CN107760885B - A method of extracting low concentration lithium from the original brine of salt lake - Google Patents
A method of extracting low concentration lithium from the original brine of salt lake Download PDFInfo
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- CN107760885B CN107760885B CN201711140377.7A CN201711140377A CN107760885B CN 107760885 B CN107760885 B CN 107760885B CN 201711140377 A CN201711140377 A CN 201711140377A CN 107760885 B CN107760885 B CN 107760885B
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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 present invention provides a kind of methods for extracting low concentration lithium from salt lake original brine, this method comprises: 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 regenerate organic phase, obtain saponification iron content organic phase；Step 3) is extracted using the saponification organic relative extractive of iron content with salt lake original brine, is obtained extraction lithium load organic phases and is saponified bottom liquid；Step 4) extracts lithium load organic phases using pickling solution pickling, obtains pickling lithium load organic phases；Pickling lithium load organic phases are mixed with hydrochloric acid solution and are stripped by step 5), obtain rich lithium aqueous solution and regeneration organic phase.This method guarantees the iron being added with FeCl by preparation iron content organic phase4 ‑Form be present in organic phase, be conducive to and the Li in brine+Form LiFeCl4, to realize the Li in brine+It is extracted and is transferred to organic phase, the product impurity extracted is few, and purity is high advantageously reduces subsequent purifying difficulty and cost.
Description
Technical field
The present invention relates to salt lake chemical field, in particular to it is a kind of from without evaporate brine evaporation and concentration and de- potassium sodium handle,
The method of low concentration lithium is extracted in salt lake original brine containing lithium.
Background technique
Lithium is widely used in the numerous areas such as lithium battery, aerospace, atomic energy, Nuclear Power Industry and medicine, is known as
" energy metal for pushing world's progress " is strategic resource important in national economy and 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 about global lithium of having verified and provides
The 90% of source 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 that Mg/Li ratio is high (Mg:Li molar concentration rate is 10:1~2000:1), from high Mg/Li ratio salt lake halogen
Separation and Extraction low concentration lithium is very difficult in water.
Currently, reported both at home and abroad propose the method for lithium generally only for evaporation and concentration and the de- potassium of being evaporated brine from salt lake bittern
Sodium treated old halogen, there is not yet industrialization report from without evaporate brine evaporation and concentration and salt lake original brine that de- potassium sodium is handled in it is straight
It connects and extracts low concentration lithium.
In the prior art, the method that lithium is extracted from salt lake bittern mainly has the precipitation method, calcining leaching method, ion exchange
(absorption) method, electroosmose process and solvent extraction etc..
Wherein, precipitation process is simple, technology maturation, be suitable in low Mg/Li ratio salt lake bittern extract lithium.This method
In, after lake bittern water containing lithium salts is concentrated by evaporation de- potassium sodium, acidification boron removal and separating calcium and magnesium processing, sodium carbonate, which is added, 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 process flow 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 brine is more infeasible, and precipitating reagent consumption increases, and lithium loss late is high, process costs are high.
Calcining leaching method need to will be evaporated close to the salt lake bittern of saturation, allow lithium, magnesium respectively with lithium sulfate and bischofite salt
Crystallizable mineral is precipitated, and then calcines at high temperature, and dewatering bischofite is made to form magnesia, produces after then being calcined with fresh water leaching
Object, lithium sulfate enters solution, and magnesia is not soluble in water, to realize separating magnesium and lithium.The method process is complicated, corrodes to equipment tight
Weight, the water for needing to evaporate is huge, and power consumption is big, at high cost and seriously polluted.
Ion exchange (absorption) method simple process, environmental-friendly, selectivity is strong, using adsorbent from the old halogen after concentration
Lithium is directly extracted, is mentioned with pickling, elutriant is electrolysed lithium after being concentrated by evaporation.This method by the rate of adsorption because being influenced, at brine
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 brine extract low concentration lithium cost it is higher.
In electroosmose process, the concentrated brine containing lithium that salt pan is evaporated is utilized by one or more levels electric dialyzator
Yin, yang monovalence selective ion exchange membrane carries out circulation concentration lithium, obtains the low magnesium brine of rich lithium, then also needs to remove through depth repeatedly
Foreign ion, refining and concentrating can just obtain lithium carbonate product after conversion is dry.Entire complex process, process are tediously long.In addition, electric
Dialyser is easily poisoned blocking, and process costs are high.
