CN114645144B - Method for extracting lithium by using deep eutectic solvent - Google Patents
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Abstract
The invention provides a method for extracting lithium by using a deep eutectic solvent, which comprises the following steps: preparing a deep eutectic solvent, providing an extraction water phase, an extraction step and a back extraction step. The deep eutectic solvent provided by the invention comprises the following components in mole ratio of 1: 2. 1:1 or 2:1 and hydrogen bond acceptors, do not contain diluents. In the process of extracting lithium by using the deep eutectic solvent, the diluent is not used, so that the volume of an extracted organic phase is reduced, the equipment volume is reduced, and the production cost is low. In addition, the deep eutectic solvent after extraction has large lithium load and small water solubility, the rest components in the extraction residual liquid basically do not change, the deep eutectic solvent after back extraction can be recycled, and three wastes are not generated. The method for extracting lithium by using the deep eutectic solvent provided by the invention has the advantages that the lithium-rich solution can be obtained only through extraction and back extraction, the process is simple and easy to control, the operation reliability is high, the application range is wide, and the lithium can be effectively separated and recovered from the lithium-containing solution.
Description
Technical Field
The invention relates to a complex ion lithium salt system for recovering Li + The technical field, in particular to a method for extracting lithium by using a deep eutectic solvent.
Background
Lithium is an alkali metal element and has the characteristics of the least specific gravity, strong chemical activity and the like, and the application of metal lithium and certain lithium compounds in various aspects such as batteries, refrigerants, lubricants, controlled nuclear fusion reactions and the like is becoming wider and wider. The occurrence forms of lithium resources in the nature are mainly lithium-containing ores and brine resources, china is a large country of lithium resources, meanwhile, the import of lithium resources is also a large country of lithium resources, the import of lithium raw materials is more than 50%, the international lithium market is highly monopoly, the market price of lithium products is increased in the year 2020, and therefore, the green development and the efficient recovery of the lithium resources are important subjects related to the energy safety of China.
The main raw materials for producing lithium carbonate are lithium ore and salt lake brine, and at present, the processes of acid leaching, alkaline leaching, salt phase inversion and the like are mainly used for producing lithium carbonate from lithium ore. Referring to fig. 1, fig. 1 is a schematic diagram of a process flow for producing lithium carbonate from beta-diaspore ore using an acid leaching method in the prior art. At present, the lithium carbonate is mainly produced by a salt lake brine by an adsorption method, a calcination method, a membrane electrolysis method, an extraction method and the like. Referring to fig. 2, fig. 2 is a schematic diagram of a process flow of producing lithium carbonate from salt lake brine using an adsorption method in the prior art.
As can be seen from fig. 1 and 2, although the front stages of the process flow of producing lithium carbonate from lithium ore and lithium carbonate from salt lake brine are different, the process flow comprises processes of removing impurities, concentrating and precipitating sodium carbonate at the rear end of the production. In the sodium carbonate precipitation process, a nearly saturated sodium carbonate solution is often added into a high-concentration lithium-containing solution, and because the solubility of lithium carbonate is relatively low, the lithium carbonate is separated out from the solution, and a crude lithium carbonate product with higher purity is obtained after high-temperature washing and dehydration.
In the process of lithium carbonate precipitation, lithium ions cannot be completely precipitated due to Ksp limitation of lithium carbonate, the concentration of lithium ions in the lithium precipitation mother solution is about 1.5 g/L-2.2 g/L, and in part of the process, the lithium content in the lithium precipitation mother solution even accounts for 20% of the total yield, so that the utilization rate of lithium resources is greatly reduced, and the efficiency and the economy of the lithium carbonate production process are severely restricted.
In order to improve the utilization rate of lithium resources, lithium needs to be recovered from lithium precipitation mother liquor, and the existing method for extracting lithium from lithium-containing solution comprises a solvent extraction method, wherein the solvent extraction method is to utilize the special extraction performance of extraction organic phase relative to lithium to achieve the purpose of extracting lithium, and the key point is to find a proper extraction organic phase. The processes of extracting lithium from lithium-containing solutions by solvent extraction are all proposed in chinese patent application (application number: CN 201711298057.4), chinese patent application (application number: CN 201711295127.0) and chinese patent application (application number: CN 201711298395.8), but the extraction organic phases mentioned therein all require kerosene to be added as a diluent, which has the following problems: (1) The lower effective concentration of the extractant in the extracted organic phase results in low lithium loading of the extractant after extraction, which is about 0.5g/L to 2g/L; (2) The solubility of a complex formed by extracting metal ions from an organic phase in a diluent is relatively low, three phases are easy to appear in operation, and continuous production is not facilitated.
