WO2016175613A1 - Procédé de fabrication d'hydroxyde de lithium et de carbonate de lithium, et dispositif correspondant - Google Patents

Procédé de fabrication d'hydroxyde de lithium et de carbonate de lithium, et dispositif correspondant Download PDF

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Publication number
WO2016175613A1
WO2016175613A1 PCT/KR2016/004548 KR2016004548W WO2016175613A1 WO 2016175613 A1 WO2016175613 A1 WO 2016175613A1 KR 2016004548 W KR2016004548 W KR 2016004548W WO 2016175613 A1 WO2016175613 A1 WO 2016175613A1
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Prior art keywords
lithium
solution
dialysis membrane
aqueous solution
selective dialysis
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PCT/KR2016/004548
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English (en)
Korean (ko)
Inventor
박성국
박광석
이상길
정우철
김기영
이현우
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재단법인 포항산업과학연구원
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Priority claimed from KR1020150080872A external-priority patent/KR101700684B1/ko
Application filed by 재단법인 포항산업과학연구원 filed Critical 재단법인 포항산업과학연구원
Priority to CN201680025927.8A priority Critical patent/CN107787302B/zh
Priority to JP2017556892A priority patent/JP6602893B2/ja
Priority to AU2016254855A priority patent/AU2016254855B2/en
Priority to US15/570,400 priority patent/US10759671B2/en
Priority to CA2984567A priority patent/CA2984567C/fr
Priority to EP16786799.3A priority patent/EP3290393B1/fr
Priority to RU2017141578A priority patent/RU2684384C1/ru
Priority to PL16786799T priority patent/PL3290393T3/pl
Publication of WO2016175613A1 publication Critical patent/WO2016175613A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates

Definitions

  • a method for producing lithium hydroxide and lithium carbonate, and a device thereof A method for producing lithium hydroxide and lithium carbonate, and a device thereof.
  • a chemical precipitation method is generally known as a method for removing impurities of an ionic component below a specific concentration.
  • a chemical precipitation method is generally known as a method for removing impurities of an ionic component below a specific concentration.
  • the present inventors propose an effective alternative to economically produce the lithium hydroxide and lithium carbonate using methods other than chemical precipitation and natural evaporation.
  • the lithium phosphate is separated into a lithium chloride aqueous solution and a phosphate aqueous solution by dialysis of lithium phosphate using a monovalent ion selective electrodialysis apparatus, and the lithium hydroxide aqueous solution and a hydrochloric acid aqueous solution by dialysis of the separated lithium chloride using a bipolar electrodialysis apparatus.
  • a series of methods have been developed to finally obtain lithium hydroxide and lithium carbonate in powder form from the separated lithium hydroxide aqueous solution.
  • methods for producing lithium hydroxide and lithium carbonate are presented as one embodiment of the present invention, respectively.
  • a negative electrode cell including a negative electrode separator; Monovalent anion selective dialysis membranes for selectively permeating monovalent anions; Monovalent cation selective dialysis membranes for selectively transmitting monovalent cations; And a cathode cell including an anode separator; preparing a monovalent ion selective electrodialysis apparatus, in which the lithium phosphate dissolved in the acid is disposed between the anode separator of the anode cell and the monovalent cation selective dialysis membrane, and Injecting between the cathode separator of the cathode cell and the monovalent anion selective dialysis membrane, respectively, and introducing water between the monovalent cation selective dialysis membrane and the monovalent anion selective dialysis membrane; 1 above. Applying an electric current to the ion-selective electrodialysis apparatus to obtain an aqueous solution of lithium chloride and to obtain an aqueous solution of phosphoric acid formed as a byproduct; And
  • It provides a method for producing lithium hydroxide comprising a; converting the obtained lithium chloride aqueous solution into a lithium hydroxide aqueous solution.
  • Preparing the lithium phosphate Preparing the lithium phosphate; preparing a lithium-containing solution; And injecting a phosphorus supply material into the lithium-containing solution to precipitate dissolved lithium into lithium phosphate.
  • the aqueous solution of phosphoric acid obtained by the monovalent ion selective electrodialysis apparatus may be used as the phosphorus supplying material of the step of depositing dissolved lithium into lithium phosphate by adding a phosphorus supplying material to the lithium-containing solution.
  • the aqueous hydrochloric acid solution obtained by the bipolar electrodialysis apparatus may be used as part or all of the acid of the step of dissolving the lithium phosphate in an acid.
  • the lithium-containing solution the solution extracted lithium dissolved in the sea, recycling the waste lithium battery It may be selected from a solution generated in the process, a solution leaching lithium ore, brine, lithium water containing lithium, groundwater containing lithium, lithium containing interstitial water, and combinations thereof. Injecting a phosphorus supply material into the lithium-containing solution to precipitate dissolved lithium into lithium phosphate; Previously, removing the divalent ionic impurities in the lithium-containing solution; may be further included.
