithium ore leaching solution has high purification efficiency and good phase splitting effect, can realize continuous and automatic operation, and can obtain products with stable quality. The deep purification process for the lithium ore leaching solution has the advantages of high lithium recovery rate, less waste liquid, less environmental pollution and better environmental protection.
According to the deep purification process for the lithium ore leaching solution, a centrifugal extractor is selected to extract the lithium ore leaching solution by the compound extracting agent, the separation efficiency is high, the oil content in the obtained purified lithium ore leaching solution is low, and the process requirement for preparing battery-grade lithium carbonate can be met.
The loaded organic phase is subjected to acid solution back extraction and pure water washing, so that the loaded organic phase can be recovered, metal ions and chloride ions in the loaded organic phase are removed, and the treated organic phase can be recycled as a compound extracting agent. The back extraction and pure water washing processes are carried out in a centrifugal extractor, which is beneficial to strengthening the separation effect and improving the recovery rate of the compound extractant.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The deep purification process of the lithium ore leaching solution specifically comprises the following steps:
(1) preparing a compound extractant: the compound extractant contains 5-20% (volume fraction) AD290
(2) Washing the compound extractant with alkali liquor:
preparing 10-20% NaOH solution, wherein the volume ratio of the NaOH solution to the compound extracting agent is (10-20):1, the washing grade is 1-3, and separating after washing to obtain the compound extracting agent after alkali washing.
(3) Purifying the lithium ore leaching solution by adopting a compound extracting agent washed by alkali: mixing the compound extractant after alkali washing with the lithium ore leaching solution, selecting 4-8 levels of countercurrent extraction, wherein the volume ratio of an organic phase to a water phase is (1-3):1, and separating the organic phase from the water phase to obtain a loaded organic phase and a purified lithium ore leaching solution. And (4) carrying out evaporation concentration and precipitation treatment on the purified lithium ore leaching solution to obtain a battery-grade lithium carbonate product.
(4) Recovery of the loaded organic phase
Mixing 4-6mol/L hydrochloric acid solution with a loaded organic phase, and performing 2-4-stage counter-current back extraction, wherein the volume ratio of the organic phase to the water phase is 5-10: 1; and (4) separating to obtain a chlorinated solution and an organic phase after back extraction, wherein the hydrochloric acid solution can be recycled until the concentration of impurity ions is close to saturation, and replacing with a new hydrochloric acid solution.
And (3) washing the organic phase after the back extraction by adopting pure water, wherein 1-3 levels of washing are selected, and the volume ratio of the organic phase to the water phase is (10-15):1, so that the chlorine ions remained in the organic phase are washed away, and the pollution to the lithium solution and the influence on the product quality during the extraction of the recovered organic phase are avoided.
Example 1
The impurity content in sample 1 was determined as follows:
calcium: 0.427g/L, magnesium: 0.356g/L, iron: 0.25g/L, manganese: 0.151g/L, aluminum: 0.102g/L, lithium: 9g/L, pH value 5.5;
1.1 preparing a compound extractant:
compound extractant 1: the AD290 volume fraction is 10 percent, and the balance is kerosene;
compound extractant 2: the volume fraction of AD290 is 10%, the volume fraction of tertiary carboxylic acid Versatic911 is 15%, and the balance is kerosene;
compound extractant 3: the volume fraction of AD290 is 10%, the volume fraction of Versatic911 of tertiary carbon is 15%, and the balance is white oil;
1.2 washing the compound extracting agents 1, 2 and 3 with alkaline solution respectively:
preparing a 10% NaOH solution by mass fraction, wherein the volume ratio of the compound extractant to the NaOH solution is 10:1, the washing grade is 3, and separating after washing to obtain the compound extractant after alkali washing.
