AU2017442939B2 - Method for preparing lithium hydroxide and method for preparing lithium carbonate - Google Patents
Method for preparing lithium hydroxide and method for preparing lithium carbonate Download PDFInfo
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- AU2017442939B2 AU2017442939B2 AU2017442939A AU2017442939A AU2017442939B2 AU 2017442939 B2 AU2017442939 B2 AU 2017442939B2 AU 2017442939 A AU2017442939 A AU 2017442939A AU 2017442939 A AU2017442939 A AU 2017442939A AU 2017442939 B2 AU2017442939 B2 AU 2017442939B2
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 title claims abstract description 224
- 238000000034 method Methods 0.000 title claims abstract description 82
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 16
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 16
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 312
- 239000007864 aqueous solution Substances 0.000 claims abstract description 136
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 70
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000460 chlorine Substances 0.000 claims abstract description 30
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000012528 membrane Substances 0.000 claims description 108
- 150000002500 ions Chemical class 0.000 claims description 80
- 239000002994 raw material Substances 0.000 claims description 71
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 52
- 238000000909 electrodialysis Methods 0.000 claims description 51
- 238000000502 dialysis Methods 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 239000007790 solid phase Substances 0.000 claims description 30
- 239000012071 phase Substances 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052642 spodumene Inorganic materials 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 13
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- 239000000292 calcium oxide Substances 0.000 claims description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 10
- 239000006227 byproduct Substances 0.000 claims description 9
- 239000001110 calcium chloride Substances 0.000 claims description 9
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 9
- 235000011148 calcium chloride Nutrition 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 239000013522 chelant Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- -1 hydroxide ions Chemical class 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 2
- 229910000514 dolomite Inorganic materials 0.000 claims description 2
- 239000010459 dolomite Substances 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 4
- 239000011343 solid material Substances 0.000 abstract 2
- 239000011575 calcium Substances 0.000 description 14
- 239000002253 acid Substances 0.000 description 12
- 229910052791 calcium Inorganic materials 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 238000002386 leaching Methods 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000001962 electrophoresis Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910018828 PO3H2 Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- 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
- B01D61/422—Electrodialysis
- B01D61/423—Electrodialysis comprising multiple electrodialysis steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/02—Oxides; Hydroxides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Urology & Nephrology (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The present invention relates to a method for preparing a lithium chloride aqueous solution, a method for preparing lithium hydroxide, and a method for preparing lithium carbonate. Provided is a method for preparing a lithium chloride aqueous solution, comprising the steps of: preparing a solid material comprising lithium; mixing a chlorine material and the solid material comprising lithium, and then heating the same; obtaining condensed lithium chloride by condensing gaseous lithium chloride to be generated by the heating step; and converting the condensed lithium chloride into a lithium chloride aqueous solution.
Description
[specification]
[Title] METHOD FOR PREPARING LITHIUM HYDROXIDE AND METHOD FOR PREPARING LITHIUM CARBONATE
[Technical Field] It relates to the manufacturing method of lithium hydroxide and the manufacturing method of lithium carbonate.
[Background] In the field of lithium extraction using ore raw materials, it is generally possible to use a spodumene (LiASi2O6), which contains a large amount of lithium and has a commercially available process. As a known technique, an acid roasting method using sulfuric acid and hydrochloric acid, and a lime-roasting method in which ore is calcined with CaO and leached into water are known. Among the processes, the most commonly used technology is the acid roasting method, and commercial processes using it have been established. The above acid leaching method is summarized as follows. The first a-phase spodumene ore is calcined at a high temperature to convert it to p phase spodumene, which is good for reacting with acids, that is, good for leaching lithium. Next, it is cooled, milled into a fine powder, and then heated with sulfuric acid or hydrochloric acid (usually using sulfuric acid). When the reactant after heating is leached with water, leachate, a solution containing lithium, is obtained. After going through a chemical process to filtrate and remove impurities, lithium carbonate is produced by using Na2CO. Such an acid leaching method consumes high energy and has a complicated process, which increases the manufacturing cost, and also uses strong acids such as sulfuric acid in the extraction process of lithium, which causes environmental problems. The above-described lime-roasting method is summarized as follows. As in the acid leaching method, the same raw material is used for the same spodumene, firstly, the alpha-phase spodumene ore powder and CaO are mixed, and then calcined at a high temperature to be converted into a p-phase form. Then, it is cooled and pulverized into fine powders and leached with water to obtain a LiOH a solution in a desired form. Then it is filtrated and removed impurities to obtain a product of a solid-phase LiOH through a recrystallization machine. Unlike the acid leaching method, this process has a merit that does not use acid, but has a problem of low economic efficiency due to low lithium yield and slow process.
[Disclosure]
[Problem to solve] We would like to propose an improved method for extracting lithium from lithium raw material in solid phase.