  • removing the divalent ionic impurities in the lithium-containing solution sodium hydroxide (NaOH), sodium carbonate (Na 2 C0 3 ), calcium hydroxide (Ca (0H) 2 ), sodium sulfate (Na 2 S0 4 ) and a compound selected from the combination thereof may be added to remove the chalc ions and magnesium ions.
  • the acid dissolving the lithium phosphate is hydrochloric acid (HC1), sulfuric acid (H 2 S0 4 ), nitric acid (HN0 3 ), hydrofluoric acid (HF), bromide Hydrogen acid (HBr), and combinations thereof.
  • a negative electrode cell including a negative electrode separator; Monovalent anion selective dialysis membranes for selectively permeating monovalent anions; Monovalent cation selective dialysis membranes for selectively transmitting monovalent cations; And a cathode cell including an anode separator; preparing a monovalent ion selective electrodialysis apparatus in which the anodes are disposed in order, and disposing lithium phosphate dissolved in the acid between the anode separator of the anode sal and the monovalent bivalent selective dialysis membrane, and Injecting between the negative electrode separator of the negative electrode cell and the monovalent anion selective dialysis membrane, respectively, and injecting water between the monovalent cation selective dialysis membrane and the monovalent anion selective dialysis membrane;
  • Lithium hydroxide including an electrode solution selected from lithium sulfate (Li 2 S0 4 ), lithium hydroxide (LiOH), lithium dihydrophosphate (UH 2 P0 4 ), phosphoric
  • the concentration of the electrode solution may be 0.1 to 20% by weight.
  • the electrical conductivity of the electrode solution may be 10 to 100 ms / cm.
  • the first current is applied to the ion optional electrodialysis device, the method comprising: at the same time as to give the aqueous solution of lithium chloride to give the phosphoric acid solution formed from a "by-product; in the concentration of the recovered phosphoric acid solution is 0.1 to 3.0 M Can be.
  • An anode cell including an anode; a first bipolar membrane; an anion selective dialysis membrane; Cation selective dialysis membranes, crab 2 bipolar membranes;
  • a cathode cell including a cathode; a bipolar electrodialysis apparatus arranged in this order is prepared, and the lithium chloride aqueous solution is introduced between the cation selective dialysis membrane and the anion selective dialysis membrane, and water is added to the bipolar membrane and the anion selection type.
  • the concentration of the separated hydrochloric acid aqueous solution may be 0.1 to 3.0 M.
  • the monovalent cation selective dialysis membrane and the monovalent anion selective dialysis membrane may form one pair, and a plurality of pairs of the dialysis membranes may be continuously formed.
  • the bipolar electrodialysis apparatus includes a bipolar membrane;
  • the anion-selective dialysis membrane and the cation-selective dialysis membrane may form one pair, and a plurality of pairs of the dialysis membranes may be continuously formed.
  • preparing a lithium hydroxide aqueous solution obtained by the above method and carbonizing the aqueous lithium hydroxide solution to obtain lithium carbonate.
  • the lithium hydroxide aqueous solution is carbonated to obtain lithium carbonate.
  • Step; may be performed by reaction of the lithium hydroxide aqueous solution and carbon dioxide (co 2 ).
  • monovalent negative silver is selectively selected between the first cathode cell including the first cathode and the first cathode separator and the first anode cell including the first anode and the first anode separator.
  • the first anion-selective dialysis membrane for permeation through the membrane and the first cation-selective dialysis membrane for selectively permeating the monovalent cation are continuously arranged in pairs, and an electrode for supplying the electrode solution to the first cathode cell and the first anode cell.
  • Liquid supply line A lithium phosphate supply line alternately disposed between the paired first anion selective dialysis membrane and the first cation selective dialysis membrane to supply lithium phosphate dissolved in an acid, and a water supply line to supply water; And alternately disposed between the paired bran U anion selective dialysis membrane and the first cation selective dialysis membrane to discharge a lithium chloride aqueous solution discharge line and a phosphoric acid aqueous solution to discharge the aqueous lithium chloride solution generated after electrodialysis.
  • a lithium compound manufacturing apparatus comprising a laminated electrodialysis apparatus consisting of a discharge line of aqueous solution of phosphate; the supplied lithium phosphate is continuously converted to the aqueous lithium chloride solution.
  • a third bipolar membrane, a second anion selective dialysis membrane, and a cation two cation selective dialysis membrane are disposed between the low 12 anode cell including the second anode and the second cathode cell including the second cathode.