1.3 respectively adopting compound extractants 1, 2 and 3 after alkali washing to respectively purify a sample 1: respectively introducing the compound extracting agent and the lithium ore leaching solution subjected to alkali washing into a centrifugal extractor, selecting 5-level countercurrent extraction to ensure that the volume ratio of an organic phase to a water phase is 1:1, and separating the organic phase from the water phase to obtain a loaded organic phase and a purified lithium ore leaching solution. The content of each impurity in the purified lithium ore leachate was measured (see table 1 below for details). And (4) carrying out evaporation concentration and precipitation treatment on the purified lithium ore leaching solution to obtain a battery-grade lithium carbonate product. And calculating the recovery rate.
1.4 recovery of the loaded organic phase (stripping and pure water washing both in a centrifugal extractor)
Mixing a 4mol/L hydrochloric acid solution with a loaded organic phase, and performing 2-stage countercurrent back extraction, wherein the volume ratio of the organic phase to the water phase is 5: 1; separating to obtain chlorinated solution and organic phase after back extraction, wherein the hydrochloric acid solution can be recycled until the concentration of impurity ions is close to saturation, and replacing with new hydrochloric acid solution.
And (3) washing the organic phase after the back extraction by adopting pure water, selecting 2-level washing, wherein the volume ratio of the organic phase to the water phase is 10:1, so as to wash out the chloride ions remained in the organic phase, and avoid pollution to lithium solution liquid and influence on product quality when the recovered organic phase is extracted.
TABLE 1
Example 2
The impurity content in sample 2 was determined as follows:
calcium: 0.2g/L, magnesium: 0.2g/L, iron: 0.2g/L, manganese: 0.1g/L, aluminum: 0.1g/L, lithium: 10.3g/L, and the pH value is 6;
2.1 preparing a compound extractant:
compound extractant 1: the AD290 volume fraction is 5 percent, and the balance is sulfonated kerosene;
compound extractant 2: the volume fraction of AD290 is 5%, the volume fraction of Versatic911 of tertiary carbon carboxylic acid is 20%, and the balance is sulfonated kerosene;
compound extractant 3: 5 percent of AD290, 20 percent of Versatic911 of tertiary carbon and the balance of white oil;
2.2 washing the compound extractants 1, 2 and 3 with alkaline solution respectively:
preparing a 15% NaOH solution by mass, wherein the volume ratio of the compound extractant to the NaOH solution is 12:1, the washing grade is 2, and separating after washing to obtain the compound extractant after alkali washing.
2.3 respectively adopting compound extractants 1, 2 and 3 washed by alkali to respectively purify the sample 2: and respectively introducing the compound extracting agent and the lithium ore leaching solution subjected to alkali washing into a centrifugal extractor, selecting 6-grade countercurrent extraction to ensure that the volume ratio of an organic phase to a water phase is 1:1, and separating the organic phase from the water phase to obtain a loaded organic phase and a purified lithium ore leaching solution. The content of each impurity in the purified lithium ore leachate was measured (see table 2 below for details). And (4) carrying out evaporation concentration and precipitation treatment on the purified lithium ore leaching solution to obtain a battery-grade lithium carbonate product. And calculating the recovery rate.
2.4 recovery of the loaded organic phase (stripping and washing with pure water both in a centrifugal extractor)
Mixing a hydrochloric acid solution of 5mol/L with a loaded organic phase, and selecting 3-level countercurrent back extraction, wherein the volume ratio of the organic phase to the water phase is 7: 1; separating to obtain chlorinated solution and organic phase after back extraction, wherein the hydrochloric acid solution can be recycled until the concentration of impurity ions is close to saturation, and replacing with new hydrochloric acid solution.
And (3) washing the organic phase after the back extraction by adopting pure water, wherein the volume ratio of the organic phase to the water phase is 12:1, so that chloride ions remained in the organic phase are washed away, and the pollution to lithium solution liquid and the influence on the product quality during the extraction of the recovered organic phase are avoided.