Selectivity strong, separative efficiency height, simple process, equipment investment be small, easy scale is amplified because having for solvent extraction
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 extracts lithium technology and is generally directed to evaporation and concentration of being evaporated brine, takes off at potassium sodium
Old halogen after reason, also, be to add ferric trichloride in advance in old halogen as synergic reagent, then using tributyl phosphate or with
Other material mixings mention lithium as extractant, with the mechanism extraction of solvation.In old halogen, the concentration of lithium is generally greater than 5g/L.
For example, there is extraction lithium selection during extracting lithium using solvent extraction in Chinese patent CN87103431A
Property it is not high, the foreign ions such as sodium, potassium, calcium, magnesium for especially being coexisted in brine enter back extraction product liquid, lead to subsequent purification technique
It is many and diverse, it is at high cost；In addition, the tributyl phosphate concentration used is higher, to extraction equipment seriously corroded；It also will cause extractant to exist
Molten damage is tight in saponification process；In CN103055538A, the mixture of tributyl phosphate and amide kind of extractants is extractant, extraction
Lithium selectivity is high, but this method still needs to dissolve ferric trichloride in old halogen in advance as synergic reagent, moreover, having after back extraction regeneration
Machine mutually cannot achieve higher saponification degree, cause lithium recovery of extraction low, extracts lithium process and organic phase saponification process easily causes
Ferric trichloride hydrolysis is precipitated, and causes water phase and an oil phase separation difficult；And in the patents such as CN104357676A and CN106435219A,
Although the extraction yield of lithium can be improved or solve the problems, such as that calcium phosphate+ forage system corrodes equipment, extraction lithium behaviour cannot achieve
The serialization of work.
As it can be seen that in the prior art, solvent extraction mention lithium technology only extractant composition and in terms of done a bit
Work cannot achieve the low concentration that the direct extracting and enriching concentration from the salt lake original brine without evaporation and concentration of evaporating brine is less than 5g/L
Lithium；
In addition, since ferric trichloride being directly dissolved in old brine, it is difficult to control ferric iron and be completely reformed into tetrachloro iron
Close object；When extracting to old brine, it is even more to be unable to control that can tetrachloro iron therein, which close object be changed into tetrachloro iron lithium,.
In view of the foregoing, the present inventor improves on the basis of existing technology, develops a kind of from crude salt lake halogen
Water, especially from without evaporating brine evaporation and concentration and side that de- potassium sodium is handled, extracting low concentration lithium in salt lake original brine containing lithium
Method.
Summary of the invention
To solve the above-mentioned problems, present inventor has performed sharp studies, as a result, it has been found that: ferric iron compound preparation is contained
After iron organic phase and saponification process, the salt lake original brine after being acidified is extracted, through the impurity cationic in overpickling removal co-extraction, then
Back extraction is mixed with hydrochloric acid solution, can obtain the higher rich lithium aqueous solution of purity, while obtained regeneration organic phase can also be thrown
Enter and be recycled in reaction, reduces extraction difficulty and cost, so as to complete the present invention.
The purpose of the present invention is to provide a kind of methods for extracting low concentration lithium from salt lake original brine, this method comprises:
Ferric iron compound is dissolved in hydrochloric acid by step 1), is mixed with the diluent dissolved with neutral phosphorus extractant, is made
Iron content organic phase；
Step 2), saponification treatment step 1) in regenerate organic phase obtained in iron content organic phase and/or step 5) obtained,
Obtain saponification iron content organic phase；
Become extraction salt lake original brine after step 3), the acidification of salt lake original brine, and using saponification iron content organic phase to it
It is extracted, obtain extraction lithium load organic phases and is saponified bottom liquid；
Step 4) extracts lithium load organic phases using pickling solution pickling, obtains pickling lithium load organic phases；
Pickling lithium load organic phases are mixed with hydrochloric acid solution and are stripped by step 5), obtain rich lithium aqueous solution and regeneration
Organic phase.
In step 1), the molar concentration rate of iron ion and lithium ion in salt lake original brine is 5:1~100:1 in hydrochloric acid,
Preferably 20:1~60:1.
Wherein, in step 1), the neutral phosphorus extractant is selected from phosphate (TRP), phosphonate ester (DRRP), phosphinate
(RDRP) and one of trialkyl phosphine (TRPO) or a variety of, the preferably described neutral phosphorus extractant are selected from tributyl phosphate
(TBP), one of butyl phosphonic acids dibutyl ester (DBBP) and trioctyl phosphine oxide (TOPO) or a variety of.