Disclosure of Invention
Aiming at the defect that the extracted organic phase used in the extraction of lithium by using a solvent extraction method in the prior art contains a diluent, the invention provides a method for extracting lithium by using a deep eutectic solvent, which has the advantages of large lithium loading amount, high lithium extraction efficiency, low production cost and simple process.
In order to solve the problems, the invention adopts the following technical scheme:
a method of extracting lithium using a deep eutectic solvent, comprising the steps of:
preparing a deep eutectic solvent: the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is 1: 2. 1:1 or 2:1, stirring at 40-60 ℃ to form a uniform phase, and cooling to room temperature to obtain a deep eutectic solvent; wherein the hydrogen bond donor is a beta-diketone compound with electron withdrawing substituent, and the hydrogen bond acceptor is a compound which contains P=O and/or N=O, has electron donating property and can form hydrogen bond groups;
providing an extracted aqueous phase: with lithium-containing solutionsAs an extraction aqueous phase; wherein the pH of the lithium-containing solution is 9.0 to 11.5, and Li in the lithium-containing solution + The mass concentration of (2) is 1.20 g/L-2.50 g/L, and the anions comprise Cl - 、SO 4 2- 、CO 3 2- 、NO 3 - At least one of (a) and (b);
extraction: mixing the deep eutectic solvent with the extracted water phase according to the volume ratio of 1: (1-20) stirring and mixing to extract, and phase-separating to obtain extraction residual liquid and a deep eutectic solvent loaded with lithium after extraction balance;
and (3) back extraction: the deep eutectic solvent loaded with lithium and the stripping agent are mixed according to the volume ratio of (0.5-20): and 1, oscillating and mixing to carry out back extraction, and carrying out phase separation after back extraction balance to obtain a lithium-rich solution and an empty-load deep eutectic solvent.
Preferably, the hydrogen bond donor is selected from at least one of benzoyl trifluoroacetone, thenoyl trifluoroacetone, dibenzoylmethane, naphthoyl trifluoroacetone and phenylmethylformyl pyrazolone.
Preferably, the hydrogen bond acceptor is at least one selected from triphenylphosphine oxide, trioctylphosphine oxide, tributyl phosphate, trioctyl phosphate, 2- (diethylhexyl) acetamide, and 2- (dimethylheptyl) acetamide.
Preferably, in the step of preparing the deep eutectic solvent, the temperature of the mixing reaction of the hydrogen bond donor and the hydrogen bond acceptor is 60 ℃.
Still preferably, in the step of preparing the deep eutectic solvent, the mixing reaction of the hydrogen bond donor and the hydrogen bond acceptor is performed under the condition of heating in a water bath.
Preferably, in the step of preparing the deep eutectic solvent, the hydrogen bond donor and the hydrogen bond acceptor are mixed and stirred for 30-120 min.
Preferably, the lithium-containing solution is lithium-precipitating mother solution separated after lithium carbonate is prepared by precipitation, wherein Li is contained in the lithium-precipitating mother solution + The mass concentration of (2) is 1.5 g/L-2.2 g/L, na + The mass concentration of (C) is 35 g/L-60 g/L, ca 2+ And Mg (magnesium) 2+ Not higher than 0.1g/L.
Preferably, in the extraction step, the extraction temperature is 10-35 ℃, the stirring rotation speed is 100-300 rpm, and the extraction time is 5-60 min.
Preferably, in the back extraction step, the back extraction agent is hydrochloric acid with the concentration of 0.05 mol/L-6 mol/L.
Preferably, in the back extraction step, the back extraction temperature is 10-35 ℃, the oscillation speed is 50-300 rpm, and the back extraction time is 2-60 min.