TABLE 2
Example 3
The impurity content in sample 3 was determined as follows:
calcium: 0.8g/L, magnesium: 1.0g/L, iron: 0.9g/L, manganese: 1.0g/L, aluminum: 0.9g/L, lithium: 11.6g/L and the pH value is 6.5;
3.1 preparing a compound extractant:
compound extractant 1: the AD290 volume fraction is 15 percent, and the balance is sulfonated kerosene;
compound extractant 2: the volume fraction of AD290 is 15%, the volume fraction of Versatic911 of tertiary carbon is 20%, and the balance is sulfonated kerosene;
compound extractant 3: the volume fraction of AD290 is 15%, the volume fraction of Versatic911 of tertiary carbon is 20%, and the balance is white oil;
3.2 washing the compound extractants 1, 2 and 3 with alkaline solution respectively:
preparing a NaOH solution with the mass fraction of 20%, wherein the volume ratio of the compound extractant to the NaOH solution is 20:1, the washing grade is 1 grade, and separating after washing to obtain the compound extractant after alkali washing.
3.3 respectively adopting compound extractants 1, 2 and 3 after being washed by alkali to respectively purify a sample 3: and respectively introducing the compound extracting agent and the lithium ore leaching solution subjected to alkali washing into a centrifugal extractor, selecting 8-grade countercurrent extraction to ensure that the volume ratio of an organic phase to a water phase is 2:1, and separating the organic phase from the water phase to obtain a loaded organic phase and a purified lithium ore leaching solution. The content of each impurity in the purified lithium ore leachate was measured (see table 3 below for details). And (4) carrying out evaporation concentration and precipitation treatment on the purified lithium ore leaching solution to obtain a battery-grade lithium carbonate product. And calculating the recovery rate.
3.4 recovery of the loaded organic phase (stripping and pure water washing both in a centrifugal extractor)
Mixing 6mol/L hydrochloric acid solution with a loaded organic phase, and selecting 4-stage countercurrent back extraction, wherein the volume ratio of the organic phase to the water phase is 8: 1; separating to obtain chlorinated solution and organic phase after back extraction, wherein the hydrochloric acid solution can be recycled until the concentration of impurity ions is close to saturation, and replacing with new hydrochloric acid solution.
And (3) washing the organic phase after the back extraction by adopting pure water, selecting 2-level washing, wherein the volume ratio of the organic phase to the water phase is 14:1, so as to wash out the chloride ions remained in the organic phase, and avoid pollution to lithium solution liquid and influence on product quality when the recovered organic phase is extracted.
TABLE 3
Example 4
The impurity content in sample 4 was determined as follows:
calcium: 0.3g/L, magnesium: 0.4g/L, iron: 0.8g/L, manganese: 0.9g/L, aluminum: 0.5g/L, lithium: 12.1g/L, and the pH value is 5.8;
4.1 preparing a compound extractant:
compound extractant 1: the AD290 volume fraction is 20%, and the balance is D70 solvent oil;
compound extractant 2: the volume fraction of AD290 is 20%, the volume fraction of Versatic9 as a tertiary carbon is 10%, and the balance is D70 solvent oil;
compound extractant 3: the volume fraction of AD290 is 20%, the volume fraction of tertiary carboxylic acid Versatic9 is 10%, and the balance is white oil;
4.2 washing the compound extractants 1, 2 and 3 with alkaline solution respectively:
preparing a 10% NaOH solution by mass, wherein the volume ratio of the compound extractant to the NaOH solution is 15:1, the washing grade is 3, and separating after washing to obtain the compound extractant after alkali washing.
4.3 respectively adopting compound extractants 1, 2 and 3 after alkali washing to respectively purify a sample 4: respectively introducing the compound extracting agent and the lithium ore leaching solution subjected to alkali washing into a centrifugal extractor, selecting 5-level countercurrent extraction to ensure that the volume ratio of an organic phase to a water phase is 3:1, and separating the organic phase from the water phase to obtain a loaded organic phase and a purified lithium ore leaching solution. The content of each impurity in the purified lithium ore leachate was measured (see table 4 below for details). And (4) carrying out evaporation concentration and precipitation treatment on the purified lithium ore leaching solution to obtain a battery-grade lithium carbonate product. And calculating the recovery rate.