Wherein, in the step 2), have being regenerated obtained in the iron content organic phase and/or step 5) that are prepared in step 1)
After machine phase is mixed with saponification bottom liquid obtained in step 3), inorganic base is added in the mixing liquid and carries out saponification process.
Also, in the step 2), the iron content organic phase and/or regeneration organic phase are with the volume ratio for being saponified bottom liquid
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
It is saponified, 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 brine.
In the step 3), when extraction, saponification iron content organic phase and extraction are 10:1~1:1 with the volume ratio of original brine,
Preferably 5:1~1:1.
Wherein, in the step 4), hydrochloric acid and lithium chloride are contained in the pickling solution, wherein the concentration of hydrochloric acid is 0.5
~2.0mol/L, the concentration of lithium chloride are 0.1~1.0mol/L.
In the step 5), regenerates in organic phase and contain HFeCl4, can individually put into recycling or same in step 2)
Iron content obtained is organic in step 1) mix after investment step 2) in be recycled.
For the present invention by previously prepared iron content organic phase, the concentrated hydrochloric acid aqueous solution for the use of mass fraction being 20%~37% is straight
Meet dissolution FeCl3·6H2O solid powder guarantees the iron being added with FeCl4 -Form be present in organic phase, be conducive to and halogen
Li in water+Form LiFeCl4, to realize the Li in brine+It is extracted and is transferred to organic phase；It is extracted by this method
Impurity is few in product, and purity is high advantageously reduces subsequent purifying difficulty and cost.
Specific embodiment
Present invention will now be described in detail, and the features and advantages of the invention will become more with these explanations
It is clear, clear.
Dedicated word " exemplary " means " 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 present invention provides it is a kind of from salt lake original brine extract low concentration lithium method, the salt lake original brine 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 brine, the concentration of lithium
Lower, the concentration of the preferably described lithium is 0.05~5g/L, more preferable 0.05~1g/L.
It is described from salt lake original brine extract low concentration lithium method include:
Step 1): iron content organic phase is prepared
The salt lake original brine without evaporate brine evaporation and concentration and the processing of de- potassium sodium is taken, Li therein is detected+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 valence iron, the hydrate including iron chloride, iron oxide, iron hydroxide and the substance.It is preferable to use can be straight
Connect the iron chloride preparation iron content organic phase of dissolution.Since iron chloride has stronger hygroscopicity, more preferably use FeCl3〃
6H2O solid powder prepares iron content organic phase.
By Fe3+Solid powder is dissolved in hydrochloric acid, obtains iron-containing aqueous hydrochloric acid solution；Wherein, according in hydrochloric acid iron and
The molar concentration rate of lithium in the original brine of salt lake is 5:1~100:1, and the molar concentration rate of the preferably described Fe:Li is 20:1~60:
1；
It is preferred that the hydrochloric acid is the concentrated hydrochloric acid aqueous solution that HCl mass fraction is 20%~37%, the hydrochloric acid energy of the concentration
Higher chlorine ion concentration is enough provided, guarantees Fe with FeCl4 -Form be present in hydrochloric acid, and and H+In conjunction with formation HFeCl4。
Neutral phosphorus extractant is taken, boiling point under normal pressure is dissolved in and is diluted in 200 DEG C or more of aliphatic hydrocarbon or arene
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 of phosphine oxide (TRPO) is a variety of；
Preferably, the neutral phosphorus extractant be selected from tributyl phosphate (TBP), butyl phosphonic acids dibutyl ester (DBBP) and
One of trioctyl phosphine oxide (TOPO) is a variety of.The substance is to HFeCl4With good solubility.
The diluent is selected from kerosene, sulfonated kerosene and machine oil, it is preferable to use 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 be 1:10~10:1, preferably 1:10~5:1, more preferably
For 1:10~2.5:1, so that neutral phosphorus extractant can sufficiently dissolution/dispersion in diluent, also, it is neutral Phosphorus
Extractant concentration with higher in diluent.
When extracting iron-containing aqueous hydrochloric acid solution using the organic extraction agent solution, HFeCl in hydrochloric acid can be improved4Extraction
The extraction efficiency being transferred in the organic extraction agent solution.
