CN110527850A - A method of based on ketone group functionalized ion liquid extraction and separation lithium - Google Patents
A method of based on ketone group functionalized ion liquid extraction and separation lithium 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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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
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Abstract
The present invention relates to a kind of methods based on ketone group functionalized ion liquid extraction and separation lithium.This method is using the ketone group functionalized ion liquid that is synthesized by quaternary ammonium salt or quaternary alkylphosphonium salt and β-diketone through two-step process as extractant, it is extraction organic phase with the hexamethylene of ketone group functionalized ion liquid or trihydrocarbyl phosphine oxide solution, using the brine containing lithium ion as material liquid, load organic phases and raffinate are separated to obtain after extracting, load organic phases are stripped using stripping agent, the lithium solution purified after centrifugation and recyclable ionic liquid.The ionic liquid that the present invention synthesizes and water are immiscible, good separating effect high to the extraction efficiency of lithium, renewable recycling.
Description
Technical field
The present invention relates to it is a kind of using ketone group functionalized ion liquid extraction brine in lithium method, belong to metal separation and
Ion liquid abstraction technical field.
Background technique
Due to application of the lithium battery in terms of the consumer electronics and electric car in industry, so that lithium resource demand is shown
The promotion of work, wherein, lithium carbonate can be not only used for positive electrode and electrolyte in lithium battery, and produce other positive electrodes
Basic raw material.Still containing the lithium of higher concentration in a large amount of sinker mother liquors caused by lithium carbonate production technology, if directly arranging
Putting will cause to waste.However, there is energy consumption is high, complex process, Yi Yin for the processing techniques such as existing freezing analysis sodium, precipitating analysis lithium
The disadvantages of entering foreign ion is not suitable for industrial applications.And solvent extraction is recognized because of the advantages that easy to operate, output is big
To be expected to become the High efficiency recovery of lithium resource in sinker mother liquor.But since sinker mother liquor is alkaline system, TBP- is not achieved
FeCl3The acidity of the tradition such as kerosene salt lake extraction lithium system, it is therefore desirable to seek a kind of suitable extracting system and be returned from the salt water
Receive lithium.
To Li under β-diketone kind of extractants alkaline condition+Extraction have extraordinary effect.Chinese patent (publication number
CN107779612A a kind of technique for extracting lithium from alkaline brine using β-diketone as extractant) is disclosed.But it is traditional
Solvent-extraction system usually requires kerosene, chloroform, toluene etc. as solvent and accelerates phase point to reduce the viscosity of extraction organic phase
From etc..But these solvents have very strong volatility, cause the increase of production cost and can cause environmental pollution.
The features such as high stability of ionic liquid, low-steam pressure, liquid journey is wide, becomes a kind of novel green solvent,
It is expected to replace traditional volatile organic solvent.Chinese patent (publication number CN107673435A) utilizes hydroxy functionalized ion
Liquid extracts aromatic compound as extractant from aqueous solution.But it is commonly used for the extraction of the glyoxaline ion liquid of extraction system
Mechanism is usually cation exchange, causes glyoxaline cation to be switched in raffinate, causes the loss of ionic liquid and to ring
The pollution in border.Therefore need a kind of more environmentally protective ionic liquid, make its both can under alkaline condition to lithium ion have compared with
High extraction efficiency, while avoiding cation exchange mechanism.
Summary of the invention
In order to solve the above-mentioned problems of the prior art, ketone group functionalized ion liquid is utilized the present invention provides a kind of
The method of extraction and separation lithium ion.Non-volatile first with ionic liquid, the advantages that stability is good, selects strong-hydrophobicity quaternary ammonium salt
Or quaternary alkylphosphonium salt is introduced into ionic liquid anion and ketone is prepared as ionic liquid cation, while by β-diketone functional group
Base functionalized ion liquid.Use ketone group functionalized ion liquid as extractant, the lithium ion in alkaline brine is extracted
Separation is taken, the extraction system extraction efficiency is high and avoids the loss of ionic liquid cation.
What the purpose of the present invention was realized particular by following technical scheme:
Step 1) synthesizes ketone group functionalized ion liquid: using two-step process；The first step is that β-diketone and ammonia pass through acid
Alkali neutralization reaction generates ketone ammonium salt；Second step is that ion-exchange reactions occurs for ketone ammonium salt and quaternary ammonium salt or quaternary alkylphosphonium salt, obtains ketone group
Functionalized ion liquid.