The deep eutectic solvent provided by the invention comprises the following components in mole ratio of 1: 2. 1:1 or 2:1 and hydrogen bond acceptors, do not contain diluents. In the process of extracting lithium by using the deep eutectic solvent, the diluent is not used, so that the volume of an extracted organic phase is reduced, the equipment volume is reduced, and the production cost is low. Moreover, the deep eutectic solvent after extraction has large lithium loading capacity and small water solubility, the rest components in the extraction residual liquid basically do not change, the deep eutectic solvent after back extraction can be recycled, three wastes are not generated, and the lithium recovery rate is high.
The method for extracting lithium by using the deep eutectic solvent provided by the embodiment of the invention has the advantages that the lithium-rich solution can be obtained only through the steps of extraction and back extraction, the process is simple and easy to control, the operation reliability is high, the application range is wide, and the lithium can be effectively separated and recovered from the lithium-containing solution.
Drawings
FIG. 1 is a schematic diagram of a prior art process for producing lithium carbonate from beta-lithuite ore using acid leaching;
FIG. 2 is a schematic diagram of a prior art process for producing lithium carbonate from salt lake brine using an adsorption process;
fig. 3 is a process flow diagram of a method of extracting lithium using a deep eutectic solvent in accordance with an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following detailed description of the embodiments of the present invention will be given with reference to the accompanying drawings. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in the drawings and described in accordance with the drawings are merely exemplary and the invention is not limited to these embodiments.
It should be noted here that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to the solution according to the present invention are shown in the drawings, while other details not greatly related to the present invention are omitted.
According to the defect that the diluent is contained in an extraction organic phase used in the extraction of lithium by using a solvent extraction method in the prior art, the inventor provides a method for extracting lithium by using a deep eutectic solvent, and the method has the advantages of high lithium loading capacity, high lithium extraction efficiency, low production cost and simple process.
Referring to fig. 3, fig. 3 is a process flow diagram of a method for extracting lithium using a deep eutectic solvent according to an embodiment of the present invention.
A method of extracting lithium using a deep eutectic solvent, comprising the steps of:
step S1, preparing deep eutectic solvent
Specifically, the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is 1: 2. 1:1 or 2:1, stirring at 40-60 ℃ to form a uniform phase, and cooling to room temperature to obtain a deep eutectic solvent; wherein the hydrogen bond donor is a beta-diketone compound with electron withdrawing substituent, and the hydrogen bond acceptor is a compound which contains P=O and/or N=O, has electron donating property and can form hydrogen bond groups;
more specifically, the hydrogen bond donor is selected from at least one of benzoyl trifluoroacetone, thenoyl trifluoroacetone, dibenzoylmethane, naphthoyl trifluoroacetone, and phenylmethylformyl pyrazolone.
More specifically, the hydrogen bond acceptor is at least one selected from triphenylphosphine oxide, trioctylphosphine oxide, tributyl phosphate, trioctyl phosphate, 2- (diethylhexyl) acetamide and 2- (dimethylheptyl) acetamide.
It is worth mentioning that the hydrogen bond donor and hydrogen bond acceptor provided by the invention are both solid compounds, but the extraction is performed in liquid. Therefore, in the process of preparing the deep eutectic solvent, the hydrogen bond donor and the hydrogen bond acceptor are mixed according to the molar ratio of 1:2, 1:1 or 2:1, and only in the proportion, the melting point of the mixture formed by the hydrogen bond donor and the hydrogen bond acceptor is greatly reduced compared with other independent components, so that the mixture has high selectivity to lithium; in other proportions, when cooled down to room temperature, the originally solid components precipitate from the mixture and cannot be used for further extraction because hydrogen bonds cannot be quantitatively formed.
The strength of the hydrogen bond formed between the hydrogen bond donor and the hydrogen bond acceptor is affected by temperature, and the temperature of the mixing reaction of the hydrogen bond donor and the hydrogen bond acceptor is 40-60 ℃, for example, 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 60 ℃.
More specifically, the temperature at which the hydrogen bond donor and the hydrogen bond acceptor are mixed and reacted is preferably 60 ℃.
More specifically, the mixing reaction of the hydrogen bond donor and the hydrogen bond acceptor is preferably performed under the condition of heating in a water bath.
In addition, the mixing and stirring time of the hydrogen bond donor and the hydrogen bond acceptor is not particularly limited, and it is only necessary to ensure that all of the hydrogen bond donor and the hydrogen bond acceptor are changed from solid to liquid, specifically, the mixing and stirring time of the hydrogen bond donor and the hydrogen bond acceptor is preferably 30min to 120min, and may be, for example, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min or 120min.
