CN1558871A - Method for recovering lithium chloride from brine and installation for carrying out said method - Google Patents
Method for recovering lithium chloride from brine and installation for carrying out said method Download PDFInfo
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- CN1558871A CN1558871A CNA01823738XA CN01823738A CN1558871A CN 1558871 A CN1558871 A CN 1558871A CN A01823738X A CNA01823738X A CN A01823738XA CN 01823738 A CN01823738 A CN 01823738A CN 1558871 A CN1558871 A CN 1558871A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/04—Processes using organic exchangers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
- B01J49/53—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents for cationic exchangers
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- 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
Abstract
The invention relates to a method for recovering lithium chloride from brine and to an installation for carrying out said method. The method for recovering LiCl from brine using selective sorptive extraction of the lithium substantially comprises the following steps: obtaining a solution enriched with LiCl in a sorption/desorption complex by means of a desorption liquid and an LiCl solution obtained in circulation operation, said LiCl solution having a concentration of 10 kg/m3 to 17 kg/m3; carrying out an ion exchange purification of the enriched solution of Ca and Mg admixtures; concentrating the purified eluates according to the electrodialysis method up to an LiCl concentration of 100 kg/m3 to 150 kg/m3 while obtaining a desalted solution having an LiCl concentration of 0.2 kg/m3 to 0.5 kg/m3 that is used for lithium desorption from the sorption agent; washing and drying the LiCl crystals obtained by evaporation of the solution concentrated to an LiCl content of 600 kg/m3 to 800 kg/m3 and cooling. The water-free lithium thus obtained has a high degree of purity and is suitable for the production of metal lithium and the alloys thereof.
Description
Technical field
The present invention relates to the equipment that obtains method and enforcement this method of lithium chloride from saline solution.The present invention relates to the lithium hydrometallurgy widely, relates in particular to from its solution and from natural saline solution and obtains lithium chloride.
Known a kind of method (United States Patent (USP) 4.291.001 number) is used for from solution, for example from synthetic crystal lithium aluminium alkali LiCl2Al (OH) the macropore of ion exchange resin
3NH
2Obtain lithium chloride in the saline solution of O, and be used for sorption column at the immobilized filtering layer that has sorbing agent and utilize this sorbing agent in lithium elution (desorb) with then concentrate the process of eluant through column system.Be this salt to the additional noncompetitive metal of eluant, for example NaCl or CaCl
2Move described column system saline solution being heated to for example 60 ℃ or above temperature.Use salt to cause additional preparation consumption for eluant concentrates, and because sodium-chlor and Repone K cause eluant impure.
United States Patent (USP) 4.291.001 has illustrated a kind of equipment that obtains lithium chloride from saline solution, contain the equipment and the device that is used for concentrating eluant-lithium chloride solution that obtains lithium chloride from saline solution that is useful on, wherein three posts of filling sorbing agent are subordinated to described thickening equipment, described post reciprocally connects by means of pipeline system, is connected with the saline solution source and with the fresh water container simultaneously.This equipment has salt dosing unit and the device that is used to draw spissated lithium chloride in addition.
Carry out optionally from saline solution in first post by means of described device that lithium extracts, elution lithium chloride and its then concentrate from sorbing agent in another second post.
Described equipment only can ad hoc apply to discontinuous in service under the condition of Solid Bed sorbing agent.In the equipment of this type, can not obtain the lithium chloride enriched material in inclusion-free ground, because it is subjected to enter the pollution that the salt in the liquid is provided inevitably in the process of concentrating.
The production area that this known equipment requirements the is suitable in addition and complicated Controlling System of big metal needs summation process guiding is arranged.
Known a kind of from WO94/19280 from method as acquisition lithium chloride the saline solution of sorption-desorb aggregate (hereinafter being called SDK), make the sorption extract by lithium selectivity particle sorbing agent contact method according to RU2113405 and RU2050184 from saline solution, and comprise that the water by means of desalination obtains lithium chloride solution concentrating as eluant and after continuing simultaneously in the lithium sorption according to RU2050330.Adopting composition according to this invention is LiCl2Al (OH)
3NH
2The aluminum-lithium chloride double-hydroxide of O is as sorbing agent.Carry out in that the classification convection current is in service in this lithium sorption and desorb.By requirement, select the duration of stay duration of sorbing agent in the sorption district with the saturated fully sorbing agent of lithium chloride.By determining duration of stay duration in desorption zone for from sorbing agent, fully extracting the lithium chloride required time.Before desorb, by it and increased sorbing agent saturated again that contacts and carry out within the predetermined time balancedly saturated lithium in the sorption district of the lithium chloride solution stream of predetermined depth, this sorbing agent that has guaranteed lithium chloride is the saturation ratio capacity that can reach capacity again, washs sorption particulate impurity component simultaneously.
The sorption duration from balancedly with the saturated sorbing agent of lithium for the first time the condition of stocking volume set about being scheduled to, described first time, stocking volume was identical with new sorbing agent stocking volume.The lithium of sorbing agent is saturated to ultimate value again, the highest as far as possible lithium chloride concentration and carrying out under the condition of the highest as far as possible concentration in the solution in the contacted process during correspondingly in desorb in the sorbing agent when guaranteeing in sorption.
Concentrating with known method by being undertaken by electrodialysis under the condition that has ion exchange resin of the lithium chloride eluant of making, this not only works to the concentrated of lithium chloride solution, can also purge calcium impurities again and magnesium addition works to it.
Be used for higher mineralization from the salt flowage sorbing agent that adopted of sorption lithium optionally, to have the two oxyhydroxide LiCl2Al (OH) of aluminum-lithium chloride that textural defect and lithium lack in its composition
3NH
2O (hereinafter being called DHAL-Cl) makes for the basis, and described sorbing agent is corresponding to the sorption capacity of every gram 6 ± 1mg lithium.Sorbent particles carries out according to the method that illustrates among RU2050184 and the WO94/19513.
The method that is used for the lithium of sorption chloride form with a kind of equipment has been described in WO94/19280.The integral part of described equipment is the sorption-desorb aggregate (being called SDK in the below) of Higges post type, has the U-shaped right cylinder of filler particles sorbing agent.
Described SDK has the sorption zone that is installed in post and the ball valve faucet in the desorbent zone and uses during the conducting sorbing agent in cylinder.The sectional area ratio of sorption zone and desorbent zone is 1.5: 1.0.In SDK, arrange: be used for transmitting primary saline solution and the pipeline that is used for therefrom drawing saline solution to the sorption district; Be used for transmitting eluant and the pipeline that is used for therefrom drawing eluant to desorption zone; Be used for drawing the regenerated sorbing agent and being used for the regenerated sorbing agent is transmitted the into pipeline in the sorption district of SDK from desorption zone; And the pipeline that is used to transmit the solution that is used for again saturated solution and washing sorbing agent, described pipeline is installed in the below that is used for transmitting to the sorption district pipeline of original saline solution.
SDK by means of pipeline and magnetic valve with: the container of original saline solution is connected with the container of the container of elution solution and eluant; Be connected with the collection container of the liquid that uses as washing fluid when the sorting sorbing agent; The device that the strainer of using with sorbing agent-separation method and being used for concentrates eluant is connected.Described device contains electrodialyzer and is used for the equipment of slurrying, the equipment of described slurrying is connected with strainer with the container of the water of eluant container, desalination, and with the container of lithium chloride solution and resin regeneration in electrodialyzer after the regenerated magnesium chloride and the container of calcium chloride be connected.
