WO2018043881A1 - Procédé de préparation de chlorure de lithiuim et procédé de préparation de carbonate de lithium - Google Patents

Procédé de préparation de chlorure de lithiuim et procédé de préparation de carbonate de lithium Download PDF

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Publication number
WO2018043881A1
WO2018043881A1 PCT/KR2017/006401 KR2017006401W WO2018043881A1 WO 2018043881 A1 WO2018043881 A1 WO 2018043881A1 KR 2017006401 W KR2017006401 W KR 2017006401W WO 2018043881 A1 WO2018043881 A1 WO 2018043881A1
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lithium
lithium chloride
carbonate
chloride
water
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PCT/KR2017/006401
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English (en)
Korean (ko)
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김성연
김경석
이소연
최재혁
홍완기
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포스코
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Publication of WO2018043881A1 publication Critical patent/WO2018043881A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/04—Chlorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D7/00—Carbonates of sodium, potassium or alkali metals in general
    • C01D7/22—Purification
    • C01D7/26—Purification by precipitation or adsorption

Definitions

  • a method for producing lithium chloride and a method for producing lithium carbonate is a method for producing lithium chloride.
  • lithium carbonate is used as a raw material for manufacturing battery batteries.
  • a method of manufacturing such lithium carbonate the following methods are known.
  • the concentration of lithium in the brine is about 0.3 to 1.5g / L
  • the lithium in the brine is extracted in the form of lithium carbonate mainly by the pressurized addition of C0 2
  • the solubility of the lithium carbonate is 0 ° C
  • the amount of lithium carbonate in the brine is 1.59 to 7.95 g / L, assuming that all of the lithium contained in the brine is converted to lithium carbonate. Since most of the concentration is lower than the solubility of lithium carbonate, the amount of lithium carbonate precipitated is very low, and thus there is a problem in that the lithium recovery rate is very low.
  • this method does not have a fast reaction rate between the calcium hydroxide and the lithium phosphate, and it takes a long time to obtain lithium ions up to an economic level.
  • the concentration of lithium ions in the obtained lithium hydroxide aqueous solution is low, and the recovery rate of lithium ions is not high.
  • the reaction rate of calcium hydroxide and lithium phosphate is not very fast, and only a low concentration of lithium ions of about 5, ⁇ 00 ⁇ ⁇ can be recovered within an economically acceptable reaction time. Accordingly, it is necessary to concentrate the solution at a high concentration before producing lithium carbonate in a subsequent process, an additional process for concentration is required, and energy consumption due to evaporation is increased.
  • lithium chloride is extracted from a lithium phosphate-iron compound which is a cathode material of a lithium battery containing lithium.
  • the method of preparation is shown.
  • leaching a lithium phosphate-iron compound with hydrochloric acid to leach the components into a solution to obtain a solution containing iron phosphate, lithium phosphate and iron chloride, and increase the pH of the solution to 2.0-2.5 to precipitate iron phosphate
  • the pH of the filtrate was adjusted to 6.0-7.0 by adding an alkali substance to the filtrate.
  • CaCl 2 was added to precipitate and remove phosphate, and the remaining filtrate was evaporated and concentrated to precipitate LiCl crystals. Obtain LiCl.
  • an embodiment of the present invention to provide a method for producing an environmentally friendly lithium chloride aqueous solution capable of extracting lithium ions at a high concentration in a short time from the lithium-containing phosphate.
  • Another object of the present invention is to provide a method for economically preparing lithium carbonate from an aqueous lithium chloride solution.
  • a step of uniformly mixing a phosphate containing lithium and calcium chloride to form a mixture (hereinafter referred to as a mixture ⁇ 1) (hereinafter ⁇ 1); And heating the mixture 1 at a high temperature of 450 ° C.
  • slurry -1 which is a mixture of poorly soluble chloroapatite (Cloroapat i te, CAp) and water-soluble lithium chloride (hereinafter, step -3); And solid-liquid separation of the slurry -1 to obtain chloroapatite (hereinafter referred to as CAp-1) and an aqueous lithium chloride solution (hereinafter referred to as an aqueous solution -1) (hereinafter referred to as -4). .