Note that, when the hydrogen bond donor and the hydrogen bond acceptor are mixed and stirred to form a uniform phase, no solid is precipitated when the mixture is cooled to room temperature, a deep eutectic solvent is obtained.
Step S2, providing an extracted water phase
Specifically, a lithium-containing solution is taken as an extraction water phase; wherein the pH of the lithium-containing solution in which Li is present is 9.0 to 11.5 + The mass concentration of (C) is 1.20 g/L-2.50 g/L, and the anions can be Cl - 、SO 4 2- 、CO 3 2- 、NO 3 - At least one of (a) and (b);
li in lithium-containing solution + Can improve Li within a certain concentration range + Is returned to (a)Yield when Li in lithium-containing solution + When the content is too low, the recovery cost is high, and the recovery benefit is poor. The Li is + The mass concentration of (C) may be, for example, 1.20g/L, 1.40g/L, 1.60g/L, 1.80g/L, 2.0g/L, 2.20g/L, 2.40g/L or 2.50g/L.
In addition, the anions in the lithium-containing solution can be anions existing in the lithium-containing solution per se or anions introduced in the comprehensive utilization process of the lithium-containing solution;
specifically, the lithium-containing solution is a lithium-precipitating mother solution separated after lithium carbonate is prepared by adopting a precipitation method, wherein Li in the lithium-precipitating mother solution + The mass concentration of (2) is 1.5 g/L-2.2 g/L, na + The mass concentration of (C) is 35 g/L-60 g/L, ca 2+ And Mg (magnesium) 2+ Not higher than 0.1g/L.
It should be noted that, if the initial pH of the lithium-containing brine cannot meet the above requirement, the lithium-containing alkaline brine with the pH of 9-12 can be obtained by adding sodium hydroxide solution, sodium carbonate solution or ammonia solution thereto; the amount and concentration of the substance used for adjusting the pH of the sodium hydroxide solution, sodium carbonate solution or ammonia solution are not particularly limited.
The steps S1 and S2 are not limited in order, and may or may not be performed simultaneously.
Step S3, extraction
Mixing the deep eutectic solvent with the extracted water phase according to the volume ratio of 1: (1-20) stirring and mixing to extract, and phase-separating to obtain extraction residual liquid and a deep eutectic solvent loaded with lithium after extraction balance;
in the above extraction step, in order to reduce volatilization of the organic matters and to ensure rapid extraction, it is preferable to conduct the extraction under the condition of 10 to 35 ℃, for example, the extraction temperature may be 10 ℃, 15 ℃,20 ℃, 25 ℃, 30 ℃ or 35 ℃. In the preferred embodiment of the present invention, room temperature conditions are preferred for cost savings.
During the extraction, the extracted organic phase and the extracted aqueous phase are stirred to accelerate the extraction rate, preferably at a stirring rate of 100rpm to 300rpm, which may be, for example, 100rpm, 150rpm, 200rpm, 250rpm or 300rpm.
Generally, the extraction time is controlled to be 5 min-60 min, for example, the extraction time may be 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 50min or 60min.
After the extraction is balanced, the mixed system needs to be split, and the split phase mode can be performed by natural sedimentation, namely a standing mode, or can be performed by a centrifugal mode, and in the preferred embodiment of the invention, the separation of the extraction residual liquid and the deep eutectic solvent loaded with lithium is preferably realized by the standing phase.
After the layering operation is completed, the extraction residual liquid is analyzed and tested, and Li in the extraction residual liquid can be obtained + Mass concentration, lithium extraction rate, and lithium loading in a lithium loaded deep eutectic solvent.
In the process of extracting lithium by using the deep eutectic solvent, the diluent is not used, so that the volume of an extracted organic phase is reduced, the equipment volume is reduced, and the production cost is low. In addition, the deep eutectic solvent after extraction has large lithium loading capacity and small water solubility, and the rest components in the extraction residual liquid are basically unchanged.
Step S3, back extraction
The deep eutectic solvent loaded with lithium and the stripping agent are mixed according to the volume ratio of (0.5-20): and 1, oscillating and mixing to carry out back extraction, and carrying out phase separation after back extraction balance to obtain a lithium-rich solution and an empty-load deep eutectic solvent.