4.4 recovery of the loaded organic phase (stripping and washing with pure water both in a centrifugal extractor)
Mixing a hydrochloric acid solution of 5mol/L with a loaded organic phase, and performing 2-stage countercurrent back extraction, wherein the volume ratio of the organic phase to the water phase is 10: 1; separating to obtain chlorinated solution and organic phase after back extraction, wherein the hydrochloric acid solution can be recycled until the concentration of impurity ions is close to saturation, and replacing with new hydrochloric acid solution.
And (3) washing the organic phase after the back extraction by adopting pure water, selecting 1-level washing, wherein the volume ratio of the organic phase to the water phase is 15:1, so as to wash out the chloride ions remained in the organic phase, and avoid pollution to lithium solution liquid and influence on product quality when the recovered organic phase is extracted.
TABLE 4
Example 5
The impurity content in sample 5 was determined as follows:
calcium: 0.3g/L, magnesium: 0.25g/L, iron: 0.5g/L, manganese: 1.0g/L, aluminum: 0.9g/L, lithium: 13.8g/L and the pH value is 3;
5.1 preparing a compound extractant:
compound extractant 1: the AD290 volume fraction is 8 percent, and the balance is sulfonated kerosene;
compound extractant 2: the volume fraction of AD290 is 8%, the volume fraction of tertiary carboxylic acid Versatic10 is 18%, and the balance is sulfonated kerosene;
compound extractant 3: the volume fraction of AD290 is 8%, the volume fraction of tertiary carboxylic acid Versatic10 is 18%, and the balance is white oil;
5.2 washing the compound extractants 1, 2 and 3 with alkaline solution respectively:
preparing a NaOH solution with the mass fraction of 12%, wherein the volume ratio of the compound extractant to the NaOH solution is 18:1, the washing grade is 2, and separating after washing to obtain the compound extractant after alkali washing.
5.3 respectively adopting compound extractants 1, 2 and 3 after alkali washing to respectively purify a sample 5: and respectively introducing the compound extracting agent and the lithium ore leaching solution subjected to alkali washing into a centrifugal extractor, selecting 7-level countercurrent extraction to ensure that the volume ratio of an organic phase to a water phase is 3:1, and separating the organic phase from the water phase to obtain a loaded organic phase and a purified lithium ore leaching solution. The content of each impurity in the purified lithium ore leachate was measured (see table 5 below for details). And (4) carrying out evaporation concentration and precipitation treatment on the purified lithium ore leaching solution to obtain a battery-grade lithium carbonate product. And calculating the recovery rate.
5.4 recovery of the loaded organic phase (stripping and pure water washing both in a centrifugal extractor)
Mixing a hydrochloric acid solution of 4.5mol/L with a loaded organic phase, and selecting 3-level countercurrent back extraction, wherein the volume ratio of the organic phase to the water phase is 6: 1; separating to obtain chlorinated solution and organic phase after back extraction, wherein the hydrochloric acid solution can be recycled until the concentration of impurity ions is close to saturation, and replacing with new hydrochloric acid solution.
And (3) washing the organic phase after the back extraction by adopting pure water, wherein the volume ratio of the organic phase to the water phase is 13:1, so that chloride ions remained in the organic phase are washed away, and the pollution to lithium solution liquid and the influence on the product quality during the extraction of the recovered organic phase are avoided.
TABLE 5
Example 6
The impurity content in sample 6 was determined as follows:
calcium: 0.75g/L, magnesium: 0.3g/L, iron: 0.5g/L, manganese: 0.4g/L, aluminum: 0.88g/L, lithium: 14.2g/L and the pH value is 4.5;
6.1 preparing a compound extractant:
compound extractant 1: the AD290 volume fraction is 18 percent, and the balance is aviation kerosene;
compound extractant 2: the volume fraction of AD290 is 18%, the volume fraction of tertiary carboxylic acid Versatic9 is 5%, the volume fraction of tertiary carboxylic acid Versatic10 is 5%, and the balance is aviation kerosene;
compound extractant 3: the volume fraction of AD290 is 18%, the volume fraction of tertiary carboxylic acid Versatic9 is 10%, the volume fraction of tertiary carboxylic acid Versatic10 is 5%, and the balance is white oil;
6.2 washing the compound extractants 1, 2 and 3 with alkaline solution respectively:
preparing a NaOH solution with the mass fraction of 18%, wherein the volume ratio of the compound extractant to the NaOH solution is 12:1, the washing grade is 3, and separating after washing to obtain the compound extractant after alkali washing.