  • the lithium-containing phosphate may be prepared directly from lithium in saline. In the step -1, the lithium-containing phosphate may be prepared directly from the lithium of the waste battery.
  • the lithium phosphate may be prepared directly from an ore such as spodumene, petalite or lepidolite.
  • the added phosphate containing lithium may be a dry powder state, a water-containing fil ter cake state, or water is added to artificially contain water three times less than the weight of the phosphate You can prepare.
  • the mixture of lithiumol-containing phosphate and calcium chloride may include a process that is mixed in the mixer.
  • the amount of calcium chloride added may be 1.25 times or more and 2.0 times or less than the lithium phosphate on a molar basis.
  • the step of heating the mixture -1 may be heated so that the temperature of the mixture is 450 ° C or more and 850 ° C or less.
  • the time for heating the mixture -1 may be 30 minutes or more and 5 hours or less after the mixture reaches 450 ° C or more.
  • the product-1 may include a portion of the calcium chloride increase in the step -1 in addition to the chloroapatite, the lithium chloride, unreacted state, the portion of the calcium chloride in the step -1 It may be included in the reaction state.
  • the product -1 may include lithium chloride in an amount that the lithium-containing phosphate reacted with calcium chloride more than 80%.
  • a heating method such as heating the container in a box furnace or tunnel furnace, or heating the container by seating in a bath may be included.
  • the mixture -1 contained in the container can be heated evenly and at the same time so that reaction can occur, or the mixture can be stirred during the heating, or the heating is suspended and the stirring process is continued and the heating is continued again. It may have a process of the manner.
  • the amount of water added to the product -1 may be determined so that the concentration of lithium ions is 10, 000 ppm or more and 200, 000 ppm or less when lithium chloride is dissolved in water in the product -1.
  • step -4 in order to recover the lithium chloride remaining in the chloroapatite-1 in the filtration process, water is added to the chloroapatite-1 and washed with water and then filtered again to obtain a lithium chloride-containing filtrate (hereinafter, the filtrate- la) can be obtained, and this filtrate -la can be mixed with the filtrate 1, which can be carried out at least once.
  • the amount of water added at each wash may be from 0.5 to 5 times the weight of the CAp-1 solid material.
  • the aqueous solution -1 may be evaporated to precipitate lithium chloride crystals, and solid-liquid separation may include a method of obtaining lithium chloride as a solid.
  • the step -4 may include a step of filtering calcium ions present in the aqueous solution -1 derived from the calcium chloride introduced in the step -1, precipitated with calcium sulfate by adding sulfuric acid to the aqueous solution -1, and then filtering and removing the calcium ions. have. And it may include a step of adding sodium hydroxide or potassium hydroxide to neutralize the solution to be acidified.
  • step -4 calci ions present in the aqueous solution -1 derived from the calcium chloride introduced in the step -1, strong alkali such as sodium hydroxide, potassium hydroxide and the like in the aqueous solution -1 was precipitated with calcium hydroxide and then filtered It may include a step of removing.
  • the step -4 may include a step of filtering out calcium ions present in the aqueous solution -1 derived from the chlorinated chlorine introduced in step -1, and adding sodium carbonate to the aqueous solution -1 to precipitate calcium carbonate and then filtering and removing the calcium ion. Can be. However, the amount added is limited to the amount that can preferentially precipitate calcium carbonate.
  • Step -4 may be obtained by adding sulfuric acid to CAp-1 obtained after filtration to form insoluble gypsum and water-soluble phosphoric acid, and may include a process of obtaining gypsum and phosphate solution by solid-liquid separation. The method may further include recovering phosphoric acid remaining in the gypsum by washing the separated gypsum with water.
