CN108004420A - The technique that lithium is extracted from the bittern of alkalescence containing lithium based on centrifugal extractor - Google Patents

The technique that lithium is extracted from the bittern of alkalescence containing lithium based on centrifugal extractor Download PDF

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CN108004420A
CN108004420A CN201711295127.0A CN201711295127A CN108004420A CN 108004420 A CN108004420 A CN 108004420A CN 201711295127 A CN201711295127 A CN 201711295127A CN 108004420 A CN108004420 A CN 108004420A
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extraction
lithium
organic phase
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bittern
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CN108004420B (en
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李丽娟
张利诚
时东
彭小五
聂峰
宋富根
韩文生
姬连敏
李慧芳
宋雪雪
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Qinghai Institute of Salt Lakes Research of CAS
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/04—Halides
    • 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
    • C22B3/409—Mixtures at least one compound being an organo-metallic compound
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
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    • 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

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Abstract

The invention discloses a kind of technique that lithium is extracted from the bittern of alkalescence containing lithium based on centrifugal extractor, it comprises the following steps：Aqueous phase extracted is provided, extraction organic phase, extraction step, washing step, stripping steps and regeneration step are provided.Process according to the invention uses brand-new extraction system, lithium is extracted from the brine systems of alkalescence containing lithium, and it is determined that the extracting and washing based on centrifugal extractor is stripped regenerated full-flow process first, and not only rest in the basic research of extraction workshop section, finally determine the series of each workshop section that the extraction system is adapted to, stream than and the technological parameter such as each reagent concentration, there is provided the industrialized producing technology route based on centrifugal extractor；The technique that lithium is extracted from the bittern of alkalescence containing lithium is particularly suitable for the filtrate systems that lithium chloride solution produces during lithium carbonate product is prepared, wherein further to extract lithium from this, it is achieved thereby that the real comprehensive cyclic utilization of salt lake bittern, has practical significance.

Description

The technique that lithium is extracted from the bittern of alkalescence containing lithium based on centrifugal extractor
Technical field
The invention belongs to salt lake chemical technology field, it relates in particular to it is a kind of based on centrifugal extractor from alkali containing lithium Property bittern in extract lithium technique.
Background technology
Lithium is metal most light in nature, has extremely strong electro-chemical activity, its metal and compound are widely used In the explosion of industry and field as thermonuclear fusion (hydrogen bomb) such as glass, ceramic aluminium metallurgy, organic chemical industry, aerospace, nuclear fusions Thing, the high-performance propellant of aircraft, rocket and guided missile and the shielding material of nuclear reactor.Lithium battery is higher than common batteries by 4~ 30 times of energy storage and there is good performance, be used as the promotion of torpedo, submarine, space vehicle very early Power.Lithium aluminium, lithium magnesium alloy are high-strength light, are aerospace and the good material of rocket, are quite favored by military project, Space Industry.21 In century, with surging and low price lithium salts the production to clean energy resource demand, the lithium energy will likely have a deep effect on the life of people It is living, thus lithium is referred to as " energy metal of 21 century ".
Extracting the effective ways of lithium from salt lake bittern at present includes solvent extraction, and solvent extraction is all inevitable Ground employs FeCl3As synergic reagent so that extract organic phase density increase, two-phase density contrast reduces, to extraction and stripping apparatus It is more demanding；Meanwhile introduce FeCl3Afterwards, it is difficult when with alkali to extractant regeneration, it is necessary to very accurately flow control System, no it will cause the problems such as extraction yield decline or extractant emulsification failure.Further, since contain synergic reagent in organic phase FeCl3, this requires extracting feed liquid (bittern) faintly acid must be kept, Fe hydrolysis is otherwise will result in, into extraction workshop section Bittern must carry out acidification, and lithium exists with the universal association of boron in Qinghai Salt Lake, and acidization necessarily has boric acid precipitation, needs Filtration treatment is wanted, therefore the extraction for lithium in alkaline system is without applicability.And can only be real currently used for the extractant majority of lithium Existing Separation of Li and Mg, it is very poor for alkali metal system effect of extracting.In short, due to synergic reagent FeCl3Presence so that technological process Complex, technique controlling difficulty is very big, and equipment investment is big.
At the same time, in the extraction equipment used in current solvent extraction industry, centrifugal extractor has facility compact, passes Matter is efficient and solute hold-up is small, its extraction process has the following advantages that：Extraction process equilibration time is short, material lagging amount Less, split-phase is rapid；Parameter adjustment is swift in response, is easy to automate；Equipment volume is small, and plant area is small, first installed reagents, thing Doses is small, small investment；Equipment is closed, and working environment is good.
Therefore, be badly in need of research and development it is a kind of based on centrifugal extractor and suitable for from alkaline bittern extraction lithium process, Instructed so as to provide technique for the production of actual industrial metaplasia.
The content of the invention
To solve the above-mentioned problems of the prior art, the present invention provides it is a kind of based on centrifugal extractor from alkali containing lithium Property bittern in extract the technique of lithium, which, can be from the brine systems of alkalescence containing lithium using being different from traditional extraction system Lithium therein is extracted, and extraction-washing-back extraction-regenerated full-flow process based on centrifugal extractor is determined, for reality Industrialized production provides processing route.
In order to reach foregoing invention purpose, present invention employs following technical solution：
A kind of technique that lithium is extracted from the bittern of alkalescence containing lithium based on centrifugal extractor, including step：
Aqueous phase extracted is provided：Aqueous phase extracted is used as using the bittern of alkalescence containing lithium；Wherein, the pH of the bittern of alkalescence containing lithium is 8 ~14, in the bittern of alkalescence containing lithium, Li+Mass concentration be 0.05g/L~10g/L, Na+Mass concentration be no more than 80g/L, K+Mass concentration be no more than 80g/L, Mg2+Mass concentration be no more than 1g/L, Ca2+Mass concentration be no more than 1g/ L；
Extraction organic phase is provided：Extractant, synergic reagent and kerosene are mixed, prepare extraction organic phase；Wherein, described Extract in organic phase, the substance withdrawl syndrome of the extractant and the synergic reagent is 0.05mol/L~0.6mol/L, described Any one of extractant in benzoyltrifluoroacetone, furoyltrifluoroacetone, thioyl trifluoroacetone, the association Extract any one of agent in trioctyl phosphine oxide, tributyl phosphate, trialkyl phosphine, 2- ethylhexyl phosphoric acids；
Extraction step：By the extraction organic phase and the aqueous phase extracted according to stream than being 1:10~10:1 in the first centrifugation Mixing in device assembly is extracted, and carries out the extraction of 2~15 stage countercurrents, split-phase obtains raffinate and load organic phases；
Washing step：, will using the hydrochloric acid solution of 0.1mol/L~12mol/L or the lithium-containing solution of identical acidity as cleaning solution It is 5 that the load organic phases and the cleaning solution compare according to stream:1~80:1 mixes in the second Centrifugical extraction device assembly, goes forward side by side 2~15 stage countercurrent of row washs, and split-phase obtains washing extraction raffinate and washing organic phase；
Stripping steps：Using the hydrochloric acid solution of 1mol/L~12mol/L as strip liquor, by the washing organic phase and described anti- Extract liquid according to stream than being 5:1~80:1 mixes in the 3rd Centrifugical extraction device assembly, and carries out the back extraction of 2~15 stage countercurrents, split-phase Obtain lithium chloride solution and empty organic phase；
Regeneration step：1 grade of regeneration is carried out to the empty organic phase as regenerated liquid using alkaline solution or 2~5 stage countercurrents regenerate, Split-phase obtains regeneration extraction raffinate and regeneration organic phase；Wherein, the empty organic phase and the stream of the regenerated liquid compare for 1:5~5:1.
