JP2013001921A - Leaching method for lithium - Google Patents
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- JP2013001921A JP2013001921A JP2011131994A JP2011131994A JP2013001921A JP 2013001921 A JP2013001921 A JP 2013001921A JP 2011131994 A JP2011131994 A JP 2011131994A JP 2011131994 A JP2011131994 A JP 2011131994A JP 2013001921 A JP2013001921 A JP 2013001921A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 92
- 238000002386 leaching Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 32
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 27
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010298 pulverizing process Methods 0.000 claims abstract description 15
- 239000011812 mixed powder Substances 0.000 claims abstract description 14
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 15
- 150000003624 transition metals Chemical class 0.000 claims description 15
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000007772 electrode material Substances 0.000 claims description 4
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 4
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical group [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 239000000571 coke Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 238000010303 mechanochemical reaction Methods 0.000 abstract description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract description 3
- 230000001939 inductive effect Effects 0.000 abstract 1
- 238000003746 solid phase reaction Methods 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011328 necessary treatment Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance 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
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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
- 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)
- Secondary Cells (AREA)
Abstract
Description
本発明は、リチウム含有金属酸化物からリチウムを浸出させるリチウムの浸出方法に関する。 The present invention relates to a lithium leaching method for leaching lithium from a lithium-containing metal oxide.
リチウムイオン二次電池は、携帯電話をはじめとする小型電子機器の電源として急速に用途が広がっており、生産量が急増することが予想される。リチウムイオン二次電池の正極材活物質であるコバルト酸リチウム等のリチウム含有金属酸化物に含まれるコバルト等の金属は、乾式処理方法によって回収されている。一方、リチウムについては、乾式処理による回収が困難であるため、再利用されることなく廃棄処理されている。 The use of lithium ion secondary batteries is rapidly expanding as a power source for small electronic devices such as mobile phones, and the production volume is expected to increase rapidly. A metal such as cobalt contained in a lithium-containing metal oxide such as lithium cobaltate which is a positive electrode material active material of a lithium ion secondary battery is recovered by a dry processing method. On the other hand, since lithium is difficult to recover by dry processing, it is discarded without being reused.
リチウムイオン二次電池の生産量の増加に伴い、廃リチウムイオン二次電池の電極に含まれるリチウムの経済的な回収方法の確立が必要となっている。リチウムを回収する方法として、リチウム含有金属酸化物を酸に浸出させ、イオン交換樹脂等を用いてリチウム以外の金属を回収し、この残渣からリチウムを回収する湿式処理方法が有望視されている。 With an increase in production of lithium ion secondary batteries, it is necessary to establish an economical method for recovering lithium contained in the electrodes of waste lithium ion secondary batteries. As a method for recovering lithium, a wet processing method in which a lithium-containing metal oxide is leached in an acid, a metal other than lithium is recovered using an ion exchange resin or the like, and lithium is recovered from this residue is promising.
廃リチウムイオン二次電池に含まれるリチウム含有金属酸化物には、リチウムイオン二次電池の電極材料であるコバルト酸リチウムがある。コバルト酸リチウムは安定な層状岩塩型構造であり、従来の湿式処理では、リチウムおよび遷移金属のリチウム金属酸化物からの浸出方法として、高濃度の塩酸、硫酸、硝酸等による酸浸出が用いられている。この方法では，高濃度の酸を使用し、さらには過酸化水素を添加して長時間の加熱処理を行い、リチウムおよび遷移金属を浸出させた後、中和反応を行い目的に応じたリチウムおよび遷移金属を回収している。この方法では、比較的酸溶液に浸出容易なリチウム以外の遷移金属に関しても酸に浸出させることになり、浸出後にリチウムと他の金属とを各々分離回収する必要があった。 Lithium-containing metal oxides included in the waste lithium ion secondary battery include lithium cobalt oxide, which is an electrode material for the lithium ion secondary battery. Lithium cobaltate has a stable layered rock-salt structure, and in conventional wet processing, acid leaching with high concentrations of hydrochloric acid, sulfuric acid, nitric acid, etc. is used as a leaching method of lithium and transition metals from lithium metal oxides. Yes. In this method, a high-concentration acid is used, hydrogen peroxide is added, and heat treatment is performed for a long time. After leaching out lithium and transition metal, a neutralization reaction is performed, and lithium and an appropriate amount are selected. Transition metal is recovered. In this method, transition metals other than lithium that are relatively easily leached into an acid solution are also leached in an acid, and it is necessary to separate and recover lithium and other metals after leaching.