[Solution of problem] An embodiment of the present invention provides a method for manufacturing lithium hydroxide comprising: preparing a solid-phase raw material containing lithium; mixing and heating a solid-phase raw material containing the lithium and a chlorine raw material; obtaining condensed lithium chloride by condensing lithium chloride of the gas phase generated in the heating step; converting the condensed lithium chloride into an aqueous solution of lithium chloride; removing divalent positive ions in the an aqueous solution of lithium chloride; and converting an aqueous solution of lithium chloride in which the divalent positive ion is removed into lithium hydroxide using an electrodialysis device including a bipolar membrane. The step of removing the divalent positive ion in the an aqueous solution of lithium chloride; may be performed by an adsorption method using chelate ion an exchange resin. The step of converting an aqueous solution of lithium chloride in which the bivalent positive ion is removed into lithium hydroxide using an electrodialysis device including a bipolar membrane; may be a step of converting an aqueous solution of lithium chloride in which the divalent positive ion is removed into lithium hydroxide using an electrodialysis device including a bipolar membrane and simultaneously obtaining an aqueous solution of hydrochloric acid as a by-product. The obtained an aqueous solution of hydrochloric acid may be used for the production of the chlorine raw material in the step of mixing and heating a solid-phase raw material containing the lithium and a chlorine raw material. In the step of converting an aqueous solution of lithium chloride in which the bivalent positive ion is removed into lithium hydroxide using an electrodialysis device including a bipolar membrane, the concentration of lithium in the an aqueous solution of lithium chloride may be 5 to 20 g/L. The electrodialysis device comprising the bipolar membrane comprises: an anode cell containing an anode; a first bipolar membrane; negative ion selective dialysis membrane; positive ion selective dialysis membrane, a second bipolar membrane; and a negative electrode cell containing a negative electrode; which is disposes sequentially. The step of converting an aqueous solution of lithium chloride in which the divalent positive ion is removed into lithium hydroxide using an electrodialysis device including a bipolar membrane and simultaneously obtaining an aqueous solution of hydrochloric acid as a by-product comprises: a step of inserting the an aqueous solution of lithium chloride is introduced between the positive ion selective dialysis membrane and the negative ion selective dialysis membrane, and water is added each between the first bipolar membrane and the negative ion selective dialysis membrane and the second bipolar membrane and the positive ion; and a step of applying a current to the bipolar electrodialysis device to obtain the aqueous solution of lithium hydroxide and simultaneously to obtain an aqueous solution of hydrochloric acid as a by-product. The weight ratio of the input of the water to the input of the an aqueous solution of lithium chloride (water: an aqueous solution of lithium chloride) may be, from 1:20 to 1:2. The step of converting an aqueous solution of lithium chloride in which the divalent positive ion is removed into lithium hydroxide using an electrodialysis device including a bipolar membrane and simultaneously obtaining an aqueous solution of hydrochloric acid as a by-product comprises: a step of generating hydroxide ions and protons by the hydrolyzed water in the first bipolar membrane and the second bipolar membrane; a step in which the lithium ion in the an aqueous solution of lithium chloride transmits the positive ion selective dialysis membrane and moves in the cathode direction; a step of forming the aqueous solution of lithium hydroxide by concentrating the hydroxide ion generated in the second bipolar membrane and the transferred lithium ion, between the positive ion selective dialysis membrane and the second bipolar membrane; a step in which the chlorine ion in the an aqueous solution of lithium chloride transmits the negative ion selective dialysis membrane and moves in the anode direction; and a step in which the proton generated in the first bipolar membrane and the transferred chlorine ion are concentrated between the negative ion selective dialysis membrane and the first bipolar membrane to form an aqueous solution of hydrochloric acid. The method further comprises: a step of concentrating and crystallizing the an aqueous solution of lithium hydroxide; and a step of drying the crystallized lithium hydroxide to obtain a lithium hydroxide in powder form, after converting an aqueous solution of lithium chloride in which the divalent positive ion is removed into lithium hydroxide using an electrodialysis device including a bipolar membrane. The condensed lithium chloride may be a solid or liquid phase. In a step of mixing and heating a solid-phase raw material containing the lithium and a chlorine raw material, an additive for improving lithium reaction can be further added a mixture of a solid-phase raw material containing lithium and a chlorine raw material. The additive may be calcium oxide, magnesium oxide, calcined dolomite or a mixture thereof. The solid-phase raw material containing lithium includes a-phase spodumene (spodumene, LiASi2O6). The chlorine raw material includes calcium chloride, sodium chloride, magnesium chloride or a mixture thereof. The lithium chloride in gas phase is produced through the following reaction scheme 1 in the step of mixing and heating a solid-phase raw material containing lithium and a chlorine raw material; and obtaining condensed lithium chloride by condensing lithium chloride of the gas phase generated in the heating step.
