WO2016175613A1 - Method for manufacturing lithium hydroxide and lithium carbonate, and device therefor - Google Patents

Abstract

The present invention relates to a method for manufacturing lithium hydroxide and lithium carbonate, and a device therefor. The present invention provides a method for manufacturing lithium hydroxide, comprising: a step of dissolving lithium phosphate in an acid; a step of preparing a monovalent ion selective-type electrodialysis device disposed in the order of a cathode cell containing a cathode separator, a monovalent anion selective-type dialysis membrane for selectively permeating a monovalent anion, a monovalent cation selective-type dialysis membrane for selectively permeating a monovalent cation, and an anode cell containing an anode separator, and injecting the lithium phosphate dissolved in the acid between the anode separator of the anode cell and the monovalent cation selective-type dialysis membrane, and between the cathode separator of the cathode cell and the monovalent anion selective-type dialysis membrane, respectively, and injecting water between the monovalent cation selective-type dialysis membrane and the monovalent anion selective-type dialysis membrane; a step of obtaining an aqueous lithium chloride solution, and at the same time, obtaining a phosphoric acid aqueous solution formed as a byproduct, by applying an electric current to the monovalent ion selective-type electrodialysis device; and a step of converting the obtained aqueous lithium chloride solution into an aqueous lithium hydroxide solution.

Description

【Specification】

 [Name of invention]

 Method for producing lithium hydroxide and lithium carbonate and apparatus therefor

Technical Field

 A method for producing lithium hydroxide and lithium carbonate, and a device thereof.

Background Art

 From a commercial point of view, in order to economically produce lithium hydroxide and lithium carbonate having a purity of a certain concentration or more, it is necessary to remove impurities present in the lithium-containing solution and to concentrate the lithium concentration to an appropriate level for carbonation.

 However, the above-mentioned impurities removal cost and lithium enrichment cost account for most of the overall cost, and researches for solving this problem are continuing.

 First, a chemical precipitation method is generally known as a method for removing impurities of an ionic component below a specific concentration. However, it is pointed out that not only is the cost of the chemical for this excessive, but also that the injected chemical becomes another impurity and needs to be purified again.

 Meanwhile, as a method for concentrating lithium, a technique of concentrating lithium by removing impurities by evaporating brine in a natural state using solar heat has been proposed. However, relying on natural evaporation takes a long time of more than one year, and thus, a vast evaporation facility (e.g., an artificial pond for evaporation) is required to solve this time problem. In addition, operating costs, maintenance and maintenance costs are additionally generated.

Therefore, in order to economically manufacture lithium hydroxide and lithium carbonate having a purity of a certain concentration or more, a technique that can replace the chemical precipitation method and the natural evaporation method is required, but the effective alternative has not been proposed until now. [Detailed Description of the Invention]

[Technical problem]

 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.

 Specifically, 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. Separately, 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. Here, methods for producing lithium hydroxide and lithium carbonate are presented as one embodiment of the present invention, respectively.

Technical Solution

 In one embodiment of the invention, dissolving lithium phosphate in acid;

 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.

Hereinafter, each step will be described. Converting the obtained lithium chloride aqueous solution into a lithium hydroxide aqueous solution; a positive electrode cell including a positive electrode; Crab 1 bipolar membrane; Anion selective dialysis membrane; Cation selective dialysis membranes, second bipolar membranes; A cathode cell including a cathode; a bipolar electrodialysis apparatus arranged in this order is prepared, and the aqueous lithium chloride solution is introduced between the bipolar selective dialysis membrane and the anion selective dialysis membrane, and water is added to the bipolar membrane and the anion. Injecting between the selective dialysis membrane and between the Crab 2 bipolar membrane and the cation selective dialysis membrane; And applying an electric current to the bipolar electrodialysis apparatus to obtain an aqueous lithium hydroxide solution and simultaneously obtaining an aqueous hydrochloric acid solution as a byproduct.

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.

Applying a current to the bipolar electrodialysis apparatus to obtain an aqueous lithium hydroxide solution and simultaneously obtaining an aqueous hydrochloric acid solution as a byproduct; Thereafter, concentrating the lithium hydroxide aqueous solution to crystallize; And drying the crystallized lithium hydroxide to obtain lithium hydroxide in powder form. In the step of preparing a lithium-containing solution, 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.

Specifically, 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.

Dissolving the lithium phosphate in an acid (ac id); 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.