The organic extraction agent solution is mixed with the iron-containing aqueous hydrochloric acid solution according to volume ratio for 1:10~10:1,
After standing split-phase, upper organic phase is taken, iron content organic phase is obtained.
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 adding after the iron content organic phase prepared in step 1) is mixed with saponification bottom liquid obtained in step 3)
The aqueous solution for entering inorganic base carries out saponification process, and saponification iron content organic phase is made.
The saponification bottom liquid is institute in the lower layer's water phase or step 3) that stratification separates in step 3) after the completion of extraction
The mixture of one or both of the old brine that the salt lake original brine stated obtains after evaporate brine evaporation and concentration and the processing of de- potassium sodium.
Saponification bottom liquid mainly plays a part of to disperse iron content organic phase and/or regenerates organic phase；In addition, due to being saponified bottom
Contain the higher chloride ion of concentration in liquid, during dispersing iron content organic phase and/or regeneration organic phase, also acts inhibition
Its interior HFeCl4The effect of decomposition.
Wherein, iron content organic phase and/or regeneration organic phase, volume ratio when mixing 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 saponification bottom liquid
Be separated into droplet, the surface area of organic phase dramatically increases, when be added inorganic base aqueous solution be saponified when, can quickly,
Sufficiently complete, it is more difficult to occur since locally excessively high caused iron solution isolates the concentration of inorganic base.
Wherein, the inorganic base is selected from sodium hydroxide, potassium hydroxide or ammonium hydroxide, it is preferable to use alkalinity is relatively strong, is easy to get
Sodium hydroxide prepare the aqueous solution of inorganic base.Wherein, the concentration of inorganic base is 1~6mol/L, preferably 4~6mol/L, energy
Enough alkali saponified iron content organic phases are enough provided.
Under stirring condition, the aqueous solution of inorganic base is added dropwise into mixing liquid with the speed of 0.1~1.0mL/min, it can
The concentration that inorganic base instills mixed liquor is controlled, prevents in saponification process that liquid local base concentration is excessively high, causes in iron content organic phase
Molten iron parse.
By saponification process, iron content organic phase can be neutralized and/or regenerate the acid in organic phase, and make to extract organic into 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, obtain saponification iron content it is organic
Phase.
Step 3): extraction
Salt lake original brine is subjected to acidification, obtains extraction with former brine；Further, using inorganic acid to salt lake original
Brine carries out acidification, such as hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid are, it is preferable to use the hydrochloric acid containing chloride ion, is extracting in this way
During, it enables to fully ensure that iron therein is constantly in FeCl containing a large amount of chloride ion in extraction solution4 -Shape
State is conducive to extract lithium from the original brine of salt lake.
It is found in research, the salt lake original brine 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 being saponified in iron content organic extractant phase brine, to Li+With compared with
Good selectivity, in brine with Li+The Na coexisted+、K+、Mg2+、Ca2+The equal seldom co-extraction of impurity cationics enters in organic phase.
The former brine of extraction obtained using saponification iron content organic phase obtained in step 2) and acidification, obtains extraction lithium
Load organic phases；Wherein, the saponification iron content organic phase and extraction are that 1:1~10:1 is mixed and extracted according to volume ratio with original brine
It takes, preferably saponification iron content organic phase and extraction are 1:1~5:1 with former brine volume ratio, can sufficiently extract the lithium in former brine
And reduce the use of organic phase.
Li by extracting, in the original brine of salt lake+With the Na in saponification iron content organic phase+Ion-exchange reactions occurs, it is organic
NaFeCl in phase4It is changed into LiFeCl4, to realize the Li in the original brine of salt lake+It is extracted and is transferred to organic phase.
After extract liquor stands split-phase, upper organic phase, as extraction lithium load organic phases are taken；Isolated water phase is to extract
Extraction raffinate, also referred to as saponification bottom liquid, saponification bottom liquid can put into step 2) and be recycled.
Step 4): pickling
Extract the lithium containing the Extraction and enrichment from the original brine of salt lake in lithium load organic phases, there is also other cation impurities,
Therefore, in order to reduce the purification difficulty of later period lithium, it is necessary to the impurity in removal extraction lithium load organic phases.
The study found that can remove the impurity in extraction lithium load organic phases using pickling solution.Wherein, the pickling solution
In contain inorganic acid and lithium salts, the preferably described pickling solution be the aqueous solution containing hydrochloric acid and lithium chloride.
