JP6703077B2 - Lithium recovery method - Google Patents
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- JP6703077B2 JP6703077B2 JP2018193798A JP2018193798A JP6703077B2 JP 6703077 B2 JP6703077 B2 JP 6703077B2 JP 2018193798 A JP2018193798 A JP 2018193798A JP 2018193798 A JP2018193798 A JP 2018193798A JP 6703077 B2 JP6703077 B2 JP 6703077B2
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- acidic solution
- carbonate
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 39
- 229910052744 lithium Inorganic materials 0.000 title claims description 39
- 238000000034 method Methods 0.000 title claims description 30
- 238000011084 recovery Methods 0.000 title claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 83
- 239000003929 acidic solution Substances 0.000 claims description 57
- 229910052759 nickel Inorganic materials 0.000 claims description 38
- 238000006386 neutralization reaction Methods 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 31
- 159000000007 calcium salts Chemical class 0.000 claims description 26
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 25
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 23
- 229910001416 lithium ion Inorganic materials 0.000 claims description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- 229910001453 nickel ion Inorganic materials 0.000 claims description 16
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 13
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 6
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims 1
- 238000010000 carbonizing Methods 0.000 claims 1
- 238000000638 solvent extraction Methods 0.000 description 14
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 13
- 238000005868 electrolysis reaction Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
この発明は、少なくともリチウムイオン及びニッケルイオンを含む酸性溶液から、ニッケルを除去してリチウムを回収する方法に関するものであり、特に、回収に要するコストの低減に資する技術を提案するものである。 The present invention relates to a method for recovering lithium by removing nickel from an acidic solution containing at least lithium ions and nickel ions, and particularly proposes a technique that contributes to reduction in cost required for recovery.
たとえば近年は、製品寿命等の理由で廃棄されるリチウムイオン電池スクラップから、そこに含まれるニッケルやコバルト等の有価金属を湿式処理等により回収することが、資源の有効活用の観点から広く検討されている。 For example, in recent years, it has been widely studied from the viewpoint of effective use of resources to recover valuable metals such as nickel and cobalt contained in lithium-ion battery scraps discarded due to their product life etc. by wet treatment. ing.
このような有価金属の回収では具体的には、はじめに、リチウムイオン電池スクラップを焙焼して有害な電解液を除去し、その後に破砕、篩別を順に行い、次いで、篩別の篩下に得られる粉末状の電池粉を浸出液に添加して浸出し、そこに含まれ得るリチウム、ニッケル、コバルト、マンガン、銅、アルミニウム等を液中に溶解させる。
そしてその後、浸出後液に溶解している各金属元素を分離させて回収する。ここでは、浸出後液に浸出しているそれぞれの金属を分離させるため、浸出後液に対し、分離させる金属に応じた複数段階の溶媒抽出もしくは中和等を順次に施し、さらには、各段階で得られたそれぞれの溶液に対して、逆抽出、電解、炭酸化その他の処理を施す。
Specifically, in the recovery of such valuable metals, first, the lithium-ion battery scrap is roasted to remove the harmful electrolyte, followed by crushing and sieving in order, and then the sieving under the sieving. The obtained powdery battery powder is added to the leaching solution and leached, and lithium, nickel, cobalt, manganese, copper, aluminum and the like which may be contained therein are dissolved in the solution.
Then, after that, each metal element dissolved in the liquid after leaching is separated and recovered. Here, in order to separate each metal leached in the post-leaching solution, the post-leaching solution is sequentially subjected to a plurality of stages of solvent extraction or neutralization according to the metal to be separated, and further, in each step. Each of the solutions obtained in step 1 is subjected to back extraction, electrolysis, carbonation and other treatments.
ところで、たとえば、上述したようなリチウムイオン電池スクラップから金属を回収する方法等では、その途中のニッケル回収のための溶媒抽出及び逆抽出後の電解で得られる電解後液等の、リチウムイオン及びニッケルイオンを含む酸性溶液から、リチウムを回収することが求められることがある。
これに関連する技術として特許文献１では、リチウムイオンを含む水溶液から、溶媒抽出によりリチウムイオンを抽出した後、逆抽出を繰り返し行い、それにより得られた高濃度リチウムイオン水溶液を炭酸塩と混合することにより、炭酸リチウムを回収することが記載されている。
By the way, for example, in the method for recovering metal from lithium-ion battery scrap as described above, lithium ion and nickel in a post-electrolysis solution obtained by electrolysis after solvent extraction and back extraction for nickel recovery in the process It is sometimes required to recover lithium from an acidic solution containing ions.