The shortcoming of this equipment at first is: it is merely able to obtain lower lithium chloride concentration (about 5kg/m
3), owing to be delivered into the eluant purity deficiency in the electrochemical appliance, lack simultaneously from sorbing agent load again the zone feed back the tank circuit of liquid to desorbent zone, also be arrangement because of the different diameter of arrangement in the slope and sorption zone and desorbent zone in the post; Long saline solution and washing fluid efflux time; Salt transmits unevenly on column section, uses eluant to concentrate the low electrodialyzer of power.
Task of the present invention is, provide improved obtain the method for lithium chloride from saline solution, described method make to environmental protection advantageously with higher purity and fully utilization ratio obtain lithium chloride and become possibility.
Task of the present invention also has, and the equipment of this method of enforcement is provided.
Method according to the feature of task of the present invention by having claim 1 is finished.The favourable expansion of this method is provided by claim 2 to 6.
Provide the task of the equipment described in the present invention to finish by the equipment of the feature that has claim 7.Favourable enforcement according to equipment of the present invention is provided by explanation claim 8 to 11.
The method according to this invention is a feature with following stage and advantage:
-directly the eluant of acquisition enrichment lithium chloride (10g/l to 17g/l) has magnesium and the calcium compounds of minimum content to 1g/l simultaneously in sorption-desorb aggregate (SDK),
-obtain lithium chloride solution, in the eluant ion exchange process, purge magnesium and calcium impurities,
-concentrate and to have purified lithium chloride solution according to electroosmose process, obtain 100kg/m
3To 150kg/m
3The electrodialysis saline solution and the 0.2kg/m of LiCl content
3To 0.5kg/m
3The desalting soln of LiCl content, described desalting soln are further used for desorb lithium from sorbing agent.
-possibility of using flexible concentrated lithium chloride solution arranged, promptly in basin, evaporate saline solution and by according to the concentrated lithium chloride solution of cold method in the mode of nature.
-separate LiClH by constantly drawing
2The part of the volatile stream of enrichment sodium-chlor reduces the sodium content in the finished product behind the O crystal,
-under the condition of constantly discharging moisture content from LiClH
2Dehydration and the dry finished product that goes out to meet the commercial quality requirement among the O.
According to the technical role of the inventive method and economical effectiveness at first by as be issued to:
-minutes two stages directly obtain the eluants of enrichment lithium chloride from SDK in the process of lithium desorb: in the volume flow of circulation fluid 1.5: 1.0 ratio of sorbing agent cycling stream is drawn simultaneously under the condition of part of lithium chloride solution, 10kg/m is arranged in lower region
3To 17kg/m
3The lithium chloride solution of concentration, and move by means of carrying out convection current for the lithium chloride solution that feeds the desired desalination of volume flow at upper area at upper area, described volume flow equates with the volume flow of the lithium chloride solution of drawing;
-use lithium type ion-exchanger ky-2 from lithium chloride solution, to purge calcium and magnesium;
Two stages of the concentrated branch of-eluant that purified according to electroosmose process carry out: produce 100kg/m with the operation of constant current electrolysis in the fs
3To 150kg/m
3The electrodialysis saline solution stream and the 3.5kg/m of LiCl content
3To 4.0kg/m
3The dialyzate stream of LiCl content; Producing the LiCl residual content in subordinate phase with the constant potential operation is 0.2kg/m
3To 0.5kg/m
3Desalting soln liquid stream and produce 7kg/m
3To 10kg/m
3The concentrated solution of LiCl content, described LiCl residual content is 0.2kg/m
3To 0.5kg/m
3Desalting soln from the Shi Xiangzhong of sorbing agent desorb lithium as strippant, described 7kg/m
3To 10kg/m
3The concentrated solution of LiCl content mix with the eluant of purification.
-by evaporation in basin or under-10 ℃ to-30 ℃ temperature lyophilize adopt the nature eluant concentrated.
-revaporization electrodialysis salt solution or by concentrating salt solution that (vaporize water) obtain naturally up to 600kg/m
3To 800kg/m
3LiCl concentration, then be cooled to 40 ℃ to 60 ℃ temperature and centrifugal LiClH
2O further evaporates the volatile matter feedback;
For the amount of the NaCl impurity in the LiCl solution of evaporation is remained on 7.0kg/m
3To 7.5kg/m
3Scope, separating LiClH
2After the O crystallization the mobile part of solution discharged from process and be used for the regeneration of cation exchanger ky-2 and to the transformation of Li type.
-under the condition of accelerating crystallization on the face of 100 ℃ to 105 ℃ of heating, dewater and dry LiClH in a vacuum
2The O crystal.
The technical role of described method and economical effectiveness are also by using according to equipment decision of the present invention.Described equipment additionally has: be used to purify the sorption-desorb aggregate (SDKER hereinafter referred to as) of eluant, have sorption branch and desorb branch, its diameter proportion is 3: 2; The device that is used for the eluant of electrodialysis thickening-purification technology, contain: the heat exchange withdrawer of the solution of electrodialysis thickener and electrodialytic desalting device, heating desalination, be used to separate the vaporizer and the condenser of wetting vapour, have the spiral vacuum drier of droplet separator, crystallizer, whizzer, spiral inclination washer and heating.All devices directly or through pump are connected by cell therefor by means of pipeline with equipment.
The technical role of described method and economical effectiveness also reach by being used for having identical sorption zone and desorb regional diameter from the main SDK that saline solution optionally extracts lithium.It also has following assembly in addition: the device that is installed in the horizontal mixing washing fluid in the annular section of post, pipe fitting, have dewatering unit, described dewatering unit be installed in from the sorbing agent of desorption zone absorption and regeneration and pass on the bottom of the container that the by-pass line of liquid is connected with feeding back to desorption zone; Have by the dewatering system of drawing eluant and constitute, above the device that laterally mixes washing fluid, be arranged in the desorb ramose lower region of SDK, and the circulation loop that is connected with eluant round-robin container.
In addition, described effect and economical effectiveness are also by arranging a pump to reach in the device of horizontal mixing washing fluid, described pump is connected with dehydration part with outlet pipe through its inlet tube, described dehydration part is installed on the height of pipe fitting of input washing fluid of SDK aggregate, is between the dehydration part.Pump described herein preferably with such being connected of dehydration part: make it possibility by the reversible liquid circulation of dehydration part.
The active effect that LiCl produces also reaches by the preferred implementing form according to equipment of the present invention, wherein in sorting in the container of the regenerated sorbing agent that SDK carries, in order to shorten the duration that washing fluid is discharged, an additional dehydration part is installed, described dehydration part is in transmission the exhausted saline solution is carried out the top of the pipe fitting of sorting, and is connected with the pipe fitting of drawing the exhausted saline solution.
Also show in a preferred embodiment in addition, being used for from the container that the desorption zone of SDK receives the regenerated sorbing agent dehydration part being installed is favourable, described dehydration part directly or by means of being used for is connected to the bypath system that the desorption zone loopback transforms solution from container with the underground pipelines of the solution of drawing conversion, and with draw the last pipeline that transforms solution and be connected, be intended to it is fed back in the desorption zone.