  • a second electrode liquid supply line which is continuously arranged in a pair and supplies a second electrode solution to the second cathode cell and the second cathode cell;
  • a lithium chloride aqueous solution supply line for supplying the lithium chloride aqueous solution discharged from the stacked electrodialysis apparatus between the second anion selective dialysis membrane and the crab di cationic selective dialysis membrane; Between the third bipolar membrane and the second negative selective dialysis membrane and between the second cation selective dialysis membrane and the low 13 bipolar membrane, respectively .
  • Lithium hydroxide aqueous solution discharge line for discharging the aqueous lithium hydroxide solution generated after the bipolar electrodialysis;
  • a hydrochloric acid aqueous solution discharge line disposed between the third bipolar membrane and the second anion selective dialysis membrane to discharge aqueous hydrochloric acid solution generated after bipolar electrodialysis;
  • a residual lithium chloride aqueous solution discharge line formed between the second negative selective dialysis membrane and the crab di cationic selective dialysis membrane to discharge residual lithium chloride aqueous solution generated after bipolar electrodialysis.
  • Consisting of the supplied lithium chloride aqueous solution may be a lithium compound manufacturing apparatus further comprising a laminated bipolar electrodialysis apparatus that is continuously converted to a lithium hydroxide aqueous solution.
  • the paired first anion selective dialysis membrane and the first cation selective dialysis membrane may have several tens to thousands of pairs consecutively arranged, and the paired third bipolar membrane and the second anion selective dialysis membrane and the The Cation-Cation-Selective Dialysis Membrane may be one in which several tens to hundreds of pairs are continuously arranged.
  • the aqueous solution of phosphate discharged from the stacked electrodialysis apparatus may be re-supply to the phosphorus supply material of the lithium phosphate manufacturing process.
  • the aqueous hydrochloric acid solution discharged from the stacked bipolar electrodialysis apparatus may be supplied to a lithium phosphate supply unit dissolved in the acid. It may further include a carbonation device for converting the discharged lithium hydroxide aqueous solution to lithium carbonate.
  • lithium hydroxide and lithium carbonate can be obtained in high purity and high concentration, respectively, with high efficiency and low process cost.
  • dialysis of lithium phosphate using a monovalent ion selective electrodialysis apparatus it is possible to obtain a lithium chloride aqueous solution in which lithium is concentrated at a high concentration while phosphoric acid as an impurity is effectively separated.
  • the lithium chloride aqueous solution is dialyzed using a bipolar electrodialysis apparatus, It is possible to obtain an aqueous lithium hydroxide solution in which lithium is concentrated at a high concentration while hydrochloric acid as an impurity is effectively separated.
  • the phosphoric acid and hydrochloric acid separated by the embodiments of the present invention can be reused by re-injecting each during the process of the present invention can economically produce lithium hydroxide and lithium carbonate.
  • lithium hydroxide and lithium carbonate in powder form can be finally obtained from the lithium hydroxide aqueous solution.
  • FIG. 1 is a flow chart summarizing a method for preparing lithium hydroxide and lithium carbonate according to embodiments of the present invention.
  • Figure 2 schematically shows a method for producing lithium chloride using a monovalent ion selective electrodialysis apparatus according to an embodiment of the present invention.
  • Figure 3 schematically shows a method of producing lithium hydroxide using a bipolar electrodialysis apparatus according to an embodiment of the present invention.
  • Figure 4 schematically shows a method for producing lithium chloride using a stacked monovalent ion selective electrodialysis apparatus according to an embodiment of the present invention.
  • FIG. 5 schematically illustrates a method of manufacturing lithium hydroxide using a stacked bipolar electrodialysis apparatus according to one embodiment of the present invention.
  • the present inventors i) converting lithium phosphate to lithium chloride; ii) converting the lithium chloride to lithium hydroxide; and iii) obtaining the lithium hydroxide itself in powder form, or carbonizing the lithium hydroxide.
  • a series of processes including a process of obtaining lithium carbonate are presented, and the following problems are considered in each of the above processes.
  • the process of converting lithium phosphate to lithium chloride corresponds to a process of dissolving lithium phosphate in an acid and then injecting it with water into a monovalent ion selective electrodialysis apparatus to separate the aqueous lithium chloride solution and the aqueous phosphoric acid solution. .
  • the monovalent ion selective electrodialysis apparatus enables this.
  • the step of converting the lithium chloride into lithium hydroxide corresponds to a process of separating the separated lithium chloride aqueous solution into a bipolar electrodialysis apparatus to separate the lithium hydroxide aqueous solution and the hydrochloric acid aqueous solution.
  • an additive such as caustic soda is added to adjust the pH to around 11 ⁇ .
  • the obtained lithium carbonate can not only contain a large amount of impurities by the additive, and additional processes such as hydrothermal cleaning are inevitable, resulting in reduced lithium recovery and increased cost.