As a technique related to this, in Patent Document 1, after extracting lithium ions from an aqueous solution containing lithium ions by solvent extraction, back extraction is repeatedly performed, and the resulting high-concentration lithium ion aqueous solution is mixed with carbonate. By doing so, it is described that lithium carbonate is recovered.
また特許文献２では、少なくともリチウム、ニッケルを含む溶液から、溶媒抽出によりニッケルとリチウムを共抽出し、その後、リチウムのみを逆抽出して得られるリチウム溶液を炭酸化し、リチウムを回収することが記載されている。
Further, in
上述した特許文献１及び２のいずれに記載された手法でも、リチウムを分離させるために溶媒抽出を行うこととしており、これに起因してコストの増大を招くという問題がある。
また、特許文献１、２に記載の手法では、酸性溶液に含まれ得る不純物の種類や濃度によっては、リチウムを効果的に分離できないことがある。
In any of the methods described in
Further, the methods described in
この発明は、従来技術が抱えるこのような問題に対処することを課題とするものであり、その目的は、リチウムの回収に要するコストを大きく増大させることなしに、リチウムイオン及びニッケルイオンを含む酸性溶液から、リチウムを有効に回収することのできるリチウム回収方法を提供することにある。 The present invention has an object to address such problems of the prior art, and an object thereof is to provide an acidic solution containing lithium ion and nickel ion without significantly increasing the cost required for recovery of lithium. It is an object of the present invention to provide a lithium recovery method capable of effectively recovering lithium from a solution.
発明者は、上述した電解後液のように、リチウムイオンが比較的少なく、かつニッケルイオンが比較的多い酸性溶液から、リチウムを有効に回収する方法について鋭意検討した結果、当該酸性溶液にカルシウム塩を添加して、酸性溶液を中和することにより、ニッケルを所定の化合物として沈殿させ、これを有効に除去できることを見出した。また、酸性溶液に硫酸イオンが含まれる場合、カルシウム塩の添加により硫酸カルシウムが生成され、これもニッケルとともに沈殿させることができるとの知見を得た。 As a result of intensive studies on a method for effectively recovering lithium from an acidic solution having a relatively small amount of lithium ions and a relatively large amount of nickel ions, such as the above-described post-electrolysis solution, the inventor has found that calcium salts are added to the acidic solution. It was found that nickel can be precipitated as a predetermined compound and neutralized effectively by neutralizing the acidic solution by adding. Further, it was found that when the acidic solution contains sulfate ions, calcium sulfate is generated by the addition of the calcium salt and can also be precipitated together with nickel.
このような知見に基づき、この発明のリチウム回収方法は、少なくともリチウムイオン、ニッケルイオン及びナトリウムイオンを含む酸性溶液から、ニッケルを除去してリチウムを回収する方法であって、前記酸性溶液にカルシウム塩を添加して該酸性溶液を中和して、ニッケルを沈殿させ、その後、固液分離によりニッケルを除去した中和後液を得る中和工程を有し、前記酸性溶液がマグネシウムイオンをさらに含み、中和工程で、カルシウム塩の添加後の酸性溶液のｐＨを１２〜１３とし、マグネシウムをニッケルとともに沈殿させ、固液分離によりマグネシウムをニッケルとともに除去するものである。 Based on such knowledge, the lithium recovery method of the present invention is a method for recovering lithium by removing nickel from an acidic solution containing at least lithium ions , nickel ions and sodium ions , wherein calcium salt is added to the acidic solution. Is added to neutralize the acidic solution to precipitate nickel, and then a neutralization step of obtaining a post-neutralization solution by removing nickel by solid-liquid separation, wherein the acidic solution further contains magnesium ions In the neutralization step, the pH of the acidic solution after the addition of the calcium salt is adjusted to 12 to 13, magnesium is precipitated with nickel, and magnesium is removed with nickel by solid-liquid separation.