β-the diketone is selected from hexafluoroacetylacetone, benzoyltrifluoroacetone, 2- thioyl trifluoroacetone, 4,4,4-
Any one in three fluoro- 1- (2- furyl) -1,3- diacetyl, 4,4,4- tri- fluoro- 1- (p-methylphenyl) -1,3- diacetyl.
The ammonia is methanol solution, ammonia or the ammonium hydroxide of ammonia.
The quaternary ammonium salt is methyl tricapryl ammonium chloride or tetrabutylammonium chloride, and the quaternary alkylphosphonium salt is tetrabutyl chlorination
Phosphorus.
Contain β-diketone functional group anion in the ketone group functionalized ion liquid, it is preferred that the β-diketone functional group
Anion is hexafluoroacetylacetone ion, benzoyltrifluoroacetone ion, 2- thioyl trifluoroacetone ion, 4,4,4- tri-
Fluoro- 1- (2- furyl) -1,3- diacetyl ion, 4,4,4- tri- fluoro- 1- (p-methylphenyl) -1,3- diacetyl ion it is any one
Kind, structural formula respectively is:
Cation in the ketone group functionalized ion liquid is quaternary ammonium radical ion or quaternary phosphonium radical ion；Preferably, described
Quaternary ammonium radical ion is any one of methyl trioctylphosphine ammonium root cation, tetrabutyl ammonium root cation, and the quaternary phosphonium radical ion is
Tetrabutyl phosphorus root cation, structural formula respectively are:
Step 2) configuration extraction organic phase: ketone group functionalized ion liquid is dissolved in hexamethylene or three hydrocarbon by a certain concentration
Extraction organic phase is obtained in base phosphine oxide；
Preferably, the concentration of ketone group functionalized ion liquid is 0.1~1.2mol/L in the extraction organic phase.
Preferably, the trihydrocarbyl phosphine oxide is liquid oxidatively phosphine Cyanex923 or trialkyl phosphine TRPO.
Step 3) extraction: using brine containing lithium as material liquid, pH is 1~14, and lithium concentration is 0.05~10g/L；It will
The extraction organic phase that step 2) obtains is that 3:1~1:10 is mixed with material liquid by volume, the condition for being 10~70 DEG C in temperature
Under, stirring extracts 5~360min, isolated raffinate and load organic phases after stratification.
Preferably, the material liquid is sinker mother liquor or salt lake bittern.
Step 4) back extraction: under conditions of temperature is 10~70 DEG C, load organic phases that step 3) is obtained with 0.01~
The hydrochloric acid or sulfuric acid solution of 12mol/L is stripped as stripping agent, wherein load organic phases and the volume ratio of stripping agent are
10:1~1:1, after stratification the chloride containing lithium of isolated purifying or the lithium solution of lithium sulfate and ketone group containing functionalization from
The extraction organic phase of sub- liquid；Gained extracts organic phase return step 3) it is recycled.
Further, the quaternary ammonium salt can also be methyl trioctylphosphine ammonium bromide or tetrabutylammonium bromide, the quaternary alkylphosphonium salt
It can be tetrabutyl phosphonium bromide phosphorus.
Further, lithium solution and extraction are organic in the separation and step 4) of raffinate and load organic phases in step 3)
Centrifuge separation may be selected in the separation of phase, it is preferred that centrifugal rotational speed 2000-8000r/min, centrifugation time 2-10min.
β-double ketone structure with excellent extraction ability is introduced into ionic liquid anion by the present invention, simultaneous selection tool
There is hydrophobic quaternary ammonium salt/quaternary alkylphosphonium salt as ionic liquid cation, has synthesized ketone group functionalization ionic liquid through two-step process
Body, and be dissolved in hexamethylene or trihydrocarbyl phosphine oxide as extraction organic phase, hybrid extraction is carried out to brine containing lithium,
Load organic phases and raffinate containing lithium are isolated to, lithium is stripped using stripping agent, is isolated to purifying
Lithium solution and the extraction organic phase that can be recycled.
The beneficial effects of the present invention are as follows:
(1) a kind of method based on ketone group functionalized ion liquid extraction and separation lithium of the present invention, realizes from brine containing lithium
The extraction organic phase of ketone group containing functionalized ion liquid can be recycled while isolating and purifying the target of lithium, technical performance is excellent
More.