Further, in the washing step, the concentration of lithium is organic not less than the load in the washing organic phase The 80% of the concentration of lithium in phase；In the washing organic phase in addition to lithium metal total concentration be not higher than the load organic phases in remove The 5% of the total concentration of the outer metal of lithium.
Further, in the regeneration step, the loading capacity of the regeneration organic phase is organic not less than the extraction The 90% of the loading capacity of phase.
Further, the alkaline solution be substance withdrawl syndrome be 0.05mol/L~4mol/L hydroxide solution, The ammonia solution or substance withdrawl syndrome that substance withdrawl syndrome is 0.05mol/L~4mol/L are 0.05mol/L~4mol/L's Any one in carbonate solution.
Further, anion is selected from Cl in the bittern of alkalescence containing lithium-、SO4 2-、CO3 2-、NO3 -At least one of.
Further, in the offer aqueous phase extracted step, by adding sodium hydroxide solution, carbon into bittern containing lithium Acid sodium solution or ammonia solution obtain the bittern of alkalescence containing lithium.
Further, the substance withdrawl syndrome of the sodium hydroxide solution, sodium carbonate liquor or ammonia solution is 0.05mol/L~4mol/L.
Further, before sodium hydroxide solution, sodium carbonate liquor or ammonia solution is added into the bittern containing lithium, The bittern containing lithium is pre-processed, removes solid precipitation therein and suspended matter.
Further, before the bittern of alkalescence containing lithium forms the aqueous phase extracted, to the bittern of alkalescence containing lithium into Row pretreatment, removes solid precipitation therein and suspended matter.
Further, the technique further includes circulation step：The regeneration organic phase is back in the extraction step As extraction organic phase, and repeat extraction step, washing step, stripping steps and the regeneration step.
Further, in the extraction step, the extraction organic phase is by the light of the first Centrifugical extraction device assembly Phase entrance is pumped into, and the aqueous phase extracted is pumped into by the heavy liquid inlet of the first Centrifugical extraction device assembly；In the washing step In, the load organic phases are pumped into by the light phase inlet of the second Centrifugical extraction device assembly, and the cleaning solution is by described second The heavy liquid inlet of Centrifugical extraction device assembly is pumped into；In the stripping steps, the washing organic phase is extracted by the described 3rd centrifugation The light phase inlet of device assembly is taken to be pumped into, the strip liquor is pumped into by the heavy liquid inlet of the 3rd Centrifugical extraction device assembly.
Further, in the regeneration step, then generating apparatus is selected from centrifugal extractor, mixer-settler, pipe reaction Any one in device.
Beneficial effect：
(1) present invention by using bixanthone compound as extractant, neutral phosphorus oxygen class compound as synergic reagent, reality The purpose that lithium therein is extracted from the bittern of alkalescence containing lithium is showed；Based on the extraction system of TBP from salt lake in compared with prior art The method that lithium is extracted in bittern, avoids synergic reagent FeCl3Use, it also avoid two-phase density contrast in extraction process it is less than normal, The problems such as technique controlling difficulty is big.
(2) process according to the invention realizes extraction-washing-back extraction-regenerated full-flow process, and not only stops Extraction workshop section basic research on, finally determine the extraction system adapt to each workshop section of centrifugal extractor series, The technological parameters such as organic phase and the stream ratio of water phase and each reagent concentration, are truly realized industrialized production first；The technique is outstanding It is suitable for the filtrate systems that lithium chloride solution produces during lithium carbonate product is prepared, with from the wherein lithium carbonate saturation Lithium is further extracted in alkaline filtrate brine systems, realizes the real comprehensive cyclic utilization of salt lake bittern.
(3) water-soluble small, its in raffinate of process according to the invention, wherein extractant, synergic reagent and diluent Remaining component does not change substantially, and organic phase can be recycled by regeneration step, and three wastes produce, and the lithium rate of recovery is reachable To 90% or so even more high.
(4) process according to the invention is simple, easily controllable, and operation is continuous, reliability is high and the degree of automation is high；Should Technique effectively can separate and recover lithium from the bittern of alkalescence containing lithium, and the purity through lithium chloride in back extraction gained lithium chloride solution is high, miscellaneous Matter is few, can be used as preparing lithium chloride products or lithium carbonate product.
Brief description of the drawings
What is carried out in conjunction with the accompanying drawings is described below, above and other aspect, feature and advantage of the embodiment of the present invention It will become clearer, in attached drawing：
Fig. 1 is the technique stream of the technique that lithium is extracted from the bittern of alkalescence containing lithium based on centrifugal extractor according to the present invention Cheng Tu；
Fig. 2 is the extraction principle schematic of extractant according to the present invention；
Fig. 3 is the extraction principle schematic of extraction system according to the present invention.
Embodiment
Hereinafter, with reference to the accompanying drawings to detailed description of the present invention embodiment.However, it is possible to come in many different forms real Apply the present invention, and the specific embodiment of the invention that should not be construed as limited to illustrate here.Conversely, there is provided these implementations Example is in order to explain the principle of the present invention and its practical application, so that others skilled in the art are it will be appreciated that the present invention Various embodiments and be suitable for the various modifications of specific intended application.
The present invention provides a kind of technique that lithium is extracted from the bittern of alkalescence containing lithium based on centrifugal extractor, which carries Supply to include extraction-washing-back extraction-regenerated full-flow process based on centrifugal extractor, and for the level of each workshop section Number, organic phase are confirmed with technological parameters such as the stream ratio of water phase and each reagent concentrations, good to form an extraction efficiency Process, so as to provide process route for the industrialization expanding production based on centrifugal extractor；Should be from the bittern of alkalescence containing lithium It is middle extraction lithium technique be particularly suitable for the filtrate systems that lithium chloride solution produces during lithium carbonate product is prepared, with from this Lithium is further extracted wherein in the alkaline filtrate brine systems of lithium carbonate saturation, it is achieved thereby that the real synthesis of salt lake bittern is followed Ring utilizes, and has practical significance.
With reference to Fig. 1, should be comprised the following steps based on the technique that lithium is extracted from the bittern of alkalescence containing lithium of centrifugal extractor：
Step S1, aqueous phase extracted is provided.
Specifically, aqueous phase extracted is used as using the bittern of alkalescence containing lithium；Wherein, the pH of the bittern of alkalescence containing lithium is 8~14, and And in the bittern of alkalescence containing lithium, Li+Mass concentration be 0.02g/L~10g/L, Na+Mass concentration be no more than 80g/L, K+Mass concentration be no more than 80g/L, Mg2+Mass concentration be no more than 1g/L, Ca2+Mass concentration be no more than 1g/L.
Anion in the bittern of alkalescence containing lithium can be Cl-、SO4 2-、CO3 2-、NO3 -Etc. the master for representing salt lake bittern type Anion is wanted, or the above-mentioned anion introduced during the comprehensive utilization of salt lake bittern；Carbon is such as prepared using lithium chloride solution During sour lithium product, generally require and add sodium carbonate into the system, so that Li therein+Separated out with the formation of lithium carbonate precipitation, And obtain lithium carbonate product through separation of solid and liquid, and filtered filtrate wherein lithium carbonate saturation for waiting operation to be formed, and contain Na+, And in alkalescence, for the filtrate can method using the present invention to Li therein+Further recycled, to form chlorination Lithium solution, and the lithium chloride solution is recycled but also as the raw material for preparing lithium carbonate product.