この発明のリチウム回収方法では、前記酸性溶液が硫酸イオンをさらに含む場合、中和工程で、カルシウム塩の添加により、前記硫酸イオンを硫酸カルシウムとして沈殿させ、固液分離により当該硫酸カルシウムをニッケルとともに除去することが好適である。 In the lithium recovery process of this invention, when the acid solution further comprises sulfate ions, in the neutralization step, by the addition of the calcium salt, the sulfate ion is precipitated as calcium sulfate, nickel the calcium sulfate by solid-liquid separation It is preferable to remove it together with.
この発明のリチウム回収方法は、中和工程の後、中和後液中のリチウムイオンを、炭酸塩の添加および／または炭酸ガスの吹込みにより炭酸化して、炭酸リチウムを得るリチウム炭酸化工程をさらに有するものとすることができる。 In the lithium recovery method of the present invention, after the neutralization step, the lithium ion in the post-neutralization solution is carbonized by adding carbonate and/or blowing carbon dioxide gas to obtain lithium carbonate. It may further have.
この場合においては、Ｌｉ炭酸化工程が、中和後液に炭酸塩を添加して粗炭酸リチウムを得た後、粗炭酸リチウムをリパルプし、炭酸ガスを吹き込んで、精製炭酸リチウムを得る炭酸リチウム精製過程を含むことができる。 In this case, in the Li carbonation step, carbonate is added to the solution after neutralization to obtain crude lithium carbonate, and then crude lithium carbonate is repulped and carbon dioxide gas is blown in to obtain purified lithium carbonate. A purification process can be included.
この発明のリチウム回収方法によれば、酸性溶液にカルシウム塩を添加して該酸性溶液を中和して、ニッケルを沈殿させ、その後、固液分離によりニッケルを除去した中和後液を得ることにより、溶媒抽出による場合に比して、コストの増大を抑制しつつ、リチウムイオン及びニッケルイオンを含む酸性溶液から、リチウムを有効に回収することができる。 According to the lithium recovery method of the present invention, a calcium salt is added to an acidic solution to neutralize the acidic solution to precipitate nickel, and then nickel is removed by solid-liquid separation to obtain a neutralized solution. As a result, lithium can be effectively recovered from the acidic solution containing lithium ions and nickel ions while suppressing an increase in cost as compared with the case of solvent extraction.
以下に、この発明の実施の形態について詳細に説明する。
この発明の一の実施形態のリチウム回収方法は、少なくともリチウムイオン及びニッケルイオンを含む酸性溶液から、ニッケルを除去してリチウムを回収する方法であって、図１に例示するように、酸性溶液にカルシウム塩を添加して該酸性溶液を中和して、ニッケルを沈殿させ、その後、固液分離によりニッケルを除去した中和後液を得る中和工程を有する。
Hereinafter, embodiments of the present invention will be described in detail.
The lithium recovery method according to one embodiment of the present invention is a method for recovering lithium by removing nickel from an acidic solution containing at least lithium ions and nickel ions, and as shown in FIG. There is a neutralization step in which a calcium salt is added to neutralize the acidic solution to precipitate nickel, and then nickel is removed by solid-liquid separation to obtain a neutralized solution.
（酸性溶液）
酸性溶液は、少なくともリチウムイオン及びニッケルイオンを含むものであれば、どのようなものであっても、この発明を適用することができる。
酸性溶液の一例としては、リチウムイオン電池スクラップに対して焙焼、破砕、篩別等を順次に行った後に得られる電池粉を、硫酸もしくは塩酸その他の鉱酸等の酸性浸出液に浸出させ、その浸出後液に溶解している金属を回収する際に得られる酸性溶液とすることができる。より詳細には、浸出後液に対して施す複数段階の溶媒抽出もしくは中和等のうち、ニッケルを回収するための溶媒抽出でニッケルを抽出するとともに逆抽出し、さらに電解採取を行ってニッケルを回収した後に得られる電解後液には、リチウムイオン及びニッケルイオンが含まれることがあり、この電解後液を上記の酸性溶液とすることができる。
(Acidic solution)
The present invention can be applied to any acidic solution as long as it contains at least lithium ions and nickel ions.
As an example of the acidic solution, roasting, crushing, sieving and the like of battery powder obtained after sequentially performing lithium ion battery scrap is leached into an acidic leachate such as sulfuric acid or hydrochloric acid or other mineral acid, It can be an acidic solution obtained when recovering the metal dissolved in the liquid after leaching. More specifically, among multiple stages of solvent extraction or neutralization performed on the liquid after leaching, nickel is extracted and back-extracted by solvent extraction for recovering nickel, and further electrolytic extraction is performed to extract nickel. The post-electrolysis solution obtained after recovery may contain lithium ions and nickel ions, and this post-electrolysis solution can be used as the above-mentioned acidic solution.