  • the bipolar electrodialysis apparatus can effectively separate the by-product hydrochloric acid while converting the lithium chloride into a high concentration of lithium hydroxide.
  • the separated lithium hydroxide aqueous solution is suitable for use in electrode materials of a secondary battery by producing lithium carbonate by adding it to a carbonation process or preparing it in powder form.
  • lithium is concentrated at a high concentration and effectively separated from the by-products inevitably generated, so that not only can each material be obtained with high efficiency, but the by-products can be transferred to a suitable process for recycling. It is economical.
  • the lithium phosphate is a lithium-containing solution (for example, a solution extracted lithium dissolved in the ocean, a solution generated in the process of recycling waste lithium batteries, a solution leaching lithium ore, brine, lithium-containing hot spring water lithium-containing groundwater, lithium High purity can be obtained by purifying divalent ions such as Ca 2+ , Mg 2+ , and the like, and then adding a phosphorus feed material.
  • a lithium-containing solution for example, a solution extracted lithium dissolved in the ocean, a solution generated in the process of recycling waste lithium batteries, a solution leaching lithium ore, brine, lithium-containing hot spring water lithium-containing groundwater, lithium High purity can be obtained by purifying divalent ions such as Ca 2+ , Mg 2+ , and the like, and then adding a phosphorus feed material.
  • Common components included in the lithium-containing solution include Li + , Na + , K + , Ca 2+ , Mg 2+ , CI “ , S0 4 2", and the like.
  • impurities in the manufacturing process of lithium chloride, lithium hydroxide, and lithium carbonate according to the embodiments of the present invention, all components except Li + may be referred to as impurities, and in particular, in the manufacturing process of lithium carbonate, the impurities are carbonated together. Became Since it may be precipitated together with lithium carbonate, it is necessary to remove the impurities (S10).
  • Ca 2+ and Mg 2+ are not only low solubility, but also difficult to remove even by hot water washing, and precipitated on the surface of the positive and ion selective dialysis membrane in the bipolar electrodialysis apparatus described later to prevent membrane contamination. It may need to be removed first because it can be triggered.
  • the removal method of Ca 2+ and Mg 2+ is not particularly limited, but may be one of the following reaction formulas 1 to 3, and the like.
  • Lithium phosphate can be obtained (S20) by adding a phosphorus feed material and then adjusting the pH appropriately.
  • the phosphorus feed material include
  • an aqueous solution of phosphate produced as a by-product is recycled.
  • the description of the process (S30-S40) for converting lithium phosphate to lithium chloride is as follows.
  • the optional dialysis membrane 140 and the monovalent anion selective dialysis membrane 130 may be used with a monovalent ion selective electrodialysis apparatus disposed between the anode cell and the cathode cell.
  • the anode cell includes the anode 160 and the anode separator 150
  • the cathode cell includes the cathode 110 and the cathode separator 120, between the anode 160 and the cathode separator 150, and the cathode 110.
  • the electrode solution is introduced between the anode and the cathode separator 120.
  • the monovalent ion selective electrodialysis apparatus 100 is schematically illustrated in FIG. 2 and will be described with reference to the same.
  • the lithium phosphate After dissolving the lithium phosphate in an acid, the lithium phosphate is dissolved between the anode separator 150 of the cathode cell and the monovalent cation selective dialysis membrane 140, and the cathode separator 120 and the monovalent anion selective dialysis membrane of the cathode cell ( 130, respectively, and the monovalent cation selective dialysis membrane 140 and the
  • Electrodialysis may be prepared by introducing water between the monovalent anion-selective dialysis membrane 130.
  • the electrode solution to be injected into the anode cell and the cathode cell, respectively is lithium sulfate (Li 2 S0 4 ), lithium hydroxide (LiOH), lithium dihydrophosphate (LiH 2 P0 4 ), phosphoric acid (3 ⁇ 4P0 4 ), and It may include an electrode solution selected from the combination of these. This electrode solution circulates to facilitate the movement of electrons in each cell.
  • the concentration of the electrode solution may be 0.1 to 20 weight 3 ⁇ 4.
  • the electrical conductivity of the electrode solution may be 10 to 100 ms / cm.
  • the electrical conductivity of the electrode solution is proportional to the concentration of the electrode solution.
  • the term "proportional" does not necessarily mean directly proportional to electricity. It also means that conductivity also tends to increase.
  • the concentration gap with each solution (ie, lithium phosphate dissolved in the acid and the water) introduced into the monovalent ion selective electrodialysis apparatus may increase. This is because a diffusion force occurs due to the difference in concentration, and the diffusion force acts in a direction opposite to the direction of movement of ions originally intended.