[Reaction scheme 1] 2LiAISi2O6 (lithium raw material)+ CaC12 (chlorine raw material)--> 2LiCI + CaO. A12O3 -2SiO2 + 2SiO2
The step of mixing and heating a solid-phase raw material containing the lithium and a chlorine raw material is performed at 800 to 1200C. The step of mixing and heating a solid-phase raw material containing the lithium and a chlorine raw material is performed in vacuum or a gas flow that does not affect reaction. In the step of obtaining condensed lithium chloride by condensing lithium chloride of the gas phase generated in the heating step, the lithium chloride of the gas phase is converted into condensed lithium chloride in a condenser in a low temperature section. The low temperature section may be 100 to 8000 C. The step of converting the condensed lithium chloride into an aqueous solution of lithium chloride may be a step of dissolving the condensed lithium chloride into water to convert it into an aqueous solution of lithium chloride. The concentration of lithium in an aqueous solution of lithium chloride can be controlled by controlling the amount of water. Another embodiment of the present invention provides a method of manufacturing lithium carbonate, comprising: preparing a solid-phase raw material containing lithium; mixing and heating a solid-phase raw material containing the lithium and a chlorine raw material; obtaining condensed lithium chloride by condensing lithium chloride of the gas phase generated in the heating step converting the condensed lithium chloride into an aqueous solution of lithium chloride; removing divalent positive ions in the an aqueous solution of lithium chloride; and converting an aqueous solution of lithium chloride in which the divalent positive ion is removed into lithium hydroxide using an electrodialysis device including a bipolar membrane; and obtaining lithium carbonate through the carbonization reaction of the obtained lithium hydroxide.
[Effect] It is possible to provide an improved method for extracting lithium from a lithium raw material on solid. Specifically, it is possible to efficiently extract high-concentration lithium without using a strong acid. More specifically, an environmentally improved method can be provided. In addition, it is possible to provide a method with improved lithium yield. It is possible to easily control the concentration of lithium for the conversion process to various lithium materials.
[Brief description of drawings] FIG. 1 is an example of the entire process for one embodiment of the present invention. FIG. 2 is a schematic view of a condenser in one embodiment of the present invention. FIG. 3 schematically shows a method of manufacturing lithium hydroxide using a bipolar electrodialysis device according to an exemplary embodiment of the present invention. FIG. 4 schematically shows a method of manufacturing lithium hydroxide using a stacked bipolar electrodialysis device according to an exemplary embodiment of the present invention.
[Description] Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, whereby the present invention is not limited, and the present invention is only defined by the scope of the claims to be described later. An embodiment of the present invention provides a method for manufacturing lithium hydroxide comprising: preparing a solid-phase raw material containing lithium; mixing and heating a solid-phase raw material containing the lithium and a chlorine raw material; obtaining condensed lithium chloride by condensing lithium chloride of the gas phase generated in the heating step; converting the condensed lithium chloride into an aqueous solution of lithium chloride; removing divalent positive ions in the an aqueous solution of lithium chloride; and converting an aqueous solution of lithium chloride in which the divalent positive ion is removed into lithium hydroxide using an electrodialysis device including a bipolar membrane; Hereinafter, each step will be described in more detail with respect to these processes. For ease of explanation, specific compounds are described as examples, but the present invention is not limited to these compounds. The present invention relates to a method for extracting lithium from a raw material on a solid containing lithium, more specifically, an ore containing lithium, and more specifically, a spodumene (LiAISi2O6) ore. It can be classified as a completely different technique from the acid roasting and lime-roasting methods, which are known techniques for extracting lithium from the spodumene ore raw materials. More specifically, in one embodiment of the present invention, lithium vapor (lithium vapor) generated in the process of chlorine roasting by mixing and calcinating the spodumene ore with calcium chloride is condensed and solidified at a relatively low temperature section after a certain section. Lithium chloride can be obtained through a condenser. Lithium chloride (LiCI) obtained from the condenser is a solid-phased or liquidized and dissolved with water to obtain leachate containing lithium. The entire process according to one embodiment of the present invention is shown in FIG. It is shown in 1. First, as the lithium raw material on the solid phase, a-phase spodumene may be used. Then, CaCl2 for the main reaction was mixed with spodumene, and then heated (fire, calcination) to 800-12000 C. The reaction that appears at this time is as follows.