In another embodiment of the present invention

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; In the negative cell and the positive cell Lithium hydroxide including an electrode solution selected from lithium sulfate (Li ₂ S0 ₄ ), lithium hydroxide (LiOH), lithium dihydrophosphate (UH ₂ P0 ₄ ), phosphoric acid (H ₃ P0 ₄ ), and a combination thereof It may be a manufacturing method of.

Specifically, the concentration of the electrode solution may be 0.1 to 20% by weight. In addition, the electrical conductivity of the electrode solution may be 10 to 100 ms / cm. Applying a current to the monovalent ion selective electrodialysis apparatus to obtain an aqueous lithium chloride solution and to obtain an aqueous solution of phosphoric acid formed as a by-product; wherein lithium ions in the lithium phosphate dissolved in the acid

Moving through the monovalent cation selective dialysis membrane toward the cathode; Chlorine ions in the lithium phosphate dissolved in the acid pass through the monovalent negative selective dialysis membrane and move in the direction of the anode; Concentrating the transferred lithium ions and the transferred chlorine ions between the monovalent cation selective dialysis membrane and the monovalent anion selective dialysis membrane to form the lithium chloride aqueous solution; And phosphoric acid ions and hydrochloric acid ^' ions in lithium phosphate dissolved in the acid remaining between the anode separator of the cathode cell and the monovalent cation selective dialysis membrane, and between the cathode separator of the anode cell and the monovalent anion selective dialysis membrane. It may be to include; forming a phosphoric acid aqueous solution.

And 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. In the step of feeding between the dialysis membrane sieve and the second bipolar membrane and the cation-selective dialysis membrane, respectively, in the weight ratio of the water input amount to the amount of the lithium chloride aqueous solution (water: lithium chloride aqueous solution), 1: 20 to 1 May be two.

Specifically, by applying a current to the bipolar electrodialysis apparatus, Obtaining an aqueous solution of lithium hydroxide and simultaneously obtaining an aqueous hydrochloric acid solution as a by-product; the water is hydrolyzed in the first bipolar membrane and the low 12 bipolar membrane to generate hydroxide ions and hydrogen ions; Moving lithium ions in the lithium chloride aqueous solution toward the cathode through the cation-selective dialysis membrane; Hydroxide ions generated in the second bipolar membrane and the transferred lithium ions are concentrated between the cation-selective dialysis membrane and the second bipolar membrane to form a lithium hydroxide aqueous solution; chlorine ions in the lithium chloride aqueous solution are the anions Penetrating the selective dialysis membrane and moving in the direction of the anode; And concentrating the hydrogen ions generated in the first bipolar membrane and the transferred chlorine ions between the anion-selective dialysis membrane and the first bipolar membrane to form an aqueous hydrochloric acid solution.

In the step of applying a current to the bipolar electrodialysis apparatus to obtain a lithium hydroxide aqueous solution and at the same time to obtain an aqueous hydrochloric acid solution as a by-product; the concentration of the separated hydrochloric acid aqueous solution may be 0.1 to 3.0 M. In the monovalent ion selective electrodialysis apparatus, 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. In another embodiment of the present invention, preparing a lithium hydroxide aqueous solution obtained by the above method; And carbonizing the aqueous lithium hydroxide solution to obtain lithium carbonate.

Meanwhile, 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 ). In another embodiment of the present invention, 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, monovalent negative silver is selectively selected. 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. It provides 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. In still another embodiment of the present invention, 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 _. 2 water supply line to supply water; Disposed between the low 12 cation selective dialysis membrane and the third bipolar membrane 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; And 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.

 【Effects of the Invention】

According to embodiments of the present invention, lithium hydroxide and lithium carbonate can be obtained in high purity and high concentration, respectively, with high efficiency and low process cost. Specifically, in the case of 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. In addition, when 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.

 In addition, 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.

 Furthermore, lithium hydroxide and lithium carbonate in powder form can be finally obtained from the lithium hydroxide aqueous solution.

[Brief Description of Drawings]

 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.

[Best form for implementation of the invention]

 Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless otherwise defined, all terms used in the present specification (including technical and scientific terms) may be used in a sense that can be commonly understood by those skilled in the art. When a part in the specification is said to "include" any component, this is not specifically described _. Unless another It does not exclude the component, it means that it may further include other components. In addition, singular forms also include the plural unless specifically stated otherwise in the text. As described above, the chemical precipitation method and the natural evaporation method are inadequate as a method for economically producing lithium hydroxide and lithium carbonate having a purity of a certain concentration or more, and therefore, a method of replacing them is required. 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. i) First of all, 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. .