  • the concentration of the electrode solution needs to be 0.1 to 20 weight 3 ⁇ 4, and the electrical conductivity needs to be 10 to 100 ms / cni.
  • the type of acid for dissolving the lithium phosphate is not particularly limited, but is selected from hydrochloric acid (HC1), sulfuric acid (S0 4 ), nitric acid (HN0 3 ), hydrofluoric acid (HF), hydrobromic acid (HBr), and combinations thereof. It may be, hydrochloric acid (HC1) is more preferred.
  • hydrochloric acid (HC1) is more preferred.
  • an aqueous hydrochloric acid solution generated as a by-product can be recycled (S62) and used as the dissolving acid, which will be described later.
  • lithium phosphate and hydrochloric acid in the lithium phosphate dissolved in the acid are reacted as shown in the following reaction formula 4, and eventually the ions moving by the electrophoretic effect are Li + , CP, P0 4 3 ' , H + Etc.
  • Li 3 P0 4 + 3HC1-> H 3 P0 4 + 3LiCl only chlorine ions that are monovalent ions of the negative silver may pass through the monovalent anion selective dialysis membrane 130, and may not penetrate phosphate ions.
  • lithium ions having monovalent bivalent silver may penetrate the monovalent bivalent selective dialysis membrane 140 in a direction opposite to the chlorine ions. Accordingly, between the monovalent bivalent selective dialysis membrane 140 and the monovalent anion selective dialysis membrane ⁇ 30, the lithium ions may be continuously concentrated together with the chlorine silver to form an aqueous lithium chloride solution.
  • the lithium chloride aqueous solution is recovered between the monovalent cation selective dialysis membrane 140 and the monovalent anion selective dialysis membrane 130, and the phosphate aqueous solution is the anode separation membrane 150 and the monovalent cation of the anode cell.
  • the selective dialysis membrane 140 and between the negative electrode separation membrane 120 and the monovalent anion selective dialysis membrane 130 of the cathode cell are separated between the selective dialysis membrane 140 and between the negative electrode separation membrane 120 and the monovalent anion selective dialysis membrane 130 of the cathode cell.
  • the concentration of the aqueous solution of phosphoric acid may be 0.1 to 3.0 ⁇ .
  • the concentration needs to be secured to 0.1 ⁇ or more.
  • diffusion force is generated due to the concentration difference, which causes voltage rise, current decrease, current efficiency decrease, and power ratio increase. Needs to be.
  • the aqueous solution of phosphoric acid is recovered to It may be reused (S52) as a phosphorus supply material of the lithium phosphate manufacturing process.
  • the lithium chloride aqueous solution separated from the aqueous solution of phosphoric acid may be used as a raw material for converting into a lithium hydroxide aqueous solution.
  • the monovalent ion selective electrodialysis apparatus 100 may be used as a stack in which a plurality of layers are sequentially stacked.
  • the monovalent ion selective electrodialysis apparatus 100 When configured as a stacked stack as described above, the monovalent cation selective dialysis membrane 140 and the monovalent anion selective dialysis membrane 130 form a pair, and these pairs are several tens to thousands of anodes. It may be a structure disposed between the cell and the cathode cell.
  • a supply line for connecting lithium phosphate and water dissolved in the acid supplied to the stack and a discharge line for connecting the lithium chloride solution and the phosphoric acid solution respectively discharged from the stack may be configured.
  • a step (S50) of converting the lithium chloride into lithium hydroxide will be described.
  • the bipolar electrodialysis apparatus 200 used in the process of converting lithium chloride to lithium hydroxide is, as shown in FIG. 3, a positive electrode cell containing a positive electrode 210, a first bipolar membrane 220, an anion selective type.
  • the cathode cells including the dialysis membrane 230, the cation selective dialysis membrane 240, the second bipolar membrane 250, and the cathode 260 may be sequentially disposed.
  • bipolar electrodialysis apparatus 200 the aqueous solution of lithium chloride is introduced between the anion-selective dialysis membrane 230 and the cation-selective dialysis membrane 240, and water is supplied to the first bipolar membrane 220 and the anion-selective membrane.
  • Bipolar electrodialysis may be prepared between the dialysis membrane 230 and between the Crab 2 bipolar membrane 250 and the cation selective dialysis membrane 240, respectively.
  • the lithium chloride aqueous solution and the bipolar into which the water is added When the electrodialysis device is applied with electricity, hydrolysis of water, which is the concentrate, occurs in each of the bipolar membranes, and cations and anions in the aqueous lithium chloride solution are directed toward the cathode 260 and the anode 210 by electrophoretic effects, respectively. Will move.
  • the weight ratio (water: lithium chloride aqueous solution) of the input amount of water to the input amount of the lithium chloride aqueous solution may be controlled to be 1:20 to 1: 2.