[Reaction scheme 1] 2LiAISi2O6 (lithium raw material)+ CaC12 (chlorine raw material)--> 2LiCI + CaO. A12O3 -2SiO2 + 2SiO2 It can be seen that the reaction has a process for chloride calcination, resulting in LiCI. In addition, when CaO is added to improve the conversion rate, a result in which the reaction rate of the lithium is improved can be obtained. The above reaction, ie, chloride calcination, can be carried out in the vacuum (about 10- atm or less) or in the flow of gas (eg nitrogen, argon, dry air, etc.) that does not affect the reaction. The conceptual diagram for vacuum and condensation is shown in Fig. It is described in 2. Lithium chloride reacted in the chloride calcination method is moved to a vacuum pump at high temperature in a vapor state, and in the process, it is obtained as solid or liquid lithium chloride in a condenser at a low temperature (100-800 0C) section installed in front of the vacuum pump. The lithium chloride obtained at this time has high solubility to water and has a merit that can be recovered as an aqueous solution of lithium chloride by simply using water without using acid. An aqueous solution of lithium chloride obtained as described above is characterized in that it can be prepared at various concentrations by adjusting the amount of water to make into a solution phase, and has a merit capable of controlling the concentration of lithium according to the subsequent process. The an aqueous solution of lithium chloride (LiCI) is an intermediate product for obtaining a lithium product from an ore raw material, and the process of manufacturing a lithium material using this is disclosed. It takes a process to remove impurities, particularly calcium(Ca) and magnesium(Mg), contained in an aqueous solution of the lithium chloride for this purpose, and it is important to remove calcium as a characteristic of the process using CaCl2 and CaO. By using for this purpose ion exchange resin, divalent positive ions such as calcium and magnesium are removed, and an aqueous solution of lithium chloride with impurities removed therefrom can be obtained. Using the obtained an aqueous solution of lithium chloride, different types of lithium materials can be prepared by various methods. As a specific example, the obtained an aqueous solution of lithium chloride may be converted into lithium hydroxide using an electrodialysis device including a bipolar membrane. It is also possible to convert to lithium carbonate by using the converted lithium hydroxide. FIG. 3 schematically shows a method of manufacturing lithium hydroxide using a bipolar electrodialysis device according to an exemplary embodiment of the present invention. In addition, FIG. 4 schematically shows a method of manufacturing lithium hydroxide using a stacked bipolar electrodialysis device according to an exemplary embodiment of the present invention. More specifically, FIG. A bipolar electrodialysis device such as 3 may be implemented in a stacked type, and FIG. 4 is only an example. The bipolar electrodialysis device 200 used in the process of converting the lithium chloride into lithium hydroxide, as shown in FIG. 3, the anode cell containing the anode 210, the first bipolar membrane 220, the negative ion selective dialysis membrane 230, the positive ion selective dialysis membrane 240, the second bipolar membrane 250, the cathode cell containing the cathode 260 may be sequentially dispose. For the bipolar electrodialysis device 200, the an aqueous solution of lithium chloride was introduced between the negative ion selective dialysis membrane 230 and the positive ion selective dialysis membrane 240. And water was added each to the first bipolar membrane 220 and the negative ion selective dialysis membrane 230 and between the second bipolar membrane 250 and the positive ion selective dialysis membrane 240. As described above, when electricity is applied to the bipolar electrodialysis device in which the aqueous solution of lithium chloride and the water is injected, hydrolysis of the concentrate liquid water occurs in each bipolar membrane. And positive and negative ions in the aqueous solution of lithium chloride are moved toward the cathode 260 and the anode 210 by an electrophoresis effect, respectively. At this time, the weight ratio (water: an aqueous solution of lithium chloride) of the input amount of the water with respect to the input amount of the aqueous solution of lithium chloride may be controlled to 1:20 to 1:2. Specifically, the input amount of the water means each an input amount of water input between the first bipolar membrane 220 and the negative ion selective dialysis membrane 230, and between the second bipolar membrane 250 and the positive ion selective dialysis membrane 240. If the input amount of the water is less than the range, the concentration of the obtained an aqueous solution of lithium chloride becomes too high, and the diffusion force due to the difference in concentration occurs to increase the voltage, decrease the current, decrease the current efficiency, and increase the electrical power ratio. On the other hand, when the input amount of the water is more than the range, the concentration of the obtained an aqueous solution of lithium chloride is too low, and an additional concentrate process is required to produce lithium hydroxide and lithium carbonate using this, and then the energy cost will happen. Here, the water used in the exemplary embodiment of the present invention is preferably pure water containing no impurities, and such pure water contains distilled water, and ion exchange water is more preferable. The hydroxide ion generated from the second bipolar membrane 250 and the transferred lithium ion can be concentrated between the positive ion selective dialysis membrane 240 and the second bipolar membrane 250 to be made into an aqueous solution of lithium hydroxide. In addition, the proton generated by the first bipolar membrane 220 and the shifted chlorine ion can be concentrated between the negative ion selective dialysis membrane 230 and the first bipolar membrane 220 to be an aqueous solution of hydrochloric acid. Accordingly, the aqueous solution of lithium hydroxide is recovered between the second bipolar membrane 250 and the positive ion selective dialysis membrane 240, and the an aqueous solution of hydrochloric acid is recovered between the first bipolar membrane 220 and negative ion selective dialysis membrane 230. As a resultantly, when the an aqueous solution of lithium chloride is used as a raw material, and the bipolar electrodialysis device 200 is used, an aqueous solution of lithium hydroxide in which lithium is concentrated with high concentration is produced, and an aqueous solution of hydrochloric acid produced simultaneously therewith. Synthesis of the chemical reaction at this time is as shown in the following reaction scheme 3.