In extraction lithium load organic phases, there are a small amount of Na+、K+、Mg2+、Ca2+Equal impurity cationics, the study found that in halogen
In water, cationic substitution sequence are as follows: H+>Li+>Na+>Mg2+>K+>Ca2+.Also, research also found, as the H in pickling solution+
In 4.0mol/L or more H can just occur in acid cleaning process for concentration+With Li+Substitution exchange.Therefore, it controls in pickling operation
H+Concentration in removal extraction lithium load organic phases impurity, guarantee lithium load capacity in extraction lithium load organic phases to Guan Chong
It wants.
It is preferred that in the pickling solution, the concentration of inorganic acid is 0.5~2.0mol/L, the concentration of lithium salts is 0.1~
1.0mol/L。
A small amount of lithium salts is added in pickling solution, is facilitated impurity cationic and is substituted by lithium ion, reduces pickling
The loss of lithium in journey.
The extraction lithium load organic phases and the dosage volume ratio of pickling solution are 1:1~50:1.
Extract lithium load organic phases, Li therein by pickling solution pickling+And H+It can will extract miscellaneous in lithium load organic phases
Matter cation replaces, so that the Na in extraction lithium load organic phases+、K+、Mg2+、Ca2+Equal impurity cationics enter water phase by back extraction；
Due to H+To Li+Substitution occur in H+Higher concentration condition just occurs, therefore, the organic phase after pickling, that is, acid
Lithium load organic phases are washed, wherein being substantially free of Na+、K+、Mg2+、Ca2+Equal impurity cationics, only remain with Li+And 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 and hydrogen are sent out
Raw ion-exchange reactions realizes the enrichment and extraction of lithium so that lithium is enriched in water phase.
Research it has also been found that, in back extraction operation, although the substitution of hydrogen is sequentially 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, can preferably 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 and hydrochloric acid solution are stripped, split-phase is stood, lower layer's water phase is rich lithium aqueous solution；
Upper organic phase is regeneration organic phase, that is, contains HFeCl4Organic phase, in the present invention with iron content organic phase
Chemical property having the same and effect.Therefore, it can be thrown jointly afterwards with organic mix of iron content obtained in step 1)
Enter in step 2) and is recycled；Alternatively, will be recycled in regeneration organic phase substitution iron content organic phase investment step 2)；Or it returns
Regeneration organic phase is received, only puts into iron content organic phase in step 2).
Regeneration organic phase can be used with repetitive cycling, without supplement addition iron and organic phase again, therefore be effectively reduced
The cost of production.
A kind of method for extracting low concentration lithium from salt lake original brine provided by the invention, has the advantages that
(1) present invention is suitable for salt lake original brine 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 guarantees the iron being added with FeCl4 -Form be present in organic phase, be conducive to and the Li in brine+Form LiFeCl4, from
And realize the Li in brine+It is extracted and is transferred to organic phase；
(3) iron content organic phase is prepared, being conducive to extraction lithium process can be with continuous operation；In addition, the iron being added is with FeCl4 -'s
Form is present in organic phase, and also helping, which prevents saponification process from having extracted into the iron loss of organic phase, enters water phase；
(4) the regeneration organic phase after being stripped in the present invention can be utilized with circulating repetition, without supplement addition iron again, be reduced
The cost of production；
(5) impurity in the product provided by the invention from the method that salt lake original brine extracts low concentration lithium, extracted
Few, purity is high advantageously reduces subsequent purifying difficulty and cost.
Embodiment
Embodiment 1
(1) iron content organic phase is prepared:
Take 100mL without the chloride type salt lake original brine of evaporate brine evaporation and concentration and de- potassium sodium, detection obtains Li therein+
Mass concentration be 0.05g/L；Then, it is 5:1 according to Fe:Li molar concentration rate, weighs the FeCl of 9.737g3·6H2O solid
Powder is dissolved in the HCl mass fraction of 1000mL to obtain iron-containing aqueous hydrochloric acid solution in 20% concentrated hydrochloric acid；
It takes the tributyl phosphate of 50mL to be dissolved in 50mL kerosene, obtains organic extraction agent solution；
Organic extraction agent solution and iron-containing combined are taken upper organic phase, contained after standing split-phase
Iron organic phase.