このような酸性溶液は、リチウムイオンを、たとえば２ｇ／Ｌ〜２０ｇ／Ｌ、典型的には５ｇ／Ｌ〜１２ｇ／Ｌで含み、ニッケルイオンを、たとえば５０ｇ／Ｌ〜１５０ｇ／Ｌ、典型的には７０ｇ／Ｌ〜１００ｇ／Ｌで含むものとすることができる。特に酸性溶液が上記の電解後液である場合に、ニッケルイオンはこのような濃度範囲となることが多い。
また、酸性溶液はさらに、硫酸イオンを、たとえば１ｇ／Ｌ〜２００ｇ／Ｌ、典型的には１０ｇ／Ｌ〜１００ｇ／Ｌで含むことがある。
Such an acidic solution comprises lithium ions, for example 2 g/L to 20 g/L, typically 5 g/L to 12 g/L and nickel ions, for example 50 g/L to 150 g/L, typically Can be contained at 70 g/L to 100 g/L. Particularly when the acidic solution is the above-mentioned post-electrolysis solution, nickel ions often fall within such a concentration range.
In addition, the acidic solution may further contain sulfate ions at, for example, 1 g/L to 200 g/L, typically 10 g/L to 100 g/L.
その他、酸性溶液に含まれ得る物質としては、ナトリウム、コバルト、マグネシウム、珪素、塩化物イオン等がある。
なかでも、酸性溶液にはマグネシウムイオンが、０．０１ｇ／Ｌ〜１０ｇ／Ｌ、典型的には０．０５ｇ／Ｌ〜５ｇ／Ｌで含まれることがあり、このようなマグネシウムは、従来の方法では炭酸リチウムの精製まで除去されずに残って品位の低下を招くので、後述するように、この発明を適用して中和工程で除去することが好適である。マグネシウムイオンは、より典型的には０．１ｇ／Ｌ〜２ｇ／Ｌ、さらには０．２ｇ／Ｌ〜２ｇ／Ｌで含まれることがある。
Other substances that can be contained in the acidic solution include sodium, cobalt, magnesium, silicon, and chloride ions.
Among them, the acidic solution may contain magnesium ions in an amount of 0.01 g/L to 10 g/L, typically 0.05 g/L to 5 g/L. However, since it remains without being removed until the purification of lithium carbonate and causes deterioration of quality, it is preferable to apply the present invention and remove it in the neutralization step as described later. Magnesium ions may be contained more typically at 0.1 g/L to 2 g/L, and even 0.2 g/L to 2 g/L.
後述する中和工程を経る前の酸性溶液のｐＨは、たとえば−１〜２、一般には０〜１である。 The pH of the acidic solution before passing through the neutralization step described later is, for example, -1 to 2, generally 0 to 1.
（中和工程）
上述したような酸性溶液に対し、従来は溶媒抽出を行うことによりリチウムを回収していたが、このようなリチウムの回収のための溶媒抽出は高コストであり、全体としての処理コストを増大させる。また、酸性溶液に、たとえばＮａ等の不純物が、４０ｇ／Ｌ以上といったある程度高濃度で含まれる場合、Ｎａ塩の析出や分相不良等の理由により溶媒抽出を行うことが困難となる。
(Neutralization process)
Conventionally, lithium was recovered by performing solvent extraction on the acidic solution as described above, but solvent extraction for recovering such lithium is expensive and increases the overall processing cost. .. Further, when the acidic solution contains impurities such as Na at a rather high concentration of 40 g/L or more, it becomes difficult to perform solvent extraction due to precipitation of Na salt, poor phase separation and the like.
それ故に、この実施形態では、上記の溶媒抽出を行わず、酸性溶液にカルシウム塩を添加して酸性溶液を中和し、それにより、酸性溶液中のニッケルイオンを固体として沈殿させ、これを固液分離により分離させて除去する。その結果、ニッケルイオンが除去されてリチウムイオンを含む中和後液が得られる。 Therefore, in this embodiment, without performing the solvent extraction described above, the calcium salt is added to the acidic solution to neutralize the acidic solution, thereby precipitating the nickel ions in the acidic solution as a solid and solidifying it. Separated and removed by liquid separation. As a result, nickel ions are removed to obtain a neutralized liquid containing lithium ions.