Specifically, when lithium phosphate is dissolved in an acid, a high concentration of lithium chloride ^'is generated by chemical reaction and at the same time, phosphoric acid is produced as a by-product. When the product is directly put into the carbonation process, lithium carbonate is produced by the carbonation of the lithium chloride and at the same time, a large amount of impurities due to the phosphoric acid are generated. On the other hand, the phosphoric acid is an expensive substance, and also includes a phosphorus (P) which is an environmentally harmful substance, in consideration of this, while recovering the phosphoric acid separately from the lithium chloride, while obtaining lithium chloride with a high concentration of lithium In order to be able to recycle, the monovalent ion selective electrodialysis apparatus enables this. ii) Meanwhile, 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. Specifically, in order to directly carbonate the separated lithium chloride aqueous solution, an additive such as caustic soda is added to adjust the pH to around 11 ^· . In this case, 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. On the other hand, since lithium hydroxide does not need to add an additive to increase the pH in the carbonation process, it is possible to produce lithium carbonate with a high recovery rate without an additional process. The bipolar electrodialysis apparatus can effectively separate the by-product hydrochloric acid while converting the lithium chloride into a high concentration of lithium hydroxide.

i i i) In addition, 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.

Overall, in each of the above processes, 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.

Summarizing such a series of processes as shown in Figure 1, it will be described with reference to this method for producing each of the materials. First, the process (S10-S20) which manufactures lithium phosphate which is a raw material of the said lithium chloride manufacturing process is demonstrated.

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.

Common components included in the lithium-containing solution include Li ⁺ , Na ⁺ , K ⁺ , Ca ²⁺ , Mg ²⁺ , CI ^" , S0 ₄ ^2", and the like. However, 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).

Among the impurities, 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.

[Banungsik 1]

Ca ²⁺ + 2NaOH—> 2Na ⁺ + Ca (0H) ₂ (i), Mg ²⁺ + 2NaOH-> 2Na ⁺ + Mg (0H) ₂ (I) [Ref. 2]

Ca ²⁺ + Na ₂ C0 ₃ —> 2Na ⁺ + CaC0 ₃ (I), Mg ²⁺ + Na ₂ C0 ₃ _> 2Na ⁺ + MgC0 ₃ (1) [Scheme 3]

Mg ²⁺ + Ca (0H) ₂ —> Ca ²⁺ + Mg (0H) ₂ (\), Ca ²⁺ + Na ₂ S0 ₄ —> 2Na + + CaS0 ₄ (i) Considering the above reaction formulas 1 to 3 ， Na ₂ , Na ₂ CO ₃ , Ca (0H) ₂ , Na ₂ S0 _4, etc. are sequentially added to the lithium-containing solution, thereby Ca ²⁺ and Mg ^{2+ are added} to Ca (0H) ₂ , Mg (0H ) can be precipitated by _{2, CaC0 2, MgC0 3,} CaS0 4 and the like.

In the lithium-containing solution to remove the Ca ²⁺ , Mg ²⁺ selectively removed

Li +, Na ⁺ , K ⁺ , and CI ^" remain. Lithium phosphate can be obtained (S20) by adding a phosphorus feed material and then adjusting the pH appropriately. Examples of the phosphorus feed material include In one embodiment of the present invention, in order to reduce the raw material cost while preventing environmental pollution, in the process of converting lithium phosphate to lithium chloride, an aqueous solution of phosphate produced as a by-product is recycled. In this regard, the description of the process (S30-S40) for converting lithium phosphate to lithium chloride is as follows. As described above, while obtaining lithium chloride with a high concentration of lithium, monovalent cations selectively permeate only monovalent and monovalent anions, respectively, to recover and recycle the phosphoric acid separately from the lithium chloride. 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. Here, 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.

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.

Specifically, 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 (¾P0 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.

In this case, the concentration of the electrode solution may be 0.1 to 20 weight ¾. In addition, the electrical conductivity of the electrode solution may be 10 to 100 ms / cm. Specifically, the electrical conductivity of the electrode solution is proportional to the concentration of the electrode solution. However, the term "proportional" does not necessarily mean directly proportional to electricity. It also means that conductivity also tends to increase.