Guarantee the grouping convection flow of contact phase in sorption-desorb aggregate according to the equipment that from saline solution, obtains lithium chloride proposed by the invention, described grouping convection flow divides two operation phase to carry out, at first transform with sealing sorbing agent circulation loop and filter saline solution (sorption) by sorbing agent and sorbing agent, and rinse out effectively by means of the impurity component in the transverse tube bundle of lines particle that mixes wash water, secondly the concentrating directly in post the circulation fluid by introducing eluant circuit and feed back eluant from the district that sorbing agent transforms makes progress the sorption district and carry out of eluant, this has prevented the eluant dilution.
There being the eluant that is bordering on isostatic LiCl concentration to be transported to ion exchange column (SDKER) to purge Ca ion and Mg ion.
After this carrying out two stage electrodialysis concentrates.The no salt solution that obtains is like this sent in the desorb branch of SDK and the electrodialysis saline solution by thermal treatment evaporation LiCl, with then crystallization LiClH
2O and the anhydrous lithium chloride of acquisition.
Description of drawings
Explain the present invention with reference to the accompanying drawings and for example.In the accompanying drawings:
Fig. 1 expresses the dependency that ratio in the relative solid phase of liquid phase is the pump around circuit of the desorb ramose round-robin circulation fluid of eluant concentration and SDK under 1.5: 1.0 the condition;
Fig. 2 expresses the lithium sorption isotherms of sorbing agent;
Fig. 3 expresses at operation of constant current electrolysis and different current densities: a-3.3; B-4.6; C-5.9; D-7.2 (A/dm
2) condition under the process of eluant desalination;
Fig. 5 is illustrated in the process of the constant potential dialysis desalination after the fs eluant concentrates in service;
Fig. 6 expresses at a-105 ℃ and b-100 ℃ of temperature drying LiClH
2The dependency of water-content and duration and temperature under the condition of O.
Fig. 7 illustrates by lyophilize and carries out the spissated process of eluant;
Fig. 8-1, Fig. 8-2, Fig. 8-3 schematically illustrate the equipment that obtains lithium chloride from saline solution.
Embodiment
The equipment of the method for the acquisition lithium chloride that the present invention proposes and this method of enforcement is realized by means of the synergy of following group of process:
1) eluant by lithium chloride optionally extracts lithium from saline solution;
2) the deep ion exchange purges Mg from eluant
2+Impurity and Ca
2+Impurity;
3) by known method, comprise electrochemical method, concentrate lithium chloride solution;
4) will be concentrated to 150kg/m
3LiCl solution heating evaporation;
5) cooling one hydration lithium chloride crystallization, the volatile part of separating and discharging enrichment of N aCl subsequently;
6) obtain to meet the Lithium chloride (anhydrous) of commercial quality requirement by drying products in a vacuum.
In other so-called post, SDK has a series of zones, carry sorbing agent and these zone corresponding continuously by these zones: hydraulically to carry out sorbing agent sorting (I), sorption (II), washing and saturated again (III, IV), desorb (V and VI) with following process.After the lithium desorb, import to sorbing agent in the container (VII) and then import feed liquor and press in the zone (I) of sorting, constitute the circulation loop of sealing thus.Carry out under pressure pulse according to passing on of sorbing agent shown in Figure 8.
In zone (I), from post, draw little component (sorbing agent degraded product), reach the affirmation of the flowed friction of sorbing agent layer thus by sorting hydraulically in the liquid flow that rises.
In sorption district (II) sorbing agent saturated after, sorbing agent is sent into washing and the zone of saturated LiCl (III, IV) again.Carry out sorbing agent is removed the washing that is contained in the salt in the saline solution with washing lotion by additional horizontal mixing at this.Sorbing agent and solution (strippant) reach the point of determining both also to have had the highest lithium content in sorbing agent in solution in region intermediate (IV).Extract eluant at this point.Passing in the desorbent zone of SDK in the sorbing agent, sorbing agent is by the first sorption district (V), by the eluant circulation, and flows by second desorption zone (VI), carries out the lithium desorb of the degree of depth with salt-free stripping workshop in second desorption zone.
Illustrated serial process makes it possible, obtains containing 10kg/m
3To 17kg/m
3LiCl content and MgCl
2And CaCl
2Impurity is at the eluant of 0.1g/l to 0.3g/l scope.
Described LiCl concentration process reaches in desorption zone at the eluant round-robin simultaneously.LiCl shown in Figure 1 concentrates and the dependency of counting by the cycle (running through) in round-robin loop.As seen from Figure 1, LiCl just has been concentrated to and in fact has been bordering on isostatic state (Fig. 2) after 2 to 4 cycles
Behind SDK, eluant is transmitted in the ion exchange column (SDKER), be filled with lithium type Zeo-karb ky-2 in the described ion exchange column, and according to the work of SDK principle, in other words, with classification convection current operation.
In zone (I), carry out the separation of little resin Composition by the hydraulic pressure sorting.In sorption district (II), use Ca ion and Mg ion saturated resin, carry out the transition in the solution at this lithium ion from eluant.
Resin ky-2 flows into zone of transition (III) from the sorption district, the Li ion is further ejected from resin to be entered in the solution, and by Ca ion and Mg ionic replacement it, the Ca ion is compared with its concentration in the original eluant in sorption district with Mg ionic concentration and is improved.Output place in zone (III) realizes fully saturated Ca ion of sorbing agent and Mg ion, and to the regeneration soln (LiCl solution) of its reversed flow no matter reach calcium and magnesium amount in sorbing agent or in solution all is the point of maximum.From then on set out and take out exhausted and contain and reach 100kg/m
3CaCl
2And MgCl
2And be bordering on 2kg/m
3The regeneration soln of LiCl.
By pass-through zone IV, Ca ion and Mg ion in the resin are replaced by lithium ion, and its concentration in regeneration soln (lithium chloride solution) almost is ten times high of concentration in the original saline solution, and 1.5M to 2.5M (64kg/m is arranged
3To 100kg/m
3).The regenerated sorbing agent is transferred in the V district and sorting part I finishes this process cycle.
Illustrated ion exchange column enables to obtain to have Ca
2+Ion and Mg
2+Content reaches 0.001kg/m respectively
3And 0.003kg/m
3Eluant.Because lithium carries out the transition to the solution from resin, lithium chloride content is brought up to 13kg/m at this
3To 18kg/m
3Carrying lithium chloride solution to carry out electrodialysis concentrates: Phase I is made 100kg/m
3To 150kg/m
3Electrodialysis saline solution and the 3.5kg/m of LiCl
3To 4.0kg/m
3Dialyzate, and Phase is concentrated into 7.0kg/m to the dialyzate of Phase I
3To 10.0kg/m
3LiCl, obtain the Li concentrated solution and have 0.2kg/m
3To 0.5kg/m
3The desalting soln of LiCl, described desalting soln are delivered in the desorbent zone of SDK and are used as strippant from particulate sorbing agent sorption lithium.
The electrodialysis saline solution of enriching stage I is flowing in and carries out preheating in heat exchanger-withdrawer, enters then to carry out revaporization in the vaporizer and follow thereafter the solution of cooling evaporation in crystallizer and constitute crystallization LiClH
2O.In whizzer LiClH
2O crystal and remaining solution separating is opened and tiltedly wash in the machine at spiral and to wash carries out the convection current washing with lithium chloride solution in this machine; Then LiClH
2The O crystal is sent in the vacuum screw moisture eliminator, obtains anhydrous lithium chloride in described vacuum screw moisture eliminator under the condition of 100 ℃ to 105 ℃ temperature and continuous drawing-off water steam.