(2) present invention has the advantages that designability using ionic liquid, and the ketone group functional group of lithium extraction will be promoted to draw
Enter into its anion, not only can guarantee the environmentally protective advantage of ionic liquid, but also have both high extraction ability.
(3) extraction efficiency of the present invention is high, and good separating effect, ionic liquid will not have loss after extraction, has wide answer
Use prospect.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated, but the present invention is not restricted to following example.
Embodiment 1
The present embodiment follows the steps below:
1) synthesis of ketone group functionalized ion liquid: β-diketone selects benzoyltrifluoroacetone, and quaternary ammonium salt selects methyl three
Octyl ammonium chloride, ammonia select the methanol of ammonia, and obtained anion is benzoyltrifluoroacetone ion, cation is methyl trioctylammonium
The ketone group functionalized ion liquid of radical ion.The methanol solution (0.2M) of benzoyltrifluoroacetone is added to 100ml by the first step
Round-bottomed flask in, place it in ice-water bath, under agitation, the methanol that excess of ammonia is slowly added dropwise with syringe is molten
Liquid is stirred to react after 5h and rotates obtained solution at 45 DEG C, removes methanol.It is added into obtained solid suitable new
The methanol solution of fresh ammonia, is stirred to react 2h.It is multiple to repeat above-mentioned experiment, until the close neutrality of solution.Revolving, consolidates what is obtained
Body ketone ammonium is placed in the vacuum oven at 70 DEG C, dry 2h.The first step is obtained ketone ammonium anhydrous acetonitrile dissolution system by second step
The ketone ammonium salt solution that concentration is 0.2M is obtained, 40ml is taken to be added in the three-necked flask of 100ml, is placed in 35 DEG C of thermostat water bath and delays
The slow uniform methyl tricapryl ammonium chloride anhydrous acetonitrile being added with equivalent.Solution becomes cloudy immediately, there is white solid
It generates, reaction mixture is stirred for 5h.Filter solid is crossed, obtained solution is rotated at 45 DEG C.The liquid of acquisition is molten again
Solution filters in methylene chloride and again to obtain limpid solution, which is repeatedly washed with a small amount of water, until using AgNO3It is molten
Liquid can not detect the chloride ion of water phase, continues vacuum rotary steam and removes solvent and remaining water, the vacuum being placed at 70 DEG C it is dry
Dry 2h is in dry case to get the ketone group functionalized ion liquid for arriving drying.
2) dry ketone group functionalized ion liquid configuration extraction organic phase: is dissolved in liquid oxidatively phosphine Cyanex923
In, it prepares and obtains the extraction organic phase that ketone group functionalized ion liquid concentration is 0.5mol/L.
3) extract: material liquid is the lithium carbonate mother liquor after lithium chloride precipitating, wherein Li+And Na+Concentration be respectively 0.5g
L-1And 23gL-1, solution ph 10.82.The extraction organic phase that material liquid and step 2) obtain is placed in sample bottle, is stirred
Mix extraction, the volume ratio for extracting organic phase and material liquid is 1:1, extraction time 30min, 25 DEG C of extraction temperature.Extraction is completed
Mixed solution isolated load organic phases and raffinate after stratification afterwards measures the concentration of lithium ion in raffinate, obtains
Lithium ion extraction efficiency is 83.88%.
4) load organic phases are stripped as stripping agent using 1.0mol/L hydrochloric acid solution, load organic phases with instead
The volume ratio for extracting agent is 1:1, Stripping times 30min, is stripped 25 DEG C of temperature.Mixed solution after the completion of back extraction divides through standing
Separate and recover lithium after layer, the extraction organic phase of isolated lithium solution and ketone group containing functionalized ion liquid, extraction organic phase into
Row recycles.It is computed, lithium ion stripping rate is 75.61%.
Embodiment 2
The present embodiment follows the steps below:
1) synthesis of ketone group functionalized ion liquid: β-diketone selects 2- thioyl trifluoroacetone, and quaternary ammonium salt selects first
Base trioctylmethylammonium chloride, ammonia select ammonium hydroxide, and obtained anion is 2- thioyl trifluoroacetone ion, cation is that methyl three is pungent
The ketone group functionalized ion liquid of base ammonium ion.Synthetic method is identical as step 1) in embodiment 1.