Specifically, the stripping agent is hydrochloric acid with the concentration of 0.05 mol/L-6 mol/L.
In the above-mentioned back extraction step, in order to reduce volatilization of the organic matters and to ensure rapid extraction, it is preferable to conduct the extraction under the condition of 10 to 35℃such as 10℃15℃20℃25℃30℃or 35 ℃. In the preferred embodiment of the present invention, room temperature conditions are preferred for cost savings.
During the extraction, the extracted organic phase and the extracted aqueous phase need to be oscillated to accelerate the extraction rate, preferably at an oscillation rate of 50rpm to 300rpm, which may be, for example, 50rpm, 100rpm, 150rpm, 200rpm, 250rpm or 300rpm.
Generally, the back extraction equilibrium is achieved by controlling the back extraction time to be 2-60 min, for example, the extraction time may be 2min, 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 50min or 60min.
After the back extraction is balanced, the phase of the mixed system needs to be separated, wherein the phase separation mode can be carried out by natural sedimentation, namely a standing mode, or can be carried out by centrifugation, and in the preferred embodiment of the invention, the separation of the lithium-rich solution and the empty-load deep eutectic solvent is preferably realized by standing phase separation.
After the back extraction is completed, the lithium-rich solution is analyzed and tested to obtain Li in the lithium-rich solution + Is a mass concentration of (a).
In addition, the empty-loaded deep eutectic solvent obtained after back extraction can be recycled, and three wastes are not generated.
The method for extracting lithium by using the deep eutectic solvent provided by the embodiment of the invention has the advantages that the lithium-rich solution can be obtained only through the steps of extraction and back extraction, the process is simple and easy to control, the operation reliability is high, the application range is wide, and the lithium can be effectively separated and recovered from the lithium-containing solution.
In order to further illustrate the present invention, a method of extracting lithium using a deep eutectic solvent provided by the present invention is described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Taking benzoyl trifluoroacetone as a hydrogen bond donor, taking trioctylphosphine oxide as a hydrogen bond acceptor, and mixing the benzoyl trifluoroacetone and the trioctylphosphine oxide according to the molar ratio of 1:1, stirring for 30min under the condition of water bath at 60 ℃ to form a uniform phase, and then cooling to room temperature without solid precipitation to obtain the deep eutectic solvent.
Taking Li + The lithium precipitation mother liquor with the mass concentration of 2.0g/L is an extraction water phase.
Under the condition of room temperature, the deep eutectic solvent and the extracted water phase are mixed according to the volume ratio of 1:2, stirring and mixing in proportion for extraction for 5min, standing for phase separation to obtain extraction residual liquid and a deep eutectic solvent loaded with lithium.
For Li in raffinate + Performing analysis and measurement to obtain Li + The mass concentration of (2) is 0.15g/L, the lithium extraction rate is 92.5%, and the lithium loading capacity in the deep eutectic solvent loaded with lithium is about 3.7g/L.
Under the room temperature condition, the volume ratio of the deep eutectic solvent loaded with lithium to 6mol/L hydrochloric acid is 10:1, carrying out back extraction by proportional vibration mixing, standing and phase separation after back extraction, and obtaining a lithium-rich solution and an empty-load deep eutectic solvent.
For Li in the lithium-rich solution + Performing analysis and measurement to obtain Li + The mass concentration of (C) is 36.5g/L.
Example 2
Taking benzoyl trifluoroacetone as a hydrogen bond donor, taking 2- (diethyl hexyl) acetamide trioctylphosphine oxide as a hydrogen bond acceptor, and mixing the two according to the molar ratio of 1:2, stirring for 20min under the condition of water bath at 60 ℃ to form a uniform phase, and then cooling to room temperature without solid precipitation to obtain the deep eutectic solvent.
Taking Li + The lithium precipitation mother liquor with the mass concentration of 1.4g/L is an extraction water phase.
Under the room temperature condition, the volume ratio of the deep eutectic solvent to the extracted water phase is 1:4, mixing and stirring in proportion for extraction for 5min, standing for phase separation to obtain extraction residual liquid and a deep eutectic solvent loaded with lithium.