Purge LiCl behind Ca impurity and the Mg impurity and concentrate and also can in basin, under warm envrionment conditions, carry out, perhaps undertaken by freeze-drying in the exsiccant area very much with air in the winter time with the method for nature.After concentrated naturally or lyophilize, spissated LiCl also is sent in heat exchanger-revivifier and the vaporizer with further evaporation and manufacturing crystalline one hydration lithium chloride, as mentioned before.
With embodiment the present invention is described below.
Example 1
From saline solution (∑
Salt≌ 500g/l; LiCl ≌ 2.5g/l) optionally after the sorption lithium, based on the particle sorbing agent of DHAL-Cl under the blended condition and according to liquid phase: the ratio water treatment of solid phase=1.5.After carrying out the lithium sorption with salt-free water, eluant contains the 5.5g/l lithium chloride.
Under same condition, handle the new part of using the saturated sorbing agent of lithium with the eluant that obtains.Carry out several cycles in this way.The eluant that drew from the last cycle is used for new sorbing agent part during next cycle.Eluant concentration process in the circulation in the desorb branch of post should so be considered.After handling for the second time, the lithium chloride concentration in eluant increases to about 9g/l, and is increased to 13g/l after the 4th processing.The results are shown in Fig. 1 from cycle of saturated sorbing agent sorption lithium of carrying out in succession under the lithium chloride condition that cycle draws in the use.This method enables to obtain the lithium chloride concentration of about 15g/l in eluant, and this is in fact corresponding to the equilibrium concentration in solution-sorbing agent system (seeing the desorption isotherm among Fig. 2).
Example 2
Eluant is after it concentrates, and composition is (g/l of unit): LiCl=12.9; NaCl=0.03; MgCl
2=0.20; CaCl
2=0.28 (the perhaps CaCl of the MgCl of 4.2millival/l and 5.05mval/l
2), in 16.51 volume, transmitted fill lithium type ky-2 resin and volume be the ion exchange column of 225ml.This processing proceeds to Ca
2+Till puncturing in the solution.Eluant has following composition (g/l of unit): LiCl=18.0 after purging Ca ion and Mg ion; NaCl=0.02; MgCl
2=0.003; CaCl
2=0.001.Ca content and Mg content ≌ 153mval in the resin.
Example 3
After eluant was transmitted the ky-2 Zeo-karb, with the lithium chloride solution regeneration eluant of 70g/l.In same post, in resin, carry out regeneration of resin before vacancy Ca and the Mg.Exhausted regrowth solution is the solution of magnesium chloride and calcium chloride, and concentration reaches 100g/l, is converted into the CaCl of the LiCl content that has about 2g/l
2, be added into (example 1) in the original saline solution.
Example 4
The eluant that has 18g/lLiCl (seeing example 2) that purges impurity component is concentrated by electrodialysis in the pond of Room 10, wherein 5 chambers are used for desalination and 5 chambers are used to concentrate, and there are 2 electrode vessels in described pond, coordinate by unified circulation loop, wherein the LiCl solution of circulation composition 15g/l to 20g/l.The spacing of chamber is 2mm.Being concentrated in current density is 3.3A/dm
2, 5.9A/dm
2And 7.2A/dm
2Constant current electrolysis operation under carry out.The linear velocity that solution passes through to be had family is 5cm/s.Process is carried out with desalination in circulation loop to LiCl solution and is concentrated.
Process control is set about carrying out from the LiCl concentration that changes the desalination circulation and concentrate the circulation.The results are shown among Fig. 3 of research is at 5.9A/dm
2And 7.2A/dm
2Concentrate under the current density and proceed to 130g/l to 150g/l (Fig. 3 a and 3b).At 3.3A/dm
2Current density under eluant be concentrated into the LiCl (Fig. 3 c) of about 100g/l.
Example 5
Obtaining ideal LiCl residual solution in the spissated process of constant current electrolysis operation eluant in dialyzate, is at 3.3A/dm
2, 4.6A/dm
2, 5.9A/dm
2And 7.2A/dm
2Current density under carry out.The result of research is shown in Figure 4.Under the condition that does not change strength of current corresponding to given strength of current, process stabilization ground proceed to respectively LiCl concentration in the dialyzate be 3.5g/l (Fig. 4 a), 4.5g/l to 5.0g/l (Fig. 4 b, c) and 6g/l (Fig. 4 d).If the concentration of the LiCl of the adding in the solution of desalination descends in film polar result, energy expenditure just rises sharp.Ideal LiCl solution be concentrated in current density i=3.3A/dm
2To 5.9A/dm
2Carry out, because can obtain LiCl content 3.5g/l to 5.0g/l minimum in the dialyzate with minimum energy consumption with this understanding.
Example 6
Have dialyzate desalination in electrodialytic cell of the LiCl content of 3.5g/l to 5.0g/l, the structure of described electrodialytic cell has illustrated in example 4.Desalination is carried out under the volts lost of unit cells 4V by constant-pressure operation.This process is undertaken by circular flow ground under the condition of the linear rate of flow of desalting soln 5cm/s.The result of research is shown in Figure 5.Desalination proceeds to the LiCl content of 0.2g/l (a) to 0.5g/l (b) under the condition of original content 3.5g/l and 5.0g/l.The concentration range of LiCl correspondingly is about 7.5g/l and 10.0g/l.
Example 7
LiCl content is that the eluant that purges impurity of 100g/l is filled into after electrodialysis concentrates in the container that heats under the continuous mixing condition in water-bath, to carry out the evaporation of LiCl solution under the condition of nature.Repeatedly evaporating the LiCl solution that the back obtains about 400g/l.LiCl solution revaporization is carried out with electric drying apparatus to about 600g/l.Cooling solution and formation LiClH
2Wash three times crystal and solution separating and with a spot of lithium chloride solution after the O crystallization.The substrate content of a hydration lithium chloride that is obtained is 99.9%.
Example 8
A hydration lithium chloride that has about 40% water-content of Huo Deing is dry under 100 ℃ to 105 ℃ temperature condition in vacuum drying oven as described in Example 7.The results are shown among Fig. 6 of research.From shown in chart as can be seen, remaining about 7.5% (the curve b) of moisture content under 100 ℃ temperature condition, and under 105 ℃ temperature condition remaining moisture content about 2% (curve a).At this, the exsiccant product does not lose the state of its bulk cargo.The composition of impurity has 0.142% in anhydrous lithium chloride, and is corresponding with highly purified lithium chloride.
Example 9
Freezing under-4 ℃ ,-15 ℃ and-22 ℃ of temperature the 250ml eluant that purges impurity (16.1g/l, LiCl material are 4.03g).Ice amount in the sample of freezing back is respectively an original solution volumetrical 84%, 96.8% and 98.5%.LiCl concentration in the remaining saline solution is 43.0g/l corresponding to given temperature; 64.4g/l and 68.7g/l (Fig. 7).This means that the concentrated of LiCl solution reaches 2.7 to 4.3 times, with 60% to 70% transition of the LiCl quality in original solution.In the transition of the industrial equipments of freezing saline solution, can bring up to 90% to this parameter.Lithium chloride content is 0.4g/l to 0.8g/l after saline solution that has separated manufacturing and ice-out, and this makes it possible to such solution is used for the lithium desorb of sorbing agent.
Example 10
Below by means of the function of Fig. 8 devices illustrated.
