JP4581553B2 - Lithium recovery method - Google Patents

Lithium recovery method Download PDF

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JP4581553B2
JP4581553B2 JP2004240375A JP2004240375A JP4581553B2 JP 4581553 B2 JP4581553 B2 JP 4581553B2 JP 2004240375 A JP2004240375 A JP 2004240375A JP 2004240375 A JP2004240375 A JP 2004240375A JP 4581553 B2 JP4581553 B2 JP 4581553B2
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lithium
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aqueous solution
lithium ions
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JP2006057142A (en
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正樹 今村
典久 土岐
賢二 竹田
法道 米里
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住友金属鉱山株式会社
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Process efficiency
    • Y02P10/21Process efficiency by recovering materials
    • Y02P10/212Recovering metals from waste
    • Y02P10/234Recovering metals from waste by hydro metallurgy
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/84Recycling of batteries

Description

  The present invention relates to a method for recovering lithium ions as lithium carbonate from an aqueous solution containing lithium ions, and more particularly to a method for recovering lithium from an aqueous solution in which a positive electrode active material separated from a battery is dissolved in recycling used lithium ion secondary batteries. About.

  In recent years, lithium ion batteries have been widely used as high energy density secondary batteries, but their recycling has not yet become practical. For example, even in the recovery of valuable metals constituting the positive electrode active material, nickel and cobalt that are easy to recover are recovered by a dry processing method, etc., but lithium, which is the main metal, is difficult to recover by dry processing. Therefore, many have been disposed of.

  Further, valuable metals such as nickel and cobalt are collected by a chemical method after a positive electrode active material separated from a battery is dissolved in an acidic solution. Even in this wet treatment, nickel, cobalt, and the like can be recovered, but lithium is difficult to recover sufficiently. That is, a method of precipitation as lithium carbonate is generally used, but since it is difficult to obtain a high concentration lithium ion aqueous solution, sufficient precipitation does not occur and it is often treated as a waste liquid.

  For example, Japanese Patent Laid-Open No. 2003-157913 discloses a method for recovering a metal from a used lithium ion battery by recovering nickel and cobalt by electrolysis, removing impurities as a hydroxide, and then recovering lithium as a carbonate. A method is described. However, the aqueous solution after removing impurities other than lithium often does not reach the desired lithium ion concentration. In this case, there is a problem that the recovery rate becomes very poor because lithium is lost due to the solubility of lithium carbonate. It was.

  On the other hand, JP 2003-245542 A describes a method of concentrating lithium using a lithium adsorbent in order to collect lithium from seawater or the like. However, since this method uses a solid adsorbent, continuous extraction and back extraction are difficult. In addition, it is a method originally intended to concentrate a small amount of lithium contained in a large amount of seawater. When the amount of lithium is large, the number of batch processes increases, so it is not a practical method for battery recycling.

JP 2003-157193 A JP 2003-245542 A

  As described above, in the recovery of lithium by wet treatment, lithium dissolved as ions is generally recovered as solid lithium carbonate by carbonation. However, if the lithium concentration in the aqueous solution is low, recovery is difficult. This is because the salt will not be in solid form unless the lithium concentration is high enough to be above the solubility of the salt.

  Specifically, in the recycling of lithium ion batteries, the lithium ion concentration of the solution in which the positive electrode active material separated from the battery is dissolved is several g / l. To recover lithium ions in a useful form, It is necessary to increase the ion concentration to several tens of g / l. However, evaporation is generally required to concentrate the solution, and in this case, enormous energy is required to evaporate water to the desired concentration, which is extremely difficult economically.

  The present invention has been made in view of such conventional circumstances, and a method for easily concentrating an aqueous solution containing low-concentration lithium ions at a low cost and recovering the lithium ions as solid lithium carbonate by carbonation. The purpose is to provide.

To achieve the above object, a method for recovering lithium provided by the present invention was adjusted to a range of pH4~10 depending on the acidic solvent extraction agent used the pH of the aqueous solution containing lithium ions to the extraction of lithium ions, the After extracting lithium ions by contacting with an acidic solvent extractant, the solvent extractant is contacted with an aqueous solution having a pH of 3.0 or less to back-extract lithium ions, and the above-described reverse extraction operation is performed using the obtained lithium ion aqueous solution The lithium ion is recovered as solid lithium carbonate by concentrating lithium ions and mixing the resulting high-concentration lithium ion aqueous solution with a water-soluble carbonate in a state maintained at 60 ° C. or higher. To do.

