CN107760885A - A kind of method that low concentration lithium is extracted in the original bittern from salt lake - Google Patents
A kind of method that low concentration lithium is extracted in the original bittern from salt lake Download PDFInfo
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- CN107760885A CN107760885A CN201711140377.7A CN201711140377A CN107760885A CN 107760885 A CN107760885 A CN 107760885A CN 201711140377 A CN201711140377 A CN 201711140377A CN 107760885 A CN107760885 A CN 107760885A
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- organic phase
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- iron content
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- bittern
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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
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/408—Mixtures using a mixture of phosphorus-based acid derivatives of different types
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a kind of method from salt lake original bittern extraction low concentration lithium, this method includes：Step 1) prepares iron content organic phase using ferric iron compound；Step 2) saponification treatment step 1) in iron content organic phase and/or step 5) in regeneration organic phase, obtain saponification iron content organic phase；Step 3) is extracted using the organic relative extractive of saponification iron content with salt lake original bittern, obtains extracting lithium load organic phases and saponification bottom liquid；Step 4) obtains pickling lithium load organic phases using Acidwash solution pickling extraction lithium load organic phases；Pickling lithium load organic phases are mixed and are stripped by step 5) with hydrochloric acid solution, obtain the rich lithium aqueous solution and regeneration organic phase.This method is by preparing iron content organic phase, and the iron for ensureing to add is with FeCl4 ‑Form be present in organic phase, be advantageous to and the Li in bittern+Form LiFeCl4, so as to realize the Li in bittern+It is extracted and is transferred to organic phase, the product impurity for extracting to obtain is few, and purity is high, advantageously reduces follow-up purifying difficulty and cost.
Description
Technical field
The present invention relates to salt lake chemical field, it is more particularly to a kind of from without evaporate brine evaporation and concentration and de- potassium sodium processing,
The method that low concentration lithium is extracted in salt lake original bittern containing lithium.
Background technology
Lithium is widely used in the numerous areas such as lithium battery, Aero-Space, atomic energy, Nuclear Power Industry and medicine, is described as
" energy metal for promoting world's progress ", it is national economy and strategic resource important in national defense construction.The main preservation of lithium resource
In salt lake bittern mineral deposit and granitic pegmatite-type mineral deposit.Wherein, the lithium resource in salt lake bittern accounts for the whole world and has verified lithium money
The 90% of source, it is mainly distributed on Bolivia, Chile, Argentina, China and the U.S..China's saline lake lithium resource accounts for national gross reserves
85%, but its distinguishing feature is Mg/Li ratio height (Mg:Li molar concentration rates are 10:1~2000:1), from high Mg/Li ratio salt lake halogen
Separation and Extraction low concentration lithium is very difficult in water.
At present, the method that lithium is carried from salt lake bittern reported both at home and abroad is normally only directed to through evaporation and concentration and the de- potassium of evaporating brine
Old halogen after sodium processing, there is not yet industrialization report is straight from the salt lake original bittern without evaporate brine evaporation and concentration and the processing of de- potassium sodium
Connect extraction low concentration lithium.
In the prior art, the method for lithium is extracted from salt lake bittern mainly the precipitation method, calcining leaching method, ion exchange
(absorption) method, electroosmose process and solvent extraction etc..
Wherein, precipitation method technique is simple, technology maturation, the salt lake bittern extraction lithium of low Mg/Li ratio in being applied to.This method
In, for lake bittern water containing lithium salts after being concentrated by evaporation de- potassium sodium, acidifying boron removal and separating calcium and magnesium processing, adding sodium carbonate makes lithium with carbonic acid
The form Precipitation of lithium.When this method handles the salt lake bittern of high Mg/Li ratio, Separation of Li and Mg poor selectivity, precipitated products impurity
Content is high, and the technological process of separating-purifying lithium is tediously long, and lithium yield is low；The salt without de- potassium sodium of evaporating brine directly is handled using this method
Lake original bittern is more infeasible, and the increase of precipitating reagent consumption, lithium loss late is high, process costs are high.
Salt lake bittern close to saturation need to be evaporated by calcining leaching method, allow lithium, magnesium respectively with lithium sulfate and bischofite salt
Crystallizable mineral separates out, and then calcines at high temperature, dewatering bischofite is formed magnesia, is produced after then being calcined with fresh water leaching
Thing, lithium sulfate enters solution, and magnesia is not soluble in water, so as to realize separating magnesium and lithium.The method flow is complicated, tight to equipment corrosion
For weight, it is necessary to which the water of evaporation is huge, power consumption is big, and cost is high, and seriously polluted.
Ion exchange (absorption) method technique is simple, environment-friendly, selectivity is strong, using adsorbent from the old halogen after concentration
Lithium is directly extracted, is carried with pickling, elutriant is electrolysed lithium after evaporation and concentration.This method by the rate of adsorption because being influenceed, at bittern
Reason amount is smaller, and the capacity of sorbent-loaded lithium is low, and concentration ratio is low, and the molten damage of adsorbent is serious.Using this method directly from without
Evaporate brine de- potassium sodium salt lake original bittern extraction low concentration lithium cost it is higher.
