JP2011031232A - Method of manufacturing lithium hydroxide - Google Patents

Method of manufacturing lithium hydroxide Download PDF

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JP2011031232A
JP2011031232A JP2009193627A JP2009193627A JP2011031232A JP 2011031232 A JP2011031232 A JP 2011031232A JP 2009193627 A JP2009193627 A JP 2009193627A JP 2009193627 A JP2009193627 A JP 2009193627A JP 2011031232 A JP2011031232 A JP 2011031232A
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lithium
lithium hydroxide
chamber
acid
cathode
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Isao Kuribayashi
功 栗林
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Kee:Kk
有限会社ケー・イー・イー
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Abstract

[PROBLEMS] There has been a demand for a highly economical manufacturing method that is effective in securing lithium hydroxide produced overseas, from a lithium source that can be stored in Japan, when it is necessary, because it does not provide long-term storage.
A cation exchange membrane and an anion exchange membrane are alternately arranged between an anode and a cathode, followed by an anode chamber partitioned by an anode and a cation membrane, followed by an acid chamber, a salt chamber, an alkali chamber, and a water electrolysis chamber. Lithium is used in the salt chamber using an electrodialysis apparatus in which a water electrolysis chamber composed of one or more pairs consisting of an anion membrane on the most cathode side is partitioned with a cathode instead of a cation membrane to form a cathode chamber A method for producing lithium hydroxide characterized by supplying an aqueous solution of salt to take out the acid from the acid chamber and taking out the lithium hydroxide aqueous solution from the alkali chamber, and further providing a purification step for reducing impurities contained in trace amounts. It is set as the manufacturing method of purity lithium hydroxide.
Lithium hydroxide can be produced cleanly and easily from lithium carbonate and lithium salts stored in Japan when necessary. A convenient and versatile method of producing lithium hydroxide is provided.
[Selection] Figure 1

Description

The present invention relates to a method for producing lithium hydroxide.

In the conventional method for producing lithium hydroxide, it is common to obtain calcium hydroxide by adding calcium hydroxide to a lithium carbonate aqueous solution. In addition, production at overseas sites where ore or irrigation as a lithium source is collected is common. In recent years, pollution control of calcium carbonate, which is a by-product in large quantities, has also become a problem locally. Lithium hydroxide absorbs carbon dioxide in the air during storage, partially transforms into lithium carbonate, solidifies during storage, or becomes a lump and interferes with powder handling work, so it is necessary for long-term storage. Needed to be manufactured when needed. From the viewpoint of ensuring domestic stability as a raw material that must be transported by long-distance transportation, the risk has increased with the recent increase in demand. Since lithium hydroxide has poor storage properties, domestic storage of lithium hydroxide as a raw material has been difficult.

In recent years, lithium hydroxide has been refined as a lithium source for producing a positive electrode active material for lithium ion secondary batteries and by a chemical method, and as high purity lithium carbonate, electronic equipment such as lithium niobate and tantalate as SAW filter materials It is used as a raw material.
Reduction of impurities contained in lithium hydroxide is desired for further precise material design.

JP 2001-259647 A Japanese Patent No. 4065386 (Japanese Patent Laid-Open No. 2003-305475) JP 2007-7655 A Patent Document 1 discloses a method and apparatus for simultaneously producing an acid and a base by electrodialysis, but differs from the configuration of the apparatus of the present invention. There is no mention of lithium salts.
Patent Documents 2 and 3 describe that an acid and an alkali are produced from a neutral salt, but there is no mention of a lithium salt, and no mention is made of the purity of the alkali.

In recent years, there has been a demand for a method capable of easily producing lithium hydroxide when necessary from a lithium source stored in Japan.
Recovered from used lithium-ion secondary batteries, which have been attracting attention as a production method or lithium resource that can produce lithium hydroxide when necessary using lithium carbonate powder that can be stored in Japan as a raw material. Therefore, there is a demand for a method capable of easily producing lithium hydroxide from lithium chloride obtained by selective adsorption from the prepared lithium salt and irrigation. It is an object of the present invention to provide a method for producing lithium hydroxide that satisfies this object.

As a result of various studies on the above-mentioned problems, the present inventor has obtained a lithium salt obtained by dissolving a large amount of domestically stored lithium carbonate in an acid, extracted from an ore containing lithium that can be stored for a long time with an acid. Electrodialysis of lithium salts obtained from stock materials such as lithium salts collected from used lithium ion batteries, lithium salts recovered from used lithium ion batteries or lithium carbonate, and lithium chloride selectively adsorbed and separated from irrigation The present inventors have found a method for producing lithium hydroxide, characterized in that an aqueous lithium hydroxide solution and an aqueous acid solution can be taken out independently by an apparatus. Furthermore, a method for reducing and removing trace amounts of alkaline earth ions with a chelate resin by providing a purification step for reducing impurities contained in trace amounts, 90-100 ° C. so as to reduce monovalent cations such as sodium and potassium. A method of repeating concentration and crystallization at a temperature of 10 ° C, a method of reducing and removing monovalent cations such as sodium and potassium and alkaline earth ions using a cation exchange resin, and / or an anion exchange resin This is a production method for reducing and removing anions such as chlorine ions and sulfate ion.