  • the input amount of water, the input amount of water introduced between the first bipolar membrane 220 and the anion-selective dialysis membrane 230, and between the second bipolar membrane 250 and the cation-selective dialysis membrane 240, respectively. Means.
  • the concentration of the obtained lithium chloride solution is too high, the diffusion force is generated by the concentration difference, the voltage rise, the current decrease, the current efficiency . Decreases, increases the power cost.
  • the water used in the embodiment of the present invention is preferably pure water that does not contain impurities, and such pure water contains distilled water, more preferably ion-exchanged water.
  • Hydroxide ions and the transferred lithium ions generated in the second bipolar membrane 250 may be concentrated between the cation selective dialysis membrane 240 and the second bipolar membrane 250 to form a lithium hydroxide aqueous solution.
  • the hydrogen ions generated in the bipolar membrane 220 and the transferred chlorine silver are concentrated between the anion-selective dialysis membrane 230 and the first bipolar membrane 220 to be made of an aqueous hydrochloric acid solution. . .
  • the lithium hydroxide aqueous solution is recovered between the second bipolar membrane 250 and the cation selective dialysis membrane 240, the hydrochloric acid
  • the aqueous solution may be recovered between the first bipolar membrane 220 and the anion selective dialysis membrane 230.
  • the aqueous hydrochloric acid solution may be used as part or all of the acid of the step of dissolving the lithium phosphate in an acid (S62).
  • the lithium hydroxide aqueous solution may be used as a raw material for producing lithium carbonate or may be recovered (S60-S70) in powder form through a crystallization and drying process.
  • the lithium carbonate can be easily produced by injecting carbon dioxide into the lithium hydroxide aqueous solution.
  • the lithium hydroxide in powder form may be prepared by concentrating the lithium hydroxide aqueous solution by vacuum evaporation to crystallize (S64-S66) and then drying it with a steam dryer.
  • the bipolar electrodialysis apparatus as shown in Figure 5, may be used as a stack stacked in plurality sequentially.
  • the third bipolar membrane 455 , the anion selective dialysis membrane 430, and the cation selective dialysis membrane 440 are disposed between the two third bipolar membranes 455 . While forming a pair of tens to hundreds of these pairs may be a structure disposed between the anode cell and the cathode cell.
  • a supply line connecting the lithium chloride aqueous solution and water supplied to the stack and water discharge lines connecting the lithium hydroxide aqueous solution and the hydrochloric acid aqueous solution discharged from the stack may be configured.
  • FIGS. 4 and 5 a stacked electrodialysis apparatus and a stacked bipolar electrodialysis apparatus according to another embodiment of the present invention will be described in detail.
  • the stacked electrodialysis apparatus includes a first cathode cell including a first cathode 310 and a first anode separator 320, a first cathode 360, and a first anode separator 350.
  • the first anion selective dialysis membrane 330 for selectively transmitting monovalent anions and the first cation selective dialysis membrane 340 for selectively exceeding monovalent cations are disposed in pairs between the first anode cells.
  • the continuous selective dialysis membrane pairs 330 and 340 may be arranged in series from tens to thousands of pairs.
  • an electrode solution supply line for supplying the electrode solution to the first cathode cell and the first anode cell, respectively, in a closed shape above and below the multilayer electrodialysis apparatus, to supply the electrode solution to the multilayer electrodialysis apparatus. It may be circulated, and may be connected through an electrode solution supply tank (not shown) and a control valve (not shown) that may replenish electrode solution to a portion of the electrode solution supply line.
  • the electrode solution supply tank may be equipped with a motor (not shown) capable of circulating the electrode solution.
  • the electrode solution used here is lithium sulfate (Li 2 S0 4 ), lithium hydroxide (LiOH), lithium dihydrate phosphate (Li3 ⁇ 4P0 4 ), phosphoric acid (H 3 P0 4 ), and . May be selected from combinations thereof.
  • the multilayer electrodialysis apparatus includes a first anion selective dialysis membrane 330 and a first cation selective type in which the lithium phosphate supply line 370 and the water supply line 375 supplying lithium phosphate and water dissolved in an acid are paired. It may be arranged to be alternately supplied between the dialysis membranes (340).
  • the lithium chloride aqueous solution discharging line 380 and the phosphoric acid aqueous solution discharging line 385 are paired to discharge the lithium chloride aqueous solution and the phosphoric acid aqueous solution generated after electrodialysis to the outside of the multilayer electrodialysis apparatus.
  • the electric power is applied to the multilayer electrodialysis apparatus described above continuously supplying lithium phosphate and water dissolved in an acid in an isolated state through the lithium phosphate supply line 370 and the water supply line 375, the electrophoretic effect
  • the lithium chloride aqueous solution and the phosphoric acid aqueous solution produced by the same are continuously discharged through the lithium chloride aqueous solution discharging line 380 and the phosphoric acid aqueous solution discharging line 385 in an isolated state.