上述したように、リチウム含有金属酸化物の酸浸出には、長時間の加熱処理、酸の使用および多量の中和剤の使用によるコストの問題があった。さらに、塩酸を使用した際には塩素ガスが発生し、硫酸を用いた際には硫化水素が発生し、取り扱いが容易ではないという問題がある。また、多量の薬剤を使用することから、環境負荷対策としての操業コストも問題となっていた。 As described above, acid leaching of lithium-containing metal oxides has cost problems due to long-time heat treatment, use of acid, and use of a large amount of neutralizing agent. Further, when hydrochloric acid is used, chlorine gas is generated, and when sulfuric acid is used, hydrogen sulfide is generated, which makes it difficult to handle. In addition, since a large amount of chemicals is used, the operation cost as a measure against the environmental load has been a problem.
加えて、浸出後のリチウムと遷移金属との分離工程も、コストを増大させる要因となっている、特許文献１では、コバルト酸リチウムを還元焙焼することによって、コバルト酸リチウムの化合物形態を変化させ、焙焼物を水で浸出することにより、焙焼物中のリチウム分を水に溶出させて、かつ、コバルトを残差中に分配させて分離回収を行っている。リチウムは水に溶解するが、コバルトなどの遷移金属は水に溶解しないので、上述したことにより、リチウムを分離回収できる。 In addition, the separation process of lithium and transition metal after leaching is also a factor that increases the cost. In Patent Document 1, by reducing and roasting lithium cobaltate, the compound form of lithium cobaltate is changed. Then, by leaching the roasted product with water, the lithium content in the roasted product is eluted in water, and cobalt is distributed in the residual to separate and recover. Lithium dissolves in water, but transition metals such as cobalt do not dissolve in water. Therefore, lithium can be separated and recovered as described above.
しかし、この還元焙焼は、水素気流中でかつ４００℃以上の温度で行うか、炭素を添加してから不活性ガス雰囲気中で７００℃以上の温度にする還元焙焼が必要であり、コストや安全面において実用化し難いものであった。 However, this reduction roasting is performed in a hydrogen stream and at a temperature of 400 ° C. or higher, or reduction roasting is performed at a temperature of 700 ° C. or higher in an inert gas atmosphere after adding carbon. It was difficult to put it into practical use in terms of safety.
本発明は、以上のような問題点を解消するためになされたものであり、より容易に低コストで、リチウム含有金属酸化物からリチウムを浸出できるようにすることを目的とする。 The present invention has been made to solve the above-described problems, and an object of the present invention is to allow lithium to be leached from a lithium-containing metal oxide more easily and at low cost.
本発明に係るリチウムの浸出方法は、遷移金属の酸化物とリチウムとが化合しているリチウム含有金属酸化物を含む粉末と炭素材料の粉末とを混合して混合粉末を作製する第１工程と、混合粉末をボールミルにより粉砕処理する第２工程と、粉砕処理した混合粉末と水とを混合してリチウムを水に浸出する第３工程とを少なくとも備える。 The lithium leaching method according to the present invention includes a first step of preparing a mixed powder by mixing a powder containing a lithium-containing metal oxide in which a transition metal oxide and lithium are combined with a carbon material powder. And a second step of pulverizing the mixed powder with a ball mill and at least a third step of mixing the pulverized mixed powder with water and leaching lithium into the water.
