JP7548642B2 - Synergistic extraction method for selective separation of lithium and transition metals from waste batteries using hydrophobic deep eutectic solvents - Google Patents
Synergistic extraction method for selective separation of lithium and transition metals from waste batteries using hydrophobic deep eutectic solvents Download PDFInfo
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- 238000000605 extraction Methods 0.000 title claims description 112
- 229910052744 lithium Inorganic materials 0.000 title claims description 69
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 68
- 239000002904 solvent Substances 0.000 title claims description 40
- 230000005496 eutectics Effects 0.000 title claims description 39
- 230000002209 hydrophobic effect Effects 0.000 title claims description 39
- 229910052723 transition metal Inorganic materials 0.000 title claims description 14
- 150000003624 transition metals Chemical class 0.000 title claims description 14
- 230000002195 synergetic effect Effects 0.000 title claims description 9
- 239000010926 waste battery Substances 0.000 title claims description 3
- 238000000926 separation method Methods 0.000 title description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 77
- 239000012074 organic phase Substances 0.000 claims description 56
- 238000002156 mixing Methods 0.000 claims description 40
- 229910052759 nickel Inorganic materials 0.000 claims description 38
- 229910017052 cobalt Inorganic materials 0.000 claims description 37
- 239000010941 cobalt Substances 0.000 claims description 37
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 37
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 30
- 239000011572 manganese Substances 0.000 claims description 29
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- 239000008346 aqueous phase Substances 0.000 claims description 27
- 229910052748 manganese Inorganic materials 0.000 claims description 27
- 239000002699 waste material Substances 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 21
- NNJVILVZKWQKPM-UHFFFAOYSA-N Lidocaine Chemical compound CCN(CC)CC(=O)NC1=C(C)C=CC=C1C NNJVILVZKWQKPM-UHFFFAOYSA-N 0.000 claims description 15
- 229960004194 lidocaine Drugs 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 238000005119 centrifugation Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- 238000005191 phase separation Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 18
- 239000002253 acid Substances 0.000 description 8
- 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 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 238000009854 hydrometallurgy Methods 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000002386 leaching Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- -1 diketone compound Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
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- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
- C22B23/0469—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods by chemical substitution, e.g. by cementation
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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Description
本発明は、湿式製錬の技術分野に属し、特に、疎水性深共晶溶媒とリン酸トリブチルの協同抽出剤、及び廃リチウム電池浸出液中のリチウムと遷移金属を抽出・分離する方法に関する。 The present invention belongs to the technical field of hydrometallurgy, and in particular to a synergistic extractant of a hydrophobic deep eutectic solvent and tributyl phosphate, and a method for extracting and separating lithium and transition metals from waste lithium battery leachate.
エネルギーと交通システムの脱炭素化が国際社会における最重要課題の一つとなっている時代において、リチウムイオン電池（ＬＩＢ）は優れたエネルギー貯蔵能力により電子機器、電気自動車、再生可能エネルギーの貯蔵などに広く使用され、交通輸送業の化石燃料に対する依存度を低下させることができる。リチウムは、その軽さからリチウムイオン電池の主要金属元素として注目を集めており、炭酸リチウムの需要は２０２５年までに５００万トンを超えると予想されている。世界の平均回収可能含有量（ＲＣ）データによると、遷移金属はすべてのリサイクル元素（特にニッケルとコバルト）リストのトップにあり、天然資源の枯渇につながる。車載用リチウムイオン電池だけの市場全体は、２０２４年までに２２１０億米ドルに達すると予想されている。しかし、リチウムイオン電池の生産量の増加は、リチウム、ニッケル、コバルトの資源不足が深刻になるだけでなく、廃リチウムイオン電池も環境汚染が深刻で、その中の有価金属の含有量と純度が自然界に存在するものよりも高く、回収しなければ、多大な資源の無駄となり、クリーンエネルギー及び資源利用の概念に反することになる。 In an era when the decarbonization of energy and transportation systems is one of the most important issues in the international community, lithium-ion batteries (LIBs) are widely used in electronic devices, electric vehicles, renewable energy storage, etc. due to their excellent energy storage capacity, which can reduce the transportation industry's dependence on fossil fuels. Lithium has attracted attention as a key metal element in lithium-ion batteries due to its light weight, and the demand for lithium carbonate is expected to exceed 5 million tons by 2025. According to the global average recoverable content (RC) data, transition metals are at the top of the list of all recycled elements (especially nickel and cobalt), which leads to the depletion of natural resources. The total market for automotive lithium-ion batteries alone is expected to reach US$221 billion by 2024. However, the increase in lithium-ion battery production not only leads to a serious shortage of lithium, nickel, and cobalt resources, but also serious environmental pollution from waste lithium-ion batteries, and the content and purity of valuable metals in them are higher than those found in nature. If they are not recovered, it will be a huge waste of resources and go against the concepts of clean energy and resource utilization.