  • the lithium chloride aqueous solution obtained in the stacked electrodialysis apparatus as described above may be supplied to the stacked bipolar electrodialysis apparatus described below, and the separated and recovered phosphoric acid aqueous solution may be resupplied (S52) to the phosphorus supply material of the lithium phosphate manufacturing process.
  • the stacked bipolar electrodialysis apparatus includes a bipolar membrane 455 and a third bipolar membrane 455 between a second anode cell including a second anode 410 and a second cathode cell including a second cathode 460.
  • the dianion selective dialysis membrane 430 and the second cation selective dialysis membrane 440 are continuously arranged in a pair. Pairs of the bipolar membranes and the optional dialysis membranes may be continuously arranged up to tens to hundreds of pairs.
  • a low 12-electrode liquid supply line (not shown) for supplying a second electrode solution to the second anode cell and the second cathode cell, respectively, is formed in a closed shape above and below the stacked bipolar electrodialysis apparatus, so that the stacked bipolar electrodialysis is performed.
  • a twelfth electrode liquid supply tank (not shown) and a second regulating valve capable of circulating the second electrode liquid through the device, and complementing the second electrode liquid in a portion of the electrode electrode supply line.
  • the second electrode solution supply tank may be equipped with a second motor (not shown) capable of circulating the second electrode solution.
  • the two-electrode solution used at this time may be selected from any one of lithium hydroxide (LiOH) and potassium chloride (KC1) or a combination thereof.
  • lithium chloride for supplying the lithium chloride aqueous solution obtained in the laminated electrodialysis apparatus to the stacked bipolar electrodialysis apparatus
  • An aqueous solution supply line 470 and a second water supply line 475 for supplying water may be disposed.
  • the lithium chloride aqueous solution supply line 470 is provided with an injection hole between the second anion selective dialysis membrane 430 and the second two-selective dialysis membrane 440, and the second water supply line 475 has a third bipolar membrane ( An injection hole may be disposed between 455 and the second anion selective dialysis membrane 430, and between the second cation selective dialysis membrane 440 and the third bipolar membrane 455, respectively.
  • a residual lithium chloride aqueous solution discharge line 485 may be formed in the stacked bipolar electrodialysis apparatus.
  • the lithium hydroxide aqueous solution discharge line 480 has an outlet formed between the second cation selective dialysis membrane 440 and the third bipolar membrane 455, and the hydrochloric acid aqueous solution discharge line 483 is the third bipolar membrane 455.
  • the aqueous hydrochloric acid solution and the residual lithium chloride aqueous solution are continuously discharged through the lithium hydroxide aqueous solution discharge line 480, the aqueous hydrochloric acid solution discharge line 483, and the residual lithium chloride aqueous solution discharge line 485 in isolation.
  • the lithium hydroxide aqueous solution obtained in the stacked bipolar electrodialysis apparatus as described above may be recovered as a powder through crystallization and drying or may be used as a raw material for producing lithium carbonate.
  • the aqueous hydrochloric acid solution obtained in the stacked bipolar electrodialysis apparatus may be a part of the acid of the “dissolving lithium phosphate in acid” or It can be used as a whole.
  • the residual lithium chloride aqueous solution discharged from the stacked bipolar electrodialysis apparatus may be partially or entirely resupplyed to the lithium chloride aqueous solution supply line 470.
  • the lithium compound manufacturing apparatus may be configured by continuously installing the stacked electrodialysis apparatus and the adaptive bipolar electrodialysis apparatus described above.
  • the multilayer electrodialysis apparatus lithium phosphate is converted into lithium chloride aqueous solution
  • the multilayer bipolar electrodialysis apparatus the converted lithium chloride aqueous solution is converted into aqueous lithium hydroxide solution.
  • the process can be carried out continuously.
  • the lithium compound manufacturing apparatus may further include a carbonation apparatus for converting the lithium hydroxide aqueous solution obtained from the stacked bipolar electrodialysis apparatus into lithium carbonate.
  • a carbonation apparatus for converting the lithium hydroxide aqueous solution obtained from the stacked bipolar electrodialysis apparatus into lithium carbonate.
  • Lithium chloride was prepared by using reagent grade lithium phosphate (purchased from High Purity Chemical Co., Ltd.) as a raw material, using a monovalent ion selective electrodialysis apparatus of FIG. 2.
  • the recovered lithium chloride aqueous solution was measured to have a lithium concentration of 18 g / L and a phosphorus concentration of 4.4 g / L.