For Li in raffinate + Performing analysis and measurement to obtain Li + The mass concentration of (2) is 0.15g/L, the lithium extraction rate is 89.3%, and the lithium loading capacity in the deep eutectic solvent loaded with lithium is about 5.0g/L.
Under the room temperature condition, the volume ratio of the deep eutectic solvent loaded with lithium to 4mol/L hydrochloric acid is 5:1, carrying out back extraction by proportional vibration mixing, standing and phase separation after back extraction, and obtaining a lithium-rich solution and an empty-load deep eutectic solvent.
For Li in the lithium-rich solution + Performing analysis and measurement to obtain Li + The mass concentration of (C) is 24.8g/L.
Example 3
Taking thiophene formyl trifluoroacetone as a hydrogen bond donor, taking triphenylphosphine oxide as a hydrogen bond acceptor, and mixing the thiophene formyl trifluoroacetone and the triphenylphosphine oxide according to the molar ratio of 2:1, stirring for 30min under the condition of water bath at 60 ℃ to form a uniform phase, and then cooling to room temperature without solid precipitation to obtain the deep eutectic solvent.
Taking Li + The lithium precipitation mother liquor with the mass concentration of 2.5g/L is an extraction water phase.
Under the condition of room temperature, the prepared deep eutectic solvent and an extracted water phase are mixed according to the volume ratio of 1:2, stirring and mixing in proportion for extraction for 5min, standing for phase separation to obtain extraction residual liquid and a deep eutectic solvent loaded with lithium.
For Li in raffinate + Performing analysis and measurement to obtain Li + The mass concentration of (2) was 0.25g/L, the lithium extraction rate was 90%, and the lithium loading in the lithium-loaded deep eutectic solvent was about 4.5g/L.
Under the room temperature condition, the volume ratio of the deep eutectic solvent loaded with lithium to 6mol/L hydrochloric acid is 6:1, carrying out back extraction by proportional vibration mixing, standing and phase separation after back extraction, and obtaining a lithium-rich solution and an empty-load deep eutectic solvent.
For Li in the lithium-rich solution + Performing analysis and measurement to obtain Li + The mass concentration of (C) is 26.8g/L.
Example 4
Taking furoyl trifluoroacetone as a hydrogen bond donor, taking trioctyl phosphate as a hydrogen bond acceptor, and mixing the two according to the molar ratio of 1:1, stirring for 10min under the condition of 40 ℃ water bath to form a uniform phase, and then cooling to room temperature without solid precipitation to obtain the deep eutectic solvent.
Taking Li + The lithium precipitation mother liquor with the mass concentration of 1.65g/L is an extraction water phase.
Under the condition of room temperature, the prepared deep eutectic solvent and an extracted water phase are mixed according to the volume ratio of 1:4, mixing and stirring in proportion for extraction for 10min, standing for phase separation to obtain extraction residual liquid and a deep eutectic solvent loaded with lithium.
For Li in raffinate + Proceeding withAnalysis and measurement to obtain Li + The mass concentration of (2) is 0.3g/L, the lithium extraction rate is 81.2%, and the lithium loading amount in the deep eutectic solvent loaded with lithium is about 5.4g/L.
Under the room temperature condition, the volume ratio of the deep eutectic solvent loaded with lithium to 4mol/L hydrochloric acid is 5:1, carrying out back extraction by proportional vibration mixing, standing and phase separation after back extraction, and obtaining a lithium-rich solution and an empty-load deep eutectic solvent.
For Li in the lithium-rich solution + Performing analysis and measurement to obtain Li + The mass concentration of (C) is 26.5g/L.
Example 5
Taking phenyl methyl formyl pyrazolone as a hydrogen bond donor, taking tributylphosphine oxide as a hydrogen bond acceptor, and mixing the phenyl methyl formyl pyrazolone and the tributylphosphine oxide according to the molar ratio of 1:1, stirring for 30min under the condition of water bath at 60 ℃ to form a uniform phase, and then cooling to room temperature without solid precipitation to obtain the deep eutectic solvent.
Taking Li + The lithium precipitation mother liquor with the mass concentration of 2.0g/L is an extraction water phase.
Under the condition of room temperature, the prepared deep eutectic solvent and an extracted water phase are mixed according to the volume ratio of 1:3, stirring and mixing in proportion for extraction for 10min, standing for phase separation to obtain extraction residual liquid and a deep eutectic solvent loaded with lithium.