What deserves to be explained is if the initial pH of the bittern containing lithium is unable to reach above-mentioned requirements, can be by adding thereto Sodium hydroxide solution, sodium carbonate liquor or ammonia solution come obtain above-mentioned pH be 8~14 the bittern of alkalescence containing lithium；These are used to adjust The substance withdrawl syndrome of the sodium hydroxide solution of whole pH, sodium carbonate liquor or ammonia solution is both preferably 0.05mol/L~4mol/ L。
Meanwhile under normal circumstances, if the above-mentioned bittern of alkalescence containing lithium that need not adjust pH or need adjust pH bittern containing lithium For actual bittern when, can be there are certain impurity, therefore lithium alkalescence bittern will contained as before aqueous phase extracted or to halogen containing lithium Before water carries out pH adjustings, preferably pre-processed, to remove solid precipitation therein and suspended matter etc..
Step S2, extraction organic phase is provided.
Specifically, extractant, synergic reagent and kerosene are mixed, prepares and form extraction organic phase.
In the extraction organic phase, the substance withdrawl syndrome of extractant and synergic reagent control for 0.05mol/L~ 0.6mol/L, extractant are any one in benzoyltrifluoroacetone, furoyltrifluoroacetone, thioyl trifluoroacetone Kind, any one of synergic reagent in trioctyl phosphine oxide, tributyl phosphate, trialkyl phosphine, 2- ethylhexyl phosphoric acids.
The alkali metal of the first main group, which easily loses outermost s electronics, in periodic table becomes M+Ion, alkali metal from Son belongs to hard lewis acid, these cations generally can be with oxygen containing coordinating group (such as carbonyl, phosphorus carbonyl strong lewis base) Form the complex compound compared with temperature.It is according to the degree of stability for forming Lewis Acids and Bases pair different, it is mutual to realize alkali metal Separation.
The solvent extraction of lithium is not achieved by general extraction system, optionally extracts lithium, and it is special just to have to look for Extractant and extraction system.According to the characteristic of lithium, the requirement to dentate, which must is fulfilled for following several respects, could occur effectively Extract effect：Meet Li+Tetrahedral coordination structure requirement；With energy and Li+The chelating functional group of stronger primary bond is formed, The carbonyl complex that can occur such as-OH or in extraction process with Enol forms；O or N dentates with hard base；With Li+Form stable chelate ring.
Above-mentioned extractant benzoyltrifluoroacetone (hereinafter referred to as HBTA) used in the present invention, furoyl trifluoropropyl Ketone (hereinafter referred to as HFTA), thioyl trifluoroacetone (hereinafter referred to as HTTA) belong to diketone compound, and diketone is a kind of acid Property chelating extractant, it is mainly the hydroxyl and Li using carbonyl or tautomerism that it, which extracts the mechanism of lithium,+With reference to；Specifically, As shown in Fig. 2, there are the tautomeric equilibrium of its ketone formula (I) and enol formula (II) in diketone, the Li in extraction process+Can be with Relatively stable chelate structure (III) is formed with diketone；Diketone after metal ion-chelant with being in neutrality, this inner complex salt is in organic phase Solubility it is very small, if as shown in figure 3, there is dentate (S) to exist, the neutral extraction to be formed and can extracted can be complexed with inner complex salt and is closed Thing, this dentate are just known as synergic reagent, i.e., trioctyl phosphine oxide (hereinafter referred to as TOPO), tricresyl phosphate fourth used in the present invention Ester (hereinafter referred to as TRPO), trialkyl phosphine, 2- ethylhexyl phosphoric acids.Usually extract when diketone is applied to extraction lithium with neutrality association Agent forms synergistic extractant system to be extracted, to meet Li+Four-coordination structure；In addition, diketone and Li after tautomerism+Coordination Six Yuans stable chelate rings are formd afterwards.Meanwhile above-mentioned coordination chelates mode mainly in Li+、Na+、K+Deng alkali metal and Ca2+、Mg2+Deng alkaline-earth metal, but the stability between the chelate that is formed of different cations can also have differences, meanwhile, no Stability between the chelate that isostructural diketone and neutral synergic reagent are formed also can be not each there are larger difference The technique that kind diketone and each neutral synergic reagent may be applicable to the present invention.
Specifically, diketone compound of the present invention is respectively provided with trifluoromethyl group, the group as extractant With stronger Draw electronic effect, strengthen the enolizability of diketone compound, and then and Li+Can preferably it combine；And Other compounds with double ketone structure, such as benzoyl acetone, dibenzoyl methane, due to not possessing drawing electron group, its To Li+Selectivity it is relatively weak, correspondingly, lithium effect of extracting is poor.In other words, though diketone compound is used as lithium ion Extractant utilize double ketone structure in carbonyl or tautomerism hydroxyl and Li+Ring this principle is combined to form, but simultaneously Each non-diketone compound can all become good lithium extractant.
More specifically, synergic reagent of the present invention is the neutral phosphine compound containing phosphine oxygen double bond, due to it Stronger electron donation, makes it have stronger Association stripping effect；And other contain C=O bond or nitrogen oxygen double bond, sulfur-to-oxygen double bond Synergic reagent due to its weaker electron donation, the Association stripping effect that it is produced is also relatively weak.
What deserves to be explained is although according to above-mentioned extraction principle, the extractant and synergic reagent also can be to Ca2+、Mg2+Deng alkali Earth metal produces complexing and is extracted, but the aqueous phase extracted based on the present invention is alkaline system, therefore wherein free Ca2+、Mg2+Will be very low Deng alkaline-earth metal concentration；That is, cation is mainly alkali metal in the aqueous phase extracted.
Step S3, extract.
Specifically, extracting workshop section is carried out based on centrifugal extractor；Specially will extraction organic phase and aqueous phase extracted It is 1 according to flowing than (hereinafter referred to as extract stream ratio):10~10:1 mixing, and the extraction of 2~15 stage countercurrents is carried out, after balance to be extracted Split-phase, obtains raffinate and load organic phases.
More specifically, extraction workshop section of the invention is using multi-stage counter current extraction, it is therefore desirable to by corresponding number Centrifugal extractor is connected, to form the first Centrifugical extraction device assembly；Usually, each centrifugal extractor is equipped with light phase inlet With heavy liquid inlet and light phase export and heavy out, extraction organic phase is entered by light phase inlet, and aqueous phase extracted is then by weight Phase entrance enters, and the raffinate produced after extraction is then discharged by heavy out, and load organic phases are discharged by light phase export.
Preferably due to which the present invention is a kind of industrialization process based on centrifugal extractor, its dosage is larger, therefore, on State extraction organic phase, aqueous phase extracted to add by way of being pumped into, the reagent addition manner of following workshop section is similar.
What deserves to be explained is after a certain extraction organic phase is determined, you can existed by measuring different extraction organic phases in advance Single-stage extraction rate under different extract stream ratios (extraction phase when extraction time) in corresponding extraction basic research, then in conjunction with extraction Balance isotherm is taken to determine the corresponding theoretical extraction series of its predetermined effect of extracting, finally on the basis of theory extracts series Fluctuation is no more than two-stage, determines final actual extraction series.It can thus be seen that during multi-stage counter current extraction, extraction Series, extract stream than it is definite be not self-existent technological parameter, but by mesh in extraction organic phase and aqueous phase extracted Mark ion concentration (refers specifically to Li in the present invention+) a unified interactional parameter combination together deciding on；In other words, If the concentration of object ion changes in aqueous phase extracted, finally the technological parameter of definite extraction workshop section may also occur It is corresponding to change, extract organic phase composition, extract stream than change similarly, to ultimately form a short series, extract organic phase less Inexpensive, the time-consuming short selection process of dosage.