In electroosmose process, concentrated brine containing lithium that salt pan is evaporated to obtain, pass through one or more levels electric dialyzator, utilize
Yin, yang monovalence selective ion exchange membrane carries out circulation concentration lithium, obtains the low magnesium bittern of rich lithium, then also needs to remove through depth repeatedly
Foreign ion, refining and concentrating, conversion can just obtain lithium carbonate product after drying.Whole complex process, flow are tediously long.It is in addition, electric
Dialyser is easily poisoned blocking, and process costs are high.
Solvent extraction is because with selectivity is strong, separative efficiency is high, technique is simple, equipment investment is small, easy scale amplification
The advantages that, it is considered to be one of most promising method of separation and Extraction lithium from salt lake brine with high magnesium-lithium ratio.
However, in the prior art, solvent extraction extraction lithium technology is generally directed to be concentrated by evaporation, at de- potassium sodium through evaporating brine
Old halogen after reason, also, be in old halogen in advance addition ferric trichloride as synergic reagent, then using tributyl phosphate or with
Other material mixings carry lithium as extractant with the mechanism extraction of solvation.In old halogen, the concentration of lithium is generally greater than 5g/L.
For example, in Chinese patent CN87103431A, extraction lithium selection during extracting lithium using solvent extraction be present
Property it is not high, the foreign ion such as the sodium that is particularly coexisted in bittern, potassium, calcium, magnesium enters back extraction product liquid, causes subsequent purification technique
Numerous and diverse, cost is high；In addition, the tributyl phosphate concentration used is higher, to extraction equipment seriously corroded；Can also extractant be caused to exist
Molten damage is tight in saponification process；In CN103055538A, the mixture of tributyl phosphate and acid amides kind of extractants is extractant,
It is high to extract lithium selectivity, but this method still needs to dissolve ferric trichloride in old halogen in advance as synergic reagent, moreover, after back extraction regeneration
Organic phase can not realize higher saponification degree, cause lithium recovery of extraction low, extract lithium process and organic phase saponification process is easily made
Hydrolyze and separate out into ferric trichloride, cause water phase and an oil phase separation difficult；And in patents such as CN104357676A and CN106435219A
In, although the extraction yield of lithium can be improved or solve the problems, such as calcium phosphate+ forage system etching apparatus, extraction can not be realized
The serialization of lithium operation.
It can be seen that in the prior art, solvent extraction puies forward lithium technology and simply done a bit in extractant composition and formula etc.
Work, low concentration of the direct extracting and enriching concentration less than 5g/L from the salt lake original bittern without evaporation and concentration of evaporating brine can not be realized
Lithium；
Further, since ferric trichloride is directly dissolved in old bittern, it is difficult to control ferric iron to be completely reformed into tetrachloro iron
Compound；When being extracted to old bittern, it is even more uncontrollable that can tetrachloro iron compound therein be changed into tetrachloro iron lithium.
In view of the foregoing, the present inventor is improved on the basis of existing technology, works out a kind of from crude salt lake halogen
Water, particularly from side without evaporate brine evaporation and concentration and the processing of de- potassium sodium, that low concentration lithium is extracted in salt lake original bittern containing lithium
Method.
The content of the invention
In order to solve the above problems, present inventor has performed studying with keen determination, as a result find：Ferric iron compound is prepared and contained
After iron organic phase and saponification process, the salt lake original bittern after extraction acidifying, the impurity cationic in co-extraction is removed through overpickling, then
Back extraction is mixed with hydrochloric acid solution, the higher rich lithium aqueous solution of purity can be obtained, while obtained regeneration organic phase can also be thrown
Enter and recycled in reaction, extraction difficulty and cost are reduced, so as to complete the present invention.
It is an object of the invention to provide a kind of method from salt lake original bittern extraction low concentration lithium, this method includes：
Step 1), ferric iron compound is dissolved in hydrochloric acid, mixed with the diluent dissolved with neutral phosphorus extractant, is made
Iron content organic phase；
Step 2), saponification treatment step 1) in the regeneration that obtains in obtained iron content organic phase and/or step 5) it is organic
Phase, obtain saponification iron content organic phase；
Turn into extraction salt lake original bittern after step 3), the acidifying of salt lake original bittern, and using saponification iron content organic phase to it
Extracted, obtain extracting lithium load organic phases and saponification bottom liquid；
Step 4), using Acidwash solution pickling extract lithium load organic phases, obtain pickling lithium load organic phases；
Step 5), pickling lithium load organic phases are mixed with hydrochloric acid solution be stripped, obtain the rich lithium aqueous solution and regeneration
Organic phase.
In step 1), the molar concentration rate of iron ion and lithium ion in the original bittern of salt lake is 5 in hydrochloric acid:1~100:1,
Preferably 20:1~60:1.
Wherein, in step 1), the neutral phosphorus extractant is selected from phosphate (TRP), phosphonate ester (DRRP), phosphinate
(RDRP) and the one or more in trialkyl phosphine (TRPO), preferably described neutral phosphorus extractant are selected from tricresyl phosphate fourth
One or more in ester (TBP), butyl phosphonic acids dibutyl ester (DBBP) and trioctyl phosphine oxide (TOPO).