(2) it is saponified iron content organic phase:
It is mixed by lower layer's water phase that split-phase separates is stood after step (1) the iron content organic phase and 100mL step (3) extraction
It closes, obtains two-phase mixture；
Take 10mL, the sodium hydrate aqueous solution that concentration is 4mol/L is dripped under agitation with the speed of 0.1mL/min
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) it extracts:
Step (1) described 100mL without evaporate brine evaporation and concentration and de- potassium sodium salt lake original brine in hydrochloric acid is added dropwise, adjust
Section obtains extraction with former brine to pH=2；
Step (2) the saponification iron content organic phase is mixed with the extraction with former brine.After standing split-phase, upper layer is taken to have
Machine phase obtains extraction lithium load organic phases；The lithium content in lower layer's raffinate water phase is detected, Li is calculated+Extraction yield be 85%.
(4) pickling:
By step (3) the extraction lithium load organic phases and 50mL, chlorination lithium concentration be 0.1mol/L, concentration of hydrochloric acid is
The pickling solution of 0.5mol/L mixes；After standing split-phase, upper organic phase is taken, pickling lithium load organic phases are obtained.
(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；Lower layer's water phase is taken, rich lithium aqueous solution is obtained；Upper organic phase is taken, is regenerated
Organic phase, regeneration organic phase return step (2) are recycled.
Embodiment 2
(1) iron content organic phase is prepared:
Take 500mL without the chloride type salt lake original brine of evaporate brine evaporation and concentration and de- potassium sodium, detection obtains Li therein+
Mass concentration be 0.2g/L；Then, it is 100:1 according to Fe:Li molar concentration rate, weighs the FeCl of 778.96g3〃6H2O solid
Powder is dissolved in the HCl mass fraction of 1000mL to obtain iron-containing aqueous hydrochloric acid solution in 37% concentrated hydrochloric acid；
It takes the butyl phosphonic acids dibutyl ester of 200mL to be dissolved in 2000mL kerosene, obtains organic extraction agent solution；
Organic extraction agent solution and iron-containing combined are taken upper organic phase, contained after standing split-phase
Iron organic phase.
(2) it is saponified iron content organic phase:
Take 500mL step (1) the iron content organic phase and the old brine after evaporate brine evaporation and concentration and de- potassium sodium of 50mL
Mixing, obtains two-phase mixture；
Take 10mL, the sodium hydrate aqueous solution that concentration is 4mol/L is added dropwise under agitation with the speed of 1mL/min
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) it extracts:
With 1 step of embodiment (3), it is computed, Li+Extraction yield be 87%.
(4) pickling:
By step (3) the extraction lithium load organic phases and 10mL, chlorination lithium concentration be 1mol/L, concentration of hydrochloric acid is
The pickling solution of 0.5mol/L mixes；After standing split-phase, upper organic phase is taken, pickling lithium load organic phases are obtained.
(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；Lower layer's water phase is taken, rich lithium aqueous solution is obtained；Upper organic phase is taken, is regenerated
Organic phase, the regeneration organic phase return step (2) are recycled.
Embodiment 3
(1) iron content organic phase is prepared:
Take 50mL without the chloride type salt lake original brine of evaporate brine evaporation and concentration and de- potassium sodium, detection obtains Li therein+
Mass concentration be 1.0g/L；It is 20:1 according to Fe:Li molar concentration rate, weighs the FeCl of 389.48g36H2O solid powder
End is dissolved in the HCl mass fraction of 500ml to obtain iron-containing aqueous hydrochloric acid solution in 37% concentrated hydrochloric acid；
It takes the trioctyl phosphine oxide of 300mL to be dissolved in 200mL kerosene, obtains organic extraction agent solution；
Take upper layer organic after standing split-phase the organic extraction agent solution and the iron-containing combined
Phase obtains iron content organic phase.
(2) it is saponified iron content organic phase:
Take 100mL step (1) the iron content organic phase and the old brine after evaporate brine evaporation and concentration and de- potassium sodium of 100mL
Mixing, obtains two-phase mixture；
Take 1mL, the sodium hydrate aqueous solution that concentration is 6mol/L is added dropwise under agitation with the speed of 0.1mL/min
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) it extracts:
Step (1) described 50mL without evaporate brine evaporation and concentration and de- potassium sodium salt lake original brine in hydrochloric acid is added dropwise, adjust
Section obtains extraction with former brine to pH=2；
Step (2) the saponification iron content organic phase is mixed with the extraction with former brine；After standing split-phase, upper layer is taken to have
Machine phase obtains extraction lithium load organic phases.The lithium content in lower layer's raffinate water phase is detected, Li is calculated+Extraction yield be 90%.