Step S4, wash.
Specifically, it is right using the hydrochloric acid solution of 0.1mol/L~6mol/L or the lithium-containing solution of equal acidity as cleaning solution Load organic phases carry out the washing of 2~15 stage countercurrents, control the stream of load organic phases and cleaning solution than (hereinafter referred to as scrub stream ratio) For 5:1~80:1, split-phase obtains washing extraction raffinate and washing organic phase.
More specifically, washing room of the invention is washed using multi-stage countercurrent, it is therefore desirable to by corresponding number Centrifugal extractor is connected, to form the second Centrifugical extraction device assembly；Load organic phases are entered by light phase inlet, and cleaning solution is by heavy phase Entrance enters, and the washed rear washing extraction raffinate produced is then discharged by heavy out, and washing organic phase is discharged by light phase export.
In extraction Li+During inevitably can because the competition of otheralkali metal ion extract and produce entrainment, therefore into Before row back extraction, it need to be washed by multi-stage countercurrent and remove this part entrainment alkali metal ion washing, it will be clear that in the mistake of washing Cheng Zhong, inevitably causes Li+Loss, therefore, during washing, general control Li+Loss late less than 20% and in addition to lithium Entrainment alkali metal eluting rate be not less than 95%；In other words, washed by multi-stage countercurrent so that lithium in washing organic phase Concentration is not less than 80% of the concentration of lithium in load organic phases, and washs the concentration of the alkali metal in addition to lithium in organic phase not higher than negative Carry organic phase in addition to lithium the concentration of alkali metal 5%.
Therefore, during above-mentioned multi-stage countercurrent washs, alkali metal contains according to lithium in load organic phases and in addition to lithium Amount, and above-mentioned washing purpose, carry out the specific concentration and scrub stream ratio for adjusting cleaning solution, so that the sun in washing organic phase Ion is mainly lithium.
Step S5, it is stripped.
Specifically, it is inverse to 2~15 grades of washing organic phase progress using the hydrochloric acid solution of 1mol/L~6mol/L as strip liquor The stream of stream back extraction, control washing organic phase and strip liquor is 5 than (hereinafter referred to as back extraction stream ratio):1~80:1, after stripping equilibria Split-phase, obtains lithium chloride solution and empty organic phase.
Stripping process is lithium by the process of organic opposite water phase transfer, equivalent to the back reaction of extraction process, therefore it is similar , can be by measuring the strip liquor of various concentrations in advance not after the content of lithium in washing organic phase is determined in extraction step With single-stage back extraction ratio of the back extraction stream than under, determine that it makes a reservation for the corresponding theory of back extraction effect then in conjunction with stripping equilibria thermoisopleth Series is stripped, finally fluctuation is no more than two-stage on the basis of theory is stripped series, determines final actual back extraction series.Thus As can be seen that although the technique of back extraction relatively extraction is slightly simple, the technological parameter being related to is also less slightly, in multi-stage countercurrent stripping process In, back extraction series, back extraction stream ratio definite liquid be not be self-existent technological parameter, but by target in washing organic phase from Sub- concentration (refers specifically to Li in the present invention+) and a unified interactional parameter combination together deciding on of strip liquor；Change Sentence is talked about, if the concentration of object ion changes in washing organic phase, finally the technological parameter of definite stripping section is It may also occur to change accordingly, strip liquor concentration, back extraction flow the change of ratio similarly, to ultimately form a short series, few back extraction Inexpensive, the time-consuming short selection process of liquid dosage.
Step S6, regenerate.
Due to obtained after back extraction have in vain machine meet entrainment or extraction part strip liquor hydrochloric acid, this part hydrochloric acid is not if handled This part sky organic phase can be recycled to follow-up extraction workshop section and bring considerable influence, therefore in order to reduce extraction organic phase Waste, empty organic phase should be regenerated, so that it recovers the ability of extraction lithium, so that organic phase is recycled.
Specifically, using alkaline solution as regenerated liquid, 1 grade of regeneration is carried out to empty organic phase or 2~5 stage countercurrents regenerate, control The stream of the empty organic phase of system and regenerated liquid is 1 than (hereinafter referred to as recovery stream ratio):5~5:1, split-phase, which obtains regeneration extraction raffinate and regeneration, to be had Machine phase, such regeneration organic phase, which may return in step S3, to be used as extracting organic phase realization recycling.
More specifically, it is molten to may be selected from the hydroxide that substance withdrawl syndrome is 0.05mol/L~4mol/L for alkaline solution The ammonia solution or substance withdrawl syndrome that liquid, substance withdrawl syndrome are 0.05mol/L~4mol/L are 0.05mol/L~4mol/ Any one in the carbonate solution of L.
What deserves to be explained is in regenerative process, to regenerate extraction of the loading capacity of organic phase not less than extraction organic phase The 90% of the amount of trying to please is as regeneration target；Thus, it is necessary to by adjusting regeneration series and regenerated liquid during regenerated Species or its concentration reach above-mentioned regeneration requirements.
In this way, extracting lithium therein from the bittern of alkalescence containing lithium by above-mentioned steps S1~S6, the extraction process is more existing There is the extraction system using TBP as extractant in technology, without using synergic reagent FeCl3, it is close to avoid two-phase in extraction process The problems such as degree difference is less than normal, technique controlling difficulty is big；Also, extractant in the technique, synergic reagent and diluent it is water-soluble small, Remaining component does not change substantially in raffinate, and organic phase can be recycled by regeneration step, and three wastes produce, lithium The rate of recovery is more than 90%；Easily controllable meanwhile technique is simple, operating reliability is high, can effectively be separated from the bittern of alkalescence containing lithium Lithium is recycled, the purity through lithium chloride in back extraction gained lithium chloride solution is high, and impurity is few.
In addition, the technique is carried out based on centrifugal extractor, it is the actual life of industrialization for being different from extraction infrastest Production. art.It is understood by one of ordinary skill in the art, when extraction infrastest be extended in the present invention based on centrifugal extractor During actual industrial production, also need to consider influence of the operation stream than, the factor such as mixing intensity, split-phase situation, mass-transfer efficiency, these because Element extracts for actual production technique to be never related in infrastest；Meanwhile based on above-mentioned extension production institute band The new technological parameter come, can also impact other technological parameters, such as in above-mentioned technique, very big stream ratio occur (scrub stream ratio, back extraction stream ratio), this never considers in infrastest is extracted, on the one hand this is because stream ratio is to compare (volume ratio of organic phase and water phase) and time consider factor, and on the other hand, too big or too small compares in extraction base It can not almost accomplish in plinth experiment, such as above-mentioned 80:Volume of 1 stream than representing the organic phase and water phase that contact with each other Than for 80:1, this is can occur can not be real slight dissolve each other for too not big, contact interface because of two-phase volume differences in extracting infrastest The adverse consequences of existing split-phase；In other words, extract infrastest in be only capable of operation compared to it is moderate it is not too large will not be too small Technique, thus technique guidance of its technological parameter obtained to extension production is limited.Meanwhile as above-mentioned mass-transfer efficiency be also An important factor for needing to consider in commercial process, it influences extraction, whether back extraction plasma exchange reaches balance and reach To the time of balance, it is clear that if mass-transfer efficiency is too low, the corresponding equilibration time that reaches is too long, then corresponds to technique i.e. without existing Sincere justice.