Wherein, in the step 2), the regeneration that is obtained in the iron content organic phase and/or step 5) that will prepare in step 1)
After organic phase mixes with the saponification bottom liquid obtained in step 3), inorganic base progress saponification process is added in the mixing liquid.
Also, in the step 2), the iron content organic phase and/or regeneration organic phase, the volume ratio with saponification bottom liquid are
1:10~10:1, preferably 1:1~10:1.
It is described in step 2), inorganic base is soluble in water, obtain inorganic base aqueous solution, be then added dropwise in mixing liquid
Saponification is carried out, the concentration of the inorganic base aqueous solution is 1~6mol/L, preferably 4~6mol/L；
The rate of addition of inorganic base aqueous solution is 0.1~1.0mL/min.
In the step 3), the concentration of lithium is 0.05~5g/L, preferably 0.05~1g/L in the salt lake original bittern.
In the step 3), during extraction, saponification iron content organic phase is 10 with the volume ratio of former bittern with extraction:1~1:1,
Preferably 5:1~1:1.
Wherein, in the step 4), hydrochloric acid and lithium chloride are contained in the Acidwash solution, wherein, the concentration of hydrochloric acid is 0.5
~2.0mol/L, the concentration of lithium chloride is 0.1~1.0mol/L.
In the step 5), regenerate in organic phase and contain HFeCl4, can individually put into recycling or same in step 2)
Obtained iron content is organic in step 1) mix after put into step 2) in recycle.
For the present invention by previously prepared iron content organic phase, use quality fraction is 20%~37% concentrated hydrochloric acid aqueous solution
Directly dissolve FeCl3·6H2O solid powders, the iron for ensureing to add is with FeCl4 -Form be present in organic phase, be advantageous to
Li in bittern+Form LiFeCl4, so as to realize the Li in bittern+It is extracted and is transferred to organic phase；Extract to obtain by this method
Product in impurity it is few, purity is high, advantageously reduces follow-up purifying difficulty and cost.
Embodiment
Below by the present invention is described in detail, the features and advantages of the invention will become more with these explanations
To be clear, clear and definite.
Special word " exemplary " is meant " being used as example, embodiment or illustrative " herein.Here as " exemplary "
Illustrated any embodiment should not necessarily be construed as preferred or advantageous over other embodiments.
The present invention described below.
The invention provides it is a kind of from salt lake original bittern extraction low concentration lithium method, the salt lake original bittern refer to without
Chloride type salt lake bittern that evaporation and concentration of evaporating brine and de- potassium sodium are handled, containing lithium, also, in the bittern, the concentration of lithium
Relatively low, the concentration of preferably described lithium is 0.05~5g/L, more preferably 0.05~1g/L.
The method from salt lake original bittern extraction low concentration lithium includes：
Step 1)：Prepare iron content organic phase
The salt lake original bittern without evaporate brine evaporation and concentration and the processing of de- potassium sodium is taken, detects Li therein+Mass concentration.
In the present invention, using containing Fe3+Solid powder prepares iron content organic phase.The Fe3+Solid powder is to contain three
The inorganic compound of valency iron, including iron chloride, iron oxide, the hydrate of iron hydroxide and the material.It is preferred that use can be straight
The iron chloride for connecing dissolving prepares iron content organic phase.Because iron chloride has stronger hygroscopicity, therefore, more preferably using FeCl3〃
6H2O solid powders prepare iron content organic phase.
By Fe3+Solid powder is dissolved in hydrochloric acid, obtains the aqueous hydrochloric acid solution of iron content；Wherein, according to the iron in hydrochloric acid and
The molar concentration rate of lithium in the original bittern of salt lake is 5:1~100:1, preferably described Fe:Li molar concentration rate is 20:1~
60:1；
It is preferred that the hydrochloric acid is the concentrated hydrochloric acid aqueous solution that HCl mass fractions are 20%~37%, the hydrochloric acid energy of the concentration
It is enough that higher chlorine ion concentration is provided, ensure Fe with FeCl4 -Form be present in hydrochloric acid, and and H+Combine to form HFeCl4。
Neutral phosphorus extractant is taken, is dissolved in aliphatic hydrocarbon or arene dilution of the boiling point more than 200 DEG C under normal pressure
In agent, organic extraction agent solution is obtained.
The neutral phosphorus extractant is selected from phosphate (TRP), phosphonate ester (DRRP), phosphinate (RDRP) and trialkyl
One or more in phosphine oxide (TRPO)；
Preferably, the neutral phosphorus extractant be selected from tributyl phosphate (TBP), butyl phosphonic acids dibutyl ester (DBBP) and
One or more in trioctyl phosphine oxide (TOPO).The material is to HFeCl4With good solubility.
The diluent is selected from kerosene, sulfonated kerosene and machine oil, preferably using the coal that evaporation rate is slow, chemical property is stable
Oil is used as diluent.