それにより、溶媒抽出を用いる従来の手法に比して、処理に要するコストの増大を抑制することができる。
また、酸性溶液に硫酸イオンが含まれる場合、酸性溶液に添加したカルシウム塩によって、硫酸イオンが硫酸カルシウムとなり、これも固液分離で除去することができるという利点もある。
As a result, it is possible to suppress an increase in the cost required for the processing, as compared with the conventional method using solvent extraction.
Further, when the acidic solution contains sulfate ions, the calcium salt added to the acidic solution turns the sulfate ions into calcium sulfate, which can also be removed by solid-liquid separation.
なお、通常は中和に一般に用いられている水酸化ナトリウム等のナトリウム塩が考えられるが、ナトリウム塩を用いると、Ｎａが飽和して析出するため、ろ過不良や品質の悪化に繋がるといった問題がある。この発明では、カルシウム塩を用いることから、そのような問題は生じない。 Although sodium salts such as sodium hydroxide that are generally used for neutralization are conceivable, when sodium salts are used, Na is saturated and precipitates, leading to problems such as poor filtration and poor quality. is there. In the present invention, since the calcium salt is used, such a problem does not occur.
酸性溶液に添加するカルシウム塩としては、所期したｐＨまで上げることのできるものであれば特に問わず、たとえば、水酸化カルシウム、酸化カルシウム、炭酸カルシウム等を挙げることができるが、なかでも、水酸化カルシウムを添加することが反応制御や設備のスケーリング防止の点で好ましい。なお、酸化カルシウムでは添加時に発熱してしまうため、設備内部にスケールが発生し、反応槽実容積の低下や配管閉塞などの可能性があり、炭酸カルシウムでは、所定のｐＨまで上げられないことが懸念される。 The calcium salt to be added to the acidic solution is not particularly limited as long as it can raise the pH to a desired level, and examples thereof include calcium hydroxide, calcium oxide, calcium carbonate and the like. Addition of calcium oxide is preferable from the viewpoint of reaction control and prevention of equipment scaling. Since calcium oxide generates heat during addition, scale may occur inside the equipment, which may reduce the actual volume of the reaction tank and block the piping.Calcium carbonate may not raise the pH to a predetermined level. I'm worried.
カルシウム塩の添加量は、酸性溶液中のニッケルイオン及びフリー酸の中和に必要な量の、１．０倍モル当量〜１．５倍モル当量とすることが好ましい。カルシウム塩の添加量が少なすぎると、ニッケルイオンやフリー酸の一部が沈殿除去されないことが懸念され、この一方で、添加量が多すぎると、単純なコスト増加と共に、残渣発生量が増えてしまうことにより、濾過性の悪化に繋がるおそれがある。この観点から、カルシウム塩の添加量は、好ましくは１．１倍モル当量〜１．２倍モル当量とする。 The addition amount of the calcium salt is preferably 1.0-fold molar equivalent to 1.5-fold molar equivalent of the amount necessary for neutralizing the nickel ion and the free acid in the acidic solution. If the amount of calcium salt added is too small, it is feared that some of the nickel ions and free acids will not be removed by precipitation.On the other hand, if the amount added is too large, the amount of residues will increase with a simple increase in cost. If it does, the filterability may be deteriorated. From this viewpoint, the addition amount of the calcium salt is preferably 1.1-fold molar equivalent to 1.2-fold molar equivalent.
このように酸性溶液にカルシウム塩を添加することにより、カルシウム塩の添加後の酸性溶液のｐＨを９〜１３とすることが好適である。カルシウム塩の添加後の酸性溶液のｐＨが低すぎる場合は、除去対象成分であるニッケルの除去が不十分となり、炭酸リチウムの品位を下げる原因となる可能性がある。一方、カルシウム塩の添加後の酸性溶液のｐＨが高すぎる場合は、液中に不純物として両性金属が含まれていた場合に、再溶解してしまう可能性がある。 It is preferable that the pH of the acidic solution after the addition of the calcium salt is 9 to 13 by adding the calcium salt to the acidic solution in this way. If the pH of the acidic solution after the addition of the calcium salt is too low, nickel, which is a component to be removed, will be insufficiently removed, which may cause deterioration of the quality of lithium carbonate. On the other hand, if the pH of the acidic solution after the addition of the calcium salt is too high, it may be redissolved if the solution contains amphoteric metal as an impurity.
