CN109468459A - Lithium extractant and the method that lithium is extracted from salt lake bittern - Google Patents
Lithium extractant and the method that lithium is extracted from salt lake bittern 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
- C22B3/32—Carboxylic acids
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- 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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Abstract
The method of lithium is extracted the invention discloses lithium extractant and from salt lake bittern.Wherein, this method utilizes N, N- dimethyl alkylamide makees main extractant, make phase modifying agent with ketone and extracts lithium from salt lake bittern, the kind of extractants is while with outstanding lithium extracting power and selectivity, it is not easy to form the flocculate for influencing extraction process in use, and avoids the use of phosphorus-contained extractant, it is more friendly to environment.
Description
Technical field
The present invention relates to extraction chemistry fields, and lithium is extracted in particular to lithium extractant and from salt lake bittern
Method.
Background technique
Lithium is important strategic resource.In nature, the main preservation of lithium is in solid mineral and liquid mineral deposit, wherein salt
Lithium resource in lake bittern water accounts for about the whole world and has verified the 90% of lithium resource.China has salt lake bittern resource abundant, main to divide
Cloth is in areas such as Qinghai, Tibet.The saline lake lithium resource of Chaidamu Basin, Qinghai Province is very rich, LiCl reserves about 2.8 × 107t.It should
There are two outstanding features for class brine tool: (1) lithium content is high, up to 2~3g/L；(2) Mg/Li ratio is very high, usually both greater than 40 (matter
Amount ratio).Since the chemical property of lithium and magnesium is closely similar, conventional method is difficult to extract lithium from salt lake brine with high magnesium-lithium ratio
Come, and is separated with the magnesium of high concentration.
Solvent extraction is a kind of important means for purifying and separating in chemical process, it have separative efficiency high, technique and
Equipment is simple, operates serialization, is easily achieved the advantages that automatic control, it is considered to be extracts separating Li from high Mg/Li ratio brine
One of most promising method.Lithium exists in the form of an ion in salt lake bittern.Li+Radius very little, only one electronic shell,
2s, 2p are unoccupied orbital, and polarizability is very low, sp can only occur with hard bases coordination atoms such as O, N3Hydridization forms stable tetrahedron
Structure.In aqueous solution, Li+With H2Strong aquation occurs for O molecule, forms Li (H2O)4 +, extractant molecules are difficult and water
Molecule competes in conjunction with lithium ion, therefore, can directly extract Li still without discovery so far+Extractant.In Cl-Concentration it is higher and
Contain Fe3+Aqueous solution in, it may occur that following reaction: Mn++FeCl4 -=M (FeCl4)n。M(FeCl4)nIt can be by some specific knots
The Neutral-neutral Extractants (such as neutral phosphate, amide) of structure extract.M(FeCl4)nIt is by the priority that these extractants extract
HFeCl4>LiFeCl4>>Mg(FeCl4)2>NaFeCl4>KFeCl4.Around this principle, scientists have developed FeCl3Co-extraction
System with realize from salt lake bittern extract lithium and with the separation of other metal ions, principle is: being added in salt lake bittern
FeCl3, make various cations and the FeCl in brine3In conjunction with formation M (FeCl4)n, recycle the extraction such as neutral phosphate, amide
Agent is preferentially by HFeCl4And LiFeCl4It is extracted to organic phase, and Mg (FeCl4)2、NaFeCl4、KFeCl4Etc. staying in water phase, then use
It is stripped organic phase compared with concentrated hydrochloric acid, makes LiFeCl4It is converted into HFeCl4, and Li+Into water phase.
However, the extraction system and technique of the existing extraction lithium from salt lake bittern still have much room for improvement.
Summary of the invention
The present invention is to be proposed based on inventor to the discovery of following facts and problem:
Patent CN87103431 proposes a kind of tributyl phosphate (TBP)-kerosene system extraction lithium technique, and carries out half work
Industry test.Although TBP- kerosene system is to lithium extracting power with higher and selectivity, there are the following problems: (1) TBP
Seriously corroded is swollen to the extraction equipment of the materials such as PVC, PP, not only shortens the service life of equipment, the macromolecular for being swollen out
Organic matter enters extraction system, influences the mobility and split-phase of extraction system；(2) TBP density (0.979g/mL) and molecular polarity
It is larger, extracted species TBPLiFeCl4And TBPHFeCl4Density and molecular polarity further increase, in low pole coal
Solubility is smaller in oily (diluent), and extraction process easily forms third phase, is unfavorable for the stable operation of extraction process；(3)TBP
In acid or alkaline aqueous solution, it may occur that hydrolysis, especially during alkali neutralization regenerates organic phase, local base excess
It can greatly accelerate the hydrolysis of TBP, generate water-soluble bigger monobutyl phosphate (MBP) and dibutylphosphoric acid ester (DBP).MBP and DBP
Not only to LiFeCl4Without extracting power, and easily with the Fe in system3+The wax-like of kerosene, TBP and water is insoluble in conjunction with being formed
Solid causes extraction system viscosity to increase, until extraction process is unable to run；(4) solubility of TBP in water itself is about
0.1%, but solubility is larger in water by its hydrolysate MBP and DBP, therefore had in raffinate in During Process of Long-term Operation more
Phosphorus-containing matter, they are difficult by biochemical degradation or oxidative degradation into harmless gas or precipitating, and long-term accumulation can be raw to salt lake
State does great damage.Problem above limits TBP and proposes the scale application in lithium industry in salt lake bittern.
TBP extractant there are aiming at the problem that, there is scholar to propose a series of amides lithium extractants.The extraction of such amide
Agent mainly includes following compound: N, N- bis- (2- ethylhexyl) propionamide, N, N- dihexyl benzamide, N, N- dihexyl is just
Butyramide, N, N- dihexyl -2- methyl propanamide, N, N- dihexyl propionamide, N, N- bis- (2- ethylhexyl) -2- methoxyl group second
Amide, N, N- bis- (2- ethylhexyl) acetamide, N, (2- the ethylhexyl) -2- methyl propanamide of N- bis- and N, N- dihexyl are to first
Yl-benzamide.The main structure of above-mentioned amides compound are as follows: nitrogen-atoms and two Long carbon chain alkyl (carbon atom number >=
6) it is connected, carbonyl is connected with short carbon chain alkyl or aryl radical.Wherein, two Long carbon chain alkyl on nitrogen-atoms are to make to extract
Take agent that there is lower water-soluble and preferable oil-soluble.But the reprimand electronic effect of two Long carbon chain alkyl increases nitrogen-atoms
The cloud density of upper lone pair electrons, so that the amide of the structure is with clearly alkaline.Since above-mentioned amides compound is from salt
The principle that lithium is extracted in lake bittern water is similar with TBP, it is also desirable to FeCl be added in brine3As co-extraction agent.In extraction process,
It can be with the H in aqueous solution in the amide of alkalinity+In conjunction with increasing the pH value of solution, and then lead to Fe3+It hydrolyzes and generates Fe
(OH)3Flocculate seriously affects the normal operation of extraction process.Thus, this kind of extractants also fails always to mention lithium neck in salt lake
Domain obtains industrial applications.In order to improve defect existing for above-mentioned amides compound and TBP itself, amide has been researched and proposed
With the composite extractant of TBP, however can not fundamentally solve with alkalinity amide cause Fe3+Hydrolysis and TBP corrosion are set
Standby problem.