(4) pickling:
By step (3) the extraction lithium load organic phases and 10mL, chlorination lithium concentration be 0.5mol/L, concentration of hydrochloric acid is
The pickling solution of 1.0mol/L mixes；After standing split-phase, upper organic phase is taken, pickling lithium load organic phases are obtained.
(5) it is stripped:
By step (4) the pickling lithium load organic phases and 10mL, the combined that concentration is 9.0mol/L；It is quiet
After setting split-phase, upper and lower two layers of solution is obtained；Lower layer's water phase is taken, rich lithium aqueous solution is obtained；Upper organic phase is taken, obtaining regeneration has
Machine phase, the regeneration organic phase return step (2) are recycled.
Embodiment 4
(1) iron content organic phase is prepared:
Take 500mL without the chloride type salt lake original brine of evaporate brine evaporation and concentration and de- potassium sodium, detection obtains Li therein+
Mass concentration be 0.1g/L；Then, it is 60:1 according to Fe:Li molar concentration rate, weighs the FeCl of 116.84g3·6H2O solid
Powder is dissolved in the HCl mass fraction of 500mL to obtain iron-containing aqueous hydrochloric acid solution in 37% concentrated hydrochloric acid；
The tributyl phosphate of 150mL and the butyl phosphonic acids dibutyl ester of 150mL are taken, is dissolved in 200mL kerosene, obtains after mixing
To organic extraction agent solution；
Take upper layer organic after standing split-phase the organic extraction agent solution and the iron-containing combined
Phase obtains iron content organic phase.
(2) it is saponified iron content organic phase:
Take 100mL step (1) the iron content organic phase and the old brine after evaporate brine evaporation and concentration and de- potassium sodium of 100mL
Mixing, obtains two-phase mixture；
Take 10mL, the sodium hydrate aqueous solution that concentration is 4mol/L is added dropwise under agitation with the speed of 1mL/min
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) it extracts:
With 3 step of embodiment (3), it is computed, Li+Extraction yield be 89%.
(4) pickling:
By step (3) the extraction lithium load organic phases and 100mL, chlorination lithium concentration be 0.5mol/L, concentration of hydrochloric acid is
The pickling solution of 1.0mol/L mixes；After standing split-phase, upper organic phase is taken, pickling lithium load organic phases are obtained.
(5) it is stripped:
By step (4) the pickling lithium load organic phases and 10mL, the combined that concentration is 9.0mol/L；It is quiet
After setting split-phase, upper and lower two layers of solution is obtained；Lower layer's water phase is taken, rich lithium aqueous solution is obtained；Upper organic phase is taken, obtaining regeneration has
Machine phase, the regeneration organic phase return step (2) are recycled.
Embodiment 5
(1) iron content organic phase is prepared:
Take 300mL without the chloride type salt lake original brine of evaporate brine evaporation and concentration and de- potassium sodium, detection obtains Li therein+
Mass concentration be 4.0g/L；Then, it is 5:1 according to Fe:Li molar concentration rate, weighs the FeCl of 778.96g3·6H2O solid
Powder is dissolved in the HCl mass fraction of 1000mL to obtain iron-containing aqueous hydrochloric acid solution in 32% concentrated hydrochloric acid；
The tributyl phosphate of 200mL and the trioctyl phosphine oxide of 200mL are taken, is dissolved in 200mL kerosene, is had after mixing
Machine extracts agent solution；
Organic extraction agent solution and iron-containing combined are taken upper organic phase, contained after standing split-phase
Iron organic phase.
(2) it is saponified iron content organic phase:
Take 100mL step (1) the iron content organic phase and the old brine after evaporate brine evaporation and concentration and de- potassium sodium of 100mL
Mixing, obtains two-phase mixture；
Take 2mL, the sodium hydrate aqueous solution that concentration is 6mol/L is added dropwise under agitation with the speed of 0.5mL/min
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) it extracts:
It is identical with embodiment 3 step (3), it is computed, Li+Extraction yield be 92%.
(4) pickling:
By step (3) the extraction lithium load organic phases and 10mL, chlorination lithium concentration be 0.5mol/L, concentration of hydrochloric acid is
The pickling solution of 2.0mol/L mixes；After standing split-phase, upper organic phase is taken, pickling lithium load organic phases are obtained.