  • preparing a lithium chloride aqueous solution Adding sodium carbonate to the aqueous lithium chloride solution to precipitate lithium carbonate, and filtering the same to obtain a solid lithium carbonate (hereinafter referred to as lithium carbonate-1) and a filtrate (hereinafter referred to as filtrate -2) (step -5); It comprises, and the concentration of lithium ions in the lithium chloride aqueous solution provides a manufacturing method of lithium carbonate that is more than 10,000ppm.
  • the lithium chloride aqueous solution may be prepared from the method for producing a lithium chloride aqueous solution of the embodiment of the present invention.
  • step # 5 the obtained lithium carbonate ⁇ 1 may be washed with water, and the filtrate -2a obtained after washing with water may be joined to the filtrate -2, and the washing is performed at least once. Can be.
  • the step -5 may further include a step of allowing lithium phosphate to precipitate by injecting a phosphorus feed material into the filtrate -2 to recover residual lithium ions in the filtrate -2.
  • the lithium ion in the aqueous lithium chloride solution, the sodium silver and the molar ratio (lithium ion: sodium ion) in the sodium carbonate may be added in an amount of 1: 0.8 to 1: 1.2.
  • the temperature of the reaction for precipitating lithium carbonate may be more than 20 ° C and less than 100t.
  • the manufacturing method of the aqueous lithium chloride solution it is possible to produce a high concentration of lithium chloride aqueous solution of lithium ion concentration of ⁇ , ⁇ or higher, and higher than 60, 000 ppm in a short time. Therefore, before producing lithium carbonate in a subsequent process, the amount of evaporation energy required for the concentration of the lithium chloride aqueous solution is reduced, much larger amount of aqueous lithium chloride solution can be obtained in one processing unit, and the economical efficiency will be greatly improved. Can be.
  • the manufacturing method of the lithium chloride aqueous solution according to an embodiment of the present invention is an environmentally friendly manufacturing method, because it does not include an acid treatment process in the whole process.
  • FIG. 1 is a process diagram according to an embodiment of the present invention.
  • FIG. 1 is a schematic configuration diagram of a method for producing an aqueous lithium chloride solution and a method for producing lithium carbonate according to an embodiment of the present invention.
  • the present invention is not limited thereto, and various modifications can be made without departing from the technical spirit of the present invention from the viewpoint of a person skilled in the art.
  • FIG. 1 a method of manufacturing an aqueous lithium chloride solution and a method of manufacturing lithium carbonate according to an embodiment of the present invention will be described.
  • One embodiment of the present invention comprises the steps of homogeneously mixing the phosphate containing lithium, the chlorinated chlorine to form a mixture (hereinafter the mixture -1) (hereinafter step -1); And heating the mixture 1 at a high temperature of 450 ° C.
  • slurry 1 which is a mixture of poorly soluble chloroapatite (Cloroapat i te, CAp) and water-soluble lithium chloride (hereinafter, step -3); And solid-liquid separation of the slurry -1 to obtain chloroapatite (hereinafter referred to as CAp-1) and an aqueous lithium chloride solution (hereinafter referred to as aqueous solution -1) (hereinafter as step -4).
  • slurry 1 which is a mixture of poorly soluble chloroapatite (Cloroapat i te, CAp) and water-soluble lithium chloride (hereinafter, step -3); And solid-liquid separation of the slurry -1 to obtain chloroapatite (hereinafter referred to as CAp-1) and an aqueous lithium chloride solution (hereinafter referred to as aqueous solution -1) (hereinafter as step -4).
  • This method is a method that can produce a high concentration of aqueous lithium chloride solution without the acid treatment.
  • the reaction method of the lithium chloride production method according to an embodiment of the present invention described above may be improved compared to the conventional process.
  • reaction formula -1 Through the reaction of the lithium phosphate and calcium chloride at a high temperature to produce a water-soluble CAp and water-soluble LiCl for water, specifically can be carried out by the following reaction formula -1.
  • Banung the formula -1 is thermodynamically banung to reduce the free energy of water followed by the banung left only banung does not occur to the right of the product, because it requires the activation energy that happens to banung the "active at a temperature of at least 450 ° C.