According to the present invention, lithium hydroxide can be produced easily and cleanly when necessary in Japan, starting from a lithium-containing raw material that has long-term storage in Japan. A lithium hydroxide aqueous solution and an acid can be simultaneously produced by an electrodialyzer having a structure in which lithium salt is partitioned into an anode chamber, an acid chamber, a salt chamber, an alkali chamber, a water electrolysis chamber, and a cathode chamber, and the acid can be used repeatedly.
One lithium hydroxide aqueous solution removes and reduces impurities with an ion exchange resin, and then reacts with high purity lithium hydroxide and further with carbon dioxide gas to produce high purity lithium carbonate as a positive electrode active material for lithium ion secondary batteries. For firing, it can be supplied to lithium niobate, lithium tantalate or the like as a SAW filter material for electronic equipment to produce electrolyte LiPF 6 or the like.

The cation exchange membrane and the anion exchange membrane are alternately arranged between the anode and the cathode of the present invention, and the acid chamber, the salt chamber, and the alkali chamber are sequentially arranged from the anode chamber and the anode chamber side partitioned by the anode and the cation exchange membrane. An electrodialysis apparatus in which one set of water electrolysis chambers is arranged, and shows an example in which the water electrolysis chamber is a cathode chamber partitioned by a cathode instead of a cation membrane. It is a figure which shows the concept of the method of manufacturing lithium simultaneously. The cation exchange membrane and the anion exchange membrane are alternately arranged between the anode and the cathode of the present invention, and the acid chamber, the salt chamber, and the alkali chamber are sequentially arranged from the anode chamber and the anode chamber side partitioned by the anode and the cation exchange membrane. An electrodialysis apparatus in which one set of water electrolysis chambers is arranged, and shows an example in which the water electrolysis chamber is a cathode chamber partitioned by a cathode instead of a cation exchange membrane. Hydrochloric acid and hydroxylation from an aqueous solution of lithium chloride It is a figure which shows the concept of the method of manufacturing lithium simultaneously. Cation exchange membranes and anion exchange membranes are alternately arranged between the anode and the cathode of the present invention, and three sets of an acid chamber, a salt chamber, an alkali chamber, and a water electrolysis chamber are arranged between the anode and the cathode. An example of an electrodialysis apparatus in which the water electrolysis chamber closest to the cathode is a cathode chamber partitioned by a cathode instead of a cation exchange membrane, and simultaneously produces sulfuric acid and lithium hydroxide from an aqueous solution of lithium sulfate It is a figure which shows the concept of a method. Cation exchange membranes and anion exchange membranes are alternately arranged between the anode and the cathode of the present invention, and three sets of an acid chamber, a salt chamber, an alkali chamber, and a water electrolysis chamber are arranged between the anode and the cathode. An example of an electrodialysis device in which the water electrolysis chamber closest to the cathode is a cathode chamber partitioned by a cathode instead of a cation exchange membrane, and simultaneously produces hydrochloric acid and lithium hydroxide from an aqueous solution of lithium chloride It is a figure which shows the concept of a method.

The present invention will be specifically described below.
That is, the present invention provides (1) a cation exchange membrane and an anion exchange membrane arranged alternately between an anode and a cathode, and an anode chamber is formed by the anode and the cation exchange membrane. Therefore, an acid chamber partitioned by the cation exchange membrane and the anion membrane, a salt chamber partitioned by the anion exchange membrane and another cation exchange membrane, and the cation exchange membrane and another anion exchange membrane One or more pairs of an acid chamber, a salt chamber, an alkali chamber, and a water electrolysis chamber arranged in the order of a compartmented alkali chamber and a water electrolysis chamber partitioned by this anion exchange membrane and a new cation exchange membrane A water electrolysis chamber composed of an anion membrane on the most cathode side is partitioned with a cathode instead of a cation membrane, and an aqueous solution of lithium salt is supplied to the salt chamber using an electrodialyzer having a structure of the cathode chamber Is it an acid chamber? The method for producing lithium hydroxide is characterized in that an acid for repeatedly obtaining a lithium salt is taken out, and an aqueous lithium hydroxide solution is taken out from the alkaline chamber. The lithium salt used reacts sulfuric acid or hydrochloric acid with lithium carbonate. Select from lithium sulfate or lithium chloride obtained by extraction from lithium-containing ore with sulfuric acid or hydrochloric acid, lithium sulfate recovered from used lithium ion secondary batteries, lithium chloride, or irrigation. Adsorbed and separated lithium chloride and the like. (2) A method for producing lithium hydroxide by adding a method for reducing or removing a trace amount of alkaline earth metal from a lithium hydroxide aqueous solution using a chelate resin, and (3) a trace amount of the above lithium hydroxide aqueous solution. A method for producing lithium hydroxide to which a method of repeating concentration and crystallization at a temperature of 90 to 100 ° C. so as to reduce monovalent cations such as sodium and potassium, (4) from the aqueous lithium hydroxide solution described above A method of producing lithium hydroxide to which a method of reducing and removing monovalent cations such as sodium and potassium and alkaline earth metal ions using a cation exchange resin is added, (5) from the above-mentioned aqueous lithium hydroxide solution This is a production method in which an anion exchange resin is added with a method for reducing and removing anions such as chloride ions and sulfate radical ions.

In order to obtain the lithium hydroxide of the present invention, an anode chamber, an acid chamber, a salt chamber, an alkali chamber, a water electrolysis chamber, and a cathode chamber are made of an electrodialyzer composed of an alkali-resistant and acid-resistant material, An anode chamber is provided to prevent corrosion of the anode, and the cathode chamber is partitioned from an alkali chamber to prevent corrosion of the cathode.
The lithium carbonate used in the present invention may be commercially available lithium carbonate or lithium carbonate collected separately. The reason why lithium carbonate is once converted into a salt is that lithium salt has higher solubility in water and a higher concentration of aqueous solution, and therefore the electrodialyzer can be operated with lower resistance.
The electrodialyzer can be used as a material as long as it can withstand strong alkalis and strong acids. For example polypropylene, TPX, polyethylene, EPDM, plastics of a polyolefin material such as a copolymer of butene-1 and alpha-olefins can be used.