現在、廃リチウム電池の一般的な回収方法は、主に乾式製錬方及び湿式製錬法である。湿式製錬法は、高い選択性、低エネルギー消費、有害ガスを発生しないという特徴があり、乾式製錬法よりもグリーン環境保全の概念に沿っている。湿式製錬法では、まず電池をさまざまな物理的方法で前処理し、次に各種金属を酸に溶解し、精製後にＬｉ、Ｃｏ、Ｎｉ及びＭｎの酸浸出液が得られる。塩酸又は硫酸は他の浸出剤よりも経済的であり、通常湿式製錬プロセス中のリチウムイオン電池の金属の酸還元浸出に使用される。様々な金属回収法の中でも、溶媒抽出法は操作が簡単で回収率が高く、調整が容易なことから金属分離に広く用いられている。 At present, the common recovery methods for waste lithium batteries are mainly pyrometallurgy and hydrometallurgy. Hydrometallurgy has the characteristics of high selectivity, low energy consumption, and no harmful gas generation, and is more in line with the concept of green environmental protection than pyrometallurgy. In hydrometallurgy, the batteries are first pretreated by various physical methods, and then various metals are dissolved in acid, and the acid leaching solution of Li, Co, Ni and Mn is obtained after purification. Hydrochloric acid or sulfuric acid is more economical than other leaching agents and is usually used for acid reduction leaching of metals in lithium-ion batteries during the hydrometallurgy process. Among various metal recovery methods, solvent extraction is widely used for metal separation due to its simple operation, high recovery rate and easy adjustment.
特許文献１には、ニッケル・コバルト・マンガンを含む電池からニッケル・コバルト・マンガンを分離する方法が開示されており、該方法はカルボン酸系抽出剤を使用した向流多段抽出により、ニッケル・コバルト・マンガンを段階的に分離する。特許文献２には、ジケトン化合物を抽出剤として、有機ホスフィン化合物を協同抽出剤として使用し、廃リチウム電池から金属を分離する方法が開示されており、向流多段抽出後のニッケル・コバルト・マンガンの抽出率は９９％以上に達している。しかし、これらの抽出方法の多くは多段抽出を必要とするため、抽出剤のロスがある程度増加し、コストが高くなるだけでなく資源の無駄も生じまる。同時に、これらの従来の抽出剤を使用するのは抽出効果が限られているだけでなく、これらの抽出剤は揮発性、環境汚染性、有毒性などを有することにより制限され、したがって抽出効率が高いだけでなく、抽出方法が簡単で環境にも優しい「グリーン溶剤」の開発が明らかに重要である。
Patent Document 1 discloses a method for separating nickel, cobalt, and manganese from batteries containing nickel, cobalt, and manganese, in which nickel, cobalt, and manganese are separated in stages by countercurrent multi-stage extraction using a carboxylic acid extractant.