It will be embodied and above-mentioned extracted based on centrifugal extractor from the bittern of alkalescence containing lithium by specific embodiment below The technique effect of the technique of lithium.
Embodiment 1
Lithium bittern will be contained to be pre-processed, remove the impurity such as solid, precipitation and suspended matter therein.
To Li+The sodium hydroxide solution of 2mol/L is added in the carbonate type bittern that concentration is 2g/L, its pH value is adjusted to 11, obtain aqueous phase extracted.
HBTA, TOPO are mixed to acquisition extraction organic phase with kerosene；Wherein, in the extraction organic phase, HBTA and TOPO Substance withdrawl syndrome be 0.3mol/L.
The extraction organic phase that above-mentioned preparation is completed is pumped into the light phase inlet of the first Centrifugical extraction device assembly, and by extraction water Corresponding heavy liquid inlet is mutually pumped into, it is 3 to control extract stream ratio:2, the two is carried out three-level in the first centrifugal extractor component internal Counter-current extraction, split-phase obtain raffinate and load organic phases.
Using the hydrochloric acid solution of 2mol/L as cleaning solution, the heavy liquid inlet of the second Centrifugical extraction device assembly is pumped into, and will Load organic phases are pumped into corresponding light phase inlet, and it is 20 to control scrub stream ratio:1, make the two in the second Centrifugical extraction device assembly Portion carries out three-level countercurrent washing, and split-phase obtains washing extraction raffinate and washing organic phase.
Using the refined hydrochloric acid solution of 6mol/L as strip liquor, the heavy liquid inlet of the 3rd Centrifugical extraction device assembly is pumped into, And washing organic phase is pumped into corresponding light phase inlet, back extraction stream is controlled than being 20:1, make the two in the 3rd centrifugal extractor group Three-level countercurrent reextraction is carried out inside part, split-phase obtains lithium chloride solution and empty organic phase.
Using the sodium carbonate liquor of 2mol/L as regenerated liquid, the heavy liquid inlet of mixer-settler is pumped into, and machine will be had in vain The light phase inlet of mixer-settler is mutually pumped into, it is 1 to control recovery stream ratio:1, the two is carried out two level inside mixer-settler inverse Stream regeneration, split-phase obtain regeneration extraction raffinate and regeneration organic phase.
Thus, the regeneration organic phase of above-mentioned acquisition can be re-used as the extraction organic phase in next cycle, recycle, with up to To the purpose for reducing organic reagent consumption, reducing pollution, reducing extraction cost.
After testing, the extraction yield of lithium is 95% in alkaline bittern containing lithium, and the overall recovery of lithium reaches 90%, gained after back extraction The purity of lithium chloride solution is more than 90%, can be used as producing the raw material of lithium chloride products and/or lithium carbonate product.
Embodiment 2
Lithium bittern will be contained to be pre-processed, remove the impurity such as solid, precipitation and suspended matter therein.
To Li+The sodium bicarbonate solution of 2mol/L is added in carbonate or sulfate type bittern that concentration is 2g/L, by it PH value is adjusted to 11, obtains aqueous phase extracted.
HFTA, TRPO are mixed to acquisition extraction organic phase with kerosene；Wherein, in the extraction organic phase, HFTA and TRPO Substance withdrawl syndrome be 0.4mol/L.
The extraction organic phase that above-mentioned preparation is completed is pumped into the light phase inlet of the first Centrifugical extraction device assembly, and by extraction water Corresponding heavy liquid inlet is mutually pumped into, it is 1 to control extract stream ratio:2, the two is carried out six grades in the first centrifugal extractor component internal Counter-current extraction, split-phase obtain raffinate and load organic phases.
Using the hydrochloric acid solution of 2mol/L as cleaning solution, the heavy liquid inlet of the second Centrifugical extraction device assembly is pumped into, and will Load organic phases are pumped into corresponding light phase inlet, and it is 10 to control scrub stream ratio:1, make the two in the second Centrifugical extraction device assembly Portion carries out four-stage counter-current washing, and split-phase obtains washing extraction raffinate and washing organic phase.
Using the refined hydrochloric acid solution of 6mol/L as strip liquor, the heavy liquid inlet of the 3rd Centrifugical extraction device assembly is pumped into, And washing organic phase is pumped into corresponding light phase inlet, back extraction stream is controlled than being 10:1, make the two in the 3rd centrifugal extractor group Pyatyi countercurrent reextraction is carried out inside part, split-phase obtains lithium chloride solution and empty organic phase.
Using the sodium hydroxide solution of 2mol/L as regenerated liquid, the heavy liquid inlet of mixer-settler is pumped into, and will have in vain Machine is mutually pumped into the light phase inlet of mixer-settler, and it is 5 to control recovery stream ratio:1, the two is carried out two level inside mixer-settler Counter-current regeneration, split-phase obtain regeneration extraction raffinate and regeneration organic phase.
Thus, the regeneration organic phase of above-mentioned acquisition can be re-used as the extraction organic phase in next cycle, recycle, with up to To the purpose for reducing organic reagent consumption, reducing pollution, reducing extraction cost.
After testing, the extraction yield of lithium is 96.5% in alkaline bittern containing lithium, and the overall recovery of lithium reaches 92%, institute after back extraction The purity for obtaining lithium chloride solution is more than 90%, can be used as producing the raw material of lithium chloride products and/or lithium carbonate product.
Embodiment 3
Lithium bittern will be contained to be pre-processed, remove the impurity such as solid, precipitation and suspended matter therein.
To Li+The sodium bicarbonate solution of 2mol/L is added in carbonate or chloride type bittern that concentration is 0.5g/L, will Its pH value is adjusted to 10.5, obtains aqueous phase extracted.
HFTA, TRPO are mixed to acquisition extraction organic phase with kerosene；Wherein, in the extraction organic phase, HFTA and TRPO Substance withdrawl syndrome be 0.2mol/L.
The extraction organic phase that above-mentioned preparation is completed is pumped into the light phase inlet of the first Centrifugical extraction device assembly, and by extraction water Corresponding heavy liquid inlet is mutually pumped into, it is 1 to control extract stream ratio:3, the two is carried out level Four in the first centrifugal extractor component internal Counter-current extraction, split-phase obtain raffinate and load organic phases.
Using the hydrochloric acid solution of 1mol/L as cleaning solution, the heavy liquid inlet of the second Centrifugical extraction device assembly is pumped into, and will Load organic phases are pumped into corresponding light phase inlet, and it is 10 to control scrub stream ratio:1, make the two in the second Centrifugical extraction device assembly Portion carries out four-stage counter-current washing, and split-phase obtains washing extraction raffinate and washing organic phase.
Using the refined hydrochloric acid solution of 3mol/L as strip liquor, the heavy liquid inlet of the 3rd Centrifugical extraction device assembly is pumped into, And washing organic phase is pumped into corresponding light phase inlet, back extraction stream is controlled than being 10:1, make the two in the 3rd centrifugal extractor group Pyatyi countercurrent reextraction is carried out inside part, split-phase obtains lithium chloride solution and empty organic phase.
Using the sodium hydroxide solution of 2mol/L as regenerated liquid, the heavy liquid inlet of mixer-settler is pumped into, and will have in vain Machine is mutually pumped into the light phase inlet of mixer-settler, and it is 10 to control recovery stream ratio:1, the two is carried out one inside mixer-settler Level regeneration, split-phase obtain regeneration extraction raffinate and regeneration organic phase.