In consideration of it, the method that the present invention proposes lithium extractant and extracts lithium from salt lake bittern.Wherein, this method utilizes
N, N- dimethyl alkylamide extractant extract lithium from salt lake bittern, the kind of extractants with outstanding lithium extracting power and
While selective, it is not easy to form the flocculate for influencing extraction process in use, and avoid the use of phosphorus reagent, to ring
Border is more friendly.
In one aspect of the invention, the invention proposes a kind of sides for extracting lithium from salt lake bittern using extractant
Method.According to an embodiment of the invention, the extractant includes compound shown in formula (A),
Wherein, R1For C6-20Straight chained alkyl, C6-20Branched alkyl or C6-20Naphthenic base.
According to an embodiment of the invention, what is be connected directly in compound shown in formula (A) with nitrogen-atoms is two methyl, and with
The connected R of carbonyl1Group is C6-20Straight chain, branch or naphthenic base.Compound shown in formula (A) and traditional amides lithium extractant
(such as N, N- bis- (2- ethylhexyl) propionamide, N, N- dihexyl benzamide, N, N- bis- (2- ethylhexyl) acetamide, N,
N- dihexyl is to methyl benzamide etc.) there are the differences of apparent structure: on the nitrogen-atoms of compound shown in formula (A) be connected be
Two methyl, and the Long carbon chain R by being connected with carbonyl1Group offer oil-soluble, and acyl in traditional amides lithium extractant
Two Long carbon chain alkyl are connected on amine nitrogen atom.The reprimand electronic effect of alkyl enhances, methyl phase as carbon atom number increases
It is weaker for the reprimand electronic effect of Long carbon chain alkyl, thus in compound shown in formula (A) nitrogen-atoms cloud density it is obviously low
Amide nitrogen atom in traditional amides lithium extractant, so that the alkalinity of compound shown in formula (A) is markedly less than biography
The amides lithium extractant of system.The method of the invention that lithium is extracted from salt lake bittern passes through using including shown in formula (A) as a result,
The extractant of compound carries out, and is not easy to make Fe because extractant alkalinity is excessively high in extraction process3+Flocculate is hydrolyzed to form, thus
It can guarantee the stable operation of extraction process.In addition, present method avoids the use of phosphorus reagent, it is more friendly to environment
It is good, and the swelling of extraction equipment is corroded minimum.
In addition, the method according to the above embodiment of the present invention for extracting lithium from salt lake bittern using extractant can also have
There is following additional technical characteristic:
In some embodiments of the invention, R1For C8-14Straight chained alkyl or C8-14Branched alkyl.
In some embodiments of the invention, the extractant further comprises compound shown in formula (B),
Wherein, R2And R3It is separately C1-24Straight chained alkyl, C1-24Branched alkyl or C1-24Naphthenic base, and R2And R3's
Total carbon atom number is not less than 5.Compound shown in the compound of formula (A) of the class formation, solvent naphtha all have good intermiscibility,
Thus, it is possible to effectively avoid the formation of third phase in extraction process.
In some embodiments of the invention, R2And R3It is separately C1-12Straight chained alkyl or C1-12Branched alkyl, and
R2And R3Total carbon atom number be 7~15.
In some embodiments of the invention, the volume of compound shown in the formula (A) and compound shown in the formula (B)
Than for 1:(0.1~10).
In some embodiments of the invention, which comprises (1) salt lake bittern with ferric trichloride is mixed,
To obtain extraction feed liquid；(2) extractant and diluent are hybridly prepared into extraction organic phase, and with the extraction feed liquid
Mixing is extracted, to obtain load organic phases and raffinate；(3) load organic phases are washed using detergent
It washs, so as to organic phase after being washed and washing extraction raffinate；(4) organic phase after the washing is stripped using hydrochloric acid, with
Just it obtains back extraction organic phase and is stripped extraction raffinate.
In some embodiments of the invention, in step (1), it is described extraction feed liquid in hydrogen ion concentration be 0.01~
The molar ratio of 1.0mol/L, iron and lithium is (1~3): 1.
In some embodiments of the invention, before step (2), the extractant is mixed to get with diluent in advance
Organic phase is extracted, volume fraction of the extractant in the extraction organic phase is 10~99%.
In some embodiments of the invention, the diluent is selected from the solvent naphtha that boiling range is 160~300 degrees Celsius.
In some embodiments of the invention, the diluent is selected from 260# aviation kerosine, sulfonated kerosene, D70 solvent
At least one of oil and D80 solvent naphtha.
In some embodiments of the invention, in step (2), the volume ratio of the extraction organic phase and the extraction feed liquid
For (4~1): (1~4), single-stage extraction time are 3~30min, and system temperature is 10~50 degrees Celsius.
In some embodiments of the invention, in step (3), the load organic phases and the volume ratio of the detergent are
(20~50): 1, time of contact is 3~30min, and system temperature is 10~50 degrees Celsius.
In some embodiments of the invention, in step (3), the detergent is the back extraction extraction raffinate.
In some embodiments of the invention, in step (4), organic phase and the volume ratio of the hydrochloric acid are after the washing
(10~30): 1, time of contact is 2~30min, and system temperature is 10~50 degrees Celsius；The concentration of the hydrochloric acid be 5.0~
9.0mol/L。
In some embodiments of the invention, the method further includes: (5) mix lye and the back extraction organic phase
It closes, to obtain regeneration back extraction organic phase.
In some embodiments of the invention, the lye be concentration be 0.1~1.0mol/L sodium hydroxide solution, hydrogen
The volume ratio of potassium oxide solution, sodium carbonate liquor or solution of potassium carbonate, the back extraction organic phase and the lye is (10~40):
1。
In another aspect of this invention, the invention proposes a kind of composite extractants.According to an embodiment of the invention, this is multiple
Closing extractant includes compound shown in compound shown in formula (A) and formula (B),
Wherein,
R1For C6-20Straight chained alkyl, C6-20Branched alkyl or C6-20Naphthenic base；
R2And R3It is separately C1-24Straight chained alkyl, C1-24Branched alkyl or C1-24Naphthenic base, and R2And R3Total carbon
Atomicity is not less than 5.