The cation exchange membrane used in the present invention is a membrane that can pass a monovalent cation (such as lithium ion), and has at least a sulfonic acid group, a carboxylic acid group, a phosphonic acid group, a sulfate ester group, and a phosphate ester group. Any film made of a polymer having one or more kinds may be used.
Fluorine cation exchange membranes with sulfonic acid groups, cation exchange membranes with perfluorocarboxylic acid groups introduced, and cation exchange membranes of perfluorovinyl copolymers with functional groups of ethylene tetrafluoride and carboxylic acid / sulfonic acid Further, there are a cation exchange membrane in which a membrane of a perfluorocarboxylic acid polymer and a perfluorosulfonic acid polymer is bonded, a cation exchange membrane in which a perfluorosulfonic acid polymer and a perfluorocarboxylic acid polymer are laminated, and the like. Attaching reinforcing fibers, further improving the selective permeability of monovalent cations to suppress the passage of multivalent ions such as calcium and magnesium that permeate the cation exchange membrane, and anions such as OH ions and chloride ions In addition, additives may be applied for the purpose of suppressing or eliminating the passage of sulfate ions, the surface layer surface may have a dense structure, or other films may be bonded together. Neoceptor CMV, Neoceptor CMB, Neoceptor CMS, Neoceptor CMT, Neoceptor CIMS, Neoceptor CL-25T, Neoceptor CMD, Neoceptor CM-2, Neoceptor CSO (above, manufactured by Tokuyama Corporation, trade name) ), Selemion CMD, Selemion CMT, Selemion CMV, Selemion CAV, Selemion HSF, Selemion CSO, Selemion CMF, Selemion CSV, Selemion FX-151 (made by Asahi Glass Co., Ltd.), FKF, FKC, FKL, FKE (Fumatec) ), Nafion 324, Nafion 117, Nafion 115 (manufactured by DuPont, trade name), Aciplex K-501 (trade name, manufactured by Asahi Kasei Co., Ltd.), and the like.

The anion exchange membrane used in the present invention is a membrane made of a polymer having a strongly basic group of a quaternary ammonium group, a weak basicity such as a primary amino group, a secondary amino group, or a tertiary amino group. Any film made of a polymer having a functional group may be used.
Neoceptor ACM, Neoceptor AM-1, Neoceptor ACS, Neoceptor ACLE-5P, Neoceptor AHA, Neoceptor AMH, Neoceptor ACS (above, Tokuyama Co., Ltd., trade name), Selemion AMV, Selemion AMT, Selemion DSV, Selemion AAV, Selemion ASV, Selemion AHT, Selemion APS (Asahi Glass Co., Ltd., trade name), FAB, FAA (Fumatech Co., Ltd., trade name), Aciplex A-501, A-231, A-101 (Asahi Kasei) Company name, product name).

The cathode used in the present invention preferably has a low overvoltage, and the surface of a substrate such as iron, nickel, stainless steel or the like, or the surface of a substrate such as iron or stainless steel, is coated with sulfur-containing nickel, Raney nickel-based alloy or nickel oxide. A plated material made of one or more of gold, titanium, platinum, palladium and the like can be used.

The anode is a metal plate such as stainless steel or titanium, the surface is coated with at least one of ruthenium oxide, inorganic oxide and carbon, and is plated with one or more of gold, platinum, palladium, etc. Can be used. So-called insoluble electrodes are used.
The voltage range is such that oxidation in the case of a metal plate can be suppressed.

Low-voltage operation can be achieved by previously filling the acid chamber and the alkali chamber with a dilute solution of predetermined acid and lithium hydroxide, which are separately prepared to provide conductivity.

As an electrodialysis method according to the present invention, an acid chamber and an alkaline chamber are provided with acid and lithium hydroxide aqueous solution tanks, and each solution is circulated between each solution tank and the chamber. You can also. As a method of extracting the acid or lithium hydroxide aqueous solution that is generated, at the beginning of operation, a thin acid and lithium hydroxide aqueous solution that can be energized are charged to produce acid and lithium hydroxide, and the concentration reaches a predetermined level. Even in the so-called batch method, where a predetermined amount is withdrawn and then replenished with distilled water or purified water to restore the initial thin concentration, a predetermined concentration of acid and lithium hydroxide aqueous solution is charged in advance, and depending on the amount of electricity applied Alternatively, a continuous type in which acid or lithium hydroxide aqueous solution having a predetermined concentration is withdrawn by continuously adding distilled water or purified water may be used.

Similarly, the salt solution is also connected to the salt chamber and the salt tank through a salt solution circulation line, and the salt solution having a reduced concentration discharged from the salt chamber is passed through the salt tank and circulated again to the salt chamber. The cell voltage is measured, and when the measured voltage exceeds a preset voltage value, a new salt solution is supplied to the salt solution circulation line through the salt solution supply line.

As a method of monitoring the cell voltage, a conventionally known method is adopted. In order to detect the cell voltage, generally two or more platinum wire electrodes are inserted between two or more separated membranes, the voltage is measured under energization, and the cell stack between the aforementioned electrodes is measured. A method of calculating by dividing by a number can be employed. By inserting platinum wire electrodes in the anode chamber and cathode chamber, the voltage between the stacks is detected, and the cell voltage is measured, so that the average value of the concentration of the salt solution can be obtained and abnormalities can occur in any of the membranes. Even if it occurs, it can be detected and is preferable.