Thus, the regeneration organic phase of above-mentioned acquisition can be re-used as the extraction organic phase in next cycle, recycle, with up to To the purpose for reducing organic reagent consumption, reducing pollution, reducing extraction cost.
After testing, the extraction yield of lithium is 95.5% in alkaline bittern containing lithium, and the overall recovery of lithium reaches 90.2%, after back extraction The high purity 98.6% of gained lithium chloride solution, can be used as producing the raw material of lithium chloride products and/or lithium carbonate product.
Embodiment 4
Lithium bittern will be contained to be pre-processed, remove the impurity such as solid, precipitation and suspended matter therein.
To Li+The sodium bicarbonate solution of 2mol/L is added in carbonate or sulfate type bittern that concentration is 8g/L, by it PH value is adjusted to 10.5, obtains aqueous phase extracted.
HFTA, TRPO are mixed to acquisition extraction organic phase with kerosene；Wherein, in the extraction organic phase, HFTA and TRPO Substance withdrawl syndrome be 0.5mol/L.
The extraction organic phase that above-mentioned preparation is completed is pumped into the light phase inlet of the first Centrifugical extraction device assembly, and by extraction water Corresponding heavy liquid inlet is mutually pumped into, it is 1 to control extract stream ratio:3, the two is carried out eight grades in the first centrifugal extractor component internal Counter-current extraction, split-phase obtain raffinate and load organic phases.
Using the hydrochloric acid solution of 3mol/L as cleaning solution, the heavy liquid inlet of the second Centrifugical extraction device assembly is pumped into, and will Load organic phases are pumped into corresponding light phase inlet, and it is 10 to control scrub stream ratio:1, make the two in the second Centrifugical extraction device assembly Portion carries out Pyatyi countercurrent washing, and split-phase obtains washing extraction raffinate and washing organic phase.
Using the refined hydrochloric acid solution of 6mol/L as strip liquor, the heavy liquid inlet of the 3rd Centrifugical extraction device assembly is pumped into, And washing organic phase is pumped into corresponding light phase inlet, back extraction stream is controlled than being 30:1, make the two in the 3rd centrifugal extractor group Six stage countercurrent back extraction are carried out inside part, split-phase obtains lithium chloride solution and empty organic phase.
Using the sodium carbonate liquor of 2mol/L as regenerated liquid, the heavy liquid inlet of mixer-settler is pumped into, and machine will be had in vain The light phase inlet of mixer-settler is mutually pumped into, it is 1 to control recovery stream ratio:1, the two is carried out two level inside mixer-settler inverse Stream regeneration, split-phase obtain regeneration extraction raffinate and regeneration organic phase.
Thus, the regeneration organic phase of above-mentioned acquisition can be re-used as the extraction organic phase in next cycle, recycle, with up to To the purpose for reducing organic reagent consumption, reducing pollution, reducing extraction cost.
After testing, the extraction yield of lithium is 90% in alkaline bittern containing lithium, and the overall recovery of lithium reaches 88.6%, institute after back extraction The high purity 98.6% of lithium chloride solution is obtained, can be used as producing the raw material of lithium chloride products and/or lithium carbonate product.
What deserves to be explained is technique does not represent whole processes of the present invention used by above-described embodiment, only it is Wherein indivedual examples, especially for the parameters such as ratio, series are wherein flowed, by mutual adjustment, being can be changed. Such as in washing room, washing should be adjusted with the concentration of acid according to the concentration of impurity metal ion in load organic phases, When washing is higher with acid concentration, under the conditions of mixing sufficiently is ensured, washing section stream also can reach preferable than appropriate reduction Washing effect；It should also be as suitably reducing when washing is relatively low with acid concentration；Meanwhile the washing effect of washing section is not only from washing With acid, in cleaning solution washing of the lithium ion of higher concentration for foreign metal also have certain effect, therefore the tune of washing section It is whole to be judged and adjusted according to complex situations in the load organic phases for entering washing section.
Meanwhile according to the principle analysis of above-mentioned diketone and neutral phosphine oxygen class extracting substances lithium, it can be seen that be not each Diketone can obtain the above-mentioned effect of extracting of the present invention as synergic reagent as extractant and/or each neutral phosphine oxygen class material, For this reason, the present invention is extractant for other diketones and/or other neutral phosphine oxygen class materials are that synergic reagent has carried out following contrast Experiment.
Comparative example 1
Lithium bittern will be contained to be pre-processed, remove the impurity such as solid, precipitation and suspended matter therein.
To Li+The sodium bicarbonate solution of 2mol/L is added in carbonate or chloride type bittern that concentration is 2g/L, by it PH value is adjusted to 10.5, obtains aqueous phase extracted.
2,4 pentanediones, 2- ethylhexyl phosphoric acids are mixed to acquisition extraction organic phase with kerosene；Wherein, it is organic in the extraction The substance withdrawl syndrome of Xiang Zhong, 2,4 pentanediones and 2- ethylhexyl phosphoric acids is 0.3mol/L.
The extraction organic phase that above-mentioned preparation is completed is pumped into the light phase inlet of the first Centrifugical extraction device assembly, and by extraction water Corresponding heavy liquid inlet is mutually pumped into, it is 1 to control extract stream ratio:3, the two is carried out eight grades in the first centrifugal extractor component internal Counter-current extraction, split-phase obtain raffinate and load organic phases.
Using the hydrochloric acid solution of 3mol/L as cleaning solution, the heavy liquid inlet of the second Centrifugical extraction device assembly is pumped into, and will Load organic phases are pumped into corresponding light phase inlet, and it is 10 to control scrub stream ratio:1, make the two in the second Centrifugical extraction device assembly Portion carries out Pyatyi countercurrent washing, and split-phase obtains washing extraction raffinate and washing organic phase.
Using the refined hydrochloric acid solution of 6mol/L as strip liquor, the heavy liquid inlet of the 3rd Centrifugical extraction device assembly is pumped into, And washing organic phase is pumped into corresponding light phase inlet, back extraction stream is controlled than being 30:1, make the two in the 3rd centrifugal extractor group Six stage countercurrent back extraction are carried out inside part, split-phase obtains lithium chloride solution and empty organic phase.
Using the sodium carbonate liquor of 2mol/L as regenerated liquid, the heavy liquid inlet of mixer-settler is pumped into, and machine will be had in vain The light phase inlet of mixer-settler is mutually pumped into, it is 1 to control recovery stream ratio:1, the two is carried out two level inside mixer-settler inverse Stream regeneration, split-phase obtain regeneration extraction raffinate and regeneration organic phase.
Thus, the regeneration organic phase of above-mentioned acquisition can be re-used as the extraction organic phase in next cycle, recycle, with up to To the purpose for reducing organic reagent consumption, reducing pollution, reducing extraction cost.
After testing, the extraction yield of lithium is 68% in alkaline bittern containing lithium, and the overall recovery of lithium reaches 66.4%, institute after back extraction The purity for obtaining lithium chloride solution is about 88.6%.
Comparative example 2
Lithium bittern will be contained to be pre-processed, remove the impurity such as solid, precipitation and suspended matter therein.
To Li+The sodium bicarbonate solution of 2mol/L is added in carbonate or chloride type bittern that concentration is 1g/L, by it PH value is adjusted to 10.0, obtains aqueous phase extracted.
Dibenzoyl methane, tributylphosphine oxide are mixed to acquisition extraction organic phase with kerosene；Wherein, in the extraction organic phase In, the substance withdrawl syndrome of dibenzoyl methane and tributylphosphine oxide is 0.2mol/L.