上記リチウムの浸出方法において、遷移金属は、コバルト，ニッケル，マンガン，鉄，銅，クロム，およびチタンの少なくとも１つであればよい。例えば、リチウム含有金属酸化物は、コバルト酸リチウムである。コバルト酸リチウムは、電池の電極材料として用いられているものである。なお、炭素材料は、黒鉛、活性炭、石炭、コークス、木炭、および電池の電極を構成する炭素より選択されたものであればよい。 In the lithium leaching method, the transition metal may be at least one of cobalt, nickel, manganese, iron, copper, chromium, and titanium. For example, the lithium-containing metal oxide is lithium cobaltate. Lithium cobalt oxide is used as a battery electrode material. The carbon material may be any material selected from graphite, activated carbon, coal, coke, charcoal, and carbon constituting the battery electrode.
以上説明したことにより、本発明によれば、より容易に低コストで、リチウム含有金属酸化物からリチウムを浸出できるようになるという優れた効果が得られる。 As described above, according to the present invention, it is possible to obtain an excellent effect that lithium can be leached from a lithium-containing metal oxide more easily and at low cost.
以下、本発明の実施の形態について図を参照して説明する。図１は、本発明の実施の形態におけるリチウムの浸出方法を説明するためのフローチャートである。まず、ステップＳ１０１で、遷移金属の酸化物とリチウムとが化合しているリチウム含有金属酸化物を含む粉末と炭素材料の粉末とを混合して混合粉末を作製する。炭素材料としては、炭素の粉末を用いればよい。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a flowchart for explaining a lithium leaching method according to an embodiment of the present invention. First, in step S101, a powder containing a lithium-containing metal oxide in which a transition metal oxide and lithium are combined is mixed with a carbon material powder to produce a mixed powder. As the carbon material, carbon powder may be used.
次に、ステップＳ１０２で、作製した混合粉末を粉砕処理する。例えば、ボールミルを用いて粉砕処理を行えばよい。粉砕処理において用いるボールは、ジルコニア製ボール，ＳＵＳ製ボール，アルミナ製ボール，メノウ製ボールなどを用いればよく、特に制限はない。また、粉砕処理は、大気の雰囲気で行えばよい。例えば、遊星ボールミルを用いる場合、回転速度２００〜１５００ｒｐｍ、粉砕処理時間４〜８時間で処理を行えばよい。また、加える炭素粉末の量は、対象のリチウム含有金属酸化物との還元反応における化学量論式から求められる値の２〜１０倍の量を加えるとよい。 Next, in step S102, the produced mixed powder is pulverized. For example, a pulverization process may be performed using a ball mill. The balls used in the pulverization process may be zirconia balls, SUS balls, alumina balls, agate balls, or the like, and are not particularly limited. The pulverization process may be performed in an air atmosphere. For example, when a planetary ball mill is used, the processing may be performed at a rotation speed of 200 to 1500 rpm and a pulverization processing time of 4 to 8 hours. The amount of carbon powder to be added is preferably 2 to 10 times the value obtained from the stoichiometric formula in the reduction reaction with the target lithium-containing metal oxide.
この粉砕処理により、混合粉末中のリチウム含有金属酸化物と炭素とが、メカノケミカル反応により固相で反応し、リチウム含有金属酸化物が還元される。ボールミルによる粉砕用ボールを用いての回転運動による粉砕処理では、物理的な粉砕処理のみでなく、機械的エネルギーによる化学反応を起こすメカノケミカル反応を起こすことが知られている。この還元により、リチウム含有金属酸化物よりリチウムおよび遷移金属の還元体が生成される。 By this pulverization treatment, the lithium-containing metal oxide and carbon in the mixed powder react in a solid phase by a mechanochemical reaction, and the lithium-containing metal oxide is reduced. It is known that in the pulverization process by the rotational motion using the ball for pulverization by the ball mill, not only a physical pulverization process but also a mechanochemical reaction that causes a chemical reaction by mechanical energy is known. By this reduction, a reduced form of lithium and transition metal is generated from the lithium-containing metal oxide.