本発明は、上記問題点に着目して疎水性深共晶溶媒とリン酸トリブチルを用いて、廃リチウム電池中のニッケル・コバルト・マンガンを協同抽出し、ラフィネート中にリチウムを残し、一段抽出により、より高い抽出・分離効果を奏することができ、環境に優しく、運用コストも低いなどの特徴を有する。 The present invention focuses on the above problems and uses a hydrophobic deep eutectic solvent and tributyl phosphate to synergistically extract nickel, cobalt, and manganese from waste lithium batteries, leaving lithium in the raffinate. This single-stage extraction provides a higher extraction and separation effect, and is environmentally friendly and has low operating costs.
上記目的を達成するため、本発明は次の技術的手段を採用する：
（１）水相の調製：廃リチウム電池浸出液の成分を模擬し、リチウム、ニッケル、コバルト、及びマンガンの金属イオンを含む水相を調製する工程、
（２）疎水性深共晶溶媒の調製：リドカインとｎ－デカン酸を加熱混合して疎水性深共晶溶媒を得る工程、
（３）有機相の調製：工程（２）で得られた疎水性深共晶溶媒とリン酸トリブチルを混合して有機相を得る工程、
（４）工程（１）で得られた水相に工程（３）で得られた有機相を添加して混合抽出し、遠心分離して相分離した後、ニッケル・コバルト・マンガンを担持した有機相及びリチウム含有ラフィネートを得る工程、
（５）工程（４）のリチウム含有ラフィネートに沈殿剤を添加して炭酸リチウム沈殿物を得る工程、
（６）工程（４）のニッケル・コバルト・マンガンを担持した有機相に逆抽出剤を添加してニッケル・コバルト・マンガン逆抽出液及び再生有機相を得る工程。
In order to achieve the above object, the present invention adopts the following technical means:
(1) Preparation of an aqueous phase: A step of preparing an aqueous phase containing lithium, nickel, cobalt, and manganese metal ions by simulating the components of a waste lithium battery leachate;
(2) Preparation of hydrophobic deep eutectic solvent: A step of heating and mixing lidocaine and n-decanoic acid to obtain a hydrophobic deep eutectic solvent;
(3) Preparation of an organic phase: mixing the hydrophobic deep eutectic solvent obtained in step (2) with tributyl phosphate to obtain an organic phase;
(4) adding the organic phase obtained in step (3) to the aqueous phase obtained in step (1), mixing and extracting, and then centrifuging to separate the phases, to obtain an organic phase carrying nickel, cobalt and manganese and a lithium-containing raffinate;
(5) adding a precipitant to the lithium-containing raffinate of step (4) to obtain a lithium carbonate precipitate;
(6) A step of adding a stripping agent to the nickel-cobalt-manganese-loaded organic phase of the step (4) to obtain a nickel-cobalt-manganese stripped solution and a regenerated organic phase.
さらに、工程（１）において、模擬廃電池浸出液の水相のｐＨは、２～６、有価金属含有量はそれぞれＬｉ＝３００～４００ｍｇ／Ｌ、Ｎｉ＝１３００～１５００ｍｇ／Ｌ、Ｃｏ＝６００～７００ｍｇ／Ｌ、Ｍｎ＝８００～９００ｍｇ／Ｌである。 Furthermore, in step (1), the pH of the aqueous phase of the simulated waste battery leachate is 2 to 6, and the valuable metal contents are Li = 300 to 400 mg/L, Ni = 1300 to 1500 mg/L, Co = 600 to 700 mg/L, and Mn = 800 to 900 mg/L.
さらに、工程（２）で調製された疎水性深共晶溶媒中のリドカインとｎ－デカン酸とは、水素結合を介して結合し、その物質量の比は１：１となる。ｎ－デカン酸を加熱溶解した後、リドカインに加え、５０℃の水浴加熱条件下で混合して疎水性深共晶溶媒を得る。 Furthermore, the lidocaine and n-decanoic acid in the hydrophobic deep eutectic solvent prepared in step (2) are bonded via hydrogen bonds, with the ratio of the amounts of substances being 1:1. After the n-decanoic acid is heated and dissolved, it is added to the lidocaine and mixed under water bath heating conditions at 50°C to obtain the hydrophobic deep eutectic solvent.