In the lithium recovery method of the present invention, as the acidic solvent extractant, 2-ethylhexylphosphonic acid mono-2-ethylhexyl, di (2-ethylhexyl) phosphonic acid, bis (2,4,4-trimethylpentyl) Either phosphonic acid or a mixture of phenyl alkyl beta diketone and trioctyl phosphine oxide can be used.

  According to the present invention, an acidic solvent extractant is used to efficiently extract lithium ions in an aqueous solution to the extractant side, and a lithium ion concentrate is efficiently extracted by back-extracting it with an acidic aqueous solution. Obtainable. Therefore, the lithium ion concentration can be increased to a concentration sufficient to obtain solid lithium carbonate by carbonation by further repeated operation.

  Therefore, the method of the present invention can recover lithium efficiently and economically by wet treatment even in an aqueous solution having a low lithium ion concentration in which a positive electrode active material separated from a used lithium ion battery is dissolved. It is particularly useful in recycling used lithium ion batteries.

  Acidic solvent extractants are used for extraction of light elements, but no examples of applying this to extraction of lithium have been known. However, the present inventors investigated the extraction rate of lithium from the aqueous solution to the solvent extractant by changing the pH, and found that when the pH is 4 or more, lithium ions can be extracted on the solvent extractant side as the pH increases. It was.

  The method of the present invention has been made on the basis of the above findings, and an acidic solvent extractant is contact-mixed with an aqueous solution containing a low concentration (several g / l) of lithium ions, and the pH of the aqueous solution is 4 or more. It was possible to extract lithium ions into the solvent extractant by adjusting the pH to a pH range suitable for the solvent extractant used.

Examples of acidic solvent extractants include mono-2-ethylhexyl 2-ethylhexylphosphonate (pH 4-7), di (2-ethylhexyl) phosphonic acid (pH 4-6), bis (2,4,4-trimethylpentyl). ) Phosphonic acid (pH 4-8) or a mixture of phenylalkyl beta diketone and trioctyl phosphine oxide (pH 4-10). In addition, pH value described at the end of each said solvent extractant is a pH range suitable for extraction of lithium ion.

  In addition, if other metals (for example, nickel, iron, etc.) that are extracted to the acidic solvent extractant in the adjusted pH range are present as ions in the aqueous solution, other metals are also extracted to the solvent extractant side together with lithium ions. In the subsequent back extraction, it is back extracted to the aqueous solution side and concentrated in the same manner as lithium ions. Therefore, it is desirable to separate and remove these other metal ions by a neutralization operation or the like before performing an extraction operation with an acidic solvent extractant for lithium concentration.

Further, as a feature of the acidic solvent extractant, ion exchange with H + is performed by setting the pH to the acidic side, and the extracted metal ions are released. Utilizing this property, when the acidic solvent extractant from which lithium ions have been extracted is contact-mixed with a small amount of aqueous solution adjusted to pH 3.0 or less, the concentration of the first extracted lithium aqueous solution (about several g / l) Lithium ions are back-extracted into the aqueous solution at a higher concentration.

  Therefore, preferably, the aqueous solution on the back-extraction side is repeatedly used and the above-described back-extraction operation is repeated, so that the lithium ion concentration in the aqueous solution is several tens of grams sufficient to form solid lithium carbonate by carbonation. / L can be concentrated to a level of about 1. In addition, the extraction rate and back extraction rate can be controlled by accurately controlling the pH, and therefore the final lithium ion concentration in the aqueous solution can be controlled.

  The concentrated aqueous lithium ion solution thus concentrated can then be mixed with a water-soluble carbonate such as sodium carbonate or calcium carbonate to precipitate lithium ions in the aqueous solution as solid lithium carbonate. . In addition, as a water-soluble carbonate, sodium carbonate is preferable. However, lithium carbonate, which is a lithium carbonate, differs in solubility from other salts, and its solubility rapidly decreases as the aqueous solution temperature increases. That is, the solubility of lithium carbonate is 1.28% at 25 ° C., but decreases to 1.00% at 60 ° C. and further decreases to 0.7% at 100 ° C.