The volume ratio of the neutral phosphorus extractant and diluent is 1:10~10:1, preferably 1:10~5:1, more preferably
For 1:10~2.5:1, so that neutral phosphorus extractant can fully dissolution/dispersion in diluent, it is also, neutral Phosphorus
Extractant has higher concentration in diluent.
When using the aqueous hydrochloric acid solution of organic extraction agent solution extraction iron content, it is possible to increase HFeCl in hydrochloric acid4Extraction
The extraction efficiency being transferred in the organic extraction agent solution.
According to volume ratio it is 1 by the aqueous hydrochloric acid solution of the organic extraction agent solution and the iron content:10~10:1 mixing,
After standing split-phase, upper organic phase is taken, obtains iron content organic phase.
Step 2)：Saponification process iron content organic phase
Saponification step 1) in the iron content organic phase that is prepared, obtain saponification iron content organic phase；Preferably, containing preparation
Regeneration organic phase in iron organic phase and/or step 5) carries out saponification process, obtains saponification iron content organic phase.
It is furthermore preferred that after the iron content organic phase prepared in step 1) is mixed with the saponification bottom liquid obtained in step 3), add
The aqueous solution for entering inorganic base carries out saponification process, and saponification iron content organic phase is made.
Saponification bottom liquid is lower floor's aqueous phase that stratification separates after the completion of being extracted in step 3), or institute in step 3)
The mixture of one or both of the old bittern that the salt lake original bittern stated obtains after evaporate brine evaporation and concentration and the processing of de- potassium sodium.
Saponification bottom liquid mainly plays scattered iron content organic phase and/or regeneration organic phase；Further, since saponification bottom
Containing the chlorion that concentration is higher in liquid, during scattered iron content organic phase and/or regeneration organic phase, suppression is also acted
Its interior HFeCl4The effect of decomposition.
Wherein, iron content organic phase and/or regeneration organic phase, volume ratio when being mixed with saponification bottom liquid are 1:10~10:1,
Preferably 1:1~10:1；In mixed mixing liquid, iron content organic phase and/or regeneration organic phase are abundant in the liquid of saponification bottom
Be separated into droplet, the surface area of organic phase dramatically increases, when add inorganic base the aqueous solution carry out saponification when, can quickly,
Fully complete, more difficult the iron solution caused by the concentration of inorganic base is locally too high occur and isolate.
Wherein, the inorganic base is selected from sodium hydroxide, potassium hydroxide or ammoniacal liquor, preferably using alkalescence it is relatively strong, be readily available
Sodium hydroxide prepare the aqueous solution of inorganic base.Wherein, the concentration of inorganic base is 1~6mol/L, preferably 4~6mol/L, energy
It is enough that enough alkali saponified iron content organic phases are provided.
Under stirring condition, the aqueous solution of inorganic base is added dropwise into mixing liquid with 0.1~1.0mL/min speed, can
Control inorganic base to instill the concentration of mixed liquor, prevent that liquid local base concentration is too high in saponification process, causes in iron content organic phase
Molten iron parse.
By saponification process, the acid in iron content organic phase and/or regeneration organic phase can be neutralized, and it is organic extraction is entered iron content
HFeCl in phase4Or the HFeCl in regeneration organic phase4It is changed into NaFeCl4。
The aqueous solution of the inorganic base, with iron content organic phase and/or regeneration organic phase, the dosage volume ratio in saponification process
For 1:100~1:10.
By saponification process there is liquid to be sufficiently stirred after, stand split-phase, take upper organic phase, it is organic to obtain saponification iron content
Phase.
Step 3)：Extraction
Salt lake original bittern is subjected to acidification, obtains the former bittern of extraction；Further, it is former to salt lake using inorganic acid
Bittern carries out acidification, such as hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid, preferably uses the hydrochloric acid containing chlorion, is so extracting
During, enable to extract in solution and contain substantial amounts of chlorion, fully ensure that iron therein is constantly in FeCl4 -Shape
State, be advantageous to extract lithium from the original bittern of salt lake.
Found in research, the salt lake original bittern acidification is to pH=1~5, preferably pH=1~3, in acid condition
Under, especially under conditions of the pH value, when using the lithium in saponification iron content organic extractant phase bittern, to Li+With compared with
Good selectivity, in bittern with Li+The Na coexisted+、K+、Mg2+、Ca2+Enter Deng the seldom co-extraction of impurity cationic in organic phase.
The former bittern of extraction obtained using obtained saponification iron content organic phase in step 2) and acidification, obtains extraction lithium
Load organic phases；Wherein, the saponification iron content organic phase and extraction are 1 according to volume ratio with former bittern:1~10:1 mixes and extracts
Take, preferably saponification iron content organic phase is 1 with former bittern volume ratio with extraction:1~5:1, it can fully extract the lithium in former bittern
And reduce the use of organic phase.
By extracting, the Li in the original bittern of salt lake+With the Na in saponification iron content organic phase+Generation ion-exchange reactions, it is organic
NaFeCl in phase4It is changed into LiFeCl4, so as to realize the Li in the original bittern of salt lake+It is extracted and is transferred to organic phase.
