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WO2003037794A1 - Procede d'extraction de chlorure de lithium a partir de solutions alcalines salines et dispositif de mise en oeuvre de ce procede - Google Patents

Procede d'extraction de chlorure de lithium a partir de solutions alcalines salines et dispositif de mise en oeuvre de ce procede Download PDF

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Publication number
WO2003037794A1
WO2003037794A1 PCT/DE2001/004061 DE0104061W WO03037794A1 WO 2003037794 A1 WO2003037794 A1 WO 2003037794A1 DE 0104061 W DE0104061 W DE 0104061W WO 03037794 A1 WO03037794 A1 WO 03037794A1
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WO
WIPO (PCT)
Prior art keywords
solution
container
lithium chloride
pipe section
sorbent
Prior art date
Application number
PCT/DE2001/004061
Other languages
German (de)
English (en)
Inventor
Alexander Rybtsev
Valeriy Titarenko
Larisa Menzheres
Natalya Kotsupalo
Elizaveta Guschina
Luydmila Serikova
Piter Shinkarenko
Sergey Sudarev
Nikolay Nemkov
Original Assignee
Eurosina Technology Consulting & Project Development Gmbh
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Publication date
Application filed by Eurosina Technology Consulting & Project Development Gmbh filed Critical Eurosina Technology Consulting & Project Development Gmbh
Priority to CNB01823738XA priority Critical patent/CN1263678C/zh
Priority to DE10197021T priority patent/DE10197021D2/de
Priority to PCT/DE2001/004061 priority patent/WO2003037794A1/fr
Publication of WO2003037794A1 publication Critical patent/WO2003037794A1/fr