6.3 the sample 6 is purified by adopting the compound extractants 1, 2 and 3 after being washed by alkali respectively: and respectively introducing the compound extracting agent and the lithium ore leaching solution subjected to alkali washing into a centrifugal extractor, selecting 8-grade countercurrent extraction to ensure that the volume ratio of an organic phase to a water phase is 2:1, and separating the organic phase from the water phase to obtain a loaded organic phase and a purified lithium ore leaching solution. The content of each impurity in the purified lithium ore leachate was measured (see table 6 below for details). And (4) carrying out evaporation concentration and precipitation treatment on the purified lithium ore leaching solution to obtain a battery-grade lithium carbonate product. And calculating the recovery rate.
6.4 recovery of the loaded organic phase (stripping and washing with pure water both in a centrifugal extractor)
Mixing a hydrochloric acid solution of 5.5mol/L with a loaded organic phase, and selecting 4-stage countercurrent back extraction, wherein the volume ratio of the organic phase to the water phase is 9: 1; separating to obtain chlorinated solution and organic phase after back extraction, wherein the hydrochloric acid solution can be recycled until the concentration of impurity ions is close to saturation, and replacing with new hydrochloric acid solution.
And (3) washing the organic phase after the back extraction by adopting pure water, selecting 2-level washing, wherein the volume ratio of the organic phase to the water phase is 11:1, so as to wash out the chloride ions remained in the organic phase, and avoid pollution to lithium solution liquid and influence on product quality when the recovered organic phase is extracted.
TABLE 6
Example 7
The impurity content in sample 7 was determined as follows:
calcium: 0.72g/L, magnesium: 0.94g/L, iron: 0.35g/L, manganese: 0.42g/L, aluminum: 0.26g/L, lithium: 15g/L, and the pH value is 5;
7.1 preparing a compound extractant:
compound extractant 1: the AD290 volume fraction is 12 percent, and the balance is No. 260 solvent oil;
compound extractant 2: the volume fraction of AD290 is 12%, the volume fraction of tertiary carboxylic acid Versatic10 is 10%, the volume fraction of tertiary carboxylic acid Versatic9 is 5%, the volume fraction of tertiary carboxylic acid Versatic911 is 5%, and the balance is No. 260 solvent oil;
compound extractant 3: the volume fraction of AD290 is 12%, the volume fraction of Versatic10 of tertiary carboxylic acid is 10%, the volume fraction of Versatic9 of tertiary carboxylic acid is 5%, the volume fraction of Versatic911 of tertiary carboxylic acid is 5%, and the balance is white oil;
7.2 washing the compound extractants 1, 2 and 3 with alkaline solution respectively:
preparing a NaOH solution with the mass fraction of 16%, wherein the volume ratio of the compound extractant to the NaOH solution is 10:1, the washing grade is 1 grade, and separating after washing to obtain the compound extractant after alkali washing.
7.3 the sample 7 is purified by respectively adopting the compound extractants 1, 2 and 3 after alkali washing: and respectively introducing the compound extracting agent and the lithium ore leaching solution subjected to alkali washing into a centrifugal extractor, selecting 7-level countercurrent extraction to ensure that the volume ratio of an organic phase to a water phase is 2:1, and separating the organic phase from the water phase to obtain a loaded organic phase and a purified lithium ore leaching solution. The content of each impurity in the purified lithium ore leachate was measured (see table 7 below for details). And (4) carrying out evaporation concentration and precipitation treatment on the purified lithium ore leaching solution to obtain a battery-grade lithium carbonate product. And calculating the recovery rate.