2) configuration extraction organic phase: dry ketone group functionalized ion liquid is dissolved in trialkyl phosphine TRPO,
It prepares and obtains the extraction organic phase that ketone group functionalized ion liquid concentration is 0.1mol/L.
3) extract: material liquid is salt lake bittern, wherein Li+And Na+Concentration be respectively 0.05gL-1And 5gL-1, molten
Liquid pH value is 1.The extraction organic phase that material liquid and step 2) are obtained is placed in sample bottle, stirring extraction, extraction organic phase with
The volume ratio of material liquid be 1:10, extraction time 5min, 10 DEG C of extraction temperature.Mixed solution is centrifuged after the completion of extraction
Load organic phases and raffinate are obtained, centrifugal rotational speed 4000r/min, centrifugation time 5min measure lithium ion in raffinate
Concentration, obtain lithium ion extraction efficiency be 83.68%.
4) load organic phases are stripped as stripping agent using 0.01mol/L hydrochloric acid solution, load organic phases and
The volume ratio of stripping agent is 10:1, Stripping times 5min, is stripped 10 DEG C of temperature.Mixed solution after the completion of back extraction is through being centrifuged
Lithium is separated and recovered, the centrifugal rotational speed of centrifuge separation is 2000r/min, centrifugation time 2min, isolated lithium solution and ketone group containing
The extraction organic phase of functionalized ion liquid, extraction organic phase are recycled.It is computed, lithium ion stripping rate is
91.78%.
Embodiment 3
The present embodiment follows the steps below:
1) synthesis of ketone group functionalized ion liquid: β-diketone selects tri- fluoro- 1- (p-methylphenyl) -1,3- fourth two of 4,4,4-
Ketone, quaternary alkylphosphonium salt select tetrabutyl phosphorus chloride, and ammonia selects ammonia, and it is 4,4,4- tri- fluoro- 1- (p-methylphenyl) -1,3- that anion, which is made,
Diacetyl ion, the ketone group functionalized ion liquid that cation is tetrabutyl phosphorus radical ion.Step in synthetic method and embodiment 1
1) identical.
2) configuration extraction organic phase: dry ketone group functionalized ion liquid is dissolved in hexamethylene, preparation obtains ketone
Base functionalized ion liquid concentration is the extraction organic phase of 1.2mol/L.
3) extract: material liquid is the lithium carbonate mother liquor after lithium chloride precipitating, wherein Li+And Na+Concentration be respectively 10g
L-1And 39gL-1, solution ph 14.The extraction organic phase that material liquid and step 2) obtain is placed in sample bottle, stirring extraction
It taking, the volume ratio for extracting organic phase and material liquid is 3:1, extraction time 360min, 70 DEG C of extraction temperature.It is mixed after the completion of extraction
It closes solution to be centrifuged to obtain load organic phases and raffinate, centrifugal rotational speed 8000r/min, centrifugation time 10min are surveyed
The concentration for determining lithium ion in raffinate, obtaining lithium ion extraction efficiency is 93.71%.
4) load organic phases are stripped as stripping agent using 12.0mol/L sulfuric acid solution, load organic phases and
The volume ratio of stripping agent is 1:1, Stripping times 120min, is stripped temperature 70 C.Mixed solution after the completion of back extraction pass through from
The heart separates and recovers lithium, and the centrifugal rotational speed of centrifuge separation is 5000r/min, centrifugation time 10min, isolated lithium solution and contains ketone
The extraction organic phase of base functionalized ion liquid, extraction organic phase are recycled.It is computed, lithium ion stripping rate is
92.15%.
Embodiment 4
The present embodiment follows the steps below:
1) synthesis of ketone group functionalized ion liquid: β-diketone selects the fluoro- 1- of 4,4,4- tri- (2- furyl) -1,3- fourth two
Ketone, quaternary ammonium salt select methyl trioctylphosphine ammonium bromide, and ammonia selects the methanol solution of ammonia, and it is that β-diketone selects 4,4,4- that anion, which is made,
Three fluoro- 1- (2- furyl) -1,3- diacetyl ions, cation are the ketone group functionalization ionic liquid of methyl trioctylammonium radical ion
Body.Synthetic method is identical as step 1) in embodiment 1.