In composite extractant according to an embodiment of the present invention, on the one hand, in compound shown in formula (A) with the direct phase of nitrogen-atoms
What is connected is two methyl, and the R being connected with carbonyl1Group is C6-20Straight chain, branch or naphthenic base.Compound shown in formula (A) and biography
Amides lithium extractant (such as N, N- bis- (2- ethylhexyl) propionamide, N, N- dihexyl benzamide, N, the bis- (2- of N- of system
Ethylhexyl) acetamide, N, N- dihexyl is to methyl benzamide etc.) there are the differences of apparent structure: compound shown in formula (A)
Nitrogen-atoms on be connected is two methyl, and the R by being connected with carbonyl1Group offer oil-soluble, and traditional amides
Two Long carbon chain alkyl are connected in lithium extractant in amide nitrogen atom.The reprimand electronic effect of alkyl with carbon atom number increase and
Enhancing, methyl is weaker relative to the reprimand electronic effect of Long carbon chain alkyl, thus in compound shown in formula (A) nitrogen-atoms electron cloud
Density is significantly lower than the amide nitrogen atom in traditional amides lithium extractant, so that the alkalinity of compound shown in formula (A)
It is markedly less than traditional amides lithium extractant, is not easy to make Fe in extraction process3+Hydrolyze to form flocculate.On the other hand, formula
(B) polarity of compound shown in is suitable for having preferable compatibility with the organic phase in extraction system.Meanwhile formula (B) shownization
Object is closed to LiFeCl4Also there is certain extraction, and there is lower viscosity.This makes compound shown in formula (B) as formula
(A) compound modification agent shown in, it is possible to prevente effectively from extraction process third phase formation, and improve main extractant formula (A) institute
Show compound to LiFeCl4Extraction yield, while guaranteeing extraction process continuous and steady operation.
In addition, composite extractant according to the above embodiment of the present invention can also have the following additional technical features:
In some embodiments of the invention, R1For C8-14Straight chained alkyl or C8-14Branched alkyl；R2And R3Separately
For C1-12Straight chained alkyl or C1-12Branched alkyl, and R2And R3Total carbon atom number be 7~15.
In some embodiments of the invention, the volume of compound shown in the formula (A) and compound shown in the formula (B)
Than for 1:(0.1~10).
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Specific embodiment
The embodiment of the present invention is described below in detail.The embodiments described below is exemplary, and is only used for explaining this hair
It is bright, and be not considered as limiting the invention.Particular technique or condition are not specified in embodiment, according to text in the art
It offers described technology or conditions or is carried out according to product description.Reagents or instruments used without specified manufacturer,
For can be with conventional products that are commercially available.
In one aspect of the invention, the invention proposes a kind of sides for extracting lithium from salt lake bittern using extractant
Method.According to an embodiment of the invention, the extractant includes compound shown in formula (A),
Wherein, R1For C6-20Straight chained alkyl, C6-20Branched alkyl or C6-20Naphthenic base.
According to an embodiment of the invention, what is be connected directly in compound shown in formula (A) with nitrogen-atoms is two methyl, and with
The connected R of carbonyl1Group is C6-20Straight chain, branch or naphthenic base.Compound shown in formula (A) and traditional amides lithium extractant
(such as N, N- bis- (2- ethylhexyl) propionamide, N, N- dihexyl benzamide, N, N- bis- (2- ethylhexyl) acetamide, N,
N- dihexyl is to methyl benzamide etc.) there are the differences of apparent structure: on the nitrogen-atoms of compound shown in formula (A) be connected be
Two methyl, and the Long carbon chain R by being connected with carbonyl1Group offer oil-soluble, and acyl in traditional amides lithium extractant
Two Long carbon chain alkyl are connected on amine nitrogen atom.The reprimand electronic effect of alkyl enhances, methyl phase as carbon atom number increases
It is weaker for the reprimand electronic effect of Long carbon chain alkyl, thus in compound shown in formula (A) nitrogen-atoms cloud density it is obviously low
Amide nitrogen atom in traditional amides lithium extractant, so that the alkalinity of compound shown in formula (A) is markedly less than biography
The amides lithium extractant of system.The method of the invention that lithium is extracted from salt lake bittern passes through using including shown in formula (A) as a result,
The extractant of compound carries out, and is not easy to make Fe because extractant alkalinity is excessively high in extraction process3+Flocculate is hydrolyzed to form, thus
It can guarantee the stable operation of extraction process.In addition, present method avoids the use of phosphorus reagent, it is more friendly to environment
It is good, and the swelling of extraction equipment is corroded minimum.
Oil-soluble, water-soluble loss, Atom economy and the raw material for comprehensively considering extractant are ready availability, according to the present invention
Preferred embodiment, in compound shown in formula (A), R1For C8-14Straight chained alkyl or C8-14Branched alkyl.With above-mentioned R1The formula of group
(A) compound oil-soluble shown in is suitable for, water-soluble lower, in the loss very little of water phase in extraction process, and raw material sources range
Extensively, cheap and easy to get.
According to an embodiment of the invention, extractant can further include compound shown in formula (B),
Wherein, R2And R3It is separately C1-24Straight chained alkyl, C1-24Branched alkyl or C1-24Naphthenic base, and R2And R3's
Total carbon atom number is not less than 5, and in other words, the total carbon atom number of compound shown in formula (B) is not less than 6.Inventor sends out in an experiment
It is existing, during being extracted using the extractant for including compound shown in formula (A), the extraction of compound shown in formula (A)
LiFeCl4The extraction associated matter molecular polarity formed afterwards increases, and is easy to form third phase in system.Although the formation of third phase
The technic indexs such as the extraction yield of lithium, Separation of Li and Mg coefficient, lithium sodium separation, lithium potassium separation are influenced less, but to extraction
The continuous and steady operation of process is taken to have adverse effect.In consideration of it, inventor is had found by lot of experiments with formula (B) institute
Show that compound collectively constitutes composite extractant as compound shown in modification agent and formula (A), it is possible to prevente effectively from extraction process
The formation of third phase.
Specifically, according to an embodiment of the invention, the polarity of compound shown in formula (B) is suitable for, with having in extraction system
Machine mutually has preferable compatibility.Meanwhile compound shown in formula (B) is to LiFeCl4Also have certain extraction, and have compared with
Low viscosity.This makes compound shown in formula (B) as compound modification agent shown in formula (A), it is possible to prevente effectively from extraction process
The formation of middle third phase, and compound shown in main extractant formula (A) is improved to LiFeCl4Extraction yield, while guaranteeing to extract
Journey continuous and steady operation.
Oil-soluble, water-soluble loss, Atom economy and the raw material for comprehensively considering extractant are ready availability, according to the present invention
Preferred embodiment, R2And R3It is separately C1-12Straight chained alkyl or C1-12Branched alkyl, and R2And R3Total carbon atom number be 7
~15, in other words, the total carbon atom number of compound shown in formula (B) is 8~16.With above-mentioned R2And R3Formula (B) shownization of group
Conjunction object oil-soluble is suitable for, water-soluble lower, and in the loss very little of water phase in extraction process, and raw material sources range is wide, cheap easy
?.
According to an embodiment of the invention, foregoing, compound shown in formula (A) can be applied to separately as extractant
From the method for extracting lithium in salt lake bittern, and by the way that compound shown in compound shown in formula (A) and formula (B) is formed compound extraction
Agent is taken, the formation of third phase in extraction system can be further avoided.According to an embodiment of the invention, the composite extractant Chinese style
(A) proportion of compound shown in compound and formula shown in (B) is not particularly restricted；Preferably, compound and formula shown in formula (A)
(B) volume ratio of compound shown in is 1:(0.1~10), such as 1:0.1,1:0.2,1:0.3,1:0.4,1:0.5,1:0.8,1:
1,1:2,1:3,1:5,1:8 or 1:10.Thus, it is possible to guarantee that composite extractant has to lithium extracting power with higher
And selectivity.