(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 setting split-phase, upper and lower two layers of solution is obtained；Lower layer's water phase is taken, rich lithium aqueous solution is obtained；Upper organic phase is taken, obtaining regeneration has
Machine phase, the regeneration organic phase return step (2) are recycled.
It is described the invention in detail above in conjunction with detailed description 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,
Can be with various equivalent substitutions, modifications or improvements are made to the technical scheme of the invention and its embodiments, these each fall within the present invention
In the range of.Scope of protection of the present invention is subject to the appended claims.
Claims (11)
1. a kind of method for extracting low concentration lithium from salt lake original brine, which is characterized in that this method comprises:
Ferric iron compound is dissolved in hydrochloric acid by step 1), is mixed with the diluent dissolved with neutral phosphorus extractant, and iron content is made
Organic phase；
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 HFeCl4Aqueous solution；
Neutral phosphorus extractant is dissolved in boiling point under normal pressure to obtain in 200 DEG C or more of aliphatic hydrocarbon or arene diluent
Organic extraction agent solution；
The organic extraction agent solution is contained into HFeCl with described4Aqueous solution mixing, stand split-phase after, take upper organic phase, obtain
To iron content organic phase；
Step 2), saponification treatment step 1) in regenerate organic phase obtained in iron content organic phase and/or step 5) obtained, obtain
It is saponified iron content organic phase；
Wherein, it will be obtained in regeneration organic phase obtained in the iron content organic phase and/or step 5) that are prepared in step 1) and step 3)
After the saponification bottom liquid mixing arrived, inorganic base is added in the mixing liquid and carries out saponification process；
The inorganic base is selected from sodium hydroxide, potassium hydroxide or ammonium hydroxide；
Become extraction salt lake original brine after step 3), the acidification of salt lake original brine, and it is carried out using saponification iron content organic phase
Extraction obtains extraction lithium load organic phases and is saponified bottom liquid；
The salt lake original brine acidification is to pH=1~5；
The concentration of lithium is 0.05~1g/L in the salt lake original brine；
Step 4) extracts lithium load organic phases using pickling solution pickling, obtains pickling lithium load organic phases；In the pickling solution
Contain hydrochloric acid and lithium chloride；
Pickling lithium load organic phases are mixed with hydrochloric acid solution and are stripped by step 5), are obtained rich lithium aqueous solution and are regenerated organic
Phase；
The concentration of the hydrochloric acid solution is 6.0~12.0mol/L.
2. the method according to claim 1, wherein in the step 1), iron ion and salt lake original halogen in hydrochloric acid
The molar concentration rate of lithium ion is 5:1~100:1 in water.
3. the method according to claim 1, wherein in the step 1), iron ion and salt lake original halogen in hydrochloric acid
The molar concentration rate of lithium ion is 20:1~60:1 in water.
4. the method according to claim 1, wherein 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.
5. according to the method described in claim 4, it is characterized in that, in the step 2), the iron content organic phase and/or regeneration
Organic phase, the volume ratio with saponification bottom liquid are 1:1~10:1.
6. it is the method according to claim 1, wherein in step 2), inorganic base is soluble in water, it obtains inorganic
Then aqueous alkali is added dropwise in mixing liquid and is saponified, the concentration of the inorganic base aqueous solution is 1~6mol/L；
The rate of addition of inorganic base aqueous solution is 0.1~1.0mL/min.
7. according to the method described in claim 6, it is characterized in that, the concentration of the inorganic base aqueous solution is 4 in step 2)
~6mol/L.
8. the method according to claim 1, wherein in the step 3), when extraction, saponification iron content organic phase with
Extraction is 10:1~1:1 with the volume ratio of former brine.
9. method according to claim 1 or 8, which is characterized in that in the step 3), when extraction, saponification iron content is organic
It is mutually 5:1~1:1 with the volume ratio of former brine with extraction.
10. the method according to claim 1, wherein in the step 4), the concentration of hydrochloric acid is 0.5~
2.0mol/L, the concentration of lithium chloride are 0.1~1.0mol/L.
11. according to the method described in claim 10, it is characterized in that, regenerating and containing in organic phase in the step 5)
HFeCl4, can individually put into step 2) be recycled or with iron content obtained in step 1) is organic mix after put into step 2)
Middle recycling.
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