[Reaction scheme 3] LiCI + H20 -> LiOH + HCI The an aqueous solution of hydrochloric acid can be used in the production of a chlorine raw material in the step of mixing and heating a raw material of a solid-phase containing the lithium and a chlorine raw material. For a specific example, for the production of calcium chloride, which is an example of a raw material of chlorine, a reaction of hydrochloric acid and low-cost calcium oxide can be used. In addition, the an aqueous solution of lithium hydroxide may be used as a raw material for manufacturing lithium carbonate, or may be recovered in a powder state through a crystallization and drying process. Specifically, the lithium carbonate can be easily prepared by spraying dioxide carbon into the aqueous solution of lithium hydroxide. Meanwhile, the lithium hydroxide in the powder form may be prepared by concentrating the aqueous solution of lithium hydroxide by vacuum evaporation, crystallizing it, and drying it with a steam dryer. Meanwhile, the bipolar electrodialysis device, as shown in FIG. 4, multiple may be used as stacks sequentially stacked. When the bipolar electrodialysis device is configured as a stack, the pair of the third bipolar membrane 455, the negative ion selective dialysis membrane 430 and the positive ion selective dialysis membrane 440 are paired between the two third bipolar membrane 455. It may have a structure in which hundreds to disposes between the anode cell and the cathode cell. When a bipolar electrodialysis device is used as described above, an aqueous solution of lithium chloride and water supplied to these stacks are connected to supply lines, and an aqueous solution of lithium hydroxide and an aqueous solution of hydrochloric acid discharged from these stacks, respectively. A discharge line to connect can be configured. As shown in FIG. 4, the stacked bipolar electrodialysis device is between the second anode cell containing the second anode 410 and the second cathode cell containing the second cathode 460, the third bipolar membrane 455, the second negative ion selective dialysis membrane 430 and second positive ion selective dialysis membrane 440 is paired. Then this single pair is disposes continuously. Pairs formed by these bipolar membranes and selective dialysis membranes can be disposed continuously from tens to hundreds of pairs. And the second electrode solution supply line (not shown) for supplying the second electrode solution to the second anode cell and the second cathode cell is formed in a closed type on the upper and lower sides of the stacked bipolar electrodialysis device, respectively. And then the second electrode solution can be circulated. A second electrode solution supply tank (not shown) and a second control valve (not shown) can be connected to a part of the second electrode solution supply line to replenish the second electrode solution. In addition, the second electrode liquid supply tank may be equipped with a second motor (not shown) capable of circulating the second electrode solution. Here, the second electrode solution used at this time may be selected from any one of lithium hydroxide (LiOH) and potassium chloride (KCI) or combination thereof. Meanwhile, an aqueous solution of lithium chloride supplyline 470 supplying an aqueous solution of lithium chloride obtained from the stacked bipolar electrodialysis device and a second water supplyline 475 supplying water may be disposed to the stacked bipolar electrodialysis device. At this time, the inlet is disposed between the second negative ion selective dialysis membrane 430 and the second positive ion selective dialysis membrane 440 for an aqueous solution of lithium chloride supplyline 470. In the second water supply line 475, the inlet may be disposed each between the third bipolar membrane 455 and the second negative ion selective dialysis membrane 430, and between the second positive ion selective dialysis membrane 440 and the third bipolar membrane 455. In addition, after the bipolar electrodialysis is performed, the produced an aqueous solution of lithium hydroxide, an aqueous solution of hydrochloric acid and residual an aqueous solution of lithium chloride are discharged to the outside of the stacked bipolar electrodialysis device. For this, an aqueous solution of lithium hydroxide discharge line 480, an aqueous solution of hydrochloric acid discharge line 483 and residual an aqueous solution of lithium chloride discharge line 485 may be formed in the stacked bipolar electrodialysis apparatus. At this time, in the aqueous solution of lithium hydroxide discharge line 480, an outlet is formed between the second positive ion selective dialysis membrane 440 and the third bipolar membrane 455. The an aqueous solution of hydrochloric acid discharge line 483 is formed with an outlet between the third bipolar membrane 455 and the second negative ion selective dialysis membrane 430. In the residual an aqueous solution of lithium chloride discharge line 485, an outlet may be formed between and the second negative ion selective dialysis membrane 430 and the second positive ion selective dialysis membrane 440. Electricity is applied while supplying an aqueous solution of lithium chloride and water through an aqueous solution of lithium chloride supplyline 470 and a second water supplyline 475 to the stacked bipolar electrodialysis apparatus described above. An aqueous solution of lithium hydroxide, an aqueous solution of hydrochloric acid and residual an aqueous solution of lithium chloride produced by an electrophoresis effect are respectively isolated and then continuously discharged through an aqueous solution of lithium hydroxide discharge line 480, an aqueous solution of hydrochloric acid discharge line 483, and the residual an aqueous solution of lithium chloride discharge line 485. The aqueous solution of lithium hydroxide obtained in the stacked bipolar electrodialysis apparatus may be recovered as a powder through a crystallization and drying process, or used as a raw material for manufacturing lithium carbonate. Hereinafter, an exemplary embodiment of the present invention and Comparative Example is described. However, the following example is only an exemplary embodiment of the present invention, and the present invention is not limited to the following example. Example Preparation of raw material 1 kg of a-phase spodumene powder, 1.5 kg of anhydrous calcium chloride powder and 0.6 kg of oxidation calcium powder were uniformly mixed. chloride calcination The mixed powder was put in an iron tray and introduced into a reaction tube heated to 1,0000 C. One end of the reaction tube has an inlet through which powder can be injected, and the other side consists of a structure that can install a condenser and connect a vacuum facility. An electric furnace was used to raise the temperature of the reaction tube. After adding powder, vacuum pump is operated to vacuum (10- atm) was maintained, and reaction was maintained for about 1 hour. Condenser During the reaction time, the temperature of the condenser was maintained at about 500 0C, and lithium chloride was condensed in a liquid state inside the condenser. Obtained an aqueous solution of lithium chloride After the reaction was completed, the condenser was cooled, and the pressure of the reaction tube was changed from vacuum to normal pressure, and then the lid of the reaction tube was opened to discharge the condenser. At this time, the amount of lithium chloride condensed in the condenser was about 70 g, and the reaction rate was about 94%. Lithium chloride could be easily removed from the condenser by placing the condenser in water. As a result of analyzing the components of condensed lithium chloride, 95.80% lithium chloride was present, and impurities such as 2.38% calcium chloride and 1.17% sodium chloride were present. Purification of an aqueous solution of lithium chloride It is necessary to dissolve the obtained lithium chloride in an aqueous solution state in order to enter the bipolar electrodialysis process. At this time, in the anhydrous solution of lithium chloride prepared, there is calcium (Ca) ion used in all processes in addition to lithium chloride (LiCI), which is an effective component. Calcium ion is a factor that interferes with the operation of the dialysis membrane due to precipitation and membrane adhesion in the bipolar electrodialysis device, so removal and management is necessary. In the designed bipolar electrodialysis process, the concentration of Ca ion should be controlled to 10 ppm or less, and the removal process using for this purpose ion an exchange resin is provided. The ion an exchange resin is a chelate type ion an exchange resin that has adsorption properties of ions such as Ca and Mg, and it is possible to selectively remove secondary ions such as Ca and Mg.