次に、ステップＳ１０３で、粉砕処理した混合粉末と水とを混合してリチウムを水に浸出する。上述した粉砕処理により、還元された金属酸化物の還元体の中で、リチウムは水溶性を有するので水に溶解するが、他の遷移金属は水に溶解（浸出）せず、例えば沈殿する。この処理において、水の温度は、室温（２０〜２５℃）程度でよく、数百℃などの高温の状態とする必要がない。 Next, in step S103, the pulverized mixed powder and water are mixed and lithium is leached into water. In the reduced form of the metal oxide reduced by the above-described pulverization treatment, lithium dissolves in water because it is water-soluble, but other transition metals do not dissolve (leach) in water but precipitate, for example. In this treatment, the temperature of water may be about room temperature (20 to 25 ° C.), and does not need to be a high temperature such as several hundred degrees C.
このように、本実施の形態によれば、大気中・室温（２０〜２５℃）程度の環境で、水を用いることで、リチウム含有金属酸化物を含む廃棄物よりリチウムの浸出ができるようになる。従って、塩酸，硝酸，硫酸などの酸を用いる必要がなく、中和剤などが不要となり、また、加熱処理も不要となる。この結果、操業コストを大幅に削減することが可能となる。このように、本実施の形態によれば、より容易に低コストでリチウムが回収できるようになる。 Thus, according to this embodiment, lithium can be leached from waste containing lithium-containing metal oxides by using water in the atmosphere and at an environment of room temperature (20 to 25 ° C.). Become. Accordingly, it is not necessary to use an acid such as hydrochloric acid, nitric acid, sulfuric acid, etc., and a neutralizing agent is not necessary, and heat treatment is also unnecessary. As a result, the operation cost can be greatly reduced. Thus, according to the present embodiment, lithium can be recovered more easily at low cost.
例えば、本実施の形態により得られた水中のリチウムは、この水をろ過することで不溶物（沈殿物）を除去した後、溶媒抽出法、イオン交換法、電解採取法、沈澱法などといった公知の抽出手段を用いることによって、容易にかつ高効率に分離回収することが可能である。また、還元剤として用いている炭素材料は、水に溶解せずに沈殿物となり、ろ過により容易に分離できる。従って、余剰の炭素材料は容易に回収でき、還元剤として再度利用することが容易である。この結果、炭素材料の新規購入量を抑制できることになり、さらにコストを抑制することが可能となる。 For example, the lithium in the water obtained by the present embodiment removes insoluble matters (precipitates) by filtering the water, and then a known method such as a solvent extraction method, an ion exchange method, an electrowinning method, a precipitation method, etc. By using this extraction means, it is possible to separate and recover easily and with high efficiency. In addition, the carbon material used as the reducing agent does not dissolve in water but becomes a precipitate and can be easily separated by filtration. Therefore, surplus carbon material can be easily recovered and easily reused as a reducing agent. As a result, the amount of new carbon material purchased can be reduced, and the cost can be further reduced.
[実施例]
以下、実施例を用いてより詳細に説明する。まず、実験の方法について、図２を用いて説明する。実験では、リチウム含有金属酸化物としてコバルト酸リチウムを用い、コバルト酸リチウムの粉末に３．７５：１．２５の割合で炭素粉末を混合して混合試料を作製する（ステップＳ２０１）。これは化学量論式で求められる値の約１０倍である。なお、コバルト酸リチウムは、リチウムイオン二次電池の電極材料である。また、炭素粉末としては、よく知られたアセチレンブラックを用いた。
[Example]
Hereinafter, it demonstrates in detail using an Example. First, an experimental method will be described with reference to FIG. In the experiment, lithium cobaltate is used as the lithium-containing metal oxide, and carbon powder is mixed with the lithium cobaltate powder at a ratio of 3.75: 1.25 to prepare a mixed sample (step S201). This is about 10 times the value determined by the stoichiometric formula. In addition, lithium cobaltate is an electrode material of a lithium ion secondary battery. As the carbon powder, well-known acetylene black was used.