  • reaction product of the reaction product -1 is all solid state, but at 450 ° C or more, reaction reaction of reaction product -1 begins to occur at the site where lithium phosphate and calcium chloride contact each other.
  • reaction speed is fast because a substance of eutectic composition with a melting rate of 475 C is formed in the calcium chloride composition of the molecule.
  • the reaction product of the semi-formula -1 may enter the heating step by, for example, adding the mixture -1 to a container having a volume of 1 m 3 or more.
  • the heating method may be made by heating in an industrially generalized box furnace, tunnel furnace, and to stir or suspend the heating during heating in order to allow the heat transferred to the container to be quickly transferred to the mixture
  • Heating and reaction can be promoted by various methods, such as temporarily removing the mixture from the heater, stirring the mixture temporarily, and then adding the mixture to the heater. This heating with stirring is effective in both ways. The first is to speed up the rate of temperature increase of the mixture -1 in the vessel and serve to raise the temperature evenly.
  • the process composition of melting point 475 ° C can form droplets as described above. It acts to accelerate the reaction speed faster.
  • the time taken for the reaction -1 is greatly influenced by the degree of compatibility between the lithium-containing phosphate and calcium chloride.
  • the time for heating the mixture -1 can be adjusted so as to be retarded with the subsequent process time, after the mixture reaches 450 ° C or more can be adjusted in the range of 30 minutes or more and 5 hours or less.
  • this is not necessarily limited to this range, and may be made shorter or longer, taking into account the error rate, heating energy, and productivity of lithium.
  • lithium-containing phosphate and calcium chloride In order for this reaction to occur smoothly, it is desired to mix lithium-containing phosphate and calcium chloride well on a particle basis. If the lithium-containing phosphate is in a fine powder state, it can be mixed with powdered calcium chloride and mixed in the mixer for a sufficient time, and contains lithium. If the phosphate contains a small amount of water, such as a fil ter cake, add 1 to 3 times the weight of the phosphate to mix with calcium chloride. The combiner runs until the phosphate is separated into fine particles.
  • the amount of reaction is determined by the thermodynamic energy state between the reactant and the product.
  • the reaction product contains various components other than lithium phosphate and chlorinated chloride, and since the compounding ratio of raw materials can be changed, it is difficult to define the value of thermodynamic free energy as one value, but lithium in lithium phosphate at ambient temperature of 450 ° C or higher More than 80% Is switched.
  • the equivalent of calcium chloride in the mixture -1 is 1.667 times the number of moles of lithium phosphate.
  • the preferred amount of calcium chloride is limited to 0/7 times or more and 1.3 times or less of the semiungksik -1 equivalent ratio.
  • the calcium chloride 0.7-equivalent ratio is the number-of-moles equivalent to 1.167 times the number-of-moles of lithium phosphate, and the 1.3-fold equivalent ratio is the number-of-moles corresponding to 2.167 times the number of moles of lithium phosphate.
  • the equivalent ratio is less than 0.7 times, most of the calcium chloride after the reaction participates in the reaction, so the content of Ca 2+ acting as an impurity of the aqueous solution -1 is advantageous, but the reaction rate of the reaction product -1 is lowered, so that the recovery of lithium is low. There are disadvantages to losing.
  • the equivalence ratio is 1.3 times or more, the reaction rate of reaction formula -1 is increased to increase the amount of lithium chloride produced.
  • the impurity Ca 2+ content in aqueous solution -1 increases, and the removal cost thereof increases. do.
  • both the reaction material and the product are salts, and when dissolved in water, do not bias the strong acid or the strong alkali. Depending on the amount of impurities, pH of weak acid or weak alkali is displayed.
  • water is added to the product-1 to dissolve lithium chloride in an aqueous solution.
  • Lithium chloride is very high (69-128 g) for 100 cc of water with a solubility of 0-100 ° C.
  • Lithium ions are very high (113,000-210,000 ppm).