The cell voltage is usually 1 to 3 volts. When exceeding a preset cell voltage, for example, 4 to 6 volts, it means that the concentration of the salt aqueous solution in the salt chamber is lowered to an extent that is not suitable for electrodialysis. In such a case, a new salt solution is supplied to the salt solution circulation line.

The electrodialysis apparatus of the present invention can be operated by connecting a series of solar cells having a cell voltage of about 0.7 V obtained by solar power generation to a desired voltage range, storing electricity, and using a voltage stabilizer. . Compared with conventional DC current conversion from 100V to 200V AC current, energy loss due to heat generation in the voltage stabilizer to lower the voltage, from the viewpoint of energy saving and low running cost It is particularly preferable to combine them.

Current density of electrodialysis to be used in the present invention is usually in the range of 0.3~50A / dm 2 preferably runs at a constant current density in the range of 1 to 20A / dm 2.
If the current density is constant, the cell voltage is the concentration of acid, salt aqueous solution, lithium hydroxide aqueous solution, flow rate of each solution, temperature, cation exchange membrane, electric resistance of anion exchange membrane, blister, presence / absence of scale It depends on factors such as. When the cell voltage does not decrease even when adding a new salt solution, since it is considered that scale occurs in the ion-exchange membrane, it is preferable to stop the electrodialysis immediately.

In order to further remove trace amounts of ions that have passed through the ion exchange membrane from the lithium hydroxide aqueous solution obtained by electrodialysis according to the present invention, for example, alkaline earth such as calcium and magnesium, and trace amounts of metal ions are removed by adsorption. As the chelating agent, iminodiacetic acid type or aminophosphoric acid type chelating resins can be used. The space velocity (SV) in the column is usually 2 to 10 hr −1 in the purification operation. Since these chelate resins are often shipped as sodium salts, they are converted to lithium salts with an acid treatment, water washing, and an aqueous solution of 9-11% ultrapure lithium hydroxide before use. Although not particularly limited, lithium salts of Amberlite IRC748 (manufactured by Organo) and Amberlite IRC747 (manufactured by Organo) are used.

In order to reduce monovalent alkali ions such as sodium and potassium other than lithium, the difference in solubility in water at 100 ° C., that is, sodium hydroxide (347 g / 100 g of water), potassium hydroxide (178 g / 100 g of water) and Lithium hydroxide monohydrate crystallizes, dehydrates and evaporates near the boiling point of water in the process of heating and concentrating lithium hydroxide aqueous solution using the difference in solubility of lithium hydroxide (17.5 g / 100 g of water) A multi-stage crystallization / dehydration method is used in which crystallization / dehydration is repeated using the distilled hot water. Further, in this process, a small amount of lithium hydrogen carbonate and lithium carbonate can be hydrolyzed and returned to lithium hydroxide. Since the decomposed trace amount of carbon dioxide gas is distilled, it is better to absorb the gas and remove it from the distilled water. Furthermore, sulfonic acid groups of styrene / divinylbenzene cross-linked polymers are functionalized as a cation exchange resin that completely adsorbs divalent alkaline earth calcium and magnesium, and reduces or removes monovalent cations such as sodium and potassium. A strongly acidic cation exchange resin based on a carboxylic acid group and a weak acid cation exchange resin based on a copolymer of acrylic acid or methacrylic acid and divinylbenzene having a carboxylic acid group as a functional group can be used. Either the RH type that releases hydrogen ions or the R-Li type that releases Li cations according to the amount of impurities can be used. The cation exchange resin shipped as a commercially available sodium salt is converted to a lithium salt with an acid treatment, washing with water, an aqueous solution of 9-11% ultrapure lithium hydroxide concentration or ultrapure lithium carbonate before use. The space velocity (SV) in the column is usually 1 to 10 hr −1 in the purification operation. Although not particularly limited, IR120B, IR124, IR200CT, IR252 of trade name Amberlite (manufactured by Organo), lithium salt of trade name Diaion (manufactured by Mitsubishi Chemical) SK, PK, HPK25, and the like are used.

To adsorb and reduce or remove anions such as chloride ion, sulfate ion and hydrogen carbonate ion, chloromethylation to a copolymer of styrene and divinylbenzene as an anion exchange resin, trimethylamine, dimethylamine and dimethylethanolamine Use the aminated product. The anion exchange resin shipped as a commercially available chlorine salt is washed with an ultra-high purity lithium hydroxide aqueous solution before use and converted to the OH type.
Further methyl alcohol containing traces of water, ethyl alcohol, isopropyl alcohol by anion exchange resin manufacturing process trace amount came included from sulfate ion ion (SO4 -) and chlorine ion (Cl -), amines, etc. Wash and remove. Moreover, since it is easy to oxidatively deteriorate, the contact with air is reduced, and the dissolved oxygen in the lithium hydroxide aqueous solution obtained by electrodialysis for ion exchange is reduced if necessary for long-term operation. The space velocity (SV) in the column is usually 1 to 10 hr −1 in the purification operation.
Although not particularly limited, IRA400J, IRA400T, IRA402J, 402BL, trade names Amberlite (manufactured by Organo), trade names Diaion (made by Mitsubishi Chemical) SA10A, PA300, PA318, HPA-75, WA10, WA20, WA30, SA20A OH conversion products such as PA400, trade name Levacit (manufactured by LANXESS) A-365, etc. are used.