After extract stands split-phase, upper organic phase is taken, as extracts lithium load organic phases；Isolated aqueous phase is to extract
Extraction raffinate, also referred to as saponification bottom liquid, saponification bottom liquid can put into step 2) and recycle.
Step 4)：Pickling
Extract the lithium containing the Extraction and enrichment from the original bittern of salt lake in lithium load organic phases, also in the presence of other cation impurities,
Therefore, in order to reduce the purification difficulty of later stage lithium, it is necessary to remove the impurity in extraction lithium load organic phases.
Research is found, the impurity in extraction lithium load organic phases can be removed using Acidwash solution.Wherein, the Acidwash solution
In contain inorganic acid and lithium salts, preferably described Acidwash solution is the aqueous solution containing hydrochloric acid and lithium chloride.
In lithium load organic phases are extracted, a small amount of Na be present+、K+、Mg2+、Ca2+Deng impurity cationic, research is found, in halogen
In water, the substitution order of cation is： H+>Li+>Na+>Mg2+>K+>Ca2+.Also, research also found, as the H in Acidwash solution+In more than 4.0mol/L H can just occur in acid cleaning process for concentration+With Li+Substitution exchange.Therefore, pickling operation is controlled
Middle H+Concentration for remove extract lithium load organic phases in impurity, ensure extraction lithium load organic phases in lithium load capacity to close weight
Will.
It is preferred that in the Acidwash solution, the concentration of inorganic acid is 0.5~2.0mol/L, the concentration of lithium salts for 0.1~
1.0mol/L。
A small amount of lithium salts is added in Acidwash solution, contributes to impurity cationic to be substituted by lithium ion, reduces pickling
The loss of lithium in journey.
The extraction lithium load organic phases and the dosage volume ratio of Acidwash solution are 1:1~50:1.
Lithium load organic phases, Li therein are extracted by Acidwash solution pickling+And H+It will can extract miscellaneous in lithium load organic phases
Matter cation substitutes so that the Na in extraction lithium load organic phases+、K+、Mg2+、Ca2+Deng impurity cationic by back extraction enter aqueous phase；
Due to H+To Li+Substitution occur in H+Higher concentration condition just occurs, therefore, the organic phase after pickling, i.e. acid
Lithium load organic phases are washed, wherein being substantially free of Na+、 K+、Mg2+、Ca2+Deng impurity cationic, Li is only remained with+, and it is minimal amount of
H+。
Step 5)：Back extraction
Pickling lithium load organic phases are mixed with hydrochloric acid solution and are stripped, the lithium in pickling lithium load organic phases is sent out with hydrogen
Raw ion-exchange reactions so that lithium is enriched in aqueous phase, realizes the enrichment and extraction of lithium.
Research it has also been found that, it is described back extraction operation in, although hydrogen substitution order be higher than lithium, only concentration of hydrochloric acid compared with
Under conditions of height the lithium in pickling lithium load organic phases can just be sufficiently displaced from hydrogen.
It is therefore preferable that the concentration of the hydrochloric acid solution is 6.0~12.0mol/L, preferably can make in organic phase
LiFeCl4It is changed into HFeCl4。
It is furthermore preferred that the pickling lithium load organic phases and the dosage volume ratio of hydrochloric acid solution are 1:1~50:1.
After pickling lithium load organic phases are stripped with hydrochloric acid solution, split-phase is stood, lower floor's aqueous phase is the rich lithium aqueous solution；
Upper organic phase is regeneration organic phase, i.e. contains HFeCl4Organic phase, its in the present invention with iron content organic phase
With identical chemical property and effect.Therefore, itself and organic mix of obtained iron content in step 1) can be thrown jointly afterwards
Enter in step 2) and recycle；Or regeneration organic phase is substituted in iron content organic phase input step 2) and recycled；Or
Reclaiming organic phase, iron content organic phase is only put into step 2).
Regeneration organic phase can be used with repetitive cycling, without supplementing addition iron and organic phase again, therefore be effectively reduced
The cost of production.
A kind of method from salt lake original bittern extraction low concentration lithium provided by the invention, has the advantages that：
(1) present invention is applied to salt lake original bittern of the directly processing without evaporate brine evaporation and concentration and de- potassium sodium, therefrom extracts
Low concentration lithium；
(2) the previously prepared iron content organic phase of the present invention, directly dissolves FeCl using concentrated hydrochloric acid aqueous solution3·6H2O solid powder
End, the iron for ensureing to add is with FeCl4 -Form be present in organic phase, be advantageous to and the Li in bittern+Form LiFeCl4, from
And realize the Li in bittern+It is extracted and is transferred to organic phase；
(3) iron content organic phase is prepared, being advantageous to extraction lithium process can be with continuous operation；In addition, the iron added is with FeCl4 -'s
Form is present in organic phase, and the iron loss that also helping prevents saponification process from having extracted into organic phase enters aqueous phase；
(4) the regeneration organic phase after being stripped in the present invention can be utilized with circulating repetition, without supplementing addition iron again, be reduced
The cost of production；
(5) it is provided by the invention from the method for salt lake original bittern extraction low concentration lithium, extract impurity in obtained product
Few, purity is high, advantageously reduces follow-up purifying difficulty and cost.