次に、遊星ボールミル（フリッチュ社製premium line P-7）を用いて混合試料を粉砕処理する（ステップＳ２０２）。この遊星ボールミルは、２個のジルコニア製の密閉容器（内容量５０ｍｌ）が、自転および公転することで、容器内の試料を粉砕する。粉砕処理では、ジルコニア製直径１５ｍｍの粉砕用ボールを７個用いた。また、ミルの回転速度は７００ｒｐｍ一定とした。 Next, the mixed sample is pulverized using a planetary ball mill (premium line P-7 manufactured by Fritsch) (step S202). In this planetary ball mill, two zirconia sealed containers (with an internal volume of 50 ml) rotate and revolve to pulverize the sample in the container. In the grinding treatment, seven zirconia balls for grinding having a diameter of 15 mm were used. The rotation speed of the mill was constant at 700 rpm.
次に、粉砕処理が終了したら、上記容器内より混合試料１．３３ｇを採取し（ステップＳ２０３）、採取した混合試料を水５０ｍｌに混合し、２４時間撹拌する。この撹拌には、マグネチックスターラを用いた。次に、撹拌後の混合溶液をろ過する（ステップＳ２０５）。ろ過には、ポアサイズ０．１μｍのメンブレンフィルターを用いた。次に、ろ液中のリチウムおよびコバルトの定量を行う（ステップＳ２０６）。この定量分析では、よく知られた誘導結合プラズマ質量分析装置（ＩＣＰ−ＭＳ）を用い、浸出率を算出した。算出の結果、コバルトの浸出率は０％であるが、リチウムの浸出率は５０％であった。 Next, when the pulverization process is finished, 1.33 g of the mixed sample is collected from the container (step S203), and the collected mixed sample is mixed with 50 ml of water and stirred for 24 hours. A magnetic stirrer was used for this stirring. Next, the mixed solution after stirring is filtered (step S205). For the filtration, a membrane filter having a pore size of 0.1 μm was used. Next, lithium and cobalt in the filtrate are quantified (step S206). In this quantitative analysis, the leaching rate was calculated using a well-known inductively coupled plasma mass spectrometer (ICP-MS). As a result of the calculation, the leaching rate of cobalt was 0%, but the leaching rate of lithium was 50%.
ここで、上述した実施例に対する比較の実験を行った結果について説明する。この比較実験では、上記実施例と同じコバルト酸リチウムの粉末１ｇを、粉砕処理することなく、水５０ｍｌに混合して室温下で浸出を行った。この浸出では、粉末を混合した水をマグネチックスターラにより２４時間攪拌した。次に、攪拌後の溶液をろ紙（メンブレンフィルター、０．１ｕｍ）によりろ過分離し、ろ液中の溶存元素の濃度をＩＣＰ−ＭＳで分析した。この分析結果からリチウムとコバルトの浸出率を算出したところ、リチウムの浸出率は５％程度と低く、コバルトの浸出率は０％であった。 Here, the result of a comparative experiment performed on the above-described embodiment will be described. In this comparative experiment, 1 g of the same lithium cobalt oxide powder as in the above example was mixed with 50 ml of water without pulverization and leached at room temperature. In this leaching, water mixed with powder was stirred for 24 hours with a magnetic stirrer. Next, the solution after stirring was separated by filtration with a filter paper (membrane filter, 0.1 μm), and the concentration of dissolved elements in the filtrate was analyzed by ICP-MS. When the leaching rate of lithium and cobalt was calculated from this analysis result, the leaching rate of lithium was as low as about 5%, and the leaching rate of cobalt was 0%.