For the first time be accompanied by the sorbing agent slurry sent in the LiCl solution (about 2g/l) and carry out with the sorbing agent post (SDK) of feeding, described LiCl solution flow into the container 29 from container 90.After with the sorbing agent packed column, saline solution is transported among the left sorption district II of post.Effusive original saline solution imports among the SDK by pipe fitting 4 by means of pump 2 from container 1.When flowing through sorption district (zone, a left side of post), the saline solution of poor lithium is advanced in the collection basin of saline solution 27 by pipe fitting 5 and strainer 26 dischargings.The exhausted saline solution flows out through the discharge system 101 of exhausted saline solution.The part of saline solution is incorporated into by pipe fitting 7 in the branch constituency (container 3-1) of SDK with pump 28, discharges from SDK (container 3-1) by pipe fitting 8 the separation of atomizing sorbing agent component and with saline solution in this district.Atomizing sorbing agent slurry and saline solution flow through strainer 26, separate the sorbing agent compositions with strainer 26: saline solution flows to container 27 and atomizing sorbing agent pack and be transported to further utilization in the equipment of manufacturing particle sorbing agent.With the fresh charging of particulate sorbing agent (DLAL-Cl) DHAL-Cl together with carry out from mixing by the saline solution pipe fitting 5 posts (SDK area I I) the inflow container 29; Then slurry is entered the branch constituency (container 3-1) of SDK by pipeline and pipe fitting 9 transmission with radiation pump 30.
The particulate sorbing agent enters in the lower annular part of post after the saturated lithium in the sorption branch of SDK, in addition the water that sends from container 38 is transmitted by pipe fitting 12 with pump 37.Flushing contains pump 14 by means of mixing device 13, carries out.
Washed sorbing agent flows in sorption-desorb aggregate (SDK) 3, carries out the lithium sorption in two stages in described sorption-desorb aggregate (SDK): at first by the lithium chloride of sending from container 35 through pipe fitting 15 with pump 36; Then the no salts solution of sending from container 40 through pipe fitting 17 with pump 39 is carried out the lithium desorb of the degree of depth.Eluant flows to by means of concentrated round-robin dewatering system and carries out its bottom in the zone of saturated lithium again after water carries out the lithium desorb.Be delivered into circulation from container 35 effusive eluants by means of pump 36, improve the concentration of LiCl in the eluant thus.The eluant of saturated lithium passes on and into removes to purge calcium and magnesium the container 33 from concentrating circulation loop 11.
After the lithium desorb, sorbing agent flows to the sorbing agent of container 3-2 with absorption and regeneration by valve 25; The part that enters the conversion solution among the container 3-2 when transmitting sorbing agent feeds back in the post through bypath system 18-1 and through pipe fitting 19 and 16.The sorbing agent of (regenerated) prepared transmits minute constituency (container 3-1) by valve 24.After sorting, sorbing agent is introduced in the sorption district of post (SDK) through valve 23.The sorbing agent loop ends is in SDK3 thus.By means of effusive water from container 38 sorbing agent from container 3-2 transmits into minute constituency, described water is sent among the container 3-2 through pipe fitting 20 by means of pump 37.
After desorb, eluant is sent among the area I I of ion exchange column 41 (SDKER) by pipe fitting 42 by means of pump 34 from container 33.Purge Ca
2+And Mg
2+The ionic eluant flows in the collection container 65 of the eluant that purifies through sieve-bend screen 64 by pipe fitting 43.Saturated Ca
2+And Mg
2+Ionic cation exchanger ky-2 is sent to by means of pulse of compressed air in the annular section of post, is desorb Ca then
2+And Mg
2+Ion its flow among the area I V of post and regeneration side by side herein.Be 70kg/m by pipe fitting 52-1 input concentration for this reason
3To 100kg/m
3The LiCl regeneration soln.In the desorption zone of flowing through, by pipe fitting 50 saturated with calcium chloride and the magnesium chloride and the 2kg/m that has an appointment
3The exhausted regeneration soln of LiCl content be discharged to and have in the container 1 of original solution.Li
+Type regenerated cationite ky-2 flows among the container 41-2 by valve 60, and the solution that is delivered in the container with resin feeds back desorption zone through bypath system by pipe fitting 54 and 51.From container 41-2, resin is carried out classified and separated little component by means of being delivered into by valve 59 from the next regenerated eluant of container 65 streams the container 41-1.The resin sorting is also carried out by means of the eluant of the purification that transports by pipeline and pipe fitting 45 from container 65.Be transferred to the sieve-bend screen 64 from minute constituency described slurry, on described sieve-bend screen little resin Composition opened from the LiCl solution separating, described LiCl solution flow in the container 65.
Carry out in the electrodialysis appts of the filter-press configuration mode that is concentrated in the series system manufacturing of the eluant that purifies, described filter-press configuration is made up of the mutual alternative positively charged ion and the cationic exchange membrane that constitute concentration compartments and desalting chamber.During carrying with pump 68, the eluant that purifies carries out the concentrated of fs in the electrodialysis thickener 69 from container 67; The content that solution is circulated to LiCl in desalting chamber in spissated process reaches 3.5kg/m
3To 4kg/m
3Simultaneously in spissated chamber, carry out the concentration of the LiCl in the saline solution under the electrodialysis is increased to 100kg/m
3To 150kg/m
3Concentrate, concentrated solution is collected in the container 72.The dialyzate of making in desalting chamber is transported to the desalination of carrying out subordinate phase in the container 73, by means of pump 74 described dialyzate is delivered to the electrodialytic desalting device 75 of similar structures from container 73 and is carried out dark desalination (to 0.2kg/m
3To 0.5kg/m
3LiCl).In the chamber that concentrates usefulness, obtain the about 7.5kg/m of LiCL content simultaneously
3To 10.0kg/m
3Concentrated solution, described concentrated solution is delivered into the container 67 and mixes with the eluant that purifies from container 77.LiCl content 0.2kg/m
3To 0.5kg/m
3The solution of desalination flow into in the container 40 with in the stage that is used in the lithium desorb among the SDK3.
With pump 79 the electrodialysis saline solution of lithium chloride is delivered into from container 72 in the heat exchanger device withdrawer 78, in described heat exchanger-withdrawer 78, is used for the described solution of steam raising of flash-pot 80.After preheating, LiCl solution flows in the vaporizer 80, further evaporate, in described vaporizer in a vacuum by means of condensation water devaporation water by constituting in logical hot steam of coming of steam transmission system 96 and the delivery of steam process.LiCl concentration in saline solution is increased to 750kg/m thus
3To 800kg/m
3The LiCl saline solution that revaporization is crossed discharges in the crystallizer 85.Wetting vapour is condensed in condenser 81, and is transferred to by droplet separator 83 in the collection container 84 of condensation water.The LiClH that in crystallizer, produces
2The O crystal separates with saline solution with whizzer 86 and passes on and wash in the end of washing screw 87 into.From the volatile matter of whizzer at centrifugal LiClH
2In the circulation of ground, O crystal rear section evaporation stage, and partly from system, be drawn out among the container 93-2 for preparing regeneration soln.Remove Mg ion and Ca ion simultaneously and resin is converted to Li at the regenerated of resin ky-2
+Type.
LiClH
2The O crystal washs in spiral vacuum drier 88 and the dry high-purity anhydrous lithium chloride (amount of the cation impurity of Na, K, Mg, Ca is 0.01 mass percent to 0.15 mass percent only) that meets the commercial quality requirement that produces later on.