Embodiment
Embodiment 1
(1) iron content organic phase is prepared：
Chloride type salt lake original bittern of the 100mL without evaporate brine evaporation and concentration and de- potassium sodium is taken, detection obtains Li therein+
Mass concentration be 0.05g/L；Then, according to Fe:Li molar concentration rates are 5:1, weigh 9.737g FeCl3·6H2O solids
Powder, the HCl mass fractions for being dissolved in 1000mL are in 20% concentrated hydrochloric acid, obtain the aqueous hydrochloric acid solution of iron content；
Take 50mL tributyl phosphate to be dissolved in 50mL kerosene, obtain organic extraction agent solution；
By organic extraction agent solution and the combined of iron content, after standing split-phase, upper organic phase is taken, is contained
Iron organic phase.
(2) saponification iron content organic phase：
Lower floor's aqueous phase that split-phase separates is stood after step (1) the iron content organic phase is extracted with 100mL steps (3) to mix
Close, obtain two-phase mixture；
Take 10mL, the sodium hydrate aqueous solution that concentration is 4mol/L, under agitation, dripped with 0.1mL/min speed
It is added in above-mentioned two-phase mixture；After being sufficiently stirred, split-phase is stood, upper organic phase is taken, obtains saponification iron content organic phase.
(3) extract：
Step (1) described 100mL without evaporate brine evaporation and concentration and de- potassium sodium salt lake original bittern in hydrochloric acid is added dropwise, adjust
Section obtains the former bittern of extraction to pH=2；
Step (2) the saponification iron content organic phase is mixed with the extraction with former bittern.After standing split-phase, upper strata is taken to have
Machine phase, obtain extracting lithium load organic phases；The lithium content in lower floor's raffinate aqueous phase is detected, Li is calculated+Extraction yield be 85%.
(4) pickling：
By step (3) extraction lithium load organic phases and the 50mL, chlorination lithium concentration be 0.1mol/L, concentration of hydrochloric acid be
0.5mol/L Acidwash solution mixing；After standing split-phase, upper organic phase is taken, obtains pickling lithium load organic phases.
(5) it is stripped：
By step (4) the pickling lithium load organic phases and 100mL, the combined that concentration is 6.0mol/L；
After standing split-phase, upper and lower two layers of solution is obtained；A layer aqueous phase is removed, obtains the rich lithium aqueous solution；Upper organic phase is taken, is regenerated
Organic phase, regeneration organic phase return to step (2) recycle.
Embodiment 2
(1) iron content organic phase is prepared：
Chloride type salt lake original bittern of the 500mL without evaporate brine evaporation and concentration and de- potassium sodium is taken, detection obtains Li therein+
Mass concentration be 0.2g/L；Then, according to Fe：Li molar concentration rates are 100:1, weigh 778.96g FeCl3〃6H2O consolidates
Body powder, the HCl mass fractions for being dissolved in 1000mL are in 37% concentrated hydrochloric acid, obtain the aqueous hydrochloric acid solution of iron content；
Take 200mL butyl phosphonic acids dibutyl ester to be dissolved in 2000mL kerosene, obtain organic extraction agent solution；
By organic extraction agent solution and the combined of iron content, after standing split-phase, upper organic phase is taken, is contained
Iron organic phase.
(2) saponification iron content organic phase：
Take 500mL steps (1) the iron content organic phase and the 50mL old bittern after evaporate brine evaporation and concentration and de- potassium sodium
Mixing, obtains two-phase mixture；
Take 10mL, the sodium hydrate aqueous solution that concentration is 4mol/L, under agitation, be added dropwise with 1mL/min speed
Into above-mentioned two-phase mixture；After being sufficiently stirred, split-phase is stood, upper organic phase is taken, obtains saponification iron content organic phase.
(3) extract：
With the step of embodiment 1 (3), it is computed, Li+Extraction yield be 87%.
(4) pickling：
By step (3) extraction lithium load organic phases and the 10mL, chlorination lithium concentration be 1mol/L, concentration of hydrochloric acid be
0.5mol/L Acidwash solution mixing；After standing split-phase, upper organic phase is taken, obtains pickling lithium load organic phases.
(5) it is stripped：
By step (4) the pickling lithium load organic phases and 10mL, the combined that concentration is 12.0mol/L；
After standing split-phase, upper and lower two layers of solution is obtained；A layer aqueous phase is removed, obtains the rich lithium aqueous solution；Upper organic phase is taken, is regenerated
Organic phase, the regeneration organic phase return to step (2) recycle.