2) configuration extraction organic phase: dry ketone group functionalized ion liquid is dissolved in hexamethylene, preparation obtains ketone
Base functionalized ion liquid concentration is the extraction organic phase of 1.0mol/L.
3) extract: material liquid is the lithium carbonate mother liquor after lithium chloride precipitating, wherein Li+And Na+Concentration be respectively 5gL-1And 32gL-1, solution ph 11.2.The extraction organic phase that material liquid and step 2) obtain is placed in sample bottle, is stirred
Extraction, the volume ratio for extracting organic phase and material liquid is 2:1, extraction time 20min, 35 DEG C of extraction temperature.After the completion of extraction
Mixed solution is centrifuged to obtain load organic phases and raffinate, centrifugal rotational speed 2000r/min, centrifugation time 10min,
The concentration for measuring lithium ion in raffinate, obtaining lithium ion extraction efficiency is 86.64%.
4) load organic phases are stripped as stripping agent using 12mol/L hydrochloric acid solution, load organic phases with instead
The volume ratio for extracting agent is 2:1, Stripping times 60min, is stripped 35 DEG C of temperature.Mixed solution after the completion of back extraction is through centrifugation point
From recycling lithium, the centrifugal rotational speed of centrifuge separation is 5000r/min, centrifugation time 5min, isolated lithium solution and ketone group containing function
The extraction organic phase of ionic liquid can be changed, extraction organic phase is recycled.It is computed, lithium ion stripping rate is
92.05%.
Embodiment 5
The present embodiment follows the steps below:
1) synthesis of ketone group functionalized ion liquid: β-diketone selects hexafluoroacetylacetone, and quaternary ammonium salt selects tetrabutyl bromine
Change ammonium, ammonia selects ammonium hydroxide, and it is hexafluoroacetylacetone ion that anion, which is made, and cation is the ketone group function of tetrabutylammonium radical ion
Change ionic liquid.Synthetic method is identical as step 1) in embodiment 1.
2) dry ketone group functionalized ion liquid configuration extraction organic phase: is dissolved in liquid oxidatively phosphine Cyanex923
In, it prepares and obtains the extraction organic phase that ketone group functionalized ion liquid concentration is 0.3mol/L.
3) extract: material liquid is salt lake bittern, wherein Li+And Na+Concentration be respectively 1.5gL-1And 12gL-1, molten
Liquid pH value is 3.02.The extraction organic phase that material liquid and step 2) obtain is placed in sample bottle, stirring extraction extracts organic phase
It is 1:5, extraction time 200min with the volume ratio of material liquid, 25 DEG C of extraction temperature.Mixed solution is through being centrifuged after the completion of extraction
Isolated load organic phases and raffinate, centrifugal rotational speed 8000r/min, centrifugation time 2min measure lithium in raffinate
The concentration of ion, obtaining lithium ion extraction efficiency is 68.21%.
4) load organic phases are stripped as stripping agent using 1.0mol/L sulfuric acid solution, load organic phases with instead
The volume ratio for extracting agent is 5:1, Stripping times 30min, is stripped 25 DEG C of temperature.Mixed solution after the completion of back extraction is through centrifugation point
From recycling lithium, the centrifugal rotational speed of centrifuge separation is 5000r/min, centrifugation time 5min, isolated lithium solution and ketone group containing function
The extraction organic phase of ionic liquid can be changed, extraction organic phase is recycled.It is computed, lithium ion stripping rate is
78.86%.
Embodiment 6
The present embodiment follows the steps below:
1) synthesis of ketone group functionalized ion liquid: β-diketone selects 2- thioyl trifluoroacetone, and quaternary alkylphosphonium salt selects four
Butyl phosphonium bromide, ammonia select ammonia, and it is 2- thioyl trifluoroacetone ion that anion, which is made, and cation is tetrabutyl phosphonium ion
Ketone group functionalized ion liquid.Synthetic method is identical as step 1) in embodiment 1.
2) configuration extraction organic phase: dry ketone group functionalized ion liquid is dissolved in trialkyl phosphine TRPO,
It prepares and obtains the extraction organic phase that ketone group functionalized ion liquid concentration is 0.1mol/L.