7.4 recovery of the loaded organic phase (stripping and pure water washing both in a centrifugal extractor)
Mixing 6mol/L hydrochloric acid solution with a loaded organic phase, and selecting 4-stage countercurrent back extraction, wherein the volume ratio of the organic phase to the water phase is 8: 1; separating to obtain chlorinated solution and organic phase after back extraction, wherein the hydrochloric acid solution can be recycled until the concentration of impurity ions is close to saturation, and replacing with new hydrochloric acid solution.
And (3) washing the organic phase after the back extraction by adopting pure water, selecting 1-level washing, wherein the volume ratio of the organic phase to the water phase is 10:1, so as to wash out the chloride ions remained in the organic phase, and avoid pollution to lithium solution liquid and influence on product quality when the recovered organic phase is extracted.
TABLE 7
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The compound extracting agent for deep purification of the lithium ore leaching solution is characterized in that the raw material of the compound extracting agent comprises an acidic phosphorus extracting agent AD290, the volume fraction of the acidic phosphorus extracting agent AD290 is 5-20%, and the compound extracting agent is washed by alkali liquor and then used for deep purification of the lithium ore leaching solution.
2. The compound extractant for deep purification of lithium ore leaching solution according to claim 1, wherein the raw material of the compound extractant further comprises tertiary carboxylic acid.
3. The compound extractant for deep purification of lithium ore leachate according to claim 2, wherein the volume ratio of the acidic phosphorus extractant AD209 to the tertiary carboxylic acid is (1-4): (2-4).
4. The compound extractant for deeply purifying lithium ore leaching solution according to claim 2, wherein the tertiary carboxylic acid is one or more of Versatic911, Versatic9 and Versatic 10.
5. The compound extracting agent for deep purification of lithium ore leaching solution according to any one of claims 1 to 4, wherein the raw material of the compound extracting agent further comprises white oil.
6. The deep purification process of the lithium ore leaching solution is characterized by comprising the following steps of: (1) carrying out alkali liquor washing treatment on the compound extracting agent as defined in any one of claims 1 to 5, and separating to obtain the compound extracting agent after alkali liquor washing; (2) extracting and purifying the lithium ore leaching solution by using the compound extracting agent after alkali washing; (2) and separating the mixed solution of the lithium ore leaching solution and the compound extracting agent after alkali washing to obtain a loaded organic phase and the purified lithium ore leaching solution.
7. The process for purifying the lithium ore leaching solution according to claim 6, wherein the washing with alkali solution is performed on the compound extracting agent by using 10-20% of alkali solution by mass concentration, and the volume ratio of the compound extracting agent to the alkali solution is (10-20): 1.
8. the process for purifying lithium ore leaching solution according to claim 6, wherein the lithium ore leaching solution is purified by 4-8 stage countercurrent extraction after adding the compound extractant after alkali washing to the lithium ore leaching solution; the countercurrent extraction is carried out in a centrifugal extractor, and the ratio of O/A (1-3) to 1 in the mixed solution of the lithium ore leaching solution and the compound extracting agent after alkali washing is carried out.
9. The lithium ore leaching liquor impurity removal process according to any one of claims 6 to 8, further comprising the step of recovering the loaded organic phase by a method comprising: and carrying out back extraction on the loaded organic phase by using a hydrochloric acid solution, and washing the back-extracted organic phase by using pure water to remove chloride ions in the back-extracted organic phase.
10. The lithium ore leaching solution impurity removal process according to claim 9, wherein the loaded organic phase is subjected to 2-4-stage counter-current back extraction by using 4-6mol/L hydrochloric acid solution, and the volume ratio of the organic phase to the aqueous phase in the back extraction is (5-10): 1; the pure water washes the organic phase after the back extraction at 1-3 stages, the volume ratio of the organic phase to the water phase is (10-15):1 when the pure water washes, and the back extraction and the pure water washing are both carried out in a centrifugal extractor.
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