In this regard, it is necessary to smooth the movement of ions in the monovalent ion selective electrodialysis apparatus 100, and for this purpose, The concentration and the electrical conductivity each need to be above a certain value.

However, when the concentration of the electrode solution and the electrical conductivity are too high, respectively, the rate of movement of ions inside the monovalent ion selective electrodialysis apparatus 100 becomes slow, and electrical resistance occurs to increase voltage, decrease current, This will cause a decrease in current efficiency and an increase in power ratio.

More specifically, when the concentration of the electrode solution and the electrical conductivity become too high, 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. ^■

In consideration of this comprehensively, the concentration of the electrode solution needs to be 0.1 to 20 weight ¾, 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. In one embodiment of the present invention, in the step (S50) of converting lithium chloride to lithium hydroxide, 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.

On the other hand, when electricity is applied to the monovalent ion selective electrodialysis apparatus 100 into which lithium phosphate dissolved in the acid and the water are introduced, an anion moves toward the anode 160 due to an electrophoretic effect, and the cathode The cations move toward (110).

Specifically, 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.

[Banungsik 4]

Li ₃ P0 ₄ + 3HC1-> H ₃ P0 ₄ + 3LiCl At this time, 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. In addition, 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. On the other hand, in the acid remaining between the anode separator 150 of the cathode cell and the monovalent cation selective dialysis membrane 140, and between the cathode separator 120 of the cathode cell and the monovalent anion selective dialysis membrane 130. Phosphate ions and dissolved hydrochloric acid in the dissolved lithium phosphate are concentrated to form an aqueous solution of phosphoric acid.

Accordingly, 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. 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.

As a result, when the lithium phosphate is used as a raw material and the monovalent ion selective electrodialysis apparatus 100 is used, an aqueous lithium chloride solution with a high concentration of lithium is produced, and at the same time effectively produced with an aqueous phosphate solution. Can be separated.

At this time, the concentration of the aqueous solution of phosphoric acid may be 0.1 to 3.0 Μ. Specifically, in order to recover and reuse the phosphoric acid aqueous solution (S52), the concentration needs to be secured to 0.1 Μ or more. However, when the aqueous solution of phosphoric acid having a concentration exceeding 3.0 Μ is reused, 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.

In this case, as described above, 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. In addition, 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. Meanwhile, as illustrated in FIG. 4, the monovalent ion selective electrodialysis apparatus 100 may be used as a stack in which a plurality of layers are sequentially stacked.

When the monovalent ion selective electrodialysis apparatus 100 is 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.

When using the stacked electrodialysis apparatus as described above, 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. Can be. More detailed laminated electrodialysis apparatus will be described later. Next, 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.

In this 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.

As such, 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.

In this case, 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. Specifically, 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.

If the amount of the water input is less than the above range, 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.

On the contrary, when the amount of water input is in excess of the above range, the concentration of the obtained lithium chloride solution is too low, and an additional concentration step is required to produce lithium hydroxide and lithium carbonate using the same, and energy costs are generated. do.

Here, 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. In addition, 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. . _.

Accordingly, 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.

As a result, when the lithium chloride aqueous solution is used as a raw material, and the bipolar electrodialysis apparatus 200 is used, a lithium hydroxide aqueous solution having a high concentration of lithium is produced, and at the same time, it is effectively separated from the aqueous hydrochloric acid solution. Can be. In this case, the chemical reactions are summarized as follows.

[Bungungsik 5]

 LiCl + ¾0-> LiOH + HC1

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). In addition, 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.

Specifically, the lithium carbonate can be easily produced by injecting carbon dioxide into the lithium hydroxide aqueous solution. Meanwhile, 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.

On the other hand, the bipolar electrodialysis apparatus, as shown in Figure 5, may be used as a stack stacked in plurality sequentially.

When the bipolar electrodialysis apparatus is configured as a stacked stack as described above, 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.

As such, when the stacked bipolar electrodialysis apparatus is used, 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. . Hereinafter, with reference to 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.

First, as shown in FIG. 4, 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.

And an electrode solution supply line (not shown) 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. In addition, 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 (Li¾P0 ₄ ), phosphoric acid (H ₃ P0 ₄ ), and ^. May be selected from combinations thereof.

Meanwhile, 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). In addition, 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. Alternately may be disposed between the anion selective dialysis membrane 330 and the first cation selective dialysis membrane 340. When 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 following describes a stacked bipolar electrodialysis apparatus.

As shown in FIG. 5, 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.