3) extract: material liquid is the lithium carbonate mother liquor after lithium chloride precipitating, wherein Li+And Na+Concentration be respectively 0.2g
L-1And 2.3gL-1, solution ph 1.82.The extraction organic phase that material liquid and step 2) obtain is placed in sample bottle, is stirred
Mix extraction, the volume ratio for extracting organic phase and material liquid is 3:1, extraction time 30min, 25 DEG C of extraction temperature.Extraction is completed
Mixed solution is centrifuged to obtain load organic phases and raffinate, centrifugal rotational speed 4000r/min afterwards, and centrifugation time is
5min measures the concentration of lithium ion in raffinate, and obtaining lithium ion extraction efficiency is 45.31%.
4) load organic phases are stripped as stripping agent using 0.01mol/L sulfuric acid solution, load organic phases and
The volume ratio of stripping agent is 2:1, Stripping times 60min, is stripped 25 DEG C of temperature.Mixed solution after the completion of back extraction is through being centrifuged
Lithium is separated and recovered, the centrifugal rotational speed of centrifuge separation is 2000r/min, centrifugation time 10min, isolated lithium solution and ketone group containing
The extraction organic phase of functionalized ion liquid, extraction organic phase are recycled.It is computed, lithium ion stripping rate is
90.97%.
Embodiment 7
The present embodiment follows the steps below:
1) synthesis of ketone group functionalized ion liquid: β-diketone selects the fluoro- 1- of 4,4,4- tri- (2- furyl) -1,3- fourth two
Ketone ion, quaternary ammonium salt select tetrabutylammonium chloride, and ammonia selects the methanol solution of ammonia, and it is 4,4,4- tri- fluoro- 1- (2- that anion, which is made,
Furyl) -1,3- diacetyl ion, cation is the ketone group functionalized ion liquid of tetrabutylammonium radical ion.Synthetic method with
Step 1) is identical in embodiment 1.
2) configuration extraction organic phase: dry ketone group functionalized ion liquid is dissolved in trialkyl phosphine TRPO,
It prepares and obtains the extraction organic phase that ketone group functionalized ion liquid concentration is 0.5mol/L.
3) extract: material liquid is the lithium carbonate mother liquor after lithium chloride precipitating, wherein Li+And Na+Concentration be respectively 3gL-1And 2gL-1, solution ph 7.82.The extraction organic phase that material liquid and step 2) obtain is placed in sample bottle, stirring extraction
It taking, the volume ratio for extracting organic phase and material liquid is 2:1, extraction time 30min, 25 DEG C of extraction temperature.It is mixed after the completion of extraction
It closes solution to be centrifuged to obtain load organic phases and raffinate, centrifugal rotational speed 4000r/min, centrifugation time 5min are surveyed
The concentration for determining lithium ion in raffinate, obtaining lithium ion extraction efficiency is 63.54%.
4) load organic phases are stripped as stripping agent using 2.0mol/L hydrochloric acid solution, load organic phases with instead
The volume ratio for extracting agent is 6:1, Stripping times 30min, is stripped 25 DEG C of temperature.Mixed solution after the completion of back extraction is through centrifugation point
From recycling lithium, the centrifugal rotational speed of centrifuge separation is 8000r/min, centrifugation time 2min, isolated lithium solution and ketone group containing function
The extraction organic phase of ionic liquid can be changed, extraction organic phase is recycled.It is computed, lithium ion stripping rate is
90.97%.
Embodiment 8
The present embodiment follows the steps below:
1) synthesis of ketone group functionalized ion liquid: β-diketone selects tri- fluoro- 1- (p-methylphenyl) -1,3- fourth two of 4,4,4-
Ketone, quaternary ammonium salt select methyl tricapryl ammonium chloride, and ammonia selects the methanol solution of ammonia, and it is that 4,4,4- tri- fluoro- 1- are (right that anion, which is made,
Tolyl) -1,3- diacetyl ion, cation is the ketone group functionalized ion liquid of methyl trioctylammonium radical ion.Synthesis side
Method is identical as step 1) in embodiment 1.
2) configuration extraction organic phase: dry ketone group functionalized ion liquid is dissolved in hexamethylene, preparation obtains ketone
Base functionalized ion liquid concentration is the extraction organic phase of 0.8mol/L.