  For this reason, when the temperature of the high-concentration lithium ion aqueous solution is increased to 60 ° C. or higher, the solubility of lithium carbonate becomes lower than other salts such as sodium sulfate having high solubility, and lithium carbonate is selectively precipitated as crystals. A high purity lithium carbonate solid can be obtained. The temperature of the high-concentration lithium ion aqueous solution should be high, but generally, when the temperature is 80 ° C. or higher, the operation becomes difficult or the cost increases from the viewpoint of the heat resistance of the reaction vessel and peripheral devices, and further 90 ° C. Since the boiling point is close to the above, it can be said that the temperature range of 60 to 80 ° C. is generally appropriate.

[Example 1]
The following four types were used as the acidic solvent extractant.
(1) Phenyl alkyl beta diketone (manufactured by Henkel, trade name: LIX54) 10% by volume + trioctylphosphine oxide (TOPO) 10% by volume + diluent (manufactured by Shell Chemical Japan, trade name: Shellzol A) 80 volume%
(2) 20% by volume of di (2-ethylhexyl) phosphonic acid (manufactured by Bayer, trade name D2EHPA) + 80% by volume of diluent (trade name Cleansol G, manufactured by Nippon Oil Corporation)
(3) 2-ethylhexylphosphonic acid mono-2-ethylhexyl (manufactured by Daihachi Chemical Co., Ltd., trade name PC-88A) 20% by volume + diluent (trade name Cleansol G) 80% by volume
(4) Bis (2,4,4-trimethylpentyl) phosphonic acid (manufactured by Cytec Corporation, trade name Cyanex 272) 20% by volume + diluent (trade name Clinsol G) 80% by volume

  About each acidic solvent extractant of said (1)-(4), the pH range which can extract lithium ion efficiently was confirmed. That is, lithium sulfate is dissolved in pure water to prepare a lithium ion aqueous solution (lithium ion concentration 5.16 g / l), and the aqueous solution and each acidic solvent extractant are adjusted to have a volume ratio of 1: 2. The mixture was mixed, and a pH range in which the aqueous solution and the extractant could be separated was confirmed while gradually increasing the pH of the aqueous solution by dropping a 5 wt% NaOH solution. As a result, the minimum pH at which lithium ions can be extracted and separated is 4.0 for any extractant, the maximum pH is pH 10 for the extractant (1), pH 6 for the extractant (2), pH 7 for the extractant (3), And in the extractant (4), the pH was 8. When these maximum pHs were exceeded, it was found that the extraction agent was insufficiently separated and was not suitable for the extraction operation.

  Next, the same acidic solvent extractant (1) to (4) and a lithium ion aqueous solution (lithium ion concentration 5.16 g / l) as described above are prepared, and the aqueous solution and each extractant are mixed at a volume ratio of 1: Contact mixing was performed to make 2 and 1: 4. At that time, in order to obtain a pH suitable for each extractant, a 5% by weight NaOH solution is dropped, and the extractant (1) has a pH of 9.5, the extractant (2) has a pH of 5.0, and the extractant (3). Was adjusted to pH 7.0, and the extractant (4) was adjusted to pH 8.0.

  As a result, the extraction results shown in Table 1 below were obtained. In any acidic solvent extractant, 50% or more of the lithium ion in the aqueous solution having a lithium ion concentration of 5.16 g / l as the starting solution is extracted, and the extraction rate increases when the volume ratio of the solvent extractant is increased. Rose. Thus, it was found that if the pH of the aqueous solution is adjusted to an appropriate value according to the acidic solvent extractant, lithium ions can be extracted to a practically sufficient level using the acidic solvent extractant.

  Each acidic solvent extractant from which lithium ions were extracted as described above was contact-mixed with a 1 mol / l sulfuric acid aqueous solution so that the volume ratio was 1/2 of the extractant, and lithium ion back extraction was performed. . As a result, in any acidic solvent extractant, the lithium ion concentration in the extractant, which was around 1.5 g / l in the extraction stage, is 0.01 g / l or less, and back extraction is effectively performed. I understood that.

[Example 2]
As an acidic solvent extractant, 2-ethylhexylphosphonic acid mono-2-ethylhexyl (manufactured by Daihachi Chemical Co., Ltd., trade name PC-88A) 20% by volume + diluent (manufactured by Shin Nippon Oil Co., Ltd., trade name: 80% by volume of Tecrin N20) was prepared, and the pH range where lithium ions can be efficiently extracted was confirmed in the same manner as in Example 1 above.