ここで、酸性溶液にマグネシウムイオンが含まれない場合は、ニッケルを有効に除去するため、カルシウム塩の添加後の酸性溶液のｐＨを９〜１０とすることができる。
一方、酸性溶液にマグネシウムイオンが含まれる場合は、カルシウム塩の添加後の酸性溶液のｐＨを１２〜１３とすることにより、マグネシウムも沈殿して、これもニッケルとともに除去することができる。この観点から、カルシウム塩の添加後の酸性溶液のｐＨは、１２．０〜１２．５とすることがより一層好ましい。
Here, when the acidic solution does not contain magnesium ions, the pH of the acidic solution after the addition of the calcium salt can be set to 9 to 10 in order to effectively remove nickel.
On the other hand, when the acidic solution contains magnesium ions, by adjusting the pH of the acidic solution after adding the calcium salt to 12 to 13, magnesium is also precipitated and can be removed together with nickel. From this viewpoint, the pH of the acidic solution after the addition of the calcium salt is more preferably 12.0 to 12.5.
なお、酸性溶液にカルシウム塩を添加した後、酸性溶液を所定の時間にわたって撹拌して、反応を促進させることができる。なお、反応効率改善の観点から、温度を比較的高くし、撹拌は比較的強く行うことが好ましい。 After adding the calcium salt to the acidic solution, the acidic solution can be stirred for a predetermined time to promote the reaction. From the viewpoint of improving reaction efficiency, it is preferable that the temperature is relatively high and the stirring is relatively strong.
カルシウム塩の添加によりニッケルを水酸化物等の所定の化合物として沈殿させた後は、フィルタープレスやシックナー等の公知の装置ないし方法を用いて固液分離を行い、沈殿物と中和後液とに分離することができる。沈殿物にはニッケルの化合物が含まれ、この一方で、中和後液はニッケルがほぼ除去されており、リチウムが溶解した状態で存在する。
中和後液中のニッケル濃度は５ｍｇ／Ｌ以下、特に１ｍｇ／Ｌ以下であることが好ましい。
After precipitation of nickel as a predetermined compound such as hydroxide by the addition of calcium salt, solid-liquid separation is performed using a known device or method such as a filter press or thickener, and the precipitate and the neutralized solution Can be separated into The precipitate contains a nickel compound, while the liquid after neutralization has almost all nickel removed and exists in a state in which lithium is dissolved.
The nickel concentration in the solution after neutralization is preferably 5 mg/L or less, particularly preferably 1 mg/L or less.
（リチウム炭酸化工程）
上記の中和工程でニッケルを除去して得られた中和後液に対しては、それに含まれるリチウムを回収するため、リチウム炭酸化工程を行うことができる。ここでは、中和後液に炭酸塩を添加し、又は炭酸ガスを吹き込むことにより、中和後液中のリチウムイオンを炭酸リチウムとして回収する。
炭酸塩の添加ないし炭酸ガスの吹込み後は、たとえば、液温を５０℃〜９０℃の範囲内として、必要に応じて撹拌して所定の時間を保持する。
(Lithium carbonation process)
For the post-neutralization solution obtained by removing nickel in the above-mentioned neutralization step, lithium contained therein can be recovered, so that a lithium carbonation step can be performed. Here, the carbonate ion is added to the post-neutralization liquid or the carbon dioxide gas is blown into the post-neutralization liquid to recover the lithium ions in the post-neutralization liquid as lithium carbonate.
After the addition of the carbonate or the blowing of the carbon dioxide gas, for example, the liquid temperature is set within the range of 50° C. to 90° C., and the mixture is stirred as necessary and kept for a predetermined time.
中和後液に添加する炭酸塩としては、炭酸ナトリウム等を挙げることができる。
炭酸塩の添加量は、たとえば１．０〜２．０倍モル当量、好ましくは１．０〜１．２倍モル当量とすることができる。
Examples of the carbonate added to the solution after neutralization include sodium carbonate and the like.