  • the amount of water added can be arbitrarily determined according to the concentration of the desired aqueous solution.
  • water is added to the product -1 to obtain an aqueous solution -1 by filtration, the solid CAp-1 is washed with an aqueous solution -la, and the aqueous solution -la can be joined to the aqueous solution -1 again.
  • the amount of water can be determined taking into account the lithium ion concentration of the final aqueous solution -1. Since the weight of the remaining liquid in the solid CAp-1 corresponds to 0.1 to 0.5 times that of the solid CAp-1, it is preferable to recover the liquid by adding water thereto and filtering again. In particular, as the concentration of lithium chloride in the aqueous solution -1 increases, washing with CAp-1 is preferable to increase the recovery rate of lithium chloride. There are several ways to determine the amount of water, and follow the existing method. However, in the present invention, the amount of the washing liquid is preferably 0.5 times or more and 5 times or less of the CAp-1 mass.
  • the aqueous solution -1 can theoretically obtain the concentration of lithium ions up to the solubility limit, and can easily be obtained at 4, 000 ppm or more. If the precipitate of lithium chloride is to be prepared using the aqueous solution -1, the solubility of lithium chloride can be easily reached even if the solution is evaporated a little, so that the precipitation can be facilitated. In addition, if the lithium carbonate is to be precipitated by adding sodium carbonate to the aqueous solution -1, it is not necessary to go through an expensive evaporation process. .
  • the lithium phosphate may be in the form containing other cationic components together.
  • the lithium in the lithium phosphate when the lithium in the lithium phosphate is derived from the lithium in the brine, the brine together with lithium, the amount of silver, such as calcium magnesium, iron, potassium, sodium, krum, lead, cadmium, etc.
  • a phosphorus supplying material such as a salt containing phosphoric acid or phosphoric acid is added thereto, lithium may be phosphorylated and precipitated in the form of lithium phosphate.
  • lithium phosphate is a low solubility in water ( ⁇ 0.39 g / L), it can be extracted in the form of a slurry in the phosphorylation process.
  • the cation other than the lithium becomes an impurity, and impurities may be removed in a manner generally known in the art before, after, or after the phosphorylation process.
  • lithium phosphate slurry when heated or naturally dried, it is obtained in the form of dried lithium phosphate (li thium phosphate) powder, and when the lithium phosphate slurry is filtered, lithium phosphate in a filter cake state (li thium phosphate) Is obtained.
  • the cationic impurities may be partially included in lithium phosphate as mentioned above.
  • the method may further include removing the unbanung calcium ions remaining in the aqueous solution -1.
  • the present invention provides a method of precipitating Ca 2+ ions by three methods and filtering out from aqueous solution ⁇ 1.
  • the first method of removing Ca 2+ ions from the aqueous solution -1 provides a method of precipitating Ca 2+ as a gypsum by adding sulfuric acid to the aqueous solution as in Banungsik-2.
  • a second method of removing Ca 2+ ions from the aqueous solution -1 provides a method of adding an alkali of a group 1 system such as NaOH and K0H to the aqueous solution -1.
  • a group 1 system such as NaOH and K0H
  • the solubility of Ca (0H) 2 decreases rapidly, so that it has a solubility of 0.008 dry) 1 at pH 13 and a low solubility of 0.06 g / 100cc-water. Therefore, most of Ca 2+ can be removed by precipitation as Ca (0H) 2 .
  • a third method of removing Ca 2+ ions from the aqueous solution -1 provides a method of adding sodium carbonate to an equivalent ratio of Ca 2+ .
  • Calcium carbonate is chemically much more stable than lithium carbonate and is therefore preferentially precipitated.
  • the carbonic anion C0 3 2 — reacts with the reaction formula -3 to precipitate most Ca 2+ ions as CaC0 3 .
  • the precipitate CaC0 3 has a very low solubility in water of 0.0007 g / 100 cc-water, almost all Ca 2+ ions can be removed by adding sodium carbonate by the number of moles of Ca 2+ present in the solution.