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Classifications

    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

Definitions

  • the inventions relate to a process for the production of lithium chloride from brine and a plant for carrying out the process. They generally relate to the field of wet lithium metallurgy, in particular the extraction of lithium chloride from its solutions and from natural brine.
  • a method for obtaining lithium chloride from solutions (US Pat. No. 4,291,001), for example from brine based on crystalline lithium aluminate LiCl 2AI (OH) 3 nH 2 O, synthesized in the macropores of an ion exchange resin, and for using this sorbent in the sorption columns with the resting filter layer of the sorbent on the way of lithium elution (desorption) and subsequent concentration of the eluate via a column system.
  • the salt of a non-competitive metal e.g. NaCI or CaCI 2
  • the column system is operated with brine heating up to a temperature of 60 ° C or more.
  • the use of salt for the eluate concentration leads to additional reagent consumption and to eluate contamination by sodium chloride and calcium chloride.
  • US Pat. No. 4,291,001 describes a plant for the production of lithium chloride from brine, consisting of a device for the production of lithium chloride and a device for concentrating the eluate - lithium chloride solution, which includes three columns filled with sorbent, which together, with the brine source and the container for fresh water by means of a piping system.
  • the system has a salt metering device and a device for the removal of the concentrated lithium chloride.
  • the known system takes up an important production area and has a high metal requirement and a complicated control system for process control.
  • a process for the production of lithium chloride from brine is known as a sorption-desorption complex (hereinafter referred to as SDK), which the sorption extraction of the lithium from the brine by contacting with the granular sorbent selective for lithium according to RU 2050330, produced according to the process according to RU 2113405 and RU 2050184, as well as the lithium desorption by means of the demineralized water with the extraction of the lithium chloride solution as an eluate and its subsequent concentration.
  • the chloride form of the double hydroxide of aluminum and lithium in the composition LiCl 2AI (OH) 3 nH 2 O is used as the sorbent.
  • the lithium sorption and desorption is carried out in step countercurrent operation.
  • the duration of the residence time of the sorbent in the sorption zone is chosen as it is required for complete sorbent saturation with the lithium chloride.
  • the duration of the residence time in the desorption zone is determined by the time required for a complete extraction of lithium chloride from the sorbent.
  • the sorption duration is specified on the basis of the condition of the equivalent saturation of the sorbent initial charge volume with the lithium, which is equal to the volume of the new sorbent charge.
  • the sorbent post-saturation with the lithium up to the limit value is carried out while ensuring the maximum possible concentration of lithium chloride in the sorbent during sorption and corresponding to the maximum possible concentration in the solution in the course of the phase contacts during desorption.
  • the concentration of the eluate of the lithium chloride produced in the known method is carried out by electrodialysis in the presence of an ion exchange resin, which not only causes a concentration of the solution of the lithium chloride, but also allows its post-cleaning of calcium and magnesium admixtures.
  • the sorbent used for the selective sorption of lithium from the brine with high mineralization is based on the chloride form of the double hydroxide of aluminum and lithium LiCI 2AI (OH) 3 nH 2 O (hereinafter called DHAL-CI) with construction defects and lithium deficiency in its composition prepared, which corresponds to the sorption capacity of 6 i 1 mg lithium per 1 gram of sorbent.
  • DHAL-CI lithium LiCI 2AI (OH) 3 nH 2 O
  • WO 94/19280 describes a process with a plant for the sorption of lithium in the form of its chloride.
  • a component of the plant is the sorption-desorption complex (hereinafter referred to as SDK), which is a Higgens column type with a U-shaped cylinder body filled with granulated sorbent.
  • the SDK has ball valves that are mounted in the sorption and desorption areas of the column and are used in the column body for the passage of sorbent.
  • the intersections of the sorption and desorption zones are 1.5: 1.0.
  • In the SDK are arranged: pipes for the supply of the starting brine into the sorption zone and for the discharge of the brine from it, pipes for the supply of the elution liquid into the desorption zone and for the eluate discharge from it, pipes for the discharge of the regenerated sorbent from the desorption zone and For the supply of the regenerated sorbent into the sorption area from the SDK and a pipeline for the supply of the solution for the re-saturation and the washing of the sorbent, which is mounted under the pipeline for the supply of the starting brine in the sorption zone.
  • the SDK is connected by means of the pipes and the fitting: to the containers for the starting brine and the brine, for the elution liquid and for the eluate, with the collection container for the solution, which is used as rinsing liquid in the sorbent classification and with the filter for the Sorbent separation method and with the device for concentrating the eluate, which consists of an electrodialyzer and a pulp preparation apparatus, the eluate container, the container for demineralized water and the filter, and the containers for the concentrated solution of lithium chloride and for the Regenerate (solution of magnesium chloride and calcium chloride after resin regeneration in the electrodialyzer are connected.
  • the main disadvantages of this system are as follows: only eluates with a low lithium chloride concentration ( ⁇ 5 kg / m 3 ) can be obtained, in the insufficient purity of the eluate to be fed into the electrochemical apparatus, in the absence of a channel for the return of the liquid the zone for the sorbent transfer into the desorption zone, in a significant sorbent wear due to the slanted device in the column and the different diameter of the device in the so ⁇ tions- and the desorption zone; a long drain time of the brine and the rinsing liquid; an uneven supply of brine in the column cross-section, the use of an electrodialyzer with low power for the eluate concentration.
  • the object of the invention is therefore to provide an improved process for the extraction of
  • Lithium chloride with higher purity and yield enables.
  • Another object of the invention is to provide a plant for carrying out this method.
  • the object is achieved by a method having the features of claim 1.
  • Advantageous embodiments of the method according to the invention result from the features of claims 2 to 6.
  • LiCl from 100 kg / m 3 to 150 kg / m 3 and the desalted solution with a LiCl content of 0.2 kg / m 3 to 0.5 kg / m 3 , which is further used for the lithium desorption
  • Sorbent is used, the possibility of using alternative methods for concentrating the
  • Lithium chloride solution in a natural way in tanks and graduation towers as well as by concentrating the lithium chloride solution after the freezing process, reducing the sodium admixture in the finished product by the constant
  • Circulation operation with a ratio of the volume flow of the circulating solution to
  • Liquid stream of a desalted solution with a residual LiCI content of 0.2 kg / m 3 to 0.5 kg / m 3 which in the phase of lithium desorption from the sorbent as