According to technical process of the present invention do not discharge and the cause damage rubbish of nature and contaminate environment.Desired all preparations of described process all are retained in the described technological system.Thereby the no salts solution that obtains in the concentration process is adopted in the desorb of day sorbing agent; For cation regenerant exchanger ky-2 adopts washing LiClH
2The spissated lithium chloride solution that obtains during the O crystal; The regeneration soln that contains calcium ion and magnesium ion and lithium chloride (reaching 2g/l) is used for the lithium sorption stage at SDK after the cationite ky-2 that regenerated.
From for example illustrated, with the method according to this invention with according to other following advantage of having of equipment of the present invention:
Eluant circulation (example 1) in the desorb branch of introducing SDK enables an elutriant In lithium chloride concentration improve about two with concentration in the elutriant that obtains according to prior art To three times.
Use cation exchanger ky-2 that elutriant is purged Ca2+And Mg2+To have very much The method of the acquisition LiCl solution of effect, the LiCl solution that obtains contains only 0.0003 matter Magnesium chloride and the calcium chloride (example 2) of amount percentage and 0.0001 mass percent, this than according to Few ten times of the method for prior art.
Two stage elutriant electrodialysis concentrates follows follow-up evaporating liquid and from solution In consist of a hydration lithium chloride and draw the volatile of saturated sodium-chloride from solution off and on Part make it to obtain high-purity anhydrous lithium chloride, this can be for the production of metal Lithium and on its basis metallurgical. The no salting liquid that the elutriant in two stages concentrates is used for inhaling The lithium desorb of agent, this is related to and reduces significantly fresh water consumption.
Particularly advantageously be, according to the water that from the natural villaumite that contains lithium, obtains of the present invention The technical scheme of closing the atmosphere lithium can be successfully used to the salting liquid of the various concentration of all kinds And from chemistry and biochemical manufacturability salting liquid, obtain lithium.
Label list
The container of 1 natural saline solution
2 supply with the pump of saline solution
3 (sorptions-desorb aggregate SDK) are used for optionally extracting LiCl from saline solution
The sorbent of 3-1 sorting regeneration and transmission advance container in the sorption district
3-2 receives the container of the sorbent of regeneration from desorption zone
4 are used for transmitting to SDK the pipe fitting of saline solution
5 are used for drawing the pipe fitting of the saline solution of using
6 are used for transmitting the pipe fitting that removes the sorbent of sorting regeneration with the saline solution of crossing
7 are used to discharge the pipe fitting of exhausted saline solution
8 are used for drawing the pipe fitting of the sorbing agent of fragmentation when sorting
9 are used to transmit the pipe fitting of fresh sorbing agent DHAL-Cl
10 are used to transmit compressed-air actuated pipe fitting
11 draw the dewatering system of eluant
12 are used to transmit the pipe fitting of washing water
13 are used for the device of horizontal mixing, washing water
14 are used for the pump of blended device 13
15 transmit the lithium chloride circulate soln removes the pipe fitting of desorb
16 pipe fittings to desorption zone feedback conversion solution
17 pipe fittings to desorption zone transmission dehydrating solution
18-1 is used for feeding back the bypath system that transforms solution to desorption zone from receiving the regenerated sorbing agent
Pipe fitting has dehydration part under the 18-2, is used for drawing conversion solution from the container 3-2 that receives the regenerated sorbing agent
Pipe fitting on 19 is used for from drawing conversion solution from the container 3-2 that receives the regenerated sorbing agent
20 pipe fittings are used for transforming transmission washing fluid (water) to sorbing agent
21 discharging pipe fittings
22 transmit compressed-air actuated pipe fitting
23 valves are used to control the sorbing agent that transmits regeneration and sorting to the sorption district
24 valves are used for control and transmit the regenerated sorbing agent to sorting containers 3-1
25 valves are used for control and transmit the regenerated sorbing agent from desorption zone to receiving vessel 3-2
26 strainers are used for from the solution sorbing agent phase that is separated
The collection container of 27 exhausted solution
28 pumps, the solution that is used for drooping mistake remove to carry out the sorbing agent sorting and the desalination parts of regenerating
29 containers are used for preparing fresh sorbing agent (DHAL-Cl) (by at first load the LiCl solution of lower concentration in post) at saline solution
30 radiation pumps are used for transmitting the sorbing agent slurry to the container 3-2 of sorting regenerated sorbing agent
31 pipe fittings are used for drawing sorbing agent from SDK
32 radiation pumps are used for drawing sorbing agent from SDK
33 eluant collection containers
34 supply with the pump of eluant
35 eluant round-robin containers
36 pumps are used for circulation and draw eluant
37 pumps are used for supplying water with the washing and the sorbing agent that passes on
38 water receptacles
39 pumps are used to transmit desalting soln and go to carry out the lithium desorb
The collection container of 40 desalting solns
41 are used to purify the sorption-desorb aggregate (SDKER) of eluant, ion exchange column
The 41-1 container is used for sorting regenerated cationite and it is sent to the sorption district
The 41-2 container is used for from breeding blanket reception regenerated cationite
42 pipe fittings are used to transmit the eluant that purifies
43 pipe fittings are used to transmit the eluant that has purified
44 pipe fittings are used to transmit the eluant that has purified and remove the sorting cationite
45 pipe fittings are used to discharge eluant
46 pipe fittings, the slurry of the cationite that has been used for when sorting, drawing fragmentation
47 pipe fittings are used to supply with fresh cationite
48 pipe fittings are used to supply with pressurized air
49 pipe fittings are used to unload cation exchanger
50 pipe fittings are used to draw the exhausted regeneration soln
51 pipe fittings are used for feeding back conversion solution through bypath system
The 52-1 pipe fitting is used to transmit regenerated LiCl solution
The 52-2 pipe fitting is used for washing water
53 have the following pipe fitting of dehydration part, are used for drawing the conversion solution that receives the container 41-2 of regenerated ion-exchanger from the breeding blanket
54 pipe fittings are used for drawing from container 41-2 and transform solution and receive the regenerated cationite from the breeding blanket
55 pipe fittings are used for transmitting rinse solution to container 41-2
56 pipe fittings are used to transmit pressurized air
57 pipe fittings are used for exhausted air
58 valves, be used for controlling to the sorption district transmit regenerated with sorting cationite
59 valves are used for controlling to sorting containers 41-1 and transmit the cationite of having regenerated
60 valves are used for controlling to receiving vessel 41-2 and transmit the cationite of having regenerated
61 containers are used to prepare the slurry of fresh cationite
62 radiation pumps are used for the slurry to SDKER transmission cationite
63 radiation pumps are used for drawing from SDKER the slurry of cationite
64 sieve-bend screens
The collection container of 65 eluants that purify
66 pumps are used to transmit the eluant that has purified and go to concentrate
67 dialyzate containers
68 pumps are used to pass on dialyzate
69 electrodialysis liquid thickeners
70 pumps are used to pass on electrodialysis saline solution LiCl
71 electrodialysis saline solution LiCl containers
72 electrodialysis saline solution LiCl collection containers
The container of the dialyzate of 73 fs
74 pumps are used to pass on dialyzate
75 electrodialytic desalting devices
76 pumps are used to pass on concentrated solution
77 concentrate containers
78 heat exchangers-withdrawer are used to heat the electrodialysis saline solution
79 pumps are used to transmit the electric Chinese and analyse the saline solution devaporation
80 vaporizers
The condenser of 81 wetting vapours
82 pipe fittings are used to emit wetting vapour and coagulum
83 droplet separators
84 coagulative collection containers
85 crystallizers
86 whizzers are used to separate LiClH
2The O crystal
87 spiral inclination washing machines
88 spiral Vacuumdriers
The collection container of 89 Lithium chloride (anhydrous) solution
90 containers are used to the lithium chloride flushing saline solution of preparing to dilute
91 pumps are used to transmit lithium chloride solution
92 pumps are used for transmitting the eluant purified to SDKER
The 93-1 pump is used to transmit regeneration soln
The 93-2 container is used to transmit the washings devaporation
The collection container of 94 washing solns
95 pumps are used to transmit the washing soln devaporation
96 steam transfer systems
97 fresh water transfer systems
98 vacuum systems
99 pneupress systems
100 saline solution reservoirs
101 analyze the system of exhausted saline solution
102 discharging pipe fittings
103 cooling recirculation systems.