  That is, an aqueous lithium sulfate solution adjusted to have a lithium ion concentration of 5 g / l is prepared as a starting solution, and the aqueous solution and the extractant are mixed in contact at a volume ratio of 1: 2, and the pH of the aqueous solution after mixing is adjusted. A 5% by weight NaOH solution was added dropwise to adjust to 2.0 to 7.0.

  The change in the lithium extraction rate accompanying the change in pH at that time is shown in FIG. It was found that the extraction of lithium ions started when the pH of the aqueous solution exceeded 3 and at a pH of 4 or higher, the lithium extraction rate gradually increased as the pH increased.

[Example 3]
As an acidic solvent extractant, 20% by volume of 2-ethylhexylphosphonate mono-2-ethylhexyl phosphonate (trade name PC-88A, manufactured by Daihachi Chemical Co., Ltd.) as in Example 2 above + diluent (Shin Nippon Oil Co., Ltd.) Product name: Teklin N20) Using 80% by volume, contacted with lithium sulfate aqueous solution, adjusted pH of aqueous solution after mixing to 7.0, and extracted lithium ion, lithium ion in extractant The concentration was 1.5 g / l.

  Next, the extractant from which the lithium ions have been extracted is contact-mixed with pure water so that the volume ratio of pure water to the extractant is 1: 2, and a 15 wt% sulfuric acid aqueous solution is dropped into the mixed aqueous solution. The pH was adjusted to 0.1 and lithium ions were back extracted. After the first back-extraction operation, the same back-extraction operation was repeated by using the remaining lithium ion aqueous solution and again contacting and mixing with an extractant containing lithium ions obtained separately by the extraction operation.

  This operation was repeated up to 5 times, the lithium ion concentration of the remaining lithium ion aqueous solution was measured for each operation, and the obtained results are shown in Table 2 below. From this result, it was confirmed that each time the operation was repeated, lithium ions from the extractant were back-extracted quantitatively into the aqueous solution, and finally the lithium ions in the aqueous solution could be concentrated to a concentration of about 17 g / l.

[Example 4]
A lithium carbonate aqueous solution with a lithium ion concentration of 10 g / l is mixed dropwise with a sodium carbonate aqueous solution with a concentration of 200 g / l. The temperature of the aqueous solution is adjusted to 20 ° C. and 60 ° C. to precipitate lithium carbonate as crystals. It was. The reaction temperature at this time and the sulfur quality in the recovered lithium carbonate solid are shown in Table 3 below. It has been found that if the temperature is 60 ° C. or higher, the sulfur concentration in lithium sulfate is low, and pure lithium carbonate can be produced.

It is a graph which shows the relationship between pH at the time of lithium extraction, and an extraction rate.

Claims (2)

  1. The pH of the aqueous solution containing lithium ions is adjusted to a range of pH4~10 depending on the acidic solvent extractant used for the extraction of lithium ions, after extracting lithium ions is brought into contact with the acidic solvent extractant, the solvent The extractant is brought into contact with an aqueous solution having a pH of 3.0 or less to reversely extract lithium ions, and the obtained lithium ion aqueous solution is used to repeat the above-described back extraction operation to concentrate lithium ions. A method for recovering lithium, wherein lithium ions are recovered as solid lithium carbonate by mixing with a water-soluble carbonate in a state maintained at 60 ° C or higher.
  2. As the acidic solvent extractant, mono-2-ethylhexyl 2-ethylhexylphosphonate (pH range suitable for extraction of lithium ions: pH 4-7) , di (2-ethylhexyl) phosphonic acid (same pH range: pH 4-6) ) , Bis (2,4,4-trimethylpentyl) phosphonic acid (same pH range: pH 4-8) or a mixture of phenylalkyl beta diketone and trioctylphosphine oxide (same pH range: pH 4-10) The method for recovering lithium according to claim 1, wherein:
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JP5161361B1 (en) * 2011-12-28 2013-03-13 Jx日鉱日石金属株式会社 Method for separating metal in mixed metal solution
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KR20190132444A (en) 2017-03-30 2019-11-27 제이엑스금속주식회사 Lithium Recovery Method
WO2018181607A1 (en) 2017-03-31 2018-10-04 Jx金属株式会社 Lithium recovery method
KR20190133738A (en) 2017-03-31 2019-12-03 제이엑스금속주식회사 Lithium recovery method
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KR20200024909A (en) 2017-08-02 2020-03-09 제이엑스금속주식회사 Method for dissolving lithium compound, method for producing lithium carbonate, and method for recovering lithium from lithium ion secondary battery scrap

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