For Li in raffinate + Performing analysis and measurement to obtain Li + The mass concentration of (2) was 0.35g/L, the lithium extraction rate was 82.5%, and the lithium loading in the lithium-loaded deep eutectic solvent was about 4.95g/L.
Under the room temperature condition, the volume ratio of the deep eutectic solvent loaded with lithium to 6mol/L hydrochloric acid is 10:1, carrying out back extraction by proportional vibration mixing, standing and phase separation after back extraction, and obtaining a lithium-rich solution and an empty-load deep eutectic solvent.
For Li in the lithium-rich solution + Performing analysis and measurement to obtain Li + The mass concentration of (C) is 48.5g/L.
The foregoing is merely exemplary of the application and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the application and are intended to be comprehended within the scope of the application.
Claims (8)
1. A method for extracting lithium using a deep eutectic solvent, comprising the steps of:
preparing a deep eutectic solvent: the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is 1: 2. 1:1 or 2:1, stirring at 40-60 ℃ to form a uniform phase, and cooling to room temperature to obtain a deep eutectic solvent; wherein the hydrogen bond donor is furoyl trifluoroacetone and the hydrogen bond acceptor is trioctyl phosphate; alternatively, the hydrogen bond donor is selected from at least one of benzoyl trifluoroacetone, thenoyl trifluoroacetone, dibenzoylmethane, naphthoyl trifluoroacetone and phenylmethylformyl pyrazolone, and the hydrogen bond acceptor is 2- (diethylhexyl) acetamide or 2- (dimethylheptyl) acetamide;
providing an extracted aqueous phase: taking a lithium-containing solution as an extraction water phase; wherein the pH of the lithium-containing solution is 9.0 to 11.5, and Li in the lithium-containing solution + The mass concentration of the catalyst is 1.20 g/L-2.50 g/L, and anions comprise Cl-, SO 4 2- 、CO 3 2- 、NO 3 - At least one of (a) and (b);
extraction: mixing the deep eutectic solvent with the extracted water phase according to the volume ratio of 1: (1-20) stirring and mixing to extract, and phase-separating to obtain extraction residual liquid and a deep eutectic solvent loaded with lithium after extraction balance;
and (3) back extraction: the deep eutectic solvent loaded with lithium and the stripping agent are mixed according to the volume ratio of (0.5-20): and 1, oscillating and mixing to carry out back extraction, and carrying out phase separation after back extraction balance to obtain a lithium-rich solution and an empty-load deep eutectic solvent.
2. The method of claim 1, wherein the step of preparing the deep eutectic solvent comprises mixing the hydrogen bond donor and the hydrogen bond acceptor at a temperature of 60 ℃.
3. The method for extracting lithium using a deep eutectic solvent according to claim 1 or 2, wherein in the step of preparing a deep eutectic solvent, the hydrogen bond donor and the hydrogen bond acceptor are mixed and reacted under water bath heating.
4. The method of extracting lithium using a deep eutectic solvent according to claim 1, wherein in the step of preparing the deep eutectic solvent, the hydrogen bond donor and the hydrogen bond acceptor are mixed and stirred for 30 to 120 minutes.
5. The method for extracting lithium using deep eutectic solvent according to claim 1, wherein the lithium-containing solution is a lithium precipitation mother solution separated after preparing lithium carbonate by precipitation, wherein Li is contained in the lithium precipitation mother solution + The mass concentration of (2) is 1.5 g/L-2.2 g/L, na + The mass concentration of (C) is 35 g/L-60 g/L, ca 2+ And Mg (magnesium) 2+ Not higher than 0.1g/L.
6. The method for extracting lithium using deep eutectic solvent according to claim 1, wherein in the extraction step, the extraction temperature is 10 to 35 ℃, the stirring rotation speed is 100 to 300rpm, and the extraction time is 5 to 60 minutes.
7. The method for extracting lithium using deep eutectic solvent according to claim 1, wherein in the stripping step, the stripping agent is hydrochloric acid with a concentration of 0.05mol/L to 6 mol/L.
8. The method for extracting lithium using deep eutectic solvent according to claim 1, wherein in the stripping step, the stripping temperature is 10-35 ℃, the shaking speed is 50-300 rpm, and the stripping time is 2-60 min.
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