Claims (11)
1. obtain the method for lithium chloride from saline solution, contain: by obtaining described lithium chloride with lithium to the selection sorbing agent is contacted in service the remaining under the condition in the sorption district at sorbing agent of classification convection current, described sorption district guarantees fully to use the saturated sorbing agent of lithium chloride; By its lithium chloride solution with rising mobile predetermined concentration contact again saturated in the sorption district satisfied sorbing agent, the saturated again lithium chloride of described predetermined concentration sorbing agent reaches to extreme value, and simultaneously sorbent particles is washed away impurity, and useful salt-free water concentrates the lithium chloride desorb of the fractionated convection current sorbing agent that carries out in service and follow-up lithium chloride solution, it is characterized in that
-by directly in sorption-desorb aggregate the lithium desorb by sorbing agent obtain the enrichment lithium chloride solution, at first by means of stripping workshop, then by means of the lithium chloride solution of concentration 10g/l to 17g/l;
-obtain concentration 10kg/m with circular flow
3To 17kg/m
3Lithium chloride solution; Wherein, the ratio of circulate soln volume flow and sorbing agent volume flow is 1.5: 1.0, simultaneously with the approximately equalised scope of the volume flow of the stripping workshop that will supply with in from circulation loop, draw the mobile part of lithium chloride;
-the ion-exchange of then carrying out lithium chloride solution purges magnesium and calcium;
-concentrate lithium chloride solution then until constituting LiClH
2The O crystal is LiClH
2The O crystal separates with saline solution and the saline solution feedback is concentrated;
-wash in the convection current of contact phase with no salt solution, wherein, promote the chlorinated solution that in washing process, constitutes to concentrate;
-at last the LiClH that washs out
2The O crystal dewaters and is dried to anhydrous lithium chloride.
2. the method for claim 1 is characterized in that, the eluant of thickening-purification technology carries out with ky-2 lithium type cation exchanger according to ion exchange method.
3. method as claimed in claim 1 or 2 is characterized in that, concentrating of the eluant that has purified at first divides two stages to carry out by electrodialytic method, wherein produces 100kg/m with the operation of constant current electrolysis in the fs
3To 150kg/m
3The electrodialysis saline solution stream and the 3.5kg/m of LiCl content
3To 4.0kg/m
3The dialyzate of LiCl content stream, and to obtain the LiCl residual content in subordinate phase with the constant potential operation be 0.2kg/m
3To 0.5kg/m
3No salts solution and obtain 7kg/m
3To 10kg/m
3The concentrated solution of LiCl content, described LiCl residual content is 0.2kg/m
3To 0.5kg/m
3Desalting soln carrying out the selectivity sorption, described 7kg/m from the Shi Xiangzhong of sorbing agent desorb lithium as strippant
3To 10kg/m
3The concentrated solution of LiCl content mix with the eluant of purification, and then 100kg/m
3To 150kg/m
3The electrodialysis saline solution of LiCl content by evaporation concentration to 600kg/m
3To 800kg/m
3LiCl concentration, then be cooled to 40 ℃ to 60 ℃ temperature, and the centrifugal solution that obtains like this, volatile matter is fed back further evaporates simultaneously; Wherein, the amount of the NaCl impurity in the LiCl solution of evaporation is remained on 7.0kg/m
3To 7.5kg/m
3Scope, constantly draw the part of lithium chloride solution after centrifugal for this reason and be used for cation regenerant exchanger ky-2 with and to the transformation of Li type.
4. as each described method in the claim 1～3, it is characterized in that LiClH
2The dehydration of O and drying are carried out under the condition of accelerating crystallization on the face of 100 ℃ to 105 ℃ of heating in a vacuum.
5. as each described method in the claim 1～3, it is characterized in that concentrating by evaporation moisture content in basin or then evaporating lithium chloride solution by salt solution refining effect of the eluant that has purified carried out.
6. as each described method in the claim 1～3, it is characterized in that eluant concentrates by lyophilize under-10 ℃ to-30 ℃ temperature.
7. equipment, be used for obtaining lithium from saline solution, form by the sorption-desorb aggregate-SDK (3) that is used for optionally extracting lithium chloride from saline solution, have: be used for supplying with brinish pipe fitting (4) by means of pump (2) from the container (1) that original saline solution is arranged, be used to discharge exhausted brinish pipe fitting (5), carry the exhausted saline solution to remove the pipe fitting (7) of sorting by means of pump (8) being used to of being connected with the collection container (27) of exhausted saline solution, be used to draw the slurry of the sorbing agent of fragmentation when sorting by the pipe fitting (8) of strainer (26) from exhausted saline solution separate solid phase, the pipe fitting that is used to supply with washing water (12) that is connected with washing water container (38), be used for supplying with salt-free lithium chloride solution from the container (40) that contains salt-free lithium chloride solution and remove the pipe fitting (17) of desorb by means of dosing pump (39), be used for drawing the pipe fitting (31) of selective sorbent in the lower annular part of SDK (3), be used for to atmosphere deflate pipe fitting (21) and the pipe fitting of drawing lithium chloride solution (eluant) (11) that is connected with the collection container (33) of lithium chloride solution (eluant) and is connected with the device of heating and concentrated lithium chloride solution (eluant), it is characterized in that described equipment additionally has:
Be used for lithium chloride solution (eluant) is purified the sorption-desorb aggregate-SDKER (41 of calcium and magnesium; 41-1; 41-2), have sorption branch and desorb branch, its diameter proportion is 3: 2; Be connected and directly with the container (90) of the lithium chloride washing saline solution of preparing dilution be connected pipe fitting (42) connection with supply eluant with being used for through the collection container (33) of (34) and eluant with pipeline; By means of pipeline be used for the eluant that has purified is drawn at container (65) to purify the pipe fitting (43) of eluant, supply with the radiation pump (62) of the slurry that the original cationic exchanger uses among the warp-wise SDKER (41-1) and directly is connected and is connected with sieve-bend screen (64) with the container (61) of the slurry of preparing described cationite and by means of supply with to SDKER (41-1) eluant that has purified carry out cationic exchange pipe fitting (44) and by means of pipe fitting (45) connection of discharging washings; By means of the pipe fitting that is used to supply with regenerated LiCl solution (52-1) through pump (93-1) with prepare regeneration soln container (93-1) be connected; Directly be connected with the container (1) of original saline solution by means of the pipe fitting that is used to draw the exhausted regeneration soln (50); Be connected with the collection container (40) of desalting soln through pump (39) by means of the pipe fitting (52-2) of supplying with washing water; By means of be used to feed back the pipe fitting (51) that transforms solution through bypath system directly be used for drawing the upper and lower pipe fitting (54 that transforms solution from container (41-2); 53) connect; Directly be connected through pump (92) by means of pipe fitting (55) from rinse solution LiCl to container (41-2) that supply with the collection container (65) of the eluant that purifies; By means of supplying with that compressed-air actuated pipe fitting (56) is connected with pneupress system (99) and air being discharged in the atmosphere by means of pipe fitting (57);