  • Desorbent is used and the generation of a concentrate flow with a LiCl content of 7 kg / m 3 to 10 kg / m 3 , which is mixed with the purified eluate; the use of natural eluate concentration by evaporation in basins or by freeze-drying at a temperature of -10 ° C to -30 ° C; the subsequent evaporation of the electrodialysis brine or the brine obtained by natural concentration (water evaporation) up to one
  • the technical and economic effects of the method described are also due to the use of the system according to the invention.
  • the system also has a So ⁇ tion-Desorption complex for eluate cleaning (hereinafter referred to as SDKER) with a sorption and a desorption branch whose diameters are 3: 2 to each other, a device for the electrodialysis concentration of the cleaned eluates, consisting of: Electrodialysis concentrator and electrodialysis desalinator, heat exchanger recuperator for preheating the desalinated solution, evaporator and cooler condenser for separating the wet steam with a droplet separator, crystallizer, centrifuge, slanted screw washer and heated screw vacuum dryer. All devices and apparatus are connected to one another by means of pipelines through appropriate containers directly or via pumps.
  • the main SDK for the selective extraction of lithium from the brine has the same diameters of the sorption and desorption areas. It also has the following assemblies: a device for cross-mixing the washout liquid, arranged in the toroidal part of the column, pipe section with dewatering insert, mounted in the lower part of the container for receiving the regenerated sorbent from the desorption zone and connected to a bypass line for returning the transfer solution into the desorption zone; via a circuit, formed by a drainage system for the eluate discharge, arranged in the lower region of the desorption branch of the SDK above the device for cross-mixing the wash-out liquid, and connected to the container for the eluate circulation.
  • a pump is arranged in the device for cross-mixing the wash-out liquid, which is connected via its inlet and outlet pipes to the drainage inserts, which is mounted in the SDK body at the height of the pipe section for the inlet of the wash-out liquid between the drainage inserts.
  • the pump is with the Drainage inserts are preferably connected in such a way that there is a possibility for reversible liquid circulation through the drainage inserts.
  • a drainage insert is mounted in the container for receiving the regenerated sorbent from the desorption zone of the SDK, connected to the lower pipeline for the discharge of the transfer solution directly and by means of a bypass system for the return the transfer solution from the container into the desorption zone and with the upper pipeline for the discharge of the transfer solution for the purpose of its return to the desorption zone.
  • the system proposed according to the invention for the production of lithium chloride from brine ensures the step-countercurrent flow of the contact phases in the sorption-desorption complex, which runs in two operating stages, firstly the brine filtration (sorption) through the sorbent and the sorbent transfer with a closed sorbent circuit and one effective washing of the granules of foreign matter using a cross line for mixing the washing water and secondly concentrating the eluate directly in the column by introducing a circuit for the eluate recirculation and the return flow of the eluent liquid from the zone of sorbent transfer to the upper desorption zone, which is a Eluate dilution prevented.
  • the eluate with the concentration of LiCl, which is close to equilibrium, is fed to the ion exchange column (SDKER) for the purification of Ca ions and Mg ions. Then it is directed to two-stage electrodialysis concentrating.
  • the salt-free water thus obtained is led into the desorption branch of the SDK and the electrodialysis salt liquor of the LiCl is evaporated by the heat treatment for the subsequent crystallization of the LiCI H 2 O and for the production of the anhydrous lithium chloride.
  • 1 shows a graphical representation of the dependence of the eluate concentration on the circulation circuit by means of the circulation solutions of the recirculation of the desorption branch from the SDK with a ratio of the liquid phase to the solid phase of 1.5: 1, 0;
  • Electrodialysis machine with galvanostatic operation and different current densities (A / dm 2 ): a - 3.3; b - 5.9; c - 7.2;
  • Fig. 8-1, 8-2, 8-3 Schematic representation of the plant for the production of lithium chloride from brine.
  • the SDK hereinafter referred to as the column, has a number of zones through which the sorbent is continuously passed and which correspond to the following processes: hydraulic sorbent classification (I), sorption (II), washing and post-saturation (III, IV), desorption ( V and VI). After the lithium desorption, the sorbent is passed into the container (VII) and then into the zone for the hydraulic classification (I), which forms a closed circuit. According to FIG. 8, the sorbent is passed on under compressed air pulses.
  • zone (I) a small fraction (the products of the sorbent decay) is removed from the column by hydraulic classification in the ascending flow of the liquid, whereby the resistance of the hydraulic resistance of the sorbent layer is achieved.
  • the sorbent After sorbent saturation in the sorption zone (II), the sorbent is led into the washing and post-saturation zone of the LiCI solution (III, IV). Here the sorbent is washed off from the salt contained in the brine by the additional cross-mixing with the washing liquid. In the intermediate zone (IV), sorbents reach and solution (desorbate) the point at which the maximum lithium content is determined both in the sorbent and in the solution. The eluate is removed at this point. During the forwarding of the sorbent into the desorption area of the SDK, the sorbent runs through the first desorption zone (V), through which the eluate circulates, and further through the second desorption zone (VI), where the lithium is deeply desorbed with the salt-free desorption solution.
  • the mentioned LiCI concentration is reached during the eluate recirculation in the desorption zone. 1 shows the dependence of the LiCI concentration on the number of cycles (passes) through the recirculation circuit. As follows from FIG. 1, the LiCI concentration practically reaches an equilibrium state after only 2 to 4 cycles (FIG. 2).
  • the eluate is fed into the ion exchange column (SDKER), which is filled with the cation exchange resin KY-2 in Li form and works according to the SDK principle, i.e. in counter-current operation.
  • SDKER ion exchange column
  • the small resin fraction is separated off in zone (I) by means of hydraulic classification.
  • the resin In the sorption zone (II) the resin is saturated with the Ca and Mg ions from the eluate, during which the lithium ions pass into the solution.
  • the resin KY-2 runs from the sorption zone into the transition zone (III), where the Li ions are further displaced from the resin into the solution and replaced by Ca and Mg ions, the concentration of which compared to their concentration in Starting eluate of the sorption zone is somewhat higher.
  • zone (III) the sorbent is completely saturated with the Ca and Mg ions and the regeneration solution (LiCI solution) running in the opposite direction reaches the point at which the concentration of calcium and magnesium in the sorbent and in the solution is at a maximum is.
  • the used regeneration solution is removed, which contains up to 100 kg / m 3 CaCl 2 and MgCl 2 as well as approximately 2 kg / m 3 LiCl.