In the purification step of the present invention, the aqueous solution of lithium hydroxide can be concentrated after using the above chelating agent, cation exchange resin, or anion exchange resin.
In addition, if necessary, the crystallization residual liquid in which lithium hydroxide is precipitated is again subjected to such ion removal treatment, concentrated impurities are removed, and then the precipitate is dehydrated and dehydrated and dried in hot water. In particular, the yield of lithium hydroxide can be increased.

Hereinafter, the present invention will be described in detail with reference to Examples, Comparative Examples, and Reference Examples, but the scope of the present invention is not limited to these Examples. As for the analytical method, lithium is measured by atomic absorption method, and each element other than lithium is measured by ICP method. Lithium content (%) is calculated as lithium hydroxide monohydrate by correcting alkali and alkaline earth components other than lithium as determined by ICP method from alkali titration equivalent as determined by titration method. It is shown as a numerical value multiplied by the amount 16.5494%. Chlorine ions (Cl ) and sulfate radicals (SO 4 − − ) are measured by ion chromatography.

The special grade sulfuric acid is diluted with distilled water and reacted with technical grade lithium carbonate (Kemetalfoot) granules to make the supernatant liquid lithium aqueous solution.
In an electrodialysis apparatus using a cation exchange membrane (trade name Neocepta CMB, manufactured by Astom) and an anion exchange membrane (trade name Neocepta AHA, manufactured by Astom) between the anode and the cathode, an acid chamber, a salt chamber, an alkali A direct current is passed between an anode and a cathode through an electrodialysis apparatus in which one set of a chamber and a water electrolysis chamber (cathode chamber) is arranged. Supply an aqueous solution of lithium sulfate to the salt chamber, make the aqueous solution of sulfuric acid exist in the acid chamber, and make the ultrahigh purity lithium hydroxide aqueous solution exist in the alkaline chamber, and separate the sulfuric acid from the acid chamber and the aqueous lithium hydroxide solution from the alkaline chamber, respectively. Take out. The lithium hydroxide aqueous solution taken out in a stable operation state is passed through a Limber modified product column of Amberlite IRC748. This liquid is heated and concentrated, crystallized at 98 ° C. near the boiling temperature of water, and separated and dehydrated from hot water. This crystallized product is dissolved using distilled water obtained by condensing from water vapor, heated and concentrated again, crystallized at 98 ° C., separated and dehydrated from hot water, and dried. The analysis results of the obtained lithium hydroxide monohydrate are shown in Table 1.

The supernatant obtained by diluting hydrochloric acid, a special grade reagent, with distilled water and reacting with the same lithium carbonate (technical grade, manufactured by Kemetal Foot) granules as in Example 1 is used as an aqueous lithium chloride solution. In the same electrodialysis apparatus as in Example 1, an aqueous solution of lithium hydrochloride was supplied to the salt chamber, hydrochloric acid water was present in the acid chamber, and an ultrahigh purity lithium hydroxide aqueous solution was present in the alkali chamber, and hydrochloric acid was transferred from the acid chamber to the alkaline chamber. The lithium hydroxide aqueous solution is taken out of each independently. The aqueous solution of lithium hydroxide taken out in a stable operation state is passed through a Li-modified column of Amberlite IRC748 and then a Li-modified column of Amberlite IR120B. This liquid is heated and concentrated, crystallized at 99 ° C. near the boiling temperature of water, and separated and dehydrated from hot water. This crystallized product is dissolved in distilled water obtained by condensation from water vapor, heated and concentrated again, crystallized at 99 ° C., separated and dehydrated from hot water, and dried. The analysis results of the obtained lithium hydroxide monohydrate are shown in Table 1. The resulting hydrochloric acid is repeatedly used to dissolve the lithium carbonate granules.

The liquid that has passed through the Li-modified column of Amberlite IRC748 in Example 1 is further passed through the Amberlite IRA410 OH column. Heat, concentrate and remove water vapor at around the boiling temperature, separate, dehydrate and dry the precipitate at 98 ° C. Table 1 shows the analysis results of the lithium hydroxide monohydrate obtained in Table 1.

The liquid which passed through the Li-modified column of Amberlite IRC748 in Example 2 and then the Li-modified column of Amberlite IR120B is further passed through the OH-converted column of Diaion WA20. Heat, concentrate and remove water vapor around the boiling temperature, separate, dehydrate and dry the precipitate at 97 ° C. Table 1 shows the analysis results of the lithium hydroxide monohydrate obtained in Table 1.

Lithium sulfate powder obtained by extraction with sulfuric acid from a heat-treated and β-modified lithium-containing ore (spodium) is dissolved in distilled water. The sulfuric acid was added to the salt chamber of the electrodialysis apparatus in which three sets of an acid chamber, a salt chamber, an alkali chamber, and a water electrolysis chamber were arranged between the anode chamber and the cathode chamber by the same electrode and ion exchange membrane as in Example 1. A lithium aqueous solution is supplied, a dilute sulfuric acid aqueous solution is present in the acid chamber, an ultrahigh purity lithium hydroxide aqueous solution is present in the alkali chamber, and sulfuric acid is extracted from the acid chamber and the lithium hydroxide aqueous solution is independently extracted from the alkali chamber. The lithium hydroxide aqueous solution taken out in a stable operation state is passed through a Limber modified product column of Amberlite IRC748, a Li modified product column of Amberlite IR120B and an Amberlite IRA410 OH column in order, and purified. Heat, concentrate and remove water vapor near the boiling temperature, separate the precipitate at 97 ° C. and dry. Table 1 shows the analysis results of the lithium hydroxide monohydrate obtained in Table 1.
The obtained sulfuric acid can be used for extraction from heat-treated lithium-containing ore (spo- men). It is also used to react with lithium carbonate to obtain lithium sulfate.