Embodiment 3
(1) iron content organic phase is prepared：
Chloride type salt lake original bittern of the 50mL without evaporate brine evaporation and concentration and de- potassium sodium is taken, detection obtains Li therein+
Mass concentration be 1.0g/L；According to Fe:Li molar concentration rates are 20:1, weigh 389.48g FeCl36H2O solid powder
End, the HCl mass fractions for being dissolved in 500ml are in 37% concentrated hydrochloric acid, obtain the aqueous hydrochloric acid solution of iron content；
Take 300mL trioctyl phosphine oxide to be dissolved in 200mL kerosene, obtain organic extraction agent solution；
By the organic extraction agent solution and the combined of the iron content, after standing split-phase, take upper strata organic
Phase, obtain iron content organic phase.
(2) saponification iron content organic phase：
Take 100mL steps (1) the iron content organic phase and the 100mL old bittern after evaporate brine evaporation and concentration and de- potassium sodium
Mixing, obtains two-phase mixture；
Take 1mL, the sodium hydrate aqueous solution that concentration is 6mol/L, under agitation, be added dropwise with 0.1mL/min speed
Into above-mentioned two-phase mixture；After being sufficiently stirred, split-phase is stood, upper organic phase is taken, obtains saponification iron content organic phase.
(3) extract：
Step (1) described 50mL without evaporate brine evaporation and concentration and de- potassium sodium salt lake original bittern in hydrochloric acid is added dropwise, adjust
Section obtains the former bittern of extraction to pH=2；
Step (2) the saponification iron content organic phase is mixed with the extraction with former bittern；After standing split-phase, upper strata is taken to have
Machine phase, obtain extracting lithium load organic phases.The lithium content in lower floor's raffinate aqueous phase is detected, Li is calculated+Extraction yield be 90%.
(4) pickling：
By step (3) extraction lithium load organic phases and the 10mL, chlorination lithium concentration be 0.5mol/L, concentration of hydrochloric acid be
1.0mol/L Acidwash solution mixing；After standing split-phase, upper organic phase is taken, obtains pickling lithium load organic phases.
(5) it is stripped：
By step (4) the pickling lithium load organic phases and 10mL, the combined that concentration is 9.0mol/L；
After standing split-phase, upper and lower two layers of solution is obtained；A layer aqueous phase is removed, obtains the rich lithium aqueous solution；Upper organic phase is taken, is regenerated
Organic phase, the regeneration organic phase return to step (2) recycle.
Embodiment 4
(1) iron content organic phase is prepared：
Chloride type salt lake original bittern of the 500mL without evaporate brine evaporation and concentration and de- potassium sodium is taken, detection obtains Li therein+
Mass concentration be 0.1g/L；Then, according to Fe：Li molar concentration rates are 60:1, weigh 116.84g FeCl3·6H2O consolidates
Body powder, the HCl mass fractions for being dissolved in 500mL are in 37% concentrated hydrochloric acid, obtain the aqueous hydrochloric acid solution of iron content；
150mL tributyl phosphate and 150mL butyl phosphonic acids dibutyl ester are taken, is dissolved in 200mL kerosene, obtains after mixing
To organic extraction agent solution；
By the organic extraction agent solution and the combined of the iron content, after standing split-phase, take upper strata organic
Phase, obtain iron content organic phase.
(2) saponification iron content organic phase：
Take 100mL steps (1) the iron content organic phase and the 100mL old bittern after evaporate brine evaporation and concentration and de- potassium sodium
Mixing, obtains two-phase mixture；
Take 10mL, the sodium hydrate aqueous solution that concentration is 4mol/L, under agitation, be added dropwise with 1mL/min speed
Into above-mentioned two-phase mixture；After being sufficiently stirred, split-phase is stood, upper organic phase is taken, obtains saponification iron content organic phase.
(3) extract：
With the step of embodiment 3 (3), it is computed, Li+Extraction yield be 89%.
(4) pickling：
By step (3) extraction lithium load organic phases and the 100mL, chlorination lithium concentration be 0.5mol/L, concentration of hydrochloric acid be
1.0mol/L Acidwash solution mixing；After standing split-phase, upper organic phase is taken, obtains pickling lithium load organic phases.
(5) it is stripped：
By step (4) the pickling lithium load organic phases and 10mL, the combined that concentration is 9.0mol/L；
After standing split-phase, upper and lower two layers of solution is obtained；A layer aqueous phase is removed, obtains the rich lithium aqueous solution；Upper organic phase is taken, is regenerated
Organic phase, the regeneration organic phase return to step (2) recycle.
Embodiment 5
(1) iron content organic phase is prepared：
Chloride type salt lake original bittern of the 300mL without evaporate brine evaporation and concentration and de- potassium sodium is taken, detection obtains Li therein+
Mass concentration be 4.0g/L；Then, according to Fe：Li molar concentration rates are 5:1, weigh 778.96g FeCl3·6H2O solids
Powder, the HCl mass fractions for being dissolved in 1000mL are in 32% concentrated hydrochloric acid, obtain the aqueous hydrochloric acid solution of iron content；
200mL tributyl phosphate and 200mL trioctyl phosphine oxide are taken, is dissolved in 200mL kerosene, is had after mixing
Machine extracts agent solution；
By organic extraction agent solution and the combined of iron content, after standing split-phase, upper organic phase is taken, is contained
Iron organic phase.