In an exemplary embodiment of the present invention, Amberlite IRC747UPS is used, but all other chelate ion an exchange resins having the same characteristic can be applied. The calcium removal reaction scheme is as follows.
[Reaction scheme 2] R-CH2-NH-CH2-PO3H2 + M2+ <-> R-CH2-NH-CH2-PO3M + 2H+ The test results for removing a calcium in an aqueous solution of lithium chloride in the above chelate a resin and reaction scheme environment are as follows.
[Table 1] L N K C W i a a g Dissolve 1 9 7 3 9 solution (mg/L) 0,171 0.0 .0 4.9 .9 After 1 - - 0 3 removing Ca, Mg 0,079 .2 .7
As tested in the table, when the ion exchange process is performed, the removal of calcium is more than 99%, and it is possible to manage the calcium concentration input to the process to 10 ppm or less. Conversion of lithium hydroxide to an aqueous solution of lithium chloride The conversion of an aqueous solution of lithium chloride into lithium hydroxide is a characteristic conversion method of the bipolar electrodialysis process. OH- generated by hydrolysis occurring in a bipolar dialysis membrane is combined with Li in lithium chloride to produceLiOH. An aqueous solution of lithium chloride used as a raw material can be manufactured and used in a range of various concentrations, but considering the efficiency of the electrodialysis process, the range of 5g/L-20g/L based on lithium concentration in an aqueous solution of lithium chloride can be controlled. More specifically, when maintaining the level of 15g/L, lithium conversion rate of 85% can be obtained in the example of 20g/L based on lithium concentration in an aqueous solution of lithium hydroxide. The conversion rate and the range of concentration of the raw material, an aqueous solution of lithium chloride, can be adjusted within the specified level. In the above process, the CI- ion of an aqueous solution of lithium chloride is combined with H generated in hydrolysis and has the composition of a process made of HCI. The HCI obtained at this time is 2N level in the Example condition. In the case of the obtained hydrochloric acid, CaCl2 is prepared by reacting with low-cost CaO, and sent to the chloride roasting process, which is the previous process, to be reused as a raw material to minimize by-products generated during the process. The conversion rate of lithium chloride to lithium hydroxide through this process is estimated to be 80-85%. Lithium hydroxide to lithium carbonate conversion
In addition, the obtained an aqueous solution of lithium hydroxide is precipitated as lithium hydroxide crystal when it reaches 34-35 g/L based on lithium concentration. When using this characteristic to concentrate in the recrystallization furnace, the aqueous solution of lithium hydroxide obtained in the Example is 20g/L, so it can be continuously concentrated to 34-35g/L level and separated into lithium hydroxide crystal.
. The lithium hydroxide solid thus obtained becomes the final product, and because of the characteristics of the electrodialysis process, there are no additional raw materials, it is possible to produce high purity lithium hydroxide solid. In addition, in the case of the aqueous solution of lithium hydroxide (20 g/L), a strong alkali component with a pH of 12 or higher enables vapor carbonation using carbonation gas C02. Since there is no problem of removal of Na components due to the use of sodium carbonate (Na2CO3) and sodium hydroxide (NaOH) used as a pH controlling agent, it has a merit that can simplify the lithium carbonate manufacturing process and obtain high purity. The present invention is not limited to the exemplary embodiment, but may be manufactured in various different forms, and a person having ordinary knowledge in the technical field to which the present invention belongs may be different without changing the technical idea or essential characteristics of the present invention. It will be understood that it may be implemented in a specific form. Therefore, the exemplary embodiments described above are illustrative in all respects and should be understood as non-limiting.