Lithium chloride powder obtained by extraction with hydrochloric acid from a heat-treated β-modified ore containing lithium (spodium) is dissolved in distilled water. This lithium chloride aqueous solution is supplied to the salt chamber of the same electrodialysis apparatus as in Example 5, dilute hydrochloric acid is present in the acid chamber, ultrahigh purity lithium hydroxide aqueous solution is present in the alkali chamber, and hydrochloric acid is supplied from the acid chamber to the alkali chamber. The lithium hydroxide aqueous solution is taken out of each independently. The lithium hydroxide aqueous solution taken out in a stable operation state is passed through a Limber modified product column of Amberlite IRC748, a Li modified product column of Amberlite IR120B and an Amberlite IRA410 OH column in order, and purified. Heat, concentrate and remove water vapor around the boiling temperature, separate, dehydrate and dry the precipitate at 97 ° C. Table 1 shows the analysis results of the lithium hydroxide monohydrate obtained in Table 1.
The obtained hydrochloric acid can also be used for extraction from heat-treated lithium-containing ore (spo- men). It is also used to react with lithium carbonate to obtain lithium chloride.

The lithium sulfate aqueous solution recovered from the used lithium ion secondary battery is supplied to the salt chamber of the same electrodialysis apparatus as in Example 1, the dilute sulfuric acid aqueous solution is present in the acid chamber, and the alkaline chamber is ultrahigh. Purity lithium hydroxide aqueous solution is present, and sulfuric acid is taken out from the acid chamber and lithium hydroxide aqueous solution is taken out from the alkali chamber independently. The lithium hydroxide aqueous solution taken out in a stable operation state is sequentially passed through a Li-modified column of Amberlite IRC748, a Li-modified column of Amberlite IR120B, and an OH-converted column of Levacit A365 for purification. Heat, concentrate and remove water vapor around the boiling temperature, separate, dehydrate and dry the precipitate at 97 ° C. Table 1 shows the analysis results of the lithium hydroxide monohydrate obtained in Table 1.
The obtained sulfuric acid can be used to recover a lithium source as lithium sulfate from a used lithium ion secondary battery. Moreover, you may use for making it react with lithium carbonate and obtaining lithium sulfate.

The lithium chloride aqueous solution recovered from the used lithium ion secondary battery is supplied to the salt chamber of the same electrodialysis apparatus as in Example 1, dilute hydrochloric acid is present in the acid chamber, and an ultrahigh purity lithium hydroxide aqueous solution is added to the alkali chamber. The hydrochloric acid is removed from the acid chamber and the lithium hydroxide aqueous solution is removed from the alkaline chamber independently. The lithium hydroxide aqueous solution taken out in a stable operation state is passed through a Li-modified column of Amberlite IRC748, a Li-modified column of Amberlite IR120B, and an Amberlite IRA410 OH column for purification. Heat, concentrate and remove water vapor around the boiling temperature, separate the precipitate at 97 ° C., leaving some hot water, and dry. Table 1 shows the analysis results of the lithium hydroxide monohydrate obtained in Table 1.
The obtained hydrochloric acid can be used to recover a lithium source as lithium chloride from a used lithium ion secondary battery. Moreover, you may use for making it react with lithium carbonate and obtaining lithium chloride.

Lithium chloride powder adsorbed and separated by aluminum hydroxide tablets having a layered structure from irrigation is dissolved in distilled water. This lithium chloride aqueous solution is supplied to the salt chamber of the same electrodialysis apparatus as in Example 1, dilute hydrochloric acid is present in the acid chamber, ultrahigh purity lithium hydroxide aqueous solution is present in the alkali chamber, and hydrochloric acid is supplied from the acid chamber to the alkali chamber. The lithium hydroxide aqueous solution is taken out of each independently. The lithium hydroxide aqueous solution is passed through a Limber modified product column of Amberlite IRC748, a Li modified product column of Amberlite IR120B, and an Amberlite IRA410 OH column for purification. Heat, concentrate and remove water vapor around the boiling temperature, separate the precipitate at 97 ° C., leaving some hot water, and dry. Table 1 shows the analysis results of the lithium hydroxide monohydrate obtained in Table 1.

Comparative Example 1

Dilute the special grade reagent sulfuric acid with distilled water and react with granules of technical grade lithium carbonate (manufactured by Kemetal Foot) to make the supernatant liquid lithium aqueous solution.
Using the same electrodialysis apparatus as in Example 1, an aqueous solution of lithium sulfate was supplied to the salt chamber, an aqueous sulfuric acid solution was present in the acid chamber, an ultrahigh purity lithium hydroxide aqueous solution was present in the alkaline chamber, and the sulfuric acid was fed from the acid chamber. The lithium hydroxide aqueous solution is taken out from the alkali chamber independently. The lithium hydroxide aqueous solution taken out in a stable operation state is heated and concentrated to crystallize around the boiling temperature of water, and part of hot water is separated at 90 ° C., and the crystallized product is dried to obtain lithium hydroxide. -The analysis result of monohydrate is shown in Table 1.