  • the present invention provides a method for obtaining phosphoric acid and gypsum by reacting CAp-1 obtained in the addition step -4 with sulfuric acid.
  • Banung -4 is an industrial method of obtaining gypsum by adding sulfuric acid and water to the mineral apat i te.
  • the present invention provides a method for obtaining gypsum and phosphoric acid having high economic value according to Scheme -4 from the product produced in step-4.
  • reaction of the reaction form -4 can occur quickly.
  • banung formula HCKg) gas generated at -4 is removed, by adding to a solid-liquid separation of water after the banung expression -4 banung the termination of the phosphoric acid it can be recovered 3 ⁇ 4P0 4 a high economic value.
  • Another embodiment of the present invention preparing a lithium chloride aqueous solution; And adding sodium carbonate to the aqueous lithium chloride solution to precipitate lithium carbonate and to filter it to obtain a solid lithium carbonate (hereinafter referred to as lithium carbonate-1) and a filtrate (hereinafter referred to as filtrate -2) (hereinafter referred to as -5). ; It includes, and the concentration of lithium ions in the aqueous lithium chloride solution ⁇ , ⁇ provides a method for producing lithium carbonate. Lithium carbonate can be precipitated through the reaction of lithium chloride and sodium carbonate from a high concentration aqueous lithium chloride solution having a lithium ion concentration of ⁇ , ⁇ or higher. Therefore, it is not necessary to further concentrate the lithium chloride aqueous solution to increase the concentration, it is possible to manufacture lithium carbonate economically.
  • Soda ash may be used as a raw material of the sodium carbonate. Soda ash is about 98% or more of sodium carbonate, and can be used as a source of sodium carbonate. However, it is of course possible to use other materials that can be used as a raw material of sodium carbonate, but is not limited thereto.
  • the use of a high pressure container is unnecessary as compared with the manufacturing method of lithium carbonate using a conventional CO 2 gas.
  • the installation can be made more compact.
  • the process cost can be significantly reduced.
  • the additional lithium carbonate manufacturing step as in the lithium chloride aqueous solution manufacturing method, it is possible to minimize the corrosion of the equipment, and to prevent environmental pollution since no sample such as acid or base is used.
  • the sodium carbonate may be added in an amount such that the molar ratio (lithium silver: sodium ion) of lithium ions in the lithium chloride aqueous solution and sodium carbonate to be added is 1: 0.8 to 1: 1.2. If the amount of sodium carbonate is too small, lithium carbonate may not be precipitated sufficiently, and the recovery rate of lithium may be reduced. If too much, the amount of precipitated lithium carbonate increases, but the cost of sodium carbonate may increase. More specifically, it may be added in an amount of 1: 0.9 to 1: 1. In addition, by adding sodium carbonate to the aqueous lithium chloride solution, the reaction temperature of the step of obtaining lithium carbonate and the filtrate may be 20 ° C or more and 100 ° C or less.
  • reaction temperature 20 ° C. or higher and 100 ° C. or lower. If the reaction temperature is too low, the solubility of lithium carbonate increases to decrease the recovery rate of lithium. If the reaction temperature is too high, the solubility of lithium carbonate decreases and the recovery rate of lithium increases, but the energy cost required to increase the silver content increases. Difficult to maintain Can be.
  • the solubility of lithium carbonate in water is 0.018 g / 100cc-water at 20 ° C, 0.010 g / 100cc-water at 100 ° C, and the concentrations of Li + ions are 1,249 ppm and 676 ppm, respectively.
  • the temperature at the time of filtration may be more than 15 ° C and less than 95 ° C.
  • the temperature range is limited in this way because the viscosity of the slurry becomes high when the temperature is lower than 15 ° C.
  • the filtration is not smooth.
  • the temperature is higher than 95 ° C, the energy input cost increases and the operation of the filtration equipment is difficult. .