  • the described construction of the ion exchange column allows eluates with a content of Ca 2+ and Mg 2+ to be obtained up to 0.001 kg / m 3 and 0.003 kg / m 3 .
  • the lithium chloride content increases somewhat to 13 kg / m 3 to 18 kg / m 3 because of the lithium transition from the resin into the solution.
  • the lithium chloride solution is used to concentrate electrodialysis: stage I - production of the electrodialysis salt solution 100 kg / m 3 to 150 kg / m 3 LiCl and the dialysate 3.5 kg / m 3 to 4.0 kg / m 3 , and stage II - concentration of the Dialysates from stage I to 7.0 kg / m 3 to 10.0 kg / m 3 LiCl with recovery of the Li concentrate and the desalted solution with a LiCl content of 0.2 kg / m 3 to 0.5 kg / m 3 , which is conducted as a desorbent in the desorption zone from the SDK for lithium desorption from the granulated sorbent.
  • the electrodialysis salt liquor LiCl from concentration stage I runs into the heat exchanger recuperator for preheating, then into the evaporator for subsequent evaporation with subsequent cooling of the evaporated solution in the crystallizer and for crystal formation LiCl H 2 O.
  • the LiCl H 2 O crystals are in the centrifuge from the remaining solution is separated off and washed in an inclined screw washer, where countercurrent washing takes place with a lithium chloride solution; then the LiCIH 2 O crystals are fed into the vacuum screw dryer, in which the anhydrous lithium chloride is obtained at a temperature of 100 ° C to 105 ° C and constant removal of the water vapor.
  • Concentrating the LiCI solution after cleaning the Ca and Mg admixtures can also occur naturally in the basin under the conditions of a mild one warm climates or freeze-drying in areas with a long winter period and very dry air. After the natural concentration or freeze-drying, the concentrated LiCI solution is also passed on to the heat exchanger recuperator and the evaporator for further evaporation and production of the crystalline lithium chloride monohydrate, as already described above.
  • Ca and Mg content in the resin 153 meq.
  • the eluate was passed through the cation exchange resin KY-2, it was regenerated with a lithium chloride solution of 70 g / l.
  • Resin regeneration was carried out in the same column before the absence of Ca and Mg in the resin.
  • the regenerated solution used was a solution of magnesium and calcium chloride with a concentration of up to 100 g / l, converted to CaCl 2 with a LiCl content of ⁇ 2 g / l, added to the starting salt solution (example 1).
  • the eluate which had been cleaned of foreign constituents and had a LiCl content of 18 g / l (see Example 2), was subjected to electrodialysis concentration in a 10-chamber cell, of which 5 chambers were used for desalination and 5 chambers for concentration, and the second Electrode chambers, united by a uniform circulation circuit in which the LiCI solution circulated with a concentration of 15 g / l to 20 g / l.
  • the chamber distance was 2 mm.
  • Concentration was carried out in galvanostatic operation at current densities of 3.3 A / dm 2 ; 5.9 A / dm 2 and 7.2 A / dm 2 .
  • the linear velocity of the solution flow through all chambers was 5 cm / s.
  • the process was carried out for the LiCI solution circulating for desalination and concentration.
  • the process control is based on the change in the LiCI concentration in the desalination circuit and in the concentration circuit.
  • the test results are in Fig. 3 shown.
  • concentration was carried out to 130 g / l to 150 g / l (FIGS. 3a and 3b).
  • the eluate concentration was carried out down to -100 g / l LiCl (FIG. 3c).
  • LiCI concentrations in the solution to be desalinated decrease as a result of the membrane polarization, the energy consumption increases very much.
  • the dialysate with a LiCl content of 3.5 g / l and 5.0 g / l was desalted in an electrodialysis cell, the construction of which is described in Example 4. Desalination was carried out in potentiostatic operation with a voltage drop in the unit cell of 4 V. The process was carried out in the circulating mode of the solution to be desalinated at a linear velocity of the current of 5 cm / s. carried out. The test results are shown in FIG. 5. Desalination took place up to a LiCl content of 0.2 g / l (a) and 0.5 g / l (b) at a starting content of 3.5 g / l and 5.0 g / l. The LiCl content in the concentration range corresponded to ⁇ 7.5 g / l and 10.0 g / l.
  • the eluate cleaned of foreign constituents with a LiCl content of 100 g / l became after the electrodialysis concentrate in a container which was heated in a water bath with constant mixing in order to follow the evaporation of the LiCI solution under natural conditions. After evaporation four times, a LiCI solution with ⁇ 400 g / l was obtained. Evaporation of the LiCI solution down to ⁇ 600 g / l was carried out with an electric cooker. After cooling the solution and forming LiCl H 2 O crystals, the crystals were separated from the solution and washed three times with smaller amounts of the lithium chloride solution. The content of the basic substance in the lithium chloride monohydrate obtained was 99.9%.
  • the test results are shown in Fig. 6.
  • the residual moisture is - 7.5% (curve b) at a temperature of 100 ° C and 2% at 105 ° C (curve a).
  • the dried product does not lose its bulk status.
  • the foreign constituents in anhydrous lithium chloride are 0.142%, which corresponds to a lithium chloride with a high degree of purity.
  • this characteristic value can be increased to 90%.
  • the lithium chloride content was 0.4 g / l to 0.8 g / l after separating the brine produced and defrosting ice, which it was allowed to use such solutions for the lithium desorption of the sorbent.
  • the first loading of the column (SDK) with the sorbent takes place when the sorbent pulp is fed in the LiCl solution ( ⁇ 2 g / l), which runs from the container 90 into the container 29.
  • the brine is conveyed into the left So ⁇ tions Scheme II of the column.
  • the starting salt liquor from the container 1 is passed through the pipe section 4 into the SDK 3 by means of the pump 2.
  • the So ⁇ tionszone left area of the column
  • the low in lithium brine is discharged through the pipe section 5 and the filter 26 into the collecting basin for the brine 27.
  • the used brine flows through the used brine disposal system 101.
  • Part of the brine is fed from the tank 27 with the pump 28 through the pipe section 7 into the classification zone of the SDK (tank 3-1), where the crushed sorbent fraction is separated and together with the brine through the pipe section 8 from the SDK (tank 3 -1) is dissipated.
  • the pulp of the shredded sorbent and the brine flow through the filter 26, with which the sorbent constituents are separated: the brine runs into the container 27 and the shredded sorbent is filled into sacks and transported to a plant for producing granulated sorbent for further use.
  • Fresh feeds with granulated sorbent are made by mixing DHAL-CI with the brine that flows from the column (SDK area II) through the pipe section 5 into the container 29; then the pulp with the jet pump 30 is guided through the pipeline and the pipe section 9 into the classification zone of the SDK (container 3-1).
  • the granulated sorbent comes into the lower toroidal part of the column, where the water from the container 38 is also pumped through the pipe section 12 with the pump 37. Washing is carried out using the mixing device 13, including the pump 14.
  • the washed sorbent runs into the desorption zone of the sorption-desorption complex (SDK) 3, in which a two-stage lithium desorption is carried out: first by means of the lithium chloride, which is fed from the container 35 through the pipe section 15 with the pump 36; this is followed by deep lithium desorption with the salt-free solution, which is conveyed from the container 40 through the pipe section 17 with the pump 39.