And 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. (Not shown). In addition, the second electrode solution supply tank may be equipped with a second motor (not shown) capable of circulating the second electrode solution. Here, 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.

On the other hand, 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. At this time, 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.

In addition, the lithium hydroxide aqueous solution discharge line (480) and the hydrochloric acid solution discharge line (483) for discharging the lithium hydroxide aqueous solution, hydrochloric acid solution and the residual lithium chloride aqueous solution generated after the bipolar electrodialysis to the outside of the stacked bipolar electrodialysis apparatus (483). A residual lithium chloride aqueous solution discharge line 485 may be formed in the stacked bipolar electrodialysis apparatus. At this time, 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. ) And an outlet is formed between the second anion selective dialysis membrane 430, and the residual lithium chloride aqueous solution discharge line 485 is formed between the second anion selective dialysis membrane 430 and the second cation selective dialysis membrane 440. Can be. Lithium hydroxide aqueous solution produced by the electrophoretic effect when electricity is supplied to the multilayer bipolar electrodialysis apparatus described above by supplying the lithium chloride aqueous solution and water through the lithium chloride aqueous solution supply line 470 and the second water supply line 475. 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. In addition, 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. In the case of using such a lithium compound manufacturing apparatus, by the multilayer electrodialysis apparatus, lithium phosphate is converted into lithium chloride aqueous solution, and by 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. In the above, embodiments of the present invention have been comprehensively described with reference to FIGS. 1 to 5, but one embodiment of each of the present invention may be separately implemented or may be implemented in other specific forms.

[Form for implementation of invention]

 Hereinafter, preferred embodiments of the present invention are described. However, the following examples are only preferred embodiments of the present invention and the present invention is not limited to the following embodiments. Example 1 Preparation of Lithium Hydroxide

 (1) Preparation of Lithium Chloride

 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.

Specifically, 1 M of lithium phosphate was dissolved in 3 M of hydrochloric acid to give a total of 1 L of solution, 0.5 L of water was prepared, and a current was applied to the monovalent ion selective electrodialysis apparatus as shown in FIG. 2. . At this time, in the monovalent ion selective electrodialysis apparatus, a 0.5 molar phosphoric acid solution was used as the electrode solution, and a current of 2.2 A was applied at a voltage of 12 V for 140 minutes.

 As a result, the lithium chloride aqueous solution concentrated between the monovalent cation selective dialysis membrane and the monovalent anion selective dialysis membrane of the monovalent ion selective electrodialysis apparatus was rarely recovered, and the aqueous solution of phosphoric acid separated therefrom was recovered. Theoretically, in the solution in which the lithium phosphate is dissolved in hydrochloric acid, 1 M phosphate and 3 M lithium chloride may be generated according to the following reaction formula 4.

 [Banungsik 4]

Li ₃ P0 ₄ + 3HC1-> H ₃ P0 ₄ + 3LiCl

 In fact, 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. In addition, the recovered aqueous solution of phosphoric acid, it was measured that the phosphorus concentration is 47.3g / L, lithium concentration is 4.0g / L.

 From this, it can be seen that 83.5% of lithium of lithium phosphate as a raw material was converted to lithium chloride.

 On the other hand, 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. In addition, 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.

 (2) Preparation of Lithium Hydroxide

Lithium hydroxide was prepared using the recovered lithium chloride aqueous solution as a raw material, and using the bipolar electrodialysis apparatus of FIG. 3.

 Specifically, using a lithium chloride aqueous solution of 1L having a lithium concentration of 18g / L, using a 0.5L of water in a bipolar electrodialysis apparatus as shown in Figure 3, 4.4A at a voltage of 30V for 140 minutes Was applied.

As a result, an aqueous hydrochloric acid solution was recovered between the anion-selective dialysis membrane and the first bipolar membrane of the bipolar electrodialysis apparatus, and the cation-selective type. The lithium hydroxide aqueous solution may be recovered between the dialysis membrane and the second bipolar membrane. At this time, the lithium concentration in the recovered lithium hydroxide aqueous solution was measured to be 18.9 g / L, and the lithium conversion rate was 93%. Example 2 Preparation of Lithium Carbonate

The lithium hydroxide aqueous solution recovered in Example 1 was used as a raw material, and lithium carbonate was prepared by reaction.

Specifically, 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.

On the other hand, 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.