3) extract: material liquid is the lithium carbonate mother liquor after lithium chloride precipitating, wherein Li+And Na+Concentration be respectively 7.5g
L-1And 40gL-1, solution ph 8.82.The extraction organic phase that material liquid and step 2) obtain is placed in sample bottle, is stirred
Extraction, the volume ratio for extracting organic phase and material liquid is 1:7, extraction time 30min, 25 DEG C of extraction temperature.After the completion of extraction
Mixed solution is centrifuged to obtain load organic phases and raffinate, centrifugal rotational speed 6000r/min, centrifugation time 5min,
The concentration for measuring lithium ion in raffinate, obtaining lithium ion extraction efficiency is 94.42%.
4) load organic phases are stripped as stripping agent using 6.0mol/L hydrochloric acid solution, load organic phases with instead
The volume ratio for extracting agent is 1:1, Stripping times 30min, is stripped 25 DEG C of temperature.Mixed solution after the completion of back extraction is through centrifugation point
From recycling lithium, the centrifugal rotational speed of centrifuge separation is 5000r/min, centrifugation time 5min, isolated lithium solution and ketone group containing function
The extraction organic phase of ionic liquid can be changed, extraction organic phase is recycled.It is computed, lithium ion stripping rate is
90.97%.
Claims (4)
1. a kind of method based on ketone group functionalized ion liquid extraction and separation lithium, which is characterized in that this method is according to following step
It is rapid to carry out:
1) synthesize ketone group functionalized ion liquid: the first step is that β-diketone and ammonia pass through acid-base neutralization reaction generation ketone ammonium salt；The
Two steps are that ion-exchange reactions occurs for ketone ammonium salt and quaternary ammonium salt or quaternary alkylphosphonium salt, obtain ketone group functionalized ion liquid；
β-the diketone is hexafluoroacetylacetone, benzoyltrifluoroacetone, 2- thioyl trifluoroacetone, the fluoro- 1- of 4,4,4- tri-
Any one in (2- furyl) -1,3- diacetyl, 4,4,4- tri- fluoro- 1- (p-methylphenyl) -1,3- diacetyl；
The ammonia is methanol solution, ammonia or the ammonium hydroxide of ammonia；
The quaternary ammonium salt is methyl tricapryl ammonium chloride or tetrabutylammonium chloride；The quaternary alkylphosphonium salt is tetrabutyl phosphorus chloride；
Contain β-diketone functional group in the ketone group functionalized ion liquid；
2) configuration extraction organic phase: ketone group functionalized ion liquid is dissolved in hexamethylene by a certain concentration or trihydrocarbyl phosphine aoxidizes
Extraction organic phase is obtained in object；
The concentration of ketone group functionalized ion liquid is 0.1~1.2mol/L in the extraction organic phase；
3) extract: using brine containing lithium as material liquid, pH value is 1~14, and lithium concentration is 0.05~10g/L；By step 2)
Obtained extraction organic phase is that 3:1~1:10 is mixed with material liquid by volume, under conditions of temperature is 10~70 DEG C, stirring
Extract 5~360min, isolated raffinate and load organic phases after centrifugation or stratification；
4) be stripped: under conditions of temperature is 10~70 DEG C, the load organic phases that step 3) is obtained are with 0.01~12mol/L's
Hydrochloric acid or sulfuric acid solution are stripped as stripping agent, wherein and load organic phases and the volume ratio of stripping agent are 10:1~1:1,
The lithium solution and extraction organic phase for separating to purify after centrifugation or stratification；Gained extract organic phase return step 3) circulation make
With.
2. the method according to claim 1, wherein the quaternary ammonium salt can also be tetrabutylammonium bromide or methyl three
Octyl ammonium bromide；The quaternary alkylphosphonium salt can also be tetrabutyl phosphonium bromide phosphorus.
3. the method according to claim 1, wherein the cation in the ketone group functionalized ion liquid is season
Ammonium ion or quaternary phosphonium radical ion, preferably methyl trioctylammonium radical ion, tetrabutylammonium radical ion, in tetrabutyl phosphorus radical ion
Any one, structural formula respectively is:
4. the method according to claim 1, wherein β-diketone function in the ketone group functionalized ion liquid
Group's anion, preferably hexafluoroacetylacetone ion, benzoyltrifluoroacetone ion, 2- thioyl trifluoroacetone ion, 4,
In fluoro- 1- (2- the furyl) -1,3- diacetyl of 4,4- tri- ion, 4,4,4- tri- fluoro- 1- (p-methylphenyl) -1,3- diacetyl ion
Any one, structural formula respectively is:
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