Claims (19)
1. A method for manufacturing lithium hydroxide comprising: preparing a solid-phase raw material containing lithium; mixing and heating the solid-phase raw material containing the lithium and a chlorine raw material; obtaining condensed lithium chloride by condensing lithium chloride of the gas phase generated in the heating step; converting the condensed lithium chloride into an aqueous solution of lithium chloride; removing divalent positive ions in the aqueous solution of lithium chloride; and converting the aqueous solution of lithium chloride in which the divalent positive ion is removed into lithium hydroxide using an electrodialysis device including a bipolar membrane, and in the step of converting the condensed lithium chloride into an aqueous solution of lithium chloride, the concentrated lithium chloride is dissolved in water and converted into a lithium chloride aqueous solution, and the concentration of lithium in the lithium chloride aqueous solution is controlled by controlling the amount of water; and in the step of converting the aqueous solution of lithium chloride in which the bivalent positive ion is removed into lithium hydroxide using an electrodialysis device including a bipolar membrane; the concentration of lithium in the aqueous solution of lithium chloride is 5 to 20 g/L.
2. The method of claim 1, wherein: the step of removing the divalent positive ions in the aqueous solution of lithium chloride is performed by an adsorption method using chelate ion an exchange resin.
3. The method of claim 1, wherein: the step of converting the aqueous solution of lithium chloride in which the bivalent positive ion is removed into lithium hydroxide using an electrodialysis device including a bipolar membrane; is a step of converting an aqueous solution of lithium chloride in which the divalent positive ion is removed into lithium hydroxide using an electrodialysis device including a bipolar membrane and simultaneously obtaining an aqueous solution of hydrochloric acid as a by-product.
4. The method of claim 3, wherein: the obtained an aqueous solution of hydrochloric acid is used for the production of the chlorine raw material in the step of mixing and heating a solid phase raw material containing the lithium and a chlorine raw material.
5. The method of claim 1, wherein: the electrodialysis device comprising the bipolar membrane comprises: an anode cell containing an anode; a first bipolar membrane; negative ion selective dialysis membrane; positive ion selective dialysis membrane, a second bipolar membrane; and a negative electrode cell containing a negative electrode; which is disposes sequentially.
6. The method of claim 3, wherein: the step of converting the aqueous solution of lithium chloride in which the divalent positive ion is removed into lithium hydroxide using an electrodialysis device including a bipolar membrane and simultaneously obtaining an aqueous solution of hydrochloric acid as a by-product comprises: a step of inserting the aqueous solution of lithium chloride is introduced between the positive ion selective dialysis membrane and the negative ion selective dialysis membrane, and water is added each between the first bipolar membrane and the negative ion selective dialysis membrane and the second bipolar membrane and the positive ion; and a step of applying a current to the bipolar electrodialysis device to obtain the aqueous solution of lithium hydroxide and simultaneously to obtain an aqueous solution of hydrochloric acid as a by-product.
7. The method of claim 6, wherein: the weight ratio of the input of the water to the input of the aqueous solution of lithium chloride (water: an aqueous solution of lithium chloride) is, from 1:20 to 1:2.
8. The method of claim 6, wherein: the step of converting the aqueous solution of lithium chloride in which the divalent positive ion is removed into lithium hydroxide using an electrodialysis device including a bipolar membrane and simultaneously obtaining an aqueous solution of hydrochloric acid as a by-product comprises: a step of generating hydroxide ions and protons by the hydrolyzed water in the first bipolar membrane and the second bipolar membrane; a step in which the lithium ion in the aqueous solution of lithium chloride transmits the positive ion selective dialysis membrane and moves in the cathode direction; a step of forming the aqueous solution of lithium hydroxide by concentrating the hydroxide ion generated in the second bipolar membrane and the transferred lithium ion, between the positive ion selective dialysis membrane and the second bipolar membrane; a step in which the chlorine ion in the aqueous solution of lithium chloride transmits the negative ion selective dialysis membrane and moves in the anode direction; and a step in which the proton generated in the first bipolar membrane and the transferred chlorine ion are concentrated between the negative ion selective dialysis membrane and the first bipolar membrane to form an aqueous solution of hydrochloric acid.
9. The method of claim 1, comprises: a step of concentrating and crystallizing the aqueous solution of lithium hydroxide; and a step of drying the crystallized lithium hydroxide to obtain a lithium hydroxide in powder form, after converting an aqueous solution of lithium chloride in which the divalent positive ion is removed into lithium hydroxide using an electrodialysis device including a bipolar membrane.
10. The method of claim 1, wherein: the condensed lithium chloride is a solid or liquid phase.
11. The method of claim 1, wherein: in a step of mixing and heating a solid-phase raw material containing the lithium and a chlorine raw material, an additive for improving lithium reaction is further added a mixture of a solid-phase raw material containing lithium and a chlorine raw material.
12. The method of claim 11, wherein: the additive is calcium oxide, magnesium oxide, calcined dolomite or a mixture thereof.
13. The method of claim 1, wherein: the solid-phase raw material containing lithium includes a-phase spodumene (spodumene, LiASi206).
14. The method of claim 1, wherein: the chlorine raw material includes calcium chloride, sodium chloride, magnesium chloride or a mixture thereof.