The amount of carbonate added may be, for example, 1.0 to 2.0 times the molar equivalent, preferably 1.0 to 1.2 times the molar equivalent.
このようにして得られた炭酸リチウムが、リチウム品位が目標とする品位より低い粗炭酸化リチウムであった場合、高品位の炭酸リチウムを精製するため、炭酸リチウム精製過程を行うことができる。
なおここで、炭酸リチウムの目標とするリチウム品位は、たとえば１６％以上、好ましくは１７％以上とすることができる。
When the lithium carbonate thus obtained is a crude lithium carbonate having a lithium quality lower than the target quality, the lithium carbonate refining process can be performed in order to purify the high quality lithium carbonate.
Here, the target lithium quality of lithium carbonate can be, for example, 16% or more, and preferably 17% or more.
炭酸リチウム精製過程は具体的には、図２に示すように、中和後液への炭酸塩の添加等により得られた粗炭酸リチウムに対してリパルプ洗浄を行うとともに、そこに炭酸ガスを吹き込んで、液中に炭酸を溶解させ、次いで、固液分離により、炭酸水素リチウム液と、カルシウムやマグネシウムなどを分離させる。その後、脱酸・濃縮を行った後、固液分離により、精製炭酸リチウムと濾液とに分離させる。この精製炭酸リチウム中のナトリウム等の溶解性の不純物品位が高い場合は、さらに洗浄を行うことができる。 Specifically, in the lithium carbonate refining process, as shown in FIG. 2, while repulping the crude lithium carbonate obtained by adding carbonate to the solution after neutralization and the like, the carbon dioxide gas is blown into the crude lithium carbonate. Then, the carbonic acid is dissolved in the liquid, and then the lithium hydrogen carbonate liquid is separated from calcium and magnesium by solid-liquid separation. Then, after deoxidation and concentration, solid-liquid separation is performed to separate purified lithium carbonate and a filtrate. When the quality of soluble impurities such as sodium in the purified lithium carbonate is high, further cleaning can be performed.
次に、この発明のリチウム回収方法を試験的に実施し、その効果を確認したので以下に説明する。但し、ここでの説明は単なる例示を目的としたものであり、それに限定されることを意図するものではない。 Next, the lithium recovery method of the present invention was carried out on a trial basis, and the effect thereof was confirmed. However, the description here is merely for the purpose of illustration and is not intended to be limited thereto.
（Ｃａ塩添加による脱Ｎｉ）
表１に示す組成の酸性溶液（Ｎｉ電解後液）で、Ｎｉを水酸化物とするとともに硫酸根を石膏として分離するため、水酸化Ｃａを添加し、室温にて６〜２４時間の撹拌保持後に濾過を行い、表２に示す組成の中和後液を得た。ここで、水酸化Ｃａの添加量は、液中のＮｉとフリー酸を中和するのに必要な量の１．１倍モル当量とした。
(De-Ni by adding Ca salt)
In an acidic solution (after Ni electrolysis solution) having the composition shown in Table 1, Ca was added for the purpose of separating Ni with hydroxide and sulfate with gypsum, so that stirring was maintained at room temperature for 6 to 24 hours. After that, filtration was performed to obtain a neutralized solution having the composition shown in Table 2. Here, the amount of Ca hydroxide added was 1.1 times the molar equivalent of the amount required to neutralize Ni and the free acid in the liquid.
表１及び２に示すところから、液中のニッケル濃度は中和後に十分に低下しており、ニッケルを有効に除去できたことが解かる。なお中和により、硫酸イオン濃度もある程度低下したことが解かる。 From the results shown in Tables 1 and 2, it can be seen that the nickel concentration in the liquid was sufficiently lowered after neutralization, and nickel could be effectively removed. It can be seen that the neutralization also reduced the sulfate ion concentration to some extent.
（炭酸塩によるＬｉ炭酸化）
中和後液中のＬｉに対し、Ｌｉ2ＳＯ4 ＋ Ｎａ2ＣＯ3 → Ｌｉ2ＣＯ3 ＋ Ｎａ2ＳＯ4の想定反応において１倍モル当量の炭酸Ｎａを、６０℃に加熱した中和後液に添加した後、９０℃に昇温して１時間撹拌して保持した。その後、濾過を行い、残渣側に粗炭酸リチウムを得た。
(Li carbonation by carbonate)
After neutralization, the neutralized solution was heated to 60° C. with 1 time molar equivalent of Na carbonate in the assumed reaction of Li 2 SO 4 + Na 2 CO 3 →Li 2 CO 3 + Na 2 SO 4 with respect to Li in the liquid after neutralization. After adding to the liquid, the temperature was raised to 90° C., and the mixture was stirred for 1 hour and held. Then, filtration was performed to obtain crude lithium carbonate on the residue side.