さらに、工程（３）で調製された有機相には、次の3つの構造式が含まれる。 Furthermore, the organic phase prepared in step (3) contains the following three structural formulas:
さらに、工程（３）で調製された有機相中のリン酸トリブチルと疎水性深共晶溶媒の体積比は６：４～４：６である。 Furthermore, the volume ratio of tributyl phosphate to the hydrophobic deep eutectic solvent in the organic phase prepared in step (3) is 6:4 to 4:6.
さらに、工程（４）中の抽出プロセスパラメータは、添加した水相と有機相の体積比（Ａ／Ｏ）＝３：１～１：３、抽出温度１０～３０℃、抽出段数１段、混合均一撹拌時間２０～３０分、混合均一撹拌回転数２００～５００ｒ／分であり、水相と有機相をよく混ぜた後遠心分離機に入れ、遠心分離回転数６０００～８０００ｒ／分で１０～３０分間遠心分離した後相分離して、ニッケル・コバルト・マンガンを担持した有機相及びリチウム含有ラフィネートを得る。 Furthermore, the extraction process parameters in step (4) are: volume ratio of the added aqueous phase to the organic phase (A/O) = 3:1 to 1:3, extraction temperature 10 to 30°C, number of extraction stages 1, mixing uniform stirring time 20 to 30 minutes, mixing uniform stirring rotation speed 200 to 500 r/min, the aqueous phase and the organic phase are thoroughly mixed and then placed in a centrifuge, centrifuged at a centrifugation rotation speed of 6000 to 8000 r/min for 10 to 30 minutes, and then phase separated to obtain an organic phase carrying nickel, cobalt, and manganese, and a lithium-containing raffinate.
さらに、工程（５）で添加する沈殿剤は、１．５ｍｏｌ／Ｌの炭酸ナトリウム溶液であり、添加する炭酸ナトリウムとリチウム含有ラフィネートの体積比は２である。 Furthermore, the precipitant added in step (5) is a 1.5 mol/L sodium carbonate solution, and the volume ratio of the added sodium carbonate to the lithium-containing raffinate is 2.
さらに、工程（６）の逆抽出プロセスでは、２ｍｏｌ／ＬのＨＣｌを逆抽出剤として使用し、逆抽出パラメータは添加する塩酸とニッケル・コバルト・マンガンを担持した有機相の体積比（Ａ／Ｏ）＝２：１、逆抽出温度２４℃、逆抽出段数１段、混合均一撹拌時間３０分、混合均一撹拌回転数３００ｒ／分であり、よく混ぜた後遠心分離機に入れ、遠心分離回転数８０００ｒ／分で１０分間遠心分離した後相分離してニッケル・コバルト・マンガン逆抽出液及び再生有機相を得る。 Furthermore, in the back extraction process of step (6), 2 mol/L HCl is used as the back extraction agent, and the back extraction parameters are the volume ratio (A/O) of the added hydrochloric acid to the organic phase carrying nickel, cobalt, and manganese = 2:1, the back extraction temperature is 24°C, the number of back extraction stages is 1, the mixing uniform stirring time is 30 minutes, and the mixing uniform stirring rotation speed is 300 r/min. After mixing well, the mixture is placed in a centrifuge and centrifuged at a centrifugation rotation speed of 8000 r/min for 10 minutes, followed by phase separation to obtain the nickel, cobalt, and manganese back extract and the regenerated organic phase.
以下、実施例を挙げて本発明をさらに詳細に説明するが、下記の実施例は本発明の簡単な実施例に過ぎず、本発明の権利保護範囲を代表したり限定したりするものではなく、本発明の保護範囲は特許請求の範囲を基準とする。 The present invention will be described in more detail below with reference to examples. However, the following examples are merely simple examples of the present invention and do not represent or limit the scope of protection of the rights of the present invention. The scope of protection of the present invention is based on the scope of the claims.