-be used for the device of the eluant of electrodialysis thickening-purification technology, contain: two sections electrodialysis thickener (69) of filter-press arrangement mode, described electrodialysis thickener is by means of the container (71) of pipeline and electrodialysis saline solution, the container of dialyzate (67) connects, be connected with the pump that is used to carry the electrodialysis saline solution (70) and be connected with the pump (68) of carrying electrodialysis liquid, and at this, constitute independently circulation loop with electrodialysis saline solution and dialyzate pipeline section, and form by two sections electrodialytic desalting devices (77) of press filtration make, described two sections electrodialytic desalting devices are connected with concentrate container (77) with the container (73) of no salts solution by means of pipeline, be connected with the pump of supplying with desalting soln (74) and concentrated solution (72), and constitute the independent loops loop of desalting soln and concentrated solution thus; Be connected with the collection container (65) of the eluant of purification by means of pipeline through pump (66) at the container (71) of this electrodialysis saline solution and the container (67) of dialyzate, the loop of dialyzate pipeline section is connected with the container (73) of salt-free liquid by means of pipeline and is connected with concentrate container (77), and the loop of the pipeline section of electrodialysis saline solution, comprise the loop on the pipeline section of the collection container (71) of electrodialysis saline solution and no salts solution, be connected with the collection container (40) of no salts solution;
-evaporation unit, the collection container (84) of condenser, droplet separator (83) and the condensation water of the wetting vapour (81) that contain the pump (79) that transmits the devaporation of electrodialysis saline solution, the heat exchanger (78) of electrodialysis saline solution, the vaporizer (80) that is connected with steam feedway (96), is connected with cooling recirculation system (103);
-cooling crystallizer (85) is connected with whizzer (86) with the cooling cycle system (103) of vaporizer (81), and described whizzer is being connected with the collection container (72) of electrodialysis saline solution by means of pipeline aspect it;
-spiral inclination washer (87), be connected with the collection container (40) of whizzer (86), condensation water container (84), desalting soln and the collection container (94) of washing lotion by means of pipeline, described collection container (94) is connected with the collection container (72) of electrodialysis salt through pump (95) by means of pipeline;
-heatable spiral vacuum drier (88) is connected with condensation water collection container (84) by means of collection container (89), the vacuum system (98) of pipeline and spiral inclination washer (87), anhydrous lithium chloride, the system (96) that supplies with steam.
8. equipment as claimed in claim 7, it is characterized in that, sorption-desorb aggregate the SDK (3) that optionally extracts lithium from saline solution has identical sorption branch and desorb branch diameter reaches, and has: the device (13) of the cross drive washings in the annular section of SDK; The following pipe fitting (18-2) that has dewatering unit, described dewatering unit be arranged in from the sorbing agent of desorption zone absorption and regeneration and pass on the bottom of the container (3-2) that the bypath system (18-1) of liquid is connected with feeding back to desorption zone; Constitute by the dewatering system of drawing eluant (11), be arranged in the desorb ramose lower region of SDK (3) in the top of laterally mixing the device (13) of washing fluid, and be connected by means of the circulation loop that pipeline and magnetic valve are separated the pipe fitting (15) of the lithium chloride that smokes through eluant round-robin container (35) and pump (36) and supply.
9. as claim 7 or 8 described equipment, it is characterized in that, in addition, the device (13) that has the horizontal mixing washing fluid of pump (14) exports on pipe fitting with it at its inlet pipe fitting with magnetic valve by means of pipeline and is connected with dehydration part, described dehydration part is arranged on the height of pipe fitting (12) of supply washing water of post, be installed between the dehydration part, pump described herein is connected in this wise with dehydration part: make it the possibility by the reversible liquid circulation of dehydration part.
10. as each described equipment in the claim 7～9, it is characterized in that, for sorting regenerated sorbing agent be the additional dehydration part of arrangement in the container (3-1) of its supply in the sorption district of SDK (3), described dehydration part is arranged in and transmits the top of removing the pipe fitting (4) of sorting with saline solution later, and is connected with the pipe fitting (5) that flows out the exhausted saline solution.
11. as each described equipment in the claim 7～10, it is characterized in that, at the dehydration part of container (3-2) installation that is used for receiving from the desorption zone of SDK (3) the regenerated sorbing agent, described dehydration part directly or by means of the receiving vessel (3-2) from the regenerated sorbing agent is connected to the bypath system (18-1) that desorption zone feeds back conversion solution with the following pipe fitting (18-2) of the solution of drawing conversion; Dehydration part is connected with the last pipe fitting (19) of drawing conversion solution, and is connected with the pipe fitting (16) that feeds back conversion solution to desorption zone.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/DE2001/004061 WO2003037794A1 (en) | 2001-10-25 | 2001-10-25 | Method for recovering lithium chloride from brine and installation for carrying out said method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1558871A true CN1558871A (en) | 2004-12-29 |
| CN1263678C CN1263678C (en) | 2006-07-12 |
Family
ID=5648304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB01823738XA Expired - Lifetime CN1263678C (en) | 2001-10-25 | 2001-10-25 | Method for recovering lithium chloride from brine and installation for carrying out said method |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1263678C (en) |
| DE (1) | DE10197021D2 (en) |
| WO (1) | WO2003037794A1 (en) |
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| US8753594B1 (en) | 2009-11-13 | 2014-06-17 | Simbol, Inc. | Sorbent for lithium extraction |
| US9034294B1 (en) | 2009-04-24 | 2015-05-19 | Simbol, Inc. | Preparation of lithium carbonate from lithium chloride containing brines |
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| SU1378890A1 (en) * | 1986-03-03 | 1988-03-07 | Предприятие П/Я А-7638 | Electric dialyzer of filter-press type |
| DE3712142A1 (en) * | 1986-04-11 | 1987-10-15 | Lithium Corp | METHOD FOR CLEANING SOLES |
| WO1994019280A1 (en) * | 1993-02-16 | 1994-09-01 | Nauchno-Proizvodstvennoe Aktsionernoe Obschestvo 'ekostar' | Process for obtaining lithium chloride from solutions and a device for carrying out the same |
| JPH07155563A (en) * | 1993-12-06 | 1995-06-20 | Hitachi Ltd | Nacl recovery device by electrodialysis |
| DE19541558A1 (en) * | 1995-11-08 | 1997-05-15 | Bayer Ag | Preparation of sodium-deficient lithium chloride solutions |
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- 2001-10-25 WO PCT/DE2001/004061 patent/WO2003037794A1/en active Application Filing
- 2001-10-25 DE DE10197021T patent/DE10197021D2/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1263678C (en) | 2006-07-12 |
| DE10197021D2 (en) | 2004-10-14 |
| WO2003037794A1 (en) | 2003-05-08 |
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