15. The of claim 1, wherein: the lithium chloride in gas phase is produced through the following reaction scheme 1 in the step of mixing and heating a solid-phase raw material containing lithium and a chlorine raw material; and obtaining condensed lithium chloride by condensing lithium chloride of the gas phase generated in the heating step.
[Reaction scheme 1] 2LiASi2O6 (lithium raw material)+ CaCl2 (chlorine raw material),-> 2LiCI+CaO-Al203-2SiO2+2SiO2
16. The of claim 1, wherein: the step of mixing and heating a solid-phase raw material containing the lithium and a chlorine raw material is performed at 800 to 1200°C.
17. The of claim 16, wherein: the step of mixing and heating a solid-phase raw material containing the lithium and a chlorine raw material is performed in vacuum or a gas flow that does not affect reaction.
18. The method of claim 1, wherein: in the step of obtaining condensed lithium chloride by condensing lithium chloride of the gas phase generated in the heating step, the lithium chloride of the gas phase is converted into condensed lithium chloride in a condenser in a low temperature section.
19. A method of manufacturing lithium carbonate, comprising: preparing a solid-phase raw material containing lithium; mixing and heating a solid-phase raw material containing the lithium and a chlorine raw material; obtaining condensed lithium chloride by condensing lithium chloride of the gas phase generated in the heating step converting the condensed lithium chloride into an aqueous solution of lithium chloride; removing divalent positive ions in the aqueous solution of lithium chloride; and converting the aqueous solution of lithium chloride in which the divalent positive ion is removed into lithium hydroxide using an electrodialysis device including a bipolar membrane; and obtaining lithium carbonate through the carbonization reaction of the obtained lithium hydroxide, and in the step of converting the condensed lithium chloride into an aqueous solution of lithium chloride, the concentrated lithium chloride is dissolved in water and converted into a lithium chloride aqueous solution, and the concentration of lithium in the lithium chloride aqueous solution is controlled by controlling the amount of water; and in the step of converting the aqueous solution of lithium chloride in which the bivalent positive ion is removed into lithium hydroxide using an electrodialysis device including a bipolar membrane; the concentration of lithium in the aqueous solution of lithium chloride is 5 to 20 g/L.
【Drawings】 【FIG. 1】
( ore ~ 7%)
Removing impurities Heat ( ~ 1,000℃)
LiCl vapor condenser
Process of chlorine Process of calcination electrodialysis
【FIG. 2】 LiCl vapor
Condenser High Temp. (Low temp.)
ore
Vacuum
1/3
Electrode Solution Residual LiCl
2/3 Electrode Solution 【FIG. 3】
【FIG. 4】
Residual LiCl Residual LiCl
Electrode Solution
Electrode Solution
3/3
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| US2561439A (en) * | 1947-07-08 | 1951-07-24 | Union Carbide & Carbon Corp | Method of treating lithiferous ores to recover lithium as lithium chloride |
| CA2985981A1 (en) * | 2015-05-13 | 2016-11-17 | Research Institute Of Industrial Science & Technology | Method for producing lithium hydroxide and lithium carbonate |
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| GB804962A (en) * | 1956-10-09 | 1958-11-26 | Chempatents Inc | Preparation of high purity lithium carbonate from lithium ores |
| BE566808A (en) * | 1957-06-27 | |||
| US4285914A (en) * | 1980-01-30 | 1981-08-25 | The United States Of America As Represented By The Secretary Of The Interior | Recovery of lithium from low-grade ores |
| CN1938228A (en) * | 2004-03-30 | 2007-03-28 | 托马斯及温德尔·邓恩公司 | Cyclical vacuum chlorination processes, including lithium extraction |
| JP2009269810A (en) * | 2008-05-07 | 2009-11-19 | Kee:Kk | Method for producing high-purity lithium hydroxide |
| US8741256B1 (en) * | 2009-04-24 | 2014-06-03 | Simbol Inc. | Preparation of lithium carbonate from lithium chloride containing brines |
| EP2841623B1 (en) * | 2012-04-23 | 2020-10-28 | Nemaska Lithium Inc. | Processes for preparing lithium hydroxide |
| WO2016175613A1 (en) * | 2015-04-30 | 2016-11-03 | 재단법인 포항산업과학연구원 | Method for manufacturing lithium hydroxide and lithium carbonate, and device therefor |
| KR101674394B1 (en) * | 2015-06-30 | 2016-11-10 | 재단법인 포항산업과학연구원 | Method for manufacturing lithium hydroxide and lithium carbonate |
| CN106365180B (en) * | 2016-08-29 | 2017-12-15 | 西南化工研究设计院有限公司 | A kind of technique that industrial grade methanol is extracted in the ore deposit from lithium |
| CN107298450B (en) * | 2016-08-31 | 2019-11-29 | 江苏力泰锂能科技有限公司 | The method for preparing lithium hydroxide and lithium carbonate using soluble lithium salt solution |
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| US2561439A (en) * | 1947-07-08 | 1951-07-24 | Union Carbide & Carbon Corp | Method of treating lithiferous ores to recover lithium as lithium chloride |
| CA2985981A1 (en) * | 2015-05-13 | 2016-11-17 | Research Institute Of Industrial Science & Technology | Method for producing lithium hydroxide and lithium carbonate |
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