  • SDK sorption-desorption complex
  • the eluate flows into the lower part of the zone, where it is re-saturated with the lithium with the aid of the drainage system 11 of the concentration cycle.
  • the eluate from the container 35 is pumped several times by means of the pump 36 through the sorbent of the lower part of the desorption zone of the SDK 3, which increases the LiCl concentration in the eluate.
  • the eluate saturated with lithium is passed on from the concentration circuit 11 into the container 33 for cleaning calcium and magnesium.
  • the sorbent After lithium desorption, the sorbent passes through valve 25 into container 3-2 for receiving the regenerated sorbent; a part of the transfer solution, which came into the container 3-2 during the conveying of the soothing agent, is returned to the column via the bypass system 18-1 and through the pipe sections 19 and 16.
  • the prepared (regenerated) sorbent is conveyed through the valve 24 into the classification zone (container 3-1).
  • the sorbent After classification, the sorbent is passed through valve 23 into the sorption area of the column (SDK). This closes the sorbent cycle in the SDK 3.
  • the sorbent is conveyed from the container 3-2 into the classification zone with the help of water from the container 38, which is guided through the pipe section 20 by means of the pipe 37 into the container 3-2.
  • the eluate is led from the container 33 by means of the pump 34 through the pipe section 42 into the area II of the ion exchange column 41 (SDKER).
  • the eluate cleaned from Ca 2+ and Mg 2+ ions runs through the pipe section 43 via the curved sieve 64 into the collecting container 65 for the cleaned eluate.
  • the cation exchanger KY-2 saturated with Ca 2+ and Mg 2+ ions is conveyed into the toroidal part of the column by means of a compressed air pulse, after which it runs into the region IV of the column and for the desorption of Ca 2+ and Mg 2+ ions is regenerated there at the same time.
  • the regeneration solution LiCl with a concentration of 70 kg / m 3 to 100 kg / m 3 is fed through the pipe section 52-1.
  • the used regeneration solution saturated with Ca and Mg chlorides and with a LiCl content of ⁇ 2 kg / m 3 , is drained through the pipe section 50 and passed into the container 1 with the starting solution.
  • the regenerated cation exchanger KY-2 in Li + form runs through the valve 60 into the container 41-2, and the solution fed into the container together with the resin is returned to the desorption zone via the bypass system through the pipe sections 54 and 51.
  • the resin is conveyed through the valve 59 into the container 41-1 for classification and separation of the small fraction with the aid of the purified eluate coming from the container 65.
  • the resin classification is also carried out by means of the cleaned eluate, which is fed from the container 65 through pipes and the pipe section 45. From the classification zone, the pulp is passed on to the curved screen 64, on which the small resin fraction is separated from the LiCl solution, which runs into the container 65.
  • the purified eluate is concentrated in series-produced electrodialysis apparatus in filter press design, consisting of the alternating cation and anion exchange membranes that form the chambers for concentrating and desalting.
  • the cleaned eluate is conveyed from the container 67 with the pump 68 into the electrodialysis concentrator 69 for the first stage of the concentration; in the process of concentrating, the solution circulates in the desalination chamber until the LiCl content reaches the value of 3.5 kg / m 3 to 4 kg / m 3 .
  • the LiCl concentration in the electrodialysis brine is simultaneously increased to 100 kg / m 3 to 150 kg / m 3 , which is collected in the container 72.
  • the dialysate produced in the desalination chambers is fed to the container 73 at the second stage of desalination, from which it is pumped into the electrodialysis desalder 75 of a similar design for deeper desalination (to 0.2 kg / m 3 to 0.5 kg / m 3 LiCl) is forwarded.
  • concentrate with a LiCl content of ⁇ 7.5 kg / m 3 to 10.0 kg / m 3 is obtained in the concentration chambers, which is passed from the container 77 into the container 67 and mixed with the purified eluate ,
  • the desalted solution with a LiCl content of 0.2 kg / m 3 to 0.5 kg / m 3 runs into the container 40 for use in the lithium desorption stage of the sorbent in the SDK 3.
  • the electrodialysis brine of the lithium chloride is fed from the container 72 with the pump 79 into the heat exchanger recuperator 78, in which the solution is heated with the steam coming from the evaporator 80.
  • the LiCI solution runs into the evaporator 80 for further evaporation, in which the water evaporates in vacuo and by means of the heating steam which is passed through the steam supply system 96 and the condensate which has formed in the course of the steam supply.
  • the LiCI concentration in the brine increases to 750 kg / m 3 to 800 kg / m 3 .
  • the subsequently evaporated LiCl brine is discharged into the crystallizer 85.
  • the wet steam is condensed in the cooler condenser 81 and passed on through the droplet separator 83 into the collecting container 84 for the condensate.
  • the LiCl H 2 O crystals produced in the crystallizer 85 are separated from the brine in the centrifuge 86 and passed on for washing in the end part of the slanted screw washer 87.
  • the condensate runs out of the container 84 in the top part thereof.
  • the fugate from the centrifuge is partly used in the circuit for the evaporation stage and partly removed from the system and into the container 93-2 for promoted the preparation of the regeneration solution.
  • the Mg and Ca ions are removed and the resin is transformed into the Li + form.
  • the LiCl H 2 O crystals represent an anhydrous lithium chloride of high purity in hand ice quality (the amount of the cation admixtures of Na, K, Mg, Ca is only 0.01 percent by mass to 0.15 percent by mass ).
  • the technological process according to the invention has no runoff and also does not cause wastes that are harmful to nature and pollute the environment. All the reagents required for the process remain in the described technological system.
  • the salt-free solution from the process of concentrating the lithium chloride solution is used for the lithium desorption of the sorbent;
  • the concentrated solution of lithium chloride is used, which is obtained by washing the LiCl H 2 O crystals;
  • the used regeneration solution which contains calcium and magnesium chlorides as well as lithium chloride (up to 2 g / l), is used for the stage of lithium sorption after regeneration of the cation exchanger KY-2 used in the SDK.
  • the cleaning of the eluates of Ca 2+ and Mg 2+ ions using the cation exchanger KY-2 is a very effective process for obtaining LiCI solutions which contain magnesium and calcium chlorides in amounts of only 0.0003 percent by mass and 0. Contain 0001 mass percent (Example 2), which is ten times less than according to the prior art described.
  • the salt-free solution of the second stage of eluate concentration is used for lithium desorption of the sorbent, which is associated with a significant reduction in fresh water consumption.
  • the technical solutions according to the invention can be successfully used to obtain the lithium chloride monohydrate from the lithium-containing natural chloride salt liquors of any type and with any salt concentration and from the technological salt solutions of chemical and biochemical production.