Claims

[Range of request]  [Claim 1]  Dissolving lithium phosphate in an acid;  A negative electrode cell including a negative electrode separator; Selectively penetrating monovalent anions Monovalent anion selective dialysis membrane; Monovalent cation selective dialysis membranes for selectively transmitting monovalent cyanide; And a cathode cell including an anode separator; preparing a monovalent ion selective electrodialysis apparatus in which the anodes are disposed, and disposing lithium phosphate dissolved in the acid 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, and introducing water between the monovalent cation selective dialysis membrane and the monovalent anion selective dialysis membrane; Applying a current to the monovalent ion selective electrodialysis apparatus to obtain an aqueous lithium chloride solution and to obtain an aqueous phosphoric acid solution formed as a byproduct; And  Converting the obtained lithium chloride aqueous solution to a lithium hydroxide aqueous solution; manufacturing method of lithium hydroxide comprising a. [Claim 2]  The method of claim 1,  Converting the obtained aqueous solution of lithium chloride into a lithium hydroxide aqueous solution; the positive electrode cell including a positive electrode; A first bipolar membrane; Anion selective dialysis membrane; Cation selective dialysis membranes, second bipolar membranes; A cathode cell including a cathode; prepare a bipolar electrodialysis apparatus arranged in this order. The lithium chloride aqueous solution is introduced between the cation selective dialysis membrane and the anion selective dialysis membrane, and water is supplied to the first bipolar membrane and the anion. Injecting between the selective dialysis membranes, and between the second bipolar membrane and the bilateral selective dialysis membranes; And Applying a current to the bipolar electrodialysis apparatus to obtain an aqueous lithium hydroxide solution and simultaneously obtaining an aqueous hydrochloric acid solution as a byproduct. [Claim 3]  The method of claim 2,  Preparing the lithium phosphate;  Preparing a lithium-containing solution; And  And injecting a phosphorus supply material into the lithium-containing solution to precipitate dissolved lithium with lithium phosphate. [Claim 4]  The method of claim 3,  The aqueous solution of phosphate obtained by the monovalent ion selective electrodialysis apparatus is prepared by adding a phosphorus supply material to the lithium-containing solution to precipitate dissolved lithium as lithium phosphate. Way . [Claim 5]  The method of claim 4,  The aqueous hydrochloric acid solution obtained by the bipolar electrodialysis apparatus is a method of producing lithium hydroxide, which is used as part or all of the acid of the step of dissolving the lithium phosphate in an acid. [Claim 6]  The method of claim 2,  Applying a current to the bipolar electrodialysis apparatus to obtain an aqueous lithium hydroxide solution and simultaneously obtaining an aqueous hydrochloric acid solution as a byproduct; Since the,  Concentrating the lithium hydroxide aqueous solution and crystallizing; And  Drying the crystallized lithium hydroxide, to obtain a lithium hydroxide in the form of a powder; manufacturing method of lithium hydroxide further comprising. [Claim 7]  The method of claim 6,  Preparing a lithium-containing solution; The lithium-containing solution, the solution extracted lithium dissolved in the sea, It is selected from the solution generated in the process of recycling the lithium battery, the solution leaching the lithium ore, brine, lithium-containing hot spring water, lithium-containing ground water, lithium-containing water and combinations thereof,  Method for producing lithium hydroxide. [Claim 8]  According to claim 17,  Injecting a phosphorus supply material into the lithium-containing solution to precipitate dissolved lithium into lithium phosphate; Before,  Removing divalent ionic impurities in the lithium-containing solution;  Method for producing lithium hydroxide. [Claim 9]  The method of claim 8, Removing divalent ionic impurities in the lithium-containing solution; the lithium-containing solution includes 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 to remove the chamb ions and magnet ions,  Method for producing lithium hydroxide. [Claim 10]  The method according to any one of claims 1 to 9,  Dissolving the lithium phosphate in an acid;  The acid (aci d) which dissolves the lithium phosphate, Hydrochloric acid (HC1), sulfuric acid (H ₂ S0 ₄ ), nitric acid (HN0 ₃ ), hydrofluoric acid (HF), hydrobromic acid (HBr), and combinations thereof.  