（炭酸ガス溶解による炭酸Ｌｉ精製）
上記の粗炭酸リチウムに対してリパルプを行い、Ｌｉ2ＣＯ3 ＋ ＣＯ2 ＋ Ｈ2Ｏ → ２ＬｉＨＣＯ3の想定反応において２倍モル当量相当の炭酸ガスを、室温にて２時間かけて撹拌しながら吹込み、その後、濾過を行って液側に、表３に示す組成のＬｉ濃縮液（炭酸水素Ｌｉ溶液）を得た。その後、Ｌｉ濃縮液中の溶解炭酸ガスを、７０℃以上で加熱濃縮することで脱炭酸し、精製された炭酸Ｌｉを析出させた。
(Purification of Li carbonate by dissolving carbon dioxide)
The above crude lithium carbonate was repulped, and in a supposed reaction of Li 2 CO 3 + CO 2 + H 2 O → 2LiHCO 3 , carbon dioxide gas equivalent to twice the molar equivalent was stirred at room temperature for 2 hours. Blow-in, and then filtration was performed to obtain a Li concentrated solution (Li hydrogen carbonate Li solution) having the composition shown in Table 3 on the liquid side. Then, the dissolved carbon dioxide gas in the Li concentrated solution was heated and concentrated at 70° C. or higher to decarbonate, thereby depositing purified Li carbonate.
以上より、この発明によれば、コストが嵩む溶媒抽出を行うことなしに、リチウムイオン及びニッケルイオンを含む酸性溶液から、リチウムを有効に回収できることが解かった。 From the above, according to the present invention, it was found that lithium can be effectively recovered from an acidic solution containing lithium ions and nickel ions without performing costly solvent extraction.
Claims (4)
前記酸性溶液がマグネシウムイオンをさらに含み、
中和工程で、カルシウム塩の添加後の酸性溶液のｐＨを１２〜１３とし、マグネシウムをニッケルとともに沈殿させ、固液分離によりマグネシウムをニッケルとともに除去するリチウム回収方法。 A method for recovering lithium by removing nickel from an acidic solution containing at least lithium ion , nickel ion and sodium ion , wherein a calcium salt is added to the acidic solution to neutralize the acidic solution to remove nickel. Having a neutralization step of precipitating and then obtaining a liquid after neutralization by removing nickel by solid-liquid separation,
The acidic solution further comprises magnesium ions,
In the neutralization step, the pH of the acidic solution after addition of the calcium salt is adjusted to 12 to 13, magnesium is precipitated with nickel, and magnesium is removed with nickel by solid-liquid separation.
中和工程で、カルシウム塩の添加により、前記硫酸イオンを硫酸カルシウムとして沈殿させ、固液分離により当該硫酸カルシウムをニッケルとともに除去する請求項１に記載のリチウム回収方法。 The acidic solution further comprises sulfate ions,
The lithium recovery method according to claim 1, wherein in the neutralization step, the sulfate ion is precipitated as calcium sulfate by adding a calcium salt, and the calcium sulfate is removed together with nickel by solid-liquid separation.
ウムをリパルプし、炭酸ガスを吹き込んで、精製炭酸リチウムを得る炭酸リチウム精製過
程を含む請求項３に記載のリチウム回収方法。 The Li carbonation step includes a lithium carbonate refining process in which a carbonate is added to the liquid after neutralization to obtain crude lithium carbonate, and then the crude lithium carbonate is repulped and carbon dioxide gas is blown to obtain purified lithium carbonate. Item 4. The lithium recovery method according to Item 3.
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| JP7243749B2 (en) | 2021-02-17 | 2023-03-22 | 三菱マテリアル株式会社 | Valuable metal recovery method and recovery device |
| JP7188474B2 (en) | 2021-02-17 | 2022-12-13 | 三菱マテリアル株式会社 | Method and apparatus for recovering Li |
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