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  • Materials Engineering (AREA)
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Abstract

L'invention concerne un procédé d'extraction de chlorure de lithium à partir de solutions alcalines salines, et un dispositif destiné à la mise en oeuvre de ce procédé. Ledit procédé d'extraction de LiCl à partir de solutions alcalines salines avec extraction par sorption sélective du lithium consiste essentiellement à extraire une solution enrichie en LiCl dans un complexe de sorption/désorption au moyen d'un liquide de désorption, et une solution de LiCl extraite par recirculation, présentant une concentration de 10 kg/m3 à 17 kg/m3 ; à éliminer par échange ionique des impuretés de Ca et de Mg dans la solution enrichie ; à concentrer des éluats lavés selon le procédé d'électrodialyse jusqu'à une concentration de LiCl de 100 kg/m3 à 150 kg/m3, avec obtention d'une solution dessalée présentant une teneur en LiCl de 0,2 kg/m3 à 0,5 kg/m3, employée pour la désorption de lithium de l'agent de sorption ; et, à laver et sécher les cristaux de LiCl obtenus par refroidissement d'une solution concentrée jusqu'à une teneur en LiCl de 600 kg/m3 à 800 kg/m3. Le chlorure de lithium ainsi extrait est exempt d'eau, présente un degré de pureté élevé et peut par conséquent être employé pour la production de lithium métallique et des alliages de celui-ci.
PCT/DE2001/004061 2001-10-25 2001-10-25 Procede d'extraction de chlorure de lithium a partir de solutions alcalines salines et dispositif de mise en oeuvre de ce procede WO2003037794A1 (fr)

Priority Applications (3)