Comparative Example 2

The supernatant obtained by diluting hydrochloric acid, a special grade reagent, with distilled water and reacting with granules of lithium carbonate of the same technical grade as in Example 1 (manufactured by Kemetal Foot) is used as an aqueous lithium chloride solution.
The aqueous solution of lithium hydrochloride is supplied to the salt chamber of the same electrodialysis apparatus as in Example 1, the aqueous hydrochloric acid solution is present in the acid chamber, the ultrahigh purity lithium hydroxide aqueous solution is present in the alkaline chamber, and the hydrochloric acid is supplied from the acidic chamber to the alkaline chamber. The lithium hydroxide aqueous solution is taken out of each independently. The lithium hydroxide aqueous solution taken out in a stable operation state is heated and concentrated to crystallize around the boiling temperature of water, and part of hot water is separated at 90 ° C., and the crystallized product is dried to obtain lithium hydroxide. -The analysis result of monohydrate is shown in Table 1.

Reference example 1

A hypothetical lithium hydroxide with a theoretical lithium content of 16.5494% based on the results of the analysis of lithium using the atomic absorption method of technical grade lithium carbonate (manufactured by Kemetalfoot) and other elemental analysis results obtained using the ICP method. Table 1 shows the level of impurities present in the monohydrate.

A cation exchange membrane and an anion exchange membrane are alternately arranged between the anode and the cathode, an anode chamber is formed by the anode and the cation exchange membrane, and then an acid chamber, a salt chamber, from the anode side to the cathode side, A water electrolysis chamber composed of one or more pairs of an acid chamber, a salt chamber, an alkali chamber, and a water electrolysis chamber arranged in the order of an alkali chamber and a water electrolysis chamber, and an anion membrane on the most cathode side is cationized. Use an electrodialyzer with a cathode instead of a membrane and use an electrodialyzer as a cathode chamber, so that acid and lithium hydroxide can be taken out at the same time, and long-term storage is possible when necessary from lithium carbonate and lithium salts stored in Japan. Poor lithium hydroxide can be easily produced cleanly. Furthermore, high-purity lithium hydroxide to which a purification step for reducing a small amount of impurities can be produced.
The acid taken out at the same time can be used repeatedly to obtain a lithium salt. It becomes possible to provide a convenient and versatile method for producing lithium hydroxide.

Claims (12)

  1. A cation exchange membrane and an anion exchange membrane are alternately arranged between the anode and the cathode, an anode chamber is formed by the anode and the cation exchange membrane, and then the cation exchange membrane and the anion from the anode side to the cathode side. An acid chamber partitioned by a membrane, a salt chamber partitioned by the anion exchange membrane and another cation exchange membrane, an alkali chamber partitioned by this cation exchange membrane and another anion exchange membrane, and further this anion One or more pairs of acid chambers, salt chambers, alkali chambers, and water electrolysis chambers are arranged in the order of the water electrolysis chamber partitioned by the exchange membrane and the new cation exchange membrane, and the anion membrane on the most cathode side A water electrolysis chamber constituted by a cathode is partitioned by a cathode instead of a cation membrane, and an acid solution is supplied from an acid chamber by supplying an aqueous solution of a lithium salt to the salt chamber using an electrodialysis apparatus having a cathode chamber. Lithium hydroxide Method for producing a lithium hydroxide, characterized in that retrieving the anhydrous solution.
  2. 2. The method for producing lithium hydroxide according to claim 1, wherein the lithium hydroxide is obtained by reacting lithium carbonate and sulfuric acid.
  3. 2. The method for producing lithium hydroxide according to claim 1, wherein the lithium hydroxide is obtained by reacting lithium carbonate with hydrochloric acid.
  4. 2. The method for producing lithium hydroxide according to claim 1, wherein the lithium hydroxide is lithium sulfate obtained by extraction with sulfuric acid from a lithium-containing ore.
  5. The method for producing lithium hydroxide according to claim 1, which is lithium chloride obtained by extraction with hydrochloric acid from a lithium-containing ore.
  6. 2. The method for producing lithium hydroxide according to claim 1, wherein the lithium hydroxide is recovered from a used lithium ion secondary battery.
  7. 2. The method for producing lithium hydroxide according to claim 1, wherein the lithium hydroxide is lithium chloride recovered by reacting a lithium content with hydrochloric acid from a used lithium ion secondary battery.
  8. 2. The method for producing lithium hydroxide according to claim 1, wherein the lithium hydroxide is selectively adsorbed and separated from irrigation.
  9. A method for producing lithium hydroxide, wherein the lithium hydroxide aqueous solution according to claim 1-7 is added with a method for reducing and removing trace amounts of alkaline earth metals using a chelate resin.
  10. A method for repeating concentration and crystallization at a temperature of 90 to 100 ° C so as to reduce monovalent cations such as sodium and potassium contained in a trace amount in the lithium hydroxide aqueous solution according to claim 1-8. A method for producing lithium hydroxide.
  11. 10. A hydroxylation solution comprising the lithium hydroxide aqueous solution according to claim 1 to which a method for reducing and removing monovalent cations such as sodium and potassium and alkaline earth metal ions using a cation exchange resin is added. Method for producing lithium.
  12. A method for producing an aqueous lithium hydroxide solution according to claim 1 to which a method for reducing and removing anions such as chloride ions and sulfate radical ions with an anion exchange resin is added.
JP2009193627A 2009-08-04 2009-08-04 Method of manufacturing lithium hydroxide Pending JP2011031232A (en)

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Cited By (14)