In order to facilitate understanding, below extracting lithium in the slave salt lake bittern carried out using extractant described in above-described embodiment
Method be further described in detail.According to an embodiment of the invention, this method comprises:
(1) salt lake bittern is mixed with ferric trichloride, to obtain extraction feed liquid.
According to an embodiment of the invention, above-mentioned salt lake bittern is salt lake brine with high magnesium-lithium ratio.Above-mentioned salt lake bittern can be
Untreated salt lake bittern, the salt lake bittern resulting old halogen after mentioning potassium, or potassium is mentioned except the old halogen after boron.According to without
Salt lake bittern, the salt lake bittern resulting old halogen after mentioning potassium of processing are to propose lithium feed liquid, and a certain amount of hydrochloric acid must be added, on the one hand protect
Card ferric trichloride is completely dissolved, on the one hand the acidity of adjusting feed liquid to suitable range.Preferably, using mentioning potassium except old after boron
Halogen proposes lithium feed liquid, because the presence of boron can interfere lithium extraction process in brine, and except boron process needs to add hydrochloric acid, removes boron
The concentration of hydrochloric acid meets the acidity requirements for proposing lithium process between 0.05~0.3mol/L just in brine afterwards, does not need additionally to add
Add hydrochloric acid.If the acidity of salt lake bittern to be processed is undesirable, can be adjusted by the way that HCl or NaOH are added in this step
Save acidity.
A certain amount of ferric trichloride is added as co-extraction in specific example according to the present invention, the old halogen after can removing boron to potassium is mentioned
Agent, stirring to mixed liquor are completely dissolved, to obtain extraction feed liquid.
According to an embodiment of the invention, Li in salt lake brine with high magnesium-lithium ratio+Concentration range is 0.2~10.0g/L；Magnesium lithium matter
Amount is than m (Mg)/m (Li) range (30~200): 1, Cl-Content >=5.0mol/L.Inventor has found in an experiment, if salt lake
Cl in brine-Concentration is too low, Fe3+It cannot be completely with FeCl4 -Form exist, to influence Li+Extraction and split-phase.It is added
Acidity (the i.e. H of gained extraction feed liquid after ferric trichloride+Concentration) range is 0.01~1.0mol/L, if acidity not in this range,
HCl or NaOH can be used to adjust；Extracting iron lithium molar ratio n (Fe)/n (Li) range in feed liquid is (1~3): 1.By by salt lake
Brine is prepared to obtain the extraction feed liquid for meeting above-mentioned condition, can further be conducive to the progress of extraction process and proposing for lithium
It takes.
(2) extractant and diluent are hybridly prepared into extraction organic phase, and mix and is extracted with extraction feed liquid, so as to
Obtain load organic phases and raffinate.
In the step, the extraction organic phase obtained using extractant and diluent mixed preparing will be extracted in feed liquid
LiFeCl4It is extracted in load organic phases.In some embodiments, it is come into full contact with by the way that organic phase will be extracted with extraction feed liquid,
Stratification, load organic phases are located at system upper layer, and raffinate is located at system lower layer.According to an embodiment of the invention, by above-mentioned
The extractant of embodiment is used further to extract after mixing with diluent.Wherein, volume fraction of the extractant in extraction organic phase is
10~99%, such as 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 99%.By the way that extractant is dilute
Used after releasing, can be further improved the mobility of organic phase, reduce the density of organic phase, make extraction process be easier to carry out and
Phase good separating effect is also beneficial to improve extractant to the extraction efficiency of lithium.According to an embodiment of the invention, step (2) can adopt
With single-stage extraction, multi-stage counter current extraction can also be used.
According to an embodiment of the invention, above-mentioned diluent can be the solvent naphtha for being 160~300 degrees Celsius selected from boiling range,
Such as at least one of 260# aviation kerosine, sulfonated kerosene, D70 solvent naphtha and D80 solvent naphtha.Above-mentioned diluent chemical property
Stabilization, density is low, viscosity is small, not only plays good diluting effect to extractant, can be further improved the flowing of organic phase
Property, the density of organic phase is reduced, is easier to carry out extraction process and phase good separating effect, is also beneficial to improve extractant to lithium
Extraction efficiency.In addition, the polarity of compound shown in formula (B) between above-mentioned kerosene and extraction associated matter, is more conducive to avoid
The formation of third phase in extraction process.
According to an embodiment of the invention, extraction organic phase and the volume ratio for extracting feed liquid are (4~1): (1 in step (2)
~4), that is, comparing O/A range is 4:1~1:4, and the single-stage extraction time is 3~30min, and system temperature is 10~50 degrees Celsius.It is logical
It crosses and is extracted under the above conditions using the organic relative extractive feed liquid of extraction, can be further improved extraction of the extractant to lithium
Ability and selectivity, and be conducive to the separation of load organic phases and raffinate.
(3) load organic phases are washed using detergent, so as to organic phase after being washed and washing extraction raffinate.
Inventor has found in an experiment, although extractant proposed by the present invention is very high to the selectivity of lithium, is extracting
A small amount of Mg is still had in journey2+、K+、Na+Equal foreign ions are inevitably entrained or are extracted to load organic phases.Pass through utilization
Detergent washs load organic phases, can effectively remove the Mg in load organic phases2+、K+、Na+Equal foreign ions.?
In some embodiments, by coming into full contact with detergent and load organic phases, stratification, organic phase is located in system after washing
Layer, washing extraction raffinate are located at system lower layer.According to an embodiment of the invention, single-stage washing can be used in step (3), multistage can also be used
Countercurrent washing.
According to an embodiment of the invention, the volume ratio of the load organic phases and the detergent is (20 in step (3)
~50): 1, i.e., it is 20~50 compared to O/A range, time of contact is 3~30min, and system temperature is 10~50 degrees Celsius.Pass through
Load organic phases are washed using detergent under the above conditions, can be further improved Mg2+、K+、Na+Equal foreign ions
Removal effect, and be conducive to washing after organic phase and washing extraction raffinate separation.
According to an embodiment of the invention, the specific type of detergent is not particularly restricted, as long as can will load organic
Mg in phase2+、K+、Na+Equal foreign ions are removed by way of extraction.Preferred embodiment in accordance with the present invention, washing
Back extraction extraction raffinate obtained in step (4) can be used in agent (extraction for the first time can prepare simulation back extraction extraction raffinate).Using back extraction extraction raffinate to negative
Carry the process also referred to as reflux washing that organic phase is washed.It is stripped in extraction raffinate and contains the higher LiCl of concentration and certain density salt
Acid, under the action of ferric trichloride co-extraction agent, Li+It is far longer than Mg with the binding ability of extractant2+、K+、Na+, it is stripped in extraction raffinate
The Li of high concentration+It can be by the Mg in load organic phases2+、K+、Na+It is thoroughly expelled from and, washing process does not introduce other impurities；
Meanwhile being stripped Cl in extraction raffinate-Concentration is higher, can make Fe3+Still with FeCl4 -Form stays in organic phase.According to an embodiment of the invention,
Washing extraction raffinate can be returned to be used into extraction feed liquid circulation.