  • the recovered aqueous solution of phosphoric acid it was measured that the phosphorus concentration is 47.3g / L, lithium concentration is 4.0g / L.
  • residual phosphoric acid in the aqueous lithium chloride solution may be precipitated as lithium phosphate in the conversion process to the lithium hydroxide aqueous solution, and thus can be recovered in the process.
  • the aqueous solution of phosphoric acid since there is residual lithium in the aqueous solution of phosphoric acid, the aqueous solution of phosphoric acid may be used as a raw material for extracting lithium phosphate.
  • Lithium hydroxide was prepared using the recovered lithium chloride aqueous solution as a raw material, and using the bipolar electrodialysis apparatus of FIG. 3.
  • the lithium hydroxide aqueous solution recovered in Example 1 was used as a raw material, and lithium carbonate was prepared by reaction.
  • the lithium hydroxide aqueous solution having a lithium concentration of 18.9 g / L and 60 g of carbon dioxide were placed in separate nozzles, and then sprayed at the same time to induce carbonation reaction, thereby obtaining lithium carbonate.
  • the lithium concentration in the recovered lithium hydroxide aqueous solution was measured to be 2.84 g /, where it can be seen that 85% of the lithium in the lithium hydroxide aqueous solution was converted to lithium carbonate.
  • the filtrate of the carbonation reaction can be recycled to the desalination solution of the bipolar electrodialysis apparatus.
  • the present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person of ordinary skill in the art to which the present invention pertains does not change the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

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Abstract

La présente invention concerne un procédé de fabrication d'hydroxyde de lithium et de carbonate de lithium, et un dispositif correspondant. La présente invention prévoit un procédé de fabrication d'hydroxyde de lithium, comprenant : une étape de dissolution de phosphate de lithium dans un acide; une étape de préparation d'un dispositif d'électrodialyse de type sélectif d'ions monovalents disposé dans l'ordre d'une cuve cathodique contenant un séparateur cathodique, d'une membrane de dialyse du type sélectif d'anions monovalents pour la perméation de manière sélective d'un anion monovalent, d'une membrane de dialyse du type sélectif de cations monovalents pour la perméation de manière sélective d'un cation monovalent, et d'une cuve anodique contenant un séparateur anodique, et l'injection du phosphate de lithium dissous dans l'acide entre le séparateur anodique de la cuve anodique et la membrane de dialyse du type sélectif de cations monovalents, et entre le séparateur cathodique de la cuve cathodique et la membrane de dialyse du type sélectif d'anions monovalents, respectivement, et l'injection d'eau entre la membrane de dialyse du type sélectif de cations monovalents et la membrane de dialyse du type sélectif d'anions monovalents; une étape d'obtention d'une solution aqueuse de chlorure de lithium, et en même temps, d'obtention d'une solution aqueuse d'acide phosphorique formée comme sous-produit, par l'application d'un courant électrique au dispositif d'électrodialyse type sélectif d'ions monovalents; et une étape de conversion de la solution aqueuse de chlorure de lithium obtenue dans une solution aqueuse d'hydroxyde de lithium.
PCT/KR2016/004548 2015-04-30 2016-04-29 Procédé de fabrication d'hydroxyde de lithium et de carbonate de lithium, et dispositif correspondant WO2016175613A1 (fr)

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CN201680025927.8A CN107787302B (zh) 2015-04-30 2016-04-29 氢氧化锂和碳酸锂的制备方法及其装置
JP2017556892A JP6602893B2 (ja) 2015-04-30 2016-04-29 水酸化リチウム、および炭酸リチウムの製造方法およびその装置
AU2016254855A AU2016254855B2 (en) 2015-04-30 2016-04-29 Method for manufacturing lithium hydroxide and lithium carbonate, and device therefor
US15/570,400 US10759671B2 (en) 2015-04-30 2016-04-29 Method for manufacturing lithium hydroxide and lithium carbonate, and device therefor
CA2984567A CA2984567C (fr) 2015-04-30 2016-04-29 Procede de fabrication d'hydroxyde de lithium et de carbonate de lithium, et dispositif correspondant
EP16786799.3A EP3290393B1 (fr) 2015-04-30 2016-04-29 Procédé de fabrication d'hydroxyde de lithium et de carbonate de lithium, et dispositif correspondant
RU2017141578A RU2684384C1 (ru) 2015-04-30 2016-04-29 Способ и устройство для производства гидроксида лития и карбоната лития
PL16786799T PL3290393T3 (pl) 2015-04-30 2016-04-29 Sposób wytwarzania wodorotlenku litu i węglanu litu oraz urządzenie do tego celu

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CN115386740A (zh) * 2022-08-30 2022-11-25 中南大学 一种基于电渗析原理的卤水或海水提锂方法及装置

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