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CNB01823738XA CN1263678C (zh) 2001-10-25 2001-10-25 从盐液获得氯化锂的方法和实施此方法的设备
DE10197021T DE10197021D2 (de) 2001-10-25 2001-10-25 Verfahren zur Gewinnung von Lithiumchlorid aus Salzlaugen und Anlage zur Durchführung des Verfahrens
PCT/DE2001/004061 WO2003037794A1 (fr) 2001-10-25 2001-10-25 Procede d'extraction de chlorure de lithium a partir de solutions alcalines salines et dispositif de mise en oeuvre de ce procede

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WO2011138389A1 (fr) 2010-05-05 2011-11-10 Technische Universität Bergakademie Freiberg Procédé pour appauvrir en magnésium des solutions salines chlorées et les enrichir en lithium
CN1844805B (zh) * 2006-03-12 2012-04-25 王俊 制冷机用溴化锂溶液中钙镁离子消除的方法与装置
RU2516538C2 (ru) * 2012-02-17 2014-05-20 Закрытое акционерное общество (ЗАО) "Экостра-Наутех" Способ получения литиевого концентрата из литиеносных природных рассолов и его переработки
US9012357B2 (en) 2009-12-18 2015-04-21 Simbol, Inc. Lithium extraction composition and method of preparation thereof
US9034295B2 (en) 2009-04-24 2015-05-19 Simbol, Inc. Preparation of lithium carbonate from lithium chloride containing brines
US9034294B1 (en) 2009-04-24 2015-05-19 Simbol, Inc. Preparation of lithium carbonate from lithium chloride containing brines
US9051827B1 (en) 2009-09-02 2015-06-09 Simbol Mining Corporation Selective removal of silica from silica containing brines
US9074265B2 (en) 2010-02-17 2015-07-07 Simbol, Inc. Processes for preparing highly pure lithium carbonate and other highly pure lithium containing compounds
DE102015000872A1 (de) 2015-01-23 2016-07-28 K-Utec Ag Salt Technologies Methode zur Gewinnung von Lithiumchlorid
CN106048218A (zh) * 2016-07-14 2016-10-26 四川思达能环保科技有限公司 一种氯化锂混合溶液的净化除杂方法
CN109019641A (zh) * 2018-10-12 2018-12-18 中国科学院青海盐湖研究所 从硫酸钠亚型盐湖卤水中分离镁锂并富集锂的方法
RU2688593C1 (ru) * 2018-08-16 2019-05-21 Публичное акционерное общество "Татнефть" имени В.Д. Шашина Способ сорбционного извлечения лития из литийсодержащих хлоридных рассолов
CN110395749A (zh) * 2019-08-09 2019-11-01 山东科技大学 一种利用四隔室置换反应电渗析制备氯化锂的方法
US10829676B2 (en) 2009-04-24 2020-11-10 Terralithium Llc Treated geothermal brine compositions with reduced concentration of silica, iron and lithium
US10935006B2 (en) 2009-06-24 2021-03-02 Terralithium Llc Process for producing geothermal power, selective removal of silica and iron from brines, and improved injectivity of treated brines
US11396452B2 (en) 2017-04-14 2022-07-26 Ecostar-Nautech Co., Ltd. Method for preparing lithium concentrate from lithium-bearing natural brines and processing thereof into lithium chloride or lithium carbonate
US12168748B2 (en) 2009-04-24 2024-12-17 Terralithium Llc Treated geothermal brine compositions with reduced concentration of silica, iron and lithium
WO2024243029A3 (fr) * 2023-05-19 2025-01-02 University Of Utah Research Foundation Systèmes et procédés d'extraction de lithium à partir de charges d'alimentation aqueuses
US12221671B2 (en) 2009-06-24 2025-02-11 Terralithium Llc Treated geothermal brine compositions with reduced concentrations of silica, iron and manganese

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3712142A1 (de) * 1986-04-11 1987-10-15 Lithium Corp Verfahren zum reinigen von solen
SU1378890A1 (ru) * 1986-03-03 1988-03-07 Предприятие П/Я А-7638 Электродиализатор фильтр-прессного типа
WO1994019280A1 (fr) * 1993-02-16 1994-09-01 Nauchno-Proizvodstvennoe Aktsionernoe Obschestvo 'ekostar' Procede d'obtention de chlorure de lithium a partir de solutions et son dispositif de mise en ×uvre
JPH07155563A (ja) * 1993-12-06 1995-06-20 Hitachi Ltd 電気透析によるＮａＣｌ回収装置
DE19541558A1 (de) * 1995-11-08 1997-05-15 Bayer Ag Verfahren zur Reinigung von Lithiumchlorid-Lösungen