(4) organic phase after washing is stripped using hydrochloric acid, to obtain back extraction organic phase and to be stripped extraction raffinate.
In the step, the load organic phases after washing are stripped using hydrochloric acid as stripping agent, by Li+It is stripped to water
Phase obtains Li+The higher back extraction extraction raffinate of concentration and back extraction organic phase, and ferric trichloride co-extraction agent is still with FeCl4 -Form keep
Organic phase.In some embodiments, by coming into full contact with hydrochloric acid and organic phase after washing, stratification is stripped organic phase
In system upper layer, it is stripped extraction raffinate and is located at system lower layer.According to an embodiment of the invention, single-stage back extraction can be used in step (4), it can also
It is stripped using multi-stage countercurrent.
According to an embodiment of the invention, organic phase and the volume ratio of hydrochloric acid are (10~30) after washing: 1, that is, compare O/A model
Enclosing is 10~30, and time of contact is 2~30min, and system temperature is 10~50 degrees Celsius；The concentration of hydrochloric acid is 5.0~9.0mol/
L.If the concentration of hydrochloric acid is too low or dosage is very few, system pH not can guarantee in optimum range, and will lead to Cl in system-
Concentration is too low, the FeCl in organic phase4 -Meeting portions turn is Fe3+Into water phase, difficulty is brought to the preparation of subsequent lithium product；
Iron loss in organic phase, subsequent extraction process also needs to supplement iron in extraction feed liquid, so that entire production process is discontinuous.
Inventor has found in an experiment, is stripped in the back extraction organic phase of acquisition not only containing co-extraction agent ferric trichloride, also
Containing more hydrochloric acid, in the form of carrying secretly or associated forms exist, a large amount of H+Presence make the back extraction organic phase continue and extraction
When feed liquid contacts, the Li in feed liquid is extracted+It is difficult to enter back extraction organic phase, makes to be stripped organic phase to be to extract the ability of lithium.Mirror
In this, according to an embodiment of the invention, the method for the invention for extracting lithium from salt lake bittern can further include:
(5) by lye be stripped it is organic mix, so as to obtain regeneration back extraction organic phase.
In the step, using lye as regenerative agent in and back extraction organic phase in back extraction, make be stripped organic phase restore regeneration
Ability.According to an embodiment of the invention, the specific type of above-mentioned lye is not particularly restricted, as long as can be neutralized with hydrochloric acid,
And it is easy to separate with regeneration back extraction organic phase.Preferred embodiment in accordance with the present invention, lye can use concentration for 0.1~
Sodium hydroxide solution, potassium hydroxide solution, sodium carbonate liquor or the solution of potassium carbonate of 1.0mol/L, above-mentioned lye is from a wealth of sources,
It is cheap and easy to get, and the foreign ion for being difficult to remove will not be introduced into organic phase.
According to an embodiment of the invention, back extraction organic phase and the volume ratio of lye are (10~40): 1, that is, compare O/A range
It is 10~40.Under the conditions of this is compared, back extraction organic phase is neutralized to aqueous pH values using lye is advisable for 0.5~3.0.
In another aspect of this invention, the invention proposes a kind of composite extractants.According to an embodiment of the invention, this is multiple
Closing extractant includes compound shown in compound shown in formula (A) and formula (B),
Wherein,
R1For C6-20Straight chained alkyl, C6-20Branched alkyl or C6-20Naphthenic base；
R2And R3It is separately C1-24Straight chained alkyl, C1-24Branched alkyl or C1-24Naphthenic base, and R2And R3Total carbon
Atomicity is not less than 5.
In composite extractant according to an embodiment of the present invention, on the one hand, in compound shown in formula (A) with the direct phase of nitrogen-atoms
What is connected is two methyl, and the R being connected with carbonyl1Group is C6-20Straight chain, branch or naphthenic base.Compound shown in formula (A) and biography
Amides lithium extractant (such as N, N- bis- (2- ethylhexyl) propionamide, N, N- dihexyl benzamide, N, the bis- (2- of N- of system
Ethylhexyl) acetamide, N, N- dihexyl is to methyl benzamide etc.) there are the differences of apparent structure: compound shown in formula (A)
Nitrogen-atoms on be connected is two methyl, and the R by being connected with carbonyl1Group offer oil-soluble, and traditional amides
Two Long carbon chain alkyl are connected in lithium extractant in amide nitrogen atom.The reprimand electronic effect of alkyl with carbon atom number increase and
Enhancing, methyl is weaker relative to the reprimand electronic effect of Long carbon chain alkyl, thus in compound shown in formula (A) nitrogen-atoms electron cloud
Density is significantly lower than the amide nitrogen atom in traditional amides lithium extractant, so that the alkalinity of compound shown in formula (A)
It is markedly less than traditional amides lithium extractant, is not easy to make Fe in extraction process3+Hydrolyze to form flocculate.On the other hand, formula
(B) polarity of compound shown in is suitable for having preferable compatibility with the organic phase in extraction system.Meanwhile formula (B) shownization
Object is closed to LiFeCl4Also there is certain extraction, and there is lower viscosity.This makes compound shown in formula (B) as formula
(A) compound modification agent shown in, it is possible to prevente effectively from extraction process third phase formation, and improve main extractant formula (A) institute
Show compound to LiFeCl4Extraction yield, while guaranteeing extraction process continuous and steady operation.
Oil-soluble, water-soluble loss, Atom economy and the raw material for comprehensively considering extractant are ready availability, according to the present invention
Preferred embodiment, in compound shown in formula (A), R1For C8-14Straight chained alkyl or C8-14Branched alkyl.With above-mentioned R1The formula of group
(A) compound oil-soluble shown in is suitable for, water-soluble lower, in the loss very little of water phase in extraction process, and raw material sources range
Extensively, cheap and easy to get.Preferred embodiment in accordance with the present invention, R2And R3It is separately C1-12Straight chained alkyl or C1-12Branched alkane
Base, and R2And R3Total carbon atom number be 7~15, in other words, the total carbon atom number of compound shown in formula (B) is 8~16.Have
Above-mentioned R2And R3Compound oil-soluble shown in the formula (B) of group is suitable for, water-soluble lower, in extraction process the loss of water phase very
It is small, and raw material sources range is wide, cheap and easy to get.
According to an embodiment of the invention, compound shown in compound shown in the composite extractant Chinese style (A) and formula (B) is matched
Than being not particularly restricted；Preferably, the volume ratio of compound shown in compound shown in formula (A) and formula (B) be 1:(0.1~
, such as 1:0.1,1:0.2,1:0.3,1:0.4,1:0.5,1:0.8,1:1,1:2,1:3,1:5,1:8 or 1:10 10).By
This, it is ensured that composite extractant has to lithium extracting power with higher and selectivity, and further avoids extraction system
The formation of middle third phase.
As previously mentioned, composite extractant proposed by the present invention can have selected from it is at least one following the advantages of:
1. composite extractant of the invention, the compound as shown in amides formula (A) and compound group shown in ketone formula (B)
It is compared at lithium extractant TBP is mentioned with now widely used salt lake, they are extremely low to the swelling corrosion of equipment, can greatly prolong
The update cycle of equipment.