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CN103367197A (en) * 2012-03-29 2013-10-23 无锡华瑛微电子技术有限公司 Wafer surface processing system
WO2013159194A1 (en) * 2012-04-23 2013-10-31 Nemaska Lithium Inc. Processes for preparing lithium hydroxide
JP5367190B1 (en) * 2013-03-08 2013-12-11 株式会社アストム Method for producing lithium hydroxide
WO2016132491A1 (en) * 2015-02-18 2016-08-25 独立行政法人石油天然ガス・金属鉱物資源機構 Apparatus for producing lithium hydroxide and method for producing lithium hydroxide
KR20160136314A (en) * 2014-02-24 2016-11-29 네마스카 리튬 인코포레이션 Methods for treating lithium-containing materials
CN106186006A (en) * 2016-07-27 2016-12-07 浙江鸿浩科技有限公司 A kind of purifying lithium chloride method
CN107299361A (en) * 2016-08-31 2017-10-27 江苏力泰锂能科技有限公司 The electrodialysis plant of lithium hydroxide solution is prepared using soluble lithium salt solution
CN107298450A (en) * 2016-08-31 2017-10-27 江苏力泰锂能科技有限公司 The method that lithium hydroxide and lithium carbonate are prepared using soluble lithium salt solution
KR101857458B1 (en) * 2012-08-13 2018-05-14 리드 어드밴스드 미네랄즈 피티와이 리미티드 Processing of Lithium Containing Material
KR20180074177A (en) * 2016-12-23 2018-07-03 주식회사 포스코 Method for manufacturing lithium hydroxide and lithium carbonate
JP2018520971A (en) * 2015-05-13 2018-08-02 リサーチ インスティチュート オブ インダストリアル サイエンス アンド テクノロジー Method for producing lithium hydroxide and lithium carbonate
US10167531B2 (en) 2014-03-13 2019-01-01 Reed Advanced Materials Pty Ltd Processing of lithium containing material
WO2019228577A3 (en) * 2018-05-29 2020-01-09 Membrain S.R.O. Process for preparing lithium chemical compounds by electrodialysis method and apparatus for performing this process
CN110917882A (en) * 2019-11-04 2020-03-27 杭州匠容道环境科技有限公司 Four-channel electrodialysis device for extracting lithium from salt lake and method for extracting lithium from salt lake

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CN103367197A (en) * 2012-03-29 2013-10-23 无锡华瑛微电子技术有限公司 Wafer surface processing system
WO2013159194A1 (en) * 2012-04-23 2013-10-31 Nemaska Lithium Inc. Processes for preparing lithium hydroxide
KR101857458B1 (en) * 2012-08-13 2018-05-14 리드 어드밴스드 미네랄즈 피티와이 리미티드 Processing of Lithium Containing Material
JP5367190B1 (en) * 2013-03-08 2013-12-11 株式会社アストム Method for producing lithium hydroxide
JP2017512256A (en) * 2014-02-24 2017-05-18 ネマスカ リチウム インコーポレーテッド Method for processing lithium-containing materials
KR20160136314A (en) * 2014-02-24 2016-11-29 네마스카 리튬 인코포레이션 Methods for treating lithium-containing materials
KR102153976B1 (en) 2014-02-24 2020-09-10 네마스카 리튬 인코포레이션 Methods for treating lithium-containing materials
US10167531B2 (en) 2014-03-13 2019-01-01 Reed Advanced Materials Pty Ltd Processing of lithium containing material
WO2016132491A1 (en) * 2015-02-18 2016-08-25 独立行政法人石油天然ガス・金属鉱物資源機構 Apparatus for producing lithium hydroxide and method for producing lithium hydroxide
US10661227B2 (en) 2015-05-13 2020-05-26 Research Institute Of Industrial Science & Technology Method for producing lithium hydroxide and lithium carbonate
JP2018520971A (en) * 2015-05-13 2018-08-02 リサーチ インスティチュート オブ インダストリアル サイエンス アンド テクノロジー Method for producing lithium hydroxide and lithium carbonate
CN106186006A (en) * 2016-07-27 2016-12-07 浙江鸿浩科技有限公司 A kind of purifying lithium chloride method
CN107299361A (en) * 2016-08-31 2017-10-27 江苏力泰锂能科技有限公司 The electrodialysis plant of lithium hydroxide solution is prepared using soluble lithium salt solution
CN107298450A (en) * 2016-08-31 2017-10-27 江苏力泰锂能科技有限公司 The method that lithium hydroxide and lithium carbonate are prepared using soluble lithium salt solution
CN107299361B (en) * 2016-08-31 2019-06-14 江苏力泰锂能科技有限公司 The electrodialysis plant of lithium hydroxide solution is prepared using soluble lithium salt solution
CN107298450B (en) * 2016-08-31 2019-11-29 江苏力泰锂能科技有限公司 The method for preparing lithium hydroxide and lithium carbonate using soluble lithium salt solution
KR101888181B1 (en) 2016-12-23 2018-08-13 주식회사 포스코 Method for manufacturing lithium hydroxide and lithium carbonate
KR20180074177A (en) * 2016-12-23 2018-07-03 주식회사 포스코 Method for manufacturing lithium hydroxide and lithium carbonate
WO2019228577A3 (en) * 2018-05-29 2020-01-09 Membrain S.R.O. Process for preparing lithium chemical compounds by electrodialysis method and apparatus for performing this process
CN110917882A (en) * 2019-11-04 2020-03-27 杭州匠容道环境科技有限公司 Four-channel electrodialysis device for extracting lithium from salt lake and method for extracting lithium from salt lake

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