上述した実験の結果から明らかなように、本実施の形態によれば、室温程度の温度条件で、水にリチウムを選択的に浸出させることができるようになる。 As is clear from the results of the experiment described above, according to the present embodiment, lithium can be selectively leached into water under a temperature condition of about room temperature.
以上のように、本発明によれば、高効率かつ低コストで、リチウム含有金属酸化物からリチウムをを水に浸出させることができ、湿式処理による安全・安価なリチウムの回収を可能にする。 As described above, according to the present invention, lithium can be leached into water from a lithium-containing metal oxide with high efficiency and low cost, and safe and inexpensive lithium recovery can be achieved by wet processing.
なお、本発明は以上に説明した実施の形態に限定されるものではなく、本発明の技術的思想内で、当分野において通常の知識を有する者により、多くの変形および組み合わせが実施可能であることは明白である。例えば、炭素材料としては、黒鉛、活性炭、石炭、コークス、木炭、および電池の電極を構成する炭素などを用いることができる。 The present invention is not limited to the embodiment described above, and many modifications and combinations can be implemented by those having ordinary knowledge in the art within the technical idea of the present invention. It is obvious. For example, as the carbon material, graphite, activated carbon, coal, coke, charcoal, carbon constituting a battery electrode, and the like can be used.
上述では、遷移金属がコバルトの場合（コバルト酸リチウム）について説明したが、これに限るものではなく、遷移金属は、コバルト，ニッケル，マンガン，鉄，銅，クロム，およびチタンの少なくとも１つの金属であればよい。また、コバルト酸リチウムに限らず、リチウムと２つ以上の遷移金属とから構成されたリチウム含有金属酸化物であっても、本発明により、選択的にリチウムが浸出できる。 In the above description, the case where the transition metal is cobalt (lithium cobaltate) has been described. However, the transition metal is not limited to this, and the transition metal is at least one metal of cobalt, nickel, manganese, iron, copper, chromium, and titanium. I just need it. Further, not only lithium cobaltate but also a lithium-containing metal oxide composed of lithium and two or more transition metals, lithium can be selectively leached according to the present invention.
Claims (5)
前記混合粉末をボールミルにより粉砕処理する第２工程と、
粉砕処理した前記混合粉末と水とを混合してリチウムを前記水に浸出する第３工程と
を少なくとも備えることを特徴とするリチウムの浸出方法。 A first step of preparing a mixed powder by mixing a powder containing a lithium-containing metal oxide in which an oxide of a transition metal and lithium are combined with a powder of a carbon material;
A second step of pulverizing the mixed powder with a ball mill;
And a third step of leaching lithium into the water by mixing the pulverized mixed powder and water.
前記遷移金属は、コバルト，ニッケル，マンガン，鉄，銅，クロム，およびチタンの少なくとも１つであることを特徴とするリチウムの浸出方法。 The lithium leaching method according to claim 1,
The lithium leaching method, wherein the transition metal is at least one of cobalt, nickel, manganese, iron, copper, chromium, and titanium.
前記リチウム含有金属酸化物は、コバルト酸リチウムであることを特徴とするリチウムの浸出方法。 The method of leaching lithium according to claim 2,
The lithium leaching method is characterized in that the lithium-containing metal oxide is lithium cobalt oxide.
前記リチウム含有金属酸化物は、電池の電極材料として用いられているものであることを特徴とするリチウムの浸出方法。 The lithium leaching method according to claim 3,
The method for leaching lithium, wherein the lithium-containing metal oxide is used as a battery electrode material.
前記炭素材料は、黒鉛、活性炭、石炭、コークス、木炭、および電池の電極を構成する炭素より選択されたものであることを特徴とするリチウムの浸出方法。 The lithium leaching method according to any one of claims 1 to 4,
The method for leaching lithium, wherein the carbon material is selected from graphite, activated carbon, coal, coke, charcoal, and carbon constituting a battery electrode.
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