2. the hydrolytic stability ratio TBP of compound shown in compound shown in formula (A) and formula (B) under acid or alkaline conditions
Emulsification caused by height, the loss of extractant and catabolite is lower than TBP.
3. the unique structure of compound shown in formula (A) determines that its own alkalinity is very weak, in FeCl3In co-extraction system, it is not easy
With Fe3+Flocculate is formed, this point is very important extraction process.
4. the density of compound shown in compound shown in formula (A) and formula (B) is 0.80~0.85g/cm3, hence it is evident that it is lower than
TBP(0.977g/cm3), it is larger with the density difference of water phase, be conducive to the split-phase of the processes such as extraction, washing, back extraction, regeneration.
5. compound shown in formula (B) has the property that 1. its polarity is between kerosene and extraction associated matter, with the two
There is preferable intermiscibility；2. it is to LiFeCl4Also there is certain extraction；3. viscosity is lower.The above property can bring with
Down the utility model has the advantages that 1. avoiding the formation of extraction process third phase；2. improving the extraction yield of main extractant；3. extraction process recycle stream
Dynamic property is good, can continuous and steady operation.
6. composite extractant proposed by the present invention is not phosphorous, raffinate waste water is through biochemical or photocatalysis treatment, wherein dissolving
Organic matter degradation is nontoxic carbon dioxide and nitrogen, is of great significance to salt lake ecological protection.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, without limiting the invention in any way.
Conventional method
To propose the salt lake brine with high magnesium-lithium ratio after potassium removes boron and ferric trichloride mixing as extraction feed liquid, according to the following steps
Extract lithium therein:
(1) compound shown in formula (A), compound and diluent shown in formula (B) are mixed to get extraction organic phase；
(2) extraction organic phase is mixed and is extracted with extraction feed liquid, to obtain load organic phases and raffinate；
(3) load organic phases are washed using detergent, so as to organic phase after being washed and washing extraction raffinate；
(4) organic phase after washing is stripped using hydrochloric acid, to obtain back extraction organic phase and to be stripped extraction raffinate；
(5) by lye (regenerative agent) be stripped it is organic mix, so as to obtain regeneration back extraction organic phase.
To be extracted mentions potassium except (salt lake bittern meets Cl to the salt lake brine with high magnesium-lithium ratio composition after boron as shown in table 1-It is dense
Degree >=5.0mol/L and H+For concentration in the requirement of 0.01~1.0mol/L, there is no need to add hydrochloric acid to adjust composition again):
Table 1 mentions potassium except the salt lake brine with high magnesium-lithium ratio composition after boron
Embodiment 1
According to the salt lake bittern of composition shown in conventional method processing table 1, wherein extraction organic phase is N, N- dimethyl decoyl
The mixture of amine and D70 solvent naphtha, volume fraction are respectively 40% and 60%；FeCl is added into brine shown in table 13It mixes molten
It solves and makes Fe/Li=1.5 (molar ratio), as extraction feed liquid；Extract O/A=2.0；Wash O/A=30；Stripping agent: 6mol/
LHCl is stripped O/A=30；Regenerative agent: 0.5mol/L NaOH solution regenerates O/A=20.
System is divided into the three-phase of clear after extraction.Single-stage lithium extraction yield is 61.5%, single-stage Separation of Li and Mg coefficient
(βLi/Mg), lithium sodium separation (βLi/Na), lithium potassium separation (βLi/K) respectively up to 285.3,21.5,37.7.Extract by 6 grades
It takes, 5 grades of washings, 5 grades of back extraction, the rate of recovery of lithium is stripped Li in extraction raffinate up to 99.5%+Concentration reach 32.1g/L, Mg2+、Na+、K+
Concentration be below 1mg/L, realize the extraction of lithium and efficiently separated with other impurities elements.
Embodiment 2
According to the salt lake bittern of composition shown in conventional method processing table 1, wherein extraction organic phase is N, N- dimethyl decoyl
Amine, isobutyrone, D70 solvent naphtha mixture, volume fraction is respectively 40%, 20%, 40%；Toward brine shown in table 1
Middle addition FeCl3Mixed dissolution simultaneously makes Fe/Li=1.5 (molar ratio), as extraction feed liquid；Extract O/A=2.0；Wash O/A=
20；Stripping agent: 6mol/L HCl is stripped O/A=30；Regenerative agent: 0.5mol/L NaOH solution regenerates O/A=20.
System is divided into the two-phase of clear, no interphase (third phase) after extraction.Single-stage lithium extraction yield is 68.7%, single
Grade Separation of Li and Mg coefficient (βLi/Mg), lithium sodium separation (βLi/Na), lithium potassium separation (βLi/K) respectively up to 310.8,30.4,
46.5.It is extracted by 5 grades, 4 grades of washings, 5 grades of back extraction, the rate of recovery of lithium is stripped Li in extraction raffinate up to 99.5% or more+Concentration reach
34.2g/L Mg2+、Na+、K+Concentration be below 1mg/L, realize lithium extraction and with other impurities element efficiently point
From.
Embodiment 3
According to the salt lake bittern of composition shown in conventional method processing table 1, wherein extraction organic phase is N, N- dimethyl decoyl
Amine, isobutyrone, 260# aviation kerosine mixture, volume fraction is respectively 30%, 30%, 40%；Toward shown in table 1
FeCl is added in brine3Mixed dissolution simultaneously makes Fe/Li=1.3 (molar ratio), as extraction feed liquid；Extract O/A=1.0；Washing
O/A=30；Stripping agent: 6mol/L HCl is stripped O/A=30；Regenerative agent: 0.3mol/L Na2CO3Solution regenerates O/A=20.
System is divided into two-phase after extraction.Single-stage lithium extraction yield is 55.8%, single-stage Separation of Li and Mg coefficient (βLi/Mg), lithium sodium point
From coefficient (βLi/Na), lithium potassium separation (βLi/K) respectively up to 280.2,20.3,40.5.It is extracted by 7 grades, 5 grades of washings, 5 grades
Back extraction, the rate of recovery of lithium are stripped Li in extraction raffinate up to 99.5%+Concentration reach 32.1g/L, Mg2+、Na+、K+Concentration be below
1mg/L realizes the extraction of lithium and efficiently separates with other impurities elements.
Embodiment 4
According to the salt lake bittern of composition shown in conventional method processing table 1, wherein extraction organic phase is N, N- dimethyl caprinoyl
Amine, 2- decanone, 260# aviation kerosine mixture, volume fraction is respectively 30%, 30%, 40%；Add into brine shown in table 1
Enter FeCl3Mixed dissolution simultaneously makes Fe/Li=1.3 (molar ratio), as extraction feed liquid；Extract O/A=2.0；Wash O/A=30；
Stripping agent: 6mol/L HCl is stripped O/A=20；Regenerative agent: 0.6mol/L NaOH solution regenerates O/A=30.