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1378890A1 (ru) * 1986-03-03 1988-03-07 Предприятие П/Я А-7638 Электродиализатор фильтр-прессного типа
DE3712142A1 (de) * 1986-04-11 1987-10-15 Lithium Corp Verfahren zum reinigen von solen
WO1994019280A1 (fr) * 1993-02-16 1994-09-01 Nauchno-Proizvodstvennoe Aktsionernoe Obschestvo 'ekostar' Procede d'obtention de chlorure de lithium a partir de solutions et son dispositif de mise en ×uvre
JPH07155563A (ja) * 1993-12-06 1995-06-20 Hitachi Ltd 電気透析によるＮａＣｌ回収装置
DE19541558A1 (de) * 1995-11-08 1997-05-15 Bayer Ag Verfahren zur Reinigung von Lithiumchlorid-Lösungen

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 198837, Derwent World Patents Index; Class D15, AN 1988-263267, XP002197024 *
DATABASE WPI Section Ch Week 199436, Derwent World Patents Index; Class D15, AN 1994-294183, XP002197023 *
PATENT ABSTRACTS OF JAPAN vol. 1995, no. 09 31 October 1995 (1995-10-31) *

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US10773970B2 (en) 2009-04-24 2020-09-15 Terralithium Llc Preparation of lithium carbonate from lithium chloride containing brines
US12168748B2 (en) 2009-04-24 2024-12-17 Terralithium Llc Treated geothermal brine compositions with reduced concentration of silica, iron and lithium
US11649170B2 (en) 2009-04-24 2023-05-16 Terralithium Llc Preparation of lithium carbonate from lithium chloride containing brines
US11466191B2 (en) 2009-04-24 2022-10-11 Terralithium Llc Treated geothermal brine compositions with reduced concentration of silica, iron and lithium
US9034295B2 (en) 2009-04-24 2015-05-19 Simbol, Inc. Preparation of lithium carbonate from lithium chloride containing brines
US9034294B1 (en) 2009-04-24 2015-05-19 Simbol, Inc. Preparation of lithium carbonate from lithium chloride containing brines
US10829676B2 (en) 2009-04-24 2020-11-10 Terralithium Llc Treated geothermal brine compositions with reduced concentration of silica, iron and lithium
US9834449B2 (en) 2009-04-24 2017-12-05 Alger Alternative Energy, Llc Preparation of lithium carbonate from lithium chloride containing brines
US12252409B2 (en) 2009-04-24 2025-03-18 Terralithium Llc Preparation of lithium carbonate from lithium chloride containing brines
US12221671B2 (en) 2009-06-24 2025-02-11 Terralithium Llc Treated geothermal brine compositions with reduced concentrations of silica, iron and manganese
US11828272B2 (en) 2009-06-24 2023-11-28 Terralithium Llc Process for producing geothermal power, selective removal of silica and iron from brines, and improved injectivity of treated brines
US10935006B2 (en) 2009-06-24 2021-03-02 Terralithium Llc Process for producing geothermal power, selective removal of silica and iron from brines, and improved injectivity of treated brines
US9051827B1 (en) 2009-09-02 2015-06-09 Simbol Mining Corporation Selective removal of silica from silica containing brines
US9012357B2 (en) 2009-12-18 2015-04-21 Simbol, Inc. Lithium extraction composition and method of preparation thereof
US9074265B2 (en) 2010-02-17 2015-07-07 Simbol, Inc. Processes for preparing highly pure lithium carbonate and other highly pure lithium containing compounds
DE102010019554A1 (de) 2010-05-05 2011-11-10 Technische Universität Bergakademie Freiberg Verfahren zur Abreicherung von Magnesium und Anreicherung von Lithium in chloridisch geprägten Salzlösungen
WO2011138389A1 (fr) 2010-05-05 2011-11-10 Technische Universität Bergakademie Freiberg Procédé pour appauvrir en magnésium des solutions salines chlorées et les enrichir en lithium
RU2516538C2 (ru) * 2012-02-17 2014-05-20 Закрытое акционерное общество (ЗАО) "Экостра-Наутех" Способ получения литиевого концентрата из литиеносных природных рассолов и его переработки
DE102015000872A1 (de) 2015-01-23 2016-07-28 K-Utec Ag Salt Technologies Methode zur Gewinnung von Lithiumchlorid
CN106048218A (zh) * 2016-07-14 2016-10-26 四川思达能环保科技有限公司 一种氯化锂混合溶液的净化除杂方法
US11396452B2 (en) 2017-04-14 2022-07-26 Ecostar-Nautech Co., Ltd. Method for preparing lithium concentrate from lithium-bearing natural brines and processing thereof into lithium chloride or lithium carbonate
RU2688593C1 (ru) * 2018-08-16 2019-05-21 Публичное акционерное общество "Татнефть" имени В.Д. Шашина Способ сорбционного извлечения лития из литийсодержащих хлоридных рассолов
CN109019641A (zh) * 2018-10-12 2018-12-18 中国科学院青海盐湖研究所 从硫酸钠亚型盐湖卤水中分离镁锂并富集锂的方法
CN110395749A (zh) * 2019-08-09 2019-11-01 山东科技大学 一种利用四隔室置换反应电渗析制备氯化锂的方法
WO2024243029A3 (fr) * 2023-05-19 2025-01-02 University Of Utah Research Foundation Systèmes et procédés d'extraction de lithium à partir de charges d'alimentation aqueuses

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