The extraction organic phase that above-mentioned preparation is completed is pumped into the light phase inlet of the first Centrifugical extraction device assembly, and by extraction water Corresponding heavy liquid inlet is mutually pumped into, it is 1 to control extract stream ratio:2, the two is carried out eight grades in the first centrifugal extractor component internal Counter-current extraction, split-phase obtain raffinate and load organic phases.
Using the hydrochloric acid solution of 3mol/L as cleaning solution, the heavy liquid inlet of the second Centrifugical extraction device assembly is pumped into, and will Load organic phases are pumped into corresponding light phase inlet, and it is 10 to control scrub stream ratio:1, make the two in the second Centrifugical extraction device assembly Portion carries out Pyatyi countercurrent washing, and split-phase obtains washing extraction raffinate and washing organic phase.
Using the refined hydrochloric acid solution of 6mol/L as strip liquor, the heavy liquid inlet of the 3rd Centrifugical extraction device assembly is pumped into, And washing organic phase is pumped into corresponding light phase inlet, back extraction stream is controlled than being 30:1, make the two in the 3rd centrifugal extractor group Six stage countercurrent back extraction are carried out inside part, split-phase obtains lithium chloride solution and empty organic phase.
Using the sodium carbonate liquor of 2mol/L as regenerated liquid, the heavy liquid inlet of mixer-settler is pumped into, and machine will be had in vain The light phase inlet of mixer-settler is mutually pumped into, it is 1 to control recovery stream ratio:1, the two is carried out level-one again inside mixer-settler Raw, split-phase obtains regeneration extraction raffinate and regeneration organic phase.
Thus, the regeneration organic phase of above-mentioned acquisition can be re-used as the extraction organic phase in next cycle, recycle, with up to To the purpose for reducing organic reagent consumption, reducing pollution, reducing extraction cost.
After testing, the extraction yield of lithium is 72% in alkaline bittern containing lithium, and the overall recovery of lithium is about 71.3%, institute after back extraction The purity for obtaining lithium chloride solution is about 85.5%.
Comparative example 3
Lithium bittern will be contained to be pre-processed, remove the impurity such as solid, precipitation and suspended matter therein.
To Li+The sodium bicarbonate solution of 2mol/L is added in carbonate or sulfate type bittern that concentration is 2g/L, by it PH value is adjusted to 10.8, obtains aqueous phase extracted.
Thenoyl acetone, tributyl phosphate are mixed to acquisition extraction organic phase with kerosene；Wherein, in the extraction organic phase In, the substance withdrawl syndrome of thenoyl acetone and tributyl phosphate is 0.2mol/L.
The extraction organic phase that above-mentioned preparation is completed is pumped into the light phase inlet of the first Centrifugical extraction device assembly, and by extraction water Corresponding heavy liquid inlet is mutually pumped into, it is 1 to control extract stream ratio:4, the two is carried out eight grades in the first centrifugal extractor component internal Counter-current extraction, split-phase obtain raffinate and load organic phases.
Using the hydrochloric acid solution of 3mol/L as cleaning solution, the heavy liquid inlet of the second Centrifugical extraction device assembly is pumped into, and will Load organic phases are pumped into corresponding light phase inlet, and it is 10 to control scrub stream ratio:1, make the two in the second Centrifugical extraction device assembly Portion carries out Pyatyi countercurrent washing, and split-phase obtains washing extraction raffinate and washing organic phase.
Using the refined hydrochloric acid solution of 6mol/L as strip liquor, the heavy liquid inlet of the 3rd Centrifugical extraction device assembly is pumped into, And washing organic phase is pumped into corresponding light phase inlet, back extraction stream is controlled than being 30:1, make the two in the 3rd centrifugal extractor group Six stage countercurrent back extraction are carried out inside part, split-phase obtains lithium chloride solution and empty organic phase.
Using the sodium carbonate liquor of 2mol/L as regenerated liquid, the heavy liquid inlet of mixer-settler is pumped into, and machine will be had in vain The light phase inlet of mixer-settler is mutually pumped into, it is 1 to control recovery stream ratio:1, the two is carried out level-one again inside mixer-settler Raw, split-phase obtains regeneration extraction raffinate and regeneration organic phase.
Thus, the regeneration organic phase of above-mentioned acquisition can be re-used as the extraction organic phase in next cycle, recycle, with up to To the purpose for reducing organic reagent consumption, reducing pollution, reducing extraction cost.
After testing, the extraction yield of lithium is 59% in alkaline bittern containing lithium, and the overall recovery of lithium is about 56.8%, institute after back extraction The purity for obtaining lithium chloride solution is about 82.6%.
Comparative example 4
Lithium bittern will be contained to be pre-processed, remove the impurity such as solid, precipitation and suspended matter therein.
To Li+The sodium bicarbonate solution of 2mol/L is added in carbonate or chloride type bittern that concentration is 2g/L, by it PH value is adjusted to 10.5, obtains aqueous phase extracted.
Toluyl acetone, tributylphosphine oxide are mixed to acquisition extraction organic phase with kerosene；Wherein, in the extraction organic phase In, the substance withdrawl syndrome of toluyl acetone and tributylphosphine oxide is 0.2mol/L.
The extraction organic phase that above-mentioned preparation is completed is pumped into the light phase inlet of the first Centrifugical extraction device assembly, and by extraction water Corresponding heavy liquid inlet is mutually pumped into, it is 1 to control extract stream ratio:3, the two is carried out eight grades in the first centrifugal extractor component internal Counter-current extraction, split-phase obtain raffinate and load organic phases.
Using the hydrochloric acid solution of 3mol/L as cleaning solution, the heavy liquid inlet of the second Centrifugical extraction device assembly is pumped into, and will Load organic phases are pumped into corresponding light phase inlet, and it is 10 to control scrub stream ratio:1, make the two in the second Centrifugical extraction device assembly Portion carries out Pyatyi countercurrent washing, and split-phase obtains washing extraction raffinate and washing organic phase.
Using the refined hydrochloric acid solution of 6mol/L as strip liquor, the heavy liquid inlet of the 3rd Centrifugical extraction device assembly is pumped into, And washing organic phase is pumped into corresponding light phase inlet, back extraction stream is controlled than being 30:1, make the two in the 3rd centrifugal extractor group Six stage countercurrent back extraction are carried out inside part, split-phase obtains lithium chloride solution and empty organic phase.
Using the sodium carbonate liquor of 2mol/L as regenerated liquid, the heavy liquid inlet of mixer-settler is pumped into, and machine will be had in vain The light phase inlet of mixer-settler is mutually pumped into, it is 1 to control recovery stream ratio:1, the two is carried out two level inside mixer-settler inverse Stream regeneration, split-phase obtain regeneration extraction raffinate and regeneration organic phase.
Thus, the regeneration organic phase of above-mentioned acquisition can be re-used as the extraction organic phase in next cycle, recycle, with up to To the purpose for reducing organic reagent consumption, reducing pollution, reducing extraction cost.
After testing, the extraction yield of lithium is 68% in alkaline bittern containing lithium, and the overall recovery of lithium reaches 66.4%, institute after back extraction The purity for obtaining lithium chloride solution is about 88.6%.
Extract although can be seen that to belong to diketone extractant together or belong to neutral phosphine oxygen class association together by comparative example and comparative example Agent, but there are still huge difference on effect of extracting between homologue, therefore different extractants and/or different synergic reagents Between be not simple replacement between homologue.