System is divided into two-phase after extraction.Single-stage lithium extraction yield is 64.5%, single-stage Separation of Li and Mg coefficient (βLi/Mg), lithium sodium point
From coefficient (βLi/Na), lithium potassium separation (βLi/K) respectively up to 270.3,18.5,32.6.It is extracted by 6 grades, 5 grades of washings, 5 grades
Back extraction, the rate of recovery of lithium are stripped Li in extraction raffinate up to 99.5% or more+Concentration reach 35.2g/L, Mg2+、Na+、K+Concentration it is low
In 1mg/L, realizes the extraction of lithium and efficiently separated with other impurities element.
Embodiment 5
According to the salt lake bittern of composition shown in conventional method processing table 1, wherein extraction organic phase is N, N- dimethyl caprinoyl
Amine, methyl n-heptyl ketone, D80 solvent naphtha mixture, volume fraction is respectively 30%, 30%, 40%；It is added into brine shown in table 1
FeCl3Mixed dissolution simultaneously makes Fe/Li=1.5 (molar ratio), as extraction feed liquid；Extract O/A=2.0；Wash O/A=30；Instead
Extract agent: 6mol/L HCl, is stripped O/A=20；Regenerative agent: 0.7mol/L NaOH solution regenerates O/A=30.
System is divided into two-phase after extraction.Single-stage lithium extraction yield is 63.8%, single-stage Separation of Li and Mg coefficient (βLi/Mg), lithium sodium point
From coefficient (βLi/Na), lithium potassium separation (βLi/K) respectively up to 290.1,24.9,42.6.It is extracted by 6 grades, 5 grades of washings, 5 grades
Back extraction, the rate of recovery of lithium are stripped Li in extraction raffinate up to 99.5% or more+Concentration reach 33.8g/L, Mg2+、Na+、K+Concentration it is low
In 1mg/L, realizes the extraction of lithium and efficiently separated with other impurities element.
Embodiment 6
According to the salt lake bittern of composition shown in conventional method processing table 1, wherein extraction organic phase is N, the N- dimethyl-octa last of the ten Heavenly stems
Amide (N, N- dimethyloctanamide and N, N- dimethyldecamide arbitrary proportion mixture), isobutyrone, D80 solvent naphtha
Mixture, volume fraction is respectively 40%, 30%, 30%；FeCl is added into brine shown in table 13Mixed dissolution simultaneously makes Fe/
Li=1.6 (molar ratio), as extraction feed liquid；Extract O/A=1.5；Wash O/A=30；Stripping agent: 6mol/L HCl, back extraction
O/A=20；Regenerative agent: 0.6mol/L K2CO3Solution regenerates O/A=30.
System is divided into two-phase after extraction.Single-stage lithium extraction yield is 63.9%, single-stage Separation of Li and Mg coefficient (βLi/Mg), lithium sodium point
From coefficient (βLi/Na), lithium potassium separation (βLi/K) respectively up to 275.6,28.5,32.3.It is extracted by 6 grades, 4 grades of washings, 4 grades
Back extraction, the rate of recovery of lithium are stripped Li in extraction raffinate up to 99.5% or more+Concentration reach 33.8g/L, Mg2+、Na+、K+Concentration it is low
In 1mg/L, realizes the extraction of lithium and efficiently separated with other impurities element.
Embodiment 7
According to the salt lake bittern of composition shown in conventional method processing table 1, wherein extraction organic phase is N, N- Dimethyl Lauryl Amine
Amide, 2- decanone, D70 solvent naphtha mixture, volume fraction is respectively 40%, 30%, 30%；Add into brine shown in table 1
Enter FeCl3Mixed dissolution simultaneously makes Fe/Li=1.8 (molar ratio), as extraction feed liquid；Extract O/A=2.0；Wash O/A=30；
Stripping agent: 6mol/L HCl is stripped O/A=20；Regenerative agent: 0.5mol/L NaOH solution regenerates O/A=30.
System is divided into two-phase after extraction.Single-stage lithium extraction yield is 69.2%, single-stage Separation of Li and Mg coefficient (βLi/Mg), lithium sodium point
From coefficient (βLi/Na), lithium potassium separation (βLi/K) respectively up to 280.2,24.4,37.8.It is extracted by 5 grades, 5 grades of washings, 5 grades
Back extraction, the rate of recovery of lithium are stripped Li in extraction raffinate up to 99.5% or more+Concentration reach 33.1g/L, Mg2+、Na+、K+Concentration it is low
In 1mg/L, realizes the extraction of lithium and efficiently separated with other impurities element.
Embodiment 8
According to the salt lake bittern of composition shown in conventional method processing table 1, wherein extraction organic phase is N, N- Dimethyl Lauryl Amine
Amide, methyln-hexyl ketone, 2- decanone, D80 solvent naphtha mixture, volume fraction is respectively 40%, 15%, 15%, 30%；Toward table 1
FeCl is added in shown brine3Mixed dissolution simultaneously makes Fe/Li=1.5 (molar ratio), as extraction feed liquid；Extract O/A=2.0；
Wash O/A=30；Stripping agent: 6mol/L HCl is stripped O/A=20；Regenerative agent: 0.5mol/L Na2CO3Solution regenerates O/A=
30。
System is divided into two-phase after extraction.Single-stage lithium extraction yield is 70.4%, single-stage Separation of Li and Mg coefficient (βLi/Mg), lithium sodium point
From coefficient (βLi/Na), lithium potassium separation (βLi/K) respectively up to 280.5,24.1,38.0.It is extracted by 5 grades, 5 grades of washings, 5 grades
Back extraction, the rate of recovery of lithium are stripped Li in extraction raffinate up to 99.5% or more+Concentration reach 34.2g/L, Mg2+、Na+、K+Concentration it is low
In 1mg/L, realizes the extraction of lithium and efficiently separated with other impurities element.
Embodiment 9
According to the salt lake bittern of composition shown in conventional method processing table 1, wherein extraction organic phase is N, N- Dimethyl Lauryl Amine
Amide, N, N- dimethyloctanamide, 2- propylcyclohexanone, 2- decanone, 260# aviation kerosine mixture, volume fraction is respectively
15%, 20%, 15%, 15%, 35%；FeCl is added into brine shown in table 13Mixed dissolution and make Fe/Li=1.7 (mole
Than), as extraction feed liquid；Extract O/A=2.0；Wash O/A=30；Stripping agent: 6mol/L HCl is stripped O/A=20；Regeneration
Agent: 0.5mol/L NaOH solution regenerates O/A=30.
System is divided into two-phase after extraction.Single-stage lithium extraction yield is 65.7%, single-stage Separation of Li and Mg coefficient (βLi/Mg), lithium sodium point
From coefficient (βLi/Na), lithium potassium separation (βLi/K) respectively up to 293.1,26.7,41.5.It is extracted by 6 grades, 5 grades of washings, 5 grades
Back extraction, the rate of recovery of lithium are stripped Li in extraction raffinate up to 99.5% or more+Concentration reach 32.3g/L, Mg2+、Na+、K+Concentration it is low
In 1mg/L, realizes the extraction of lithium and efficiently separated with other impurities element.