  • impurities such as sodium chloride in an aqueous solution may be present in the filter cake containing filtered lithium carbonate. Accordingly, to remove it, it is possible to obtain lithium carbonate from which impurities are removed by washing with addition of water as a solvent, followed by a solid-liquid separation step of filtration. Washing and solid-liquid separation can be performed at least once or repeatedly, until the content of impurities is lowered to the desired level.
  • lithium phosphate can be recovered by adding salts or phosphoric acid containing phosphate ions to the filtrate, and the recovered lithium phosphate-containing solution is again filtered and washed. After the impurities are removed, they can be recycled as a lithium phosphate raw material.
  • the lithium phosphate thus prepared was 22.24 kg, calcium chloride was 35.53 kg (the amount of chlorine chloride, 1.667 times lithium phosphate on the basis of the number of moles), and these were put into a mixer and mixed for 30 minutes to mix well. The mixture was then placed in a crucible and placed in a box furnace maintained at 650 ° C for 3 hours. At this time, every 30 minutes the crucible was removed from the furnace and the mixture was stirred with a metal rod and charged again.
  • the crucible was removed from the furnace and allowed to cool for one hour. 50 liters of water was added thereto and stirred well with a metal rod.
  • filtrate -1 The volume of filtrate -1 is 89.3 liters, the concentration of Li
  • the amount of lithium in the product was 2.93 kg, with a very high initial yield of 73.2% at 4.0 kg.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

La présente invention concerne un procédé de préparation d'une solution aqueuse de chlorure de lithium et un procédé de préparation de carbonate de lithium, et concerne un procédé pour: produire un mélange par mélange homogène d'un phosphate contenant du lithium et de chlorure de calcium; chauffer le mélange à une température élevée de 450 °C ou plus, générant ainsi un produit dans lequel de la chloroapatite (CAp) et du chlorure de lithium sont mélangés; ajouter de l'eau au produit, ce qui permet d'obtenir une suspension qui est un mélange de la chloroapatite peu soluble dans l'eau et du chlorure de lithium soluble dans l'eau; puis réaliser une séparation solide-liquide de la suspension, ce qui permet d'obtenir de la chloroapatite et une solution aqueuse de chlorure de lithium. De plus, la présente invention concerne un procédé de préparation de carbonate de lithium par ajout de carbonate de sodium à la solution aqueuse de chlorure de lithium. La présente invention peut fournir un procédé de préparation de carbonate de lithium, dans lequel la concentration de lithium dans la solution aqueuse est de 10 000 ppm ou plus.
PCT/KR2017/006401 2016-09-05 2017-06-19 Procédé de préparation de chlorure de lithiuim et procédé de préparation de carbonate de lithium WO2018043881A1 (fr)

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US2627452A (en) * 1949-07-06 1953-02-03 Scient Design Co Preparation of lithium chloride from spodumene
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KR20130032563A (ko) * 2011-09-23 2013-04-02 케이엔디티앤아이 주식회사 결정화 반응장치 및 이를 이용한 고순도 탄산리튬의 제조방법
KR101269161B1 (ko) * 2010-12-07 2013-05-29 재단법인 포항산업과학연구원 리튬함유용액으로부터 고순도 리튬 추출 방법
KR20160076021A (ko) * 2014-12-19 2016-06-30 재단법인 포항산업과학연구원 금속리튬의 제조 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2627452A (en) * 1949-07-06 1953-02-03 Scient Design Co Preparation of lithium chloride from spodumene
KR20120021675A (ko) * 2010-08-12 2012-03-09 재단법인 포항산업과학연구원 고순도 탄산리튬의 제조 방법
KR101269161B1 (ko) * 2010-12-07 2013-05-29 재단법인 포항산업과학연구원 리튬함유용액으로부터 고순도 리튬 추출 방법
KR20130032563A (ko) * 2011-09-23 2013-04-02 케이엔디티앤아이 주식회사 결정화 반응장치 및 이를 이용한 고순도 탄산리튬의 제조방법
KR20160076021A (ko) * 2014-12-19 2016-06-30 재단법인 포항산업과학연구원 금속리튬의 제조 방법

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