Based on the above-mentioned comparative analysis to different extractants and synergic reagent in homologue, it is seen that a complete extraction process It is the coefficient whole result of multi-party factor.In addition, what deserves to be explained is, one includes extraction-washing-back extraction-again The technique of the even more more general extraction workshop section of raw full-flow process or extracting-back extraction workshop section is increasingly complex, it is in technological design The upper factor to be considered is also more；This is because when extractant extracts object ion, to institute in material liquid (i.e. aqueous phase extracted) The foreign ion contained also has certain extraction, if the load organic phases obtained to extraction are directly stripped, loads Foreign ion in organic phase also can be by strip liquor back extraction to back extraction product liquid (lithium chloride solution i.e. in the present invention), gained Back extraction product liquid purity be difficult to ensure that.Simultaneously as extraction organic phase can carry a part of material liquid secretly in extraction process, should Part material liquid can also enter in anti-liquid with back extraction, and strip liquor acid solution can be also consumed while reducing product purity.The present invention The washing process of proposition is not only by adjusting the concentration with acid is washed compared with washing, by the foreign ion in load organic phases most The elution of big degree, while extraction section and stripping section are separated, farthest reduce due to product impurity caused by entrainment The problem of content is high, so as to improve product purity and yield.In addition, renovation process proposed by the present invention has effectively recovered back extraction The extracting power of empty organic phase afterwards, realizes the cycling and reutilization of organic phase, makes this extraction whole process entire flow, possesses Basic industrial value.
Although the present invention has shown and described with reference to specific embodiment, it should be appreciated by those skilled in the art that： In the case where not departing from the spirit and scope of the present invention limited by claim and its equivalent, can carry out herein form and Various change in details.

Claims (12)

1. a kind of technique that lithium is extracted from the bittern of alkalescence containing lithium based on centrifugal extractor, it is characterised in that including step：
Aqueous phase extracted is provided：Aqueous phase extracted is used as using the bittern of alkalescence containing lithium；Wherein, the pH of the bittern of alkalescence containing lithium is 8~14, In the bittern of alkalescence containing lithium, Li+Mass concentration be 0.05g/L~10g/L, Na+Mass concentration be no more than 80g/L, K+ Mass concentration be no more than 80g/L, Mg2+Mass concentration be no more than 1g/L, Ca2+Mass concentration be no more than 1g/L；
Extraction organic phase is provided：Extractant, synergic reagent and kerosene are mixed, prepare extraction organic phase；Wherein, in the extraction In organic phase, the substance withdrawl syndrome of the extractant and the synergic reagent is 0.05mol/L~0.6mol/L, the extraction Any one of agent in benzoyltrifluoroacetone, furoyltrifluoroacetone, thioyl trifluoroacetone, the synergic reagent Any one in trioctyl phosphine oxide, tributyl phosphate, trialkyl phosphine, 2- ethylhexyl phosphoric acids；
Extraction step：By the extraction organic phase and the aqueous phase extracted according to stream than being 1:10~10:1 in the first Centrifugical extraction Mixing in device assembly, and the extraction of 2~15 stage countercurrents is carried out, split-phase obtains raffinate and load organic phases；
Washing step：Using the hydrochloric acid solution of 0.1mol/L~12mol/L or the lithium-containing solution of identical acidity as cleaning solution, by described in It is 5 that load organic phases and the cleaning solution compare according to stream:1~80:1 mixes in the second Centrifugical extraction device assembly, and progress 2~ 15 stage countercurrents wash, and split-phase obtains washing extraction raffinate and washing organic phase；
Stripping steps：Using the hydrochloric acid solution of 0.1mol/L~12mol/L as strip liquor, by the washing organic phase and the back extraction Liquid is according to stream than being 5:1~80:1 mixes in the 3rd Centrifugical extraction device assembly, and carries out the back extraction of 2~15 stage countercurrents, and split-phase obtains Obtain lithium chloride solution and empty organic phase；
Regeneration step：1 grade of regeneration is carried out to the empty organic phase as regenerated liquid using alkaline solution or 2~5 stage countercurrents regenerate, split-phase Obtain regeneration extraction raffinate and regeneration organic phase；Wherein, the empty organic phase and the stream of the regenerated liquid compare for 1:10~10:1.
2. technique according to claim 1, it is characterised in that in the washing step, lithium in the washing organic phase Concentration be not less than the load organic phases in lithium concentration 80%；In the washing organic phase in addition to lithium metal total concentration Not higher than in the load organic phases in addition to lithium the total concentration of metal 5%.
3. technique according to claim 1, it is characterised in that in the regeneration step, the extraction of the regeneration organic phase 90% of the amount of trying to please not less than the loading capacity of the extraction organic phase.
4. the technique according to claim 1 or 3, it is characterised in that the alkaline solution is that substance withdrawl syndrome is The hydroxide solution of 0.05mol/L~4mol/L, the ammonia solution that substance withdrawl syndrome is 0.05mol/L~4mol/L or Substance withdrawl syndrome is any one in the carbonate solution of 0.05mol/L~4mol/L.
5. technique according to claim 1, it is characterised in that anion is selected from Cl in the bittern of alkalescence containing lithium-、SO4 2-、 CO3 2-、NO3 -At least one of.
6. technique according to claim 1, it is characterised in that in the offer aqueous phase extracted step, by containing lithium Sodium hydroxide solution, sodium carbonate liquor or ammonia solution are added in bittern and obtains the bittern of alkalescence containing lithium.
7. technique according to claim 6, it is characterised in that the sodium hydroxide solution, sodium carbonate liquor or ammonia are molten The substance withdrawl syndrome of liquid is 0.05mol/L~4mol/L.
8. the technique according to claim 6 or 7, it is characterised in that sodium hydroxide is molten being added into the bittern containing lithium Before liquid, sodium carbonate liquor or ammonia solution, the bittern containing lithium is pre-processed, solid precipitation therein is removed and suspends Thing.
9. technique according to claim 1, it is characterised in that the bittern of alkalescence containing lithium formed the aqueous phase extracted it Before, the bittern of alkalescence containing lithium is pre-processed, removes solid precipitation therein and suspended matter.
10. according to any techniques of claim 1-3, it is characterised in that the technique further includes circulation step：By described in Regeneration organic phase, which is back in the extraction step, to be used as extracting organic phase, and repeats the extraction step, washing step, back extraction Step and regeneration step.
11. according to any techniques of claim 1-3, it is characterised in that in the extraction step, the extraction is organic Mutually it is pumped into by the light phase inlet of the first Centrifugical extraction device assembly, the aqueous phase extracted is by the first Centrifugical extraction device assembly Heavy liquid inlet be pumped into；
In the washing step, the load organic phases are pumped into by the light phase inlet of the second Centrifugical extraction device assembly, institute Cleaning solution is stated to be pumped into by the heavy liquid inlet of the second Centrifugical extraction device assembly；
In the stripping steps, the washing organic phase is pumped into by the light phase inlet of the 3rd Centrifugical extraction device assembly, institute Strip liquor is stated to be pumped into by the heavy liquid inlet of the 3rd Centrifugical extraction device assembly.
12. according to any techniques of claim 1-3, it is characterised in that in the regeneration step, then generating apparatus is selected from Any one in centrifugal extractor, mixer-settler, tubular reactor.
CN201711295127.0A 2017-12-08 2017-12-08 Centrifugal extractor-based process for extracting lithium from lithium-containing alkaline brine Active CN108004420B (en)

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