Embodiment 10
In use, in especially acid or alkaline system, hydrolysis, degradation, oxygen often gradually occur for extractant
The side reactions such as change (are collectively referred to here in as degraded), and in addition extractant itself, which also has, is partly dissolved loss.Therefore, in extraction process
Need the fresh extractant of regular replenishment.In addition, extraction system tends to occur serious emulsification if extractant palliating degradation degree is serious, lead
Extraction process is caused to be unable to run.Therefore, the cyclical stability of extractant is the important indicator for investigating extractant.The present embodiment difference
It carries out salt lake under the same conditions using extractant proposed by the present invention and TBP and proposes the experiment of lithium extraction cycle, compare following for they
Ring stability.
Experiment condition:
It mentions lithium brine composition and is shown in Table 1；
Organic phase 1:N, N- dimethyldecamide (DMAA)+methyl n-heptyl ketone (NK)+D80 solvent naphtha, volume fraction are respectively
40%, 20%, 40%；
Organic phase 2 (control): TBP+2- nonanone+D80 solvent naphtha, volume fraction are respectively 40%, 20%, 40%；
FeCl is added into brine shown in table 13Mixed dissolution simultaneously makes Fe/Li=1.8 (molar ratio)；Extract O/A=2.0；
Wash O/A=30；Stripping agent: 6mol/L HCl is stripped O/A=20；Regenerative agent: 0.5mol/L NaOH solution regenerates O/A=
20；
Extraction mode: continuous flow upstream；Series: 6 grades of extractions, 5 grades of washings, 5 grades of back extraction, 1 grade of regeneration.
Using content of the gas Chromatographic Determination extractant in organic phase.Experimental result is shown in Table 2.As can be seen from Table 2, this hair
The cyclical stability ratio TBP high of the extractant of bright proposition is less likely to occur to emulsify in extraction process.
2 extractant cyclical stability comparative experiments of table
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (18)
1. a kind of method for extracting lithium from salt lake bittern using extractant, which is characterized in that the extractant includes formula (A) institute
Show compound,
Wherein, R1For C6-20Straight chained alkyl, C6-20Branched alkyl or C6-20Naphthenic base.
2. the method according to claim 1, wherein R1For C8-14Straight chained alkyl or C8-14Branched alkyl.
3. the method according to claim 1, wherein the extractant further comprises compound shown in formula (B),
Wherein, R2And R3It is separately C1-24Straight chained alkyl, C1-24Branched alkyl or C1-24Naphthenic base, and R2And R3Total carbon
Atomicity is not less than 5.
4. according to the method described in claim 3, it is characterized in that, R2And R3It is separately C1-12Straight chained alkyl or C1-12Branch
Alkyl group, and R2And R3Total carbon atom number be 7~15.
5. according to the method described in claim 3, it is characterized in that, compound shown in the formula (A) and the formula (B) shownization
The volume ratio for closing object is 1:(0.1~10).
6. described in any item methods according to claim 1~5, which is characterized in that the described method includes:
(1) salt lake bittern is mixed with ferric trichloride, to obtain extraction feed liquid；
(2) extractant and diluent are hybridly prepared into extraction organic phase, and mix and is extracted with the extraction feed liquid,
To obtain load organic phases and raffinate；
(3) load organic phases are washed using detergent, so as to organic phase after being washed and washing extraction raffinate；
(4) organic phase after the washing is stripped using hydrochloric acid, to obtain back extraction organic phase and to be stripped extraction raffinate.
7. according to the method described in claim 6, the hydrogen ion concentration it is characterized in that, in step (1), in the extraction feed liquid
For 0.01~1.0mol/L, the molar ratio of iron and lithium is (1~3): 1.
8. according to the method described in claim 6, it is characterized in that, the extractant is in the extraction organic phase in step (2)
In volume fraction be 10~99%.
9. according to the method described in claim 8, it is characterized in that, it is 160~300 degrees Celsius that the diluent, which is selected from boiling range,
Solvent naphtha；
Optionally, the diluent be in 260# aviation kerosine, sulfonated kerosene, D70 solvent naphtha and D80 solvent naphtha at least
One of.
10. according to the method described in claim 6, it is characterized in that, in step (2), the extraction organic phase and the extraction
The volume ratio of feed liquid is (4~1): (1~4), and the single-stage extraction time is 3~30min, and system temperature is 10~50 degrees Celsius.
11. according to the method described in claim 6, it is characterized in that, in step (3), the load organic phases and the washing
The volume ratio of agent is (20~50): 1, time of contact is 3~30min, and system temperature is 10~50 degrees Celsius.
12. according to the method described in claim 6, it is characterized in that, the detergent is the back extraction extraction raffinate in step (3).
13. according to the method described in claim 6, it is characterized in that, in step (4), organic phase and the salt after the washing
The volume ratio of acid is (10~30): 1, time of contact is 2~30min, and system temperature is 10~50 degrees Celsius；The hydrochloric acid it is dense
Degree is 5.0~9.0mol/L.
14. according to the described in any item methods of claim 6~13, which is characterized in that the method further includes:
(5) by lye with it is described back extraction it is organic mix, so as to obtain regeneration back extraction organic phase.
15. according to the method for claim 14, which is characterized in that the lye is the hydrogen that concentration is 0.1~1.0mol/L
Sodium hydroxide solution, potassium hydroxide solution, sodium carbonate liquor or solution of potassium carbonate, the volume of the back extraction organic phase and the lye
Than for (10~40): 1.
16. a kind of composite extractant, which is characterized in that including compound shown in compound shown in formula (A) and formula (B),
Wherein,
R1For C6-20Straight chained alkyl, C6-20Branched alkyl or C6-20Naphthenic base；
R2And R3It is separately C1-24Straight chained alkyl, C1-24Branched alkyl or C1-24Naphthenic base, and R2And R3Total carbon atom number
Not less than 5.
17. composite extractant according to claim 16, which is characterized in that
R1For C8-14Straight chained alkyl or C8-14Branched alkyl；
R2And R3It is separately C1-12Straight chained alkyl or C1-12Branched alkyl, and R2And R3Total carbon atom number be 7~15.
18. composite extractant according to claim 16 or 17, which is characterized in that compound and institute shown in the formula (A)
The volume ratio for stating compound shown in formula (B) is 1:(0.1~10).
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| CN110643813A (en) * | 2019-11-08 | 2020-01-03 | 湘潭大学 | Extraction system for separating calcium from calcium-containing brine by using secondary amide/alkyl ketone composite solvent to extract lithium, extraction method and application thereof |
| CN110669930A (en) * | 2019-09-23 | 2020-01-10 | 中国科学院青海盐湖研究所 | Composite extracting agent for separating lithium in solution with high magnesium-lithium ratio and extraction method |
| CN112342406A (en) * | 2019-08-09 | 2021-02-09 | 浙江新化化工股份有限公司 | Method for extracting lithium from salt lake brine |
| CN114317960A (en) * | 2020-09-29 | 2022-04-12 | 中国科学院上海有机化学研究所 | Extraction system for extracting lithium ions and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112342406A (en) * | 2019-08-09 | 2021-02-09 | 浙江新化化工股份有限公司 | Method for extracting lithium from salt lake brine |
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| CN114317960B (en) * | 2020-09-29 | 2023-08-11 | 中国科学院上海有机化学研究所 | Extraction system for extracting lithium ions and application thereof |
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