(2) saponification iron content organic phase：
Take 100mL steps (1) the iron content organic phase and the 100mL old bittern after evaporate brine evaporation and concentration and de- potassium sodium
Mixing, obtains two-phase mixture；
Take 2mL, the sodium hydrate aqueous solution that concentration is 6mol/L, under agitation, be added dropwise with 0.5mL/min speed
Into above-mentioned two-phase mixture；After being sufficiently stirred, split-phase is stood, upper organic phase is taken, obtains saponification iron content organic phase.
(3) extract：
It is identical with the step of embodiment 3 (3), it is computed, Li+Extraction yield be 92%.
(4) pickling：
By step (3) extraction lithium load organic phases and the 10mL, chlorination lithium concentration be 0.5mol/L, concentration of hydrochloric acid be
2.0mol/L Acidwash solution mixing；After standing split-phase, upper organic phase is taken, obtains pickling lithium load organic phases.
(5) it is stripped：
By step (4) the pickling lithium load organic phases and 5mL, the combined that concentration is 9.0mol/L；It is quiet
After putting split-phase, upper and lower two layers of solution is obtained；A layer aqueous phase is removed, obtains the rich lithium aqueous solution；Upper organic phase is taken, obtaining regeneration has
Machine phase, the regeneration organic phase return to step (2) recycle.
The present invention is described in detail above in association with embodiment and exemplary example, but these explanations are simultaneously
It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention,
A variety of equivalencing, modification or improvement can be carried out to technical solution of the present invention and embodiments thereof, these each fall within the present invention
In the range of.Protection scope of the present invention is determined by the appended claims.
Claims (10)
- A kind of 1. method from salt lake original bittern extraction low concentration lithium, it is characterised in that this method includes：Step 1), ferric iron compound is dissolved in hydrochloric acid, mixed with the diluent dissolved with neutral phosphorus extractant, iron content is made Organic phase；Step 2), saponification treatment step 1) in the regeneration organic phase that obtains in obtained iron content organic phase and/or step 5), obtain Saponification iron content organic phase；Turn into extraction salt lake original bittern after step 3), the acidifying of salt lake original bittern, and it is carried out using saponification iron content organic phase Extraction, obtain extracting lithium load organic phases and saponification bottom liquid；Step 4), using Acidwash solution pickling extract lithium load organic phases, obtain pickling lithium load organic phases；Step 5), pickling lithium load organic phases are mixed with hydrochloric acid solution be stripped, obtained the rich lithium aqueous solution and regenerate organic Phase.
- 2. according to the method for claim 1, it is characterised in that in the step 1), iron ion and salt lake original halogen in hydrochloric acid The molar concentration rate of lithium ion is 5 in water:1~100:1, preferably 20:1~60:1.
- 3. according to the method for claim 2, it is characterised in that in step 1), the preparation method of iron content organic phase includes：Ferric iron compound is dissolved in the aqueous hydrochloric acid solution that mass fraction is 20%~37%, is made and contains HFeCl4The aqueous solution；Neutral phosphorus extractant is dissolved under normal pressure in aliphatic hydrocarbon or arene diluent of the boiling point more than 200 DEG C, obtained Organic extraction agent solution；The organic extraction agent solution is contained into HFeCl with described4The aqueous solution mixing, stand split-phase after, take upper organic phase, obtain To iron content organic phase.
- 4. according to the method described in one of claim 1-3, it is characterised in that in the step 2), by what is prepared in step 1) It is mixed at this after the regeneration organic phase obtained in iron content organic phase and/or step 5) mixes with the saponification bottom liquid obtained in step 3) Close and inorganic base progress saponification process is added in liquid.
- 5. according to the method for claim 4, it is characterised in that in the step 2), the iron content organic phase and/or regeneration Organic phase, the volume ratio with saponification bottom liquid are 1:10~10:1, preferably 1:1~10:1.
- 6. according to the method for claim 4, it is characterised in that it is in step 2), inorganic base is soluble in water, obtain inorganic Aqueous alkali, then it is added dropwise in mixing liquid and carries out saponification, the concentration of the inorganic base aqueous solution is 1~6mol/L, preferably For 4~6mol/L；The rate of addition of inorganic base aqueous solution is 0.1~1.0mL/min.
- 7. according to the method for claim 1, it is characterised in that in the step 3), lithium is dense in the salt lake original bittern Spend for 0.05~5g/L, preferably 0.05~1g/L.
- 8. the method according to claim 1 or 7, it is characterised in that in the step 3), during extraction, saponification iron content is organic Mutually the volume ratio with extracting with former bittern is 10:1~1:1, preferably 5:1~1:1.
- 9. according to the method for claim 8, it is characterised in that in the step 4), contain hydrochloric acid in the Acidwash solution And lithium chloride, wherein, the concentration of hydrochloric acid is 0.5~2.0mol/L, and the concentration of lithium chloride is 0.1~1.0mol/L.
- 10. the method according to claim 1 or 9, it is characterised in that in the step 5), regenerate and contain in organic phase HFeCl4, can individually put into step 2) recycle or with obtained iron content is organic in step 1) mix after put into step 2) Middle recycling.
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