Method for producing lithium hydroxide. [Claim 11]  The method of claim 10, A negative electrode sal including a negative electrode separator; Monovalent anion selective dialysis membranes for selectively permeating monovalent anions; Monovalent to selectively permeate monovalent cations Cation selective dialysis membranes; And a positive electrode cell including a positive electrode separator; a monovalent bivalent selective electrodialysis apparatus disposed in this order, and lithium phosphate dissolved in the acid between the positive electrode separator membrane of the positive electrode cell and the monovalent cation selective dialysis membrane, and the 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;  The cathode cell and the anode cell are respectively, Hwangsanri the volume (Li ₂ S0 _4), lithium hydroxide (LiOH), a phosphoric acid comprises an electrode solution is selected from hydrogen lithium (Li¾P0 _4), phosphoric acid (¾P0 _4), and combinations thereof,  Method for producing lithium hydroxide. [Claim 12]  The method of claim 11,  The concentration of the electrode solution is,  0.1 to 20% by weight,  Method for producing lithium hydroxide. [Claim 13]  The method of claim 11,  The electrical conductivity of the electrode solution is  10 to 100 ms / cm,  Method for producing lithium hydroxide. [Claim 14]  The method of claim 10,  Applying a current to the monovalent ion selective electrodialysis apparatus to obtain an aqueous lithium chloride solution and at the same time obtaining an aqueous phosphoric acid solution formed as a byproduct;  Lithium ions in the lithium phosphate dissolved in the acid penetrate the monovalent cation selective dialysis membrane and move toward the cathode; Chlorine ions in lithium phosphate dissolved in the acid Penetrating the dialysis membrane and moving in the direction of the anode;  The transferred lithium silver and the transferred chlorine ions are concentrated between the monovalent cation selective dialysis membrane and the monovalent anion selective dialysis membrane to form the lithium chloride aqueous solution; And  The silver phosphate and hydrochloric acid ions in lithium phosphate dissolved in the acid remaining between the positive electrode separator of the positive cell and the monovalent cation selective dialysis membrane, and between the negative electrode separator of the negative electrode cell and the monovalent anion selective dialysis membrane, Forming the aqueous solution of phosphoric acid; comprising;  Method for producing lithium hydroxide.  [Claim 15]  The method of claim 14,  Applying a current to the monovalent ion selective electrodialysis apparatus to obtain an aqueous lithium chloride solution and to obtain an aqueous phosphoric acid solution formed as a byproduct;  The concentration of the obtained phosphoric acid aqueous solution is,  0.1 to 3.0 M,  Method for producing lithium hydroxide. [Claim 16]  The method of claim 10,  An anode cell including an anode; a first bipolar membrane; an anion selective dialysis membrane; Cation selective dialysis membranes, second bipolar membranes; A negative electrode cell including a negative electrode; preparing a bipolar electrodialysis apparatus arranged in this order, adding the lithium chloride aqueous solution between the cation selective dialysis membrane and the negative selective dialysis membrane, and water into the first bipolar membrane and the anion. In between the selective dialysis membrane " and between the second bipolar membrane and the cationic selective dialysis membrane;  The weight ratio (water: lithium chloride aqueous solution) of the input amount of water to the input amount of the lithium chloride aqueous solution is 1: 20 to 1: 2, Method for producing lithium hydroxide.  [Claim 17]  The method of claim 16, By the current applied to the bipolar electrodialysis ^apparatus. Obtaining an aqueous solution of lithium hydroxide and simultaneously obtaining an aqueous hydrochloric acid as a byproduct;  The water is hydrolyzed in the first bipolar membrane and the second bipolar membrane to generate hydroxide ions and hydrogen ions;  Moving lithium ions in the lithium chloride aqueous solution toward the cathode through the bivalent selective dialysis membrane;  Hydroxide ions and the transferred lithium ions generated in the second bipolar membrane are concentrated between the cation-selective dialysis membrane and the second bipolar membrane to form an aqueous lithium hydroxide solution;  Chlorine ions in the lithium chloride aqueous solution pass through the anion-selective dialysis membrane and move in the direction of the anode; And  Wherein the hydrogen ions and the transferred chlorine ions generated in the first bipolar membrane are concentrated between the anion-selective dialysis membrane and the first bipolar membrane to form an aqueous hydrochloric acid solution. . [Claim 18]  The method of claim 17,  Applying a current to the bipolar electrodialysis apparatus to obtain an aqueous lithium hydroxide solution and simultaneously obtaining an aqueous hydrochloric acid solution as a byproduct;  The concentration of the separated hydrochloric acid solution is,  0.1 to 3.0 M,  Method for producing lithium hydroxide. [Claim 19]  The method of claim 10, The monovalent ion selective electrodialysis apparatus is the monovalent cation selective type A method for producing lithium hydroxide, wherein the dialysis membrane and the anion-selective dialysis membrane form a pair, and a plurality of the dialysis membrane pairs are continuously formed.  [Claim 20]  The method of claim 19,  The bipolar electrodialysis apparatus includes a bipolar membrane; A method for producing lithium hydroxide, wherein the anion selective dialysis membrane and the cation selective dialysis membrane form one pair, and a plurality of the dialysis membrane pairs are continuously formed. [Claim 21]  Preparing an aqueous lithium hydroxide solution obtained by the method of claim 10; And carbonizing the aqueous lithium hydroxide solution to obtain lithium carbonate.  Method for producing lithium carbonate. [Claim 22]  The method of claim 21,  Carbonating the aqueous lithium hydroxide solution to obtain lithium carbonate; It is carried out by reaction of the lithium hydroxide aqueous solution and carbon dioxide (C0 ₂ ),  Method for producing lithium carbonate. [Claim 23]  Between the first negative electrode cell including the first negative electrode and the first negative electrode separator and the first positive electrode cell including the first positive electrode and the low U positive electrode separator, a first anion selective dialysis membrane and a monovalent cation for selectively transmitting monovalent anions Is a pair of cation selective dialysis membranes  Placed consecutively,  An electrode solution supply line for supplying an electrode solution to the first cathode cell and the first anode cell; The paired 1 negatively-selective dialysis membrane and the system 1 cation selective A lithium phosphate supply line arranged alternately between the dialysis membranes and supplying lithium phosphate dissolved in an acid, and a water supply line supplying water; And alternately disposed between the paired first negative selective dialysis membrane and the first cation selective dialysis membrane, and discharge a lithium chloride aqueous solution discharge line and a phosphoric acid aqueous solution to discharge the lithium chloride aqueous solution generated after electrodialysis. Phosphoric acid aqueous solution discharge line;  Comprising a lithium compound manufacturing apparatus comprising a laminated electrodialysis apparatus that is continuously converted to the supplied lithium phosphate aqueous solution of lithium chloride. [Claim 24]  The method of claim 23,  The third bipolar membrane, the second anion selective dialysis membrane, and the second cation selective dialysis membrane are disposed in a pair between the second positive electrode cell including the second positive electrode and the second negative electrode cell including the second negative electrode in a pair. A second electrode solution supply line for supplying a second electrode solution to the second anode cell and the second cathode cell;  A lithium chloride aqueous solution supply line for supplying the lithium chloride aqueous solution discharged from the multilayer electrodialysis apparatus between the second anion selective dialysis membrane and the second cation selective dialysis membrane;  A second water supply line for supplying water between the third bipolar membrane and the second anion selective dialysis membrane and between the second cation selective dialysis membrane and the third bipolar membrane;  A lithium hydroxide aqueous solution discharge line disposed between the second cation selective dialysis membrane and the third bipolar membrane to discharge a lithium hydroxide aqueous solution generated after 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; And It is formed between the crab dianion-selective dialysis membrane and the second cation-selective dialysis membrane to produce bipolar electrodialysis. A residual lithium chloride aqueous solution discharge line for discharging the residual lithium chloride aqueous solution; The lithium compound manufacturing apparatus further comprises a laminated bipolar electrodialysis apparatus, wherein the supplied lithium chloride aqueous solution is continuously converted to an aqueous lithium hydroxide solution.  [Claim 25]  The method of claim 24,  The paired first anion selective dialysis membrane and the first cation selective dialysis membrane; silver  An apparatus for producing a lithium compound, wherein tens to thousands of pairs are disposed in succession. [Claim 26]  The method of claim 25,  The paired system 3 bipolar membrane, the second anion selective dialysis membrane and the second cation selective dialysis membrane  An apparatus for producing a lithium compound, wherein tens to hundreds of pairs are continuously arranged. [Claim 27]  The method of claim 26,  The lithium phosphate aqueous solution discharged from the laminated electrodialysis apparatus is re-supplied to the phosphorus supply material of the lithium phosphate manufacturing process [Claim 28]  The method of claim 27,  The hydrochloric acid aqueous solution discharged from the stacked bipolar electrodialysis apparatus is re-supply to the lithium phosphate supply dissolved in the acid. [Claim 29]  The method according to any one of claims 23 to 28,  And a carbonation device for converting the discharged aqueous lithium hydroxide solution into lithium carbonate.