本発明をより良く説明し、本発明の技術的手段の理解を容易にするため、本発明の典型的だが非限定的な実施例を以下に示す。 In order to better explain the present invention and facilitate understanding of the technical means of the present invention, typical but non-limiting examples of the present invention are given below.
本実施例により提供される疎水性深共晶溶媒とリン酸トリブチルの協同抽出剤及び廃リチウム電池浸出液中のリチウムと遷移金属を抽出・分離する方法のフローチャートは、図１に示される。 The flowchart of the synergistic extractant of hydrophobic deep eutectic solvent and tributyl phosphate provided in this embodiment and the method for extracting and separating lithium and transition metals in waste lithium battery leachate is shown in Figure 1.
本実施例の模擬廃リチウム電池の酸性浸出液の成分は、以下の通りである。 The components of the acid leachate from the simulated used lithium battery in this example are as follows:
本実施例の前記抽出・分離方法によれば、調製された模擬廃リチウム電池の水相は、ｐＨ＝２であり、
本実施例の前記抽出・分離方法によれば、調製された疎水性深共晶溶媒中のリドカインとｎ－デカン酸とが水素結合を介して結合し、その物質量の比は１：１となり、ｎ－デカン酸を加熱溶解した後、リドカインに加え、５０℃の水浴加熱条件下で混合して疎水性深共晶溶媒を得、
本実施例の前記抽出・分離方法によれば、調製された疎水性深共晶溶媒をリン酸トリブチルに添加し、添加したリン酸トリブチルと疎水性深共晶溶媒の体積比は６：４で、有機相を得、
本実施例の前記抽出・分離方法によれば、水相に調製された有機相を添加し、抽出プロセスパラメータは水相と有機相の体積比（Ａ／Ｏ）＝２：１、抽出温度１０℃、抽出段数１段、混合均一撹拌時間２０分、回転数２００ｒ／分であり、よく混ぜた後遠心分離機に入れ、遠心分離回転数６０００ｒ／分で１０分間遠心分離した後相分離してニッケル・コバルト・マンガンを担持した有機相及びリチウム含有ラフィネートを得た。
According to the extraction and separation method of this embodiment, the aqueous phase of the prepared simulated waste lithium battery has a pH of 2.
According to the extraction and separation method of this embodiment, lidocaine and n-decanoic acid in the prepared hydrophobic deep eutectic solvent are bonded via hydrogen bonds, and the ratio of the amounts of substances is 1:1. After the n-decanoic acid is heated and dissolved, it is added to the lidocaine and mixed under a water bath heating condition of 50°C to obtain a hydrophobic deep eutectic solvent.
According to the extraction and separation method of this embodiment, the prepared hydrophobic deep eutectic solvent is added to tributyl phosphate, and the volume ratio of the added tributyl phosphate to the hydrophobic deep eutectic solvent is 6:4 to obtain an organic phase;
According to the extraction and separation method of this embodiment, the prepared organic phase was added to the aqueous phase, and the extraction process parameters were the volume ratio of the aqueous phase to the organic phase (A/O) = 2:1, the extraction temperature was 10°C, the number of extraction stages was 1, the mixing and uniform stirring time was 20 minutes, and the rotation speed was 200 r/min. After thorough mixing, the mixture was placed in a centrifuge and centrifuged at a centrifugation rotation speed of 6000 r/min for 10 minutes, followed by phase separation to obtain an organic phase carrying nickel, cobalt, and manganese, and a lithium-containing raffinate.
本実施例の前記抽出・分離方法によれば、リチウム含有ラフィネートに濃度１．５ｍｏｌ／Ｌの炭酸ナトリウム溶液を添加し、添加した炭酸ナトリウム溶液とリチウム含有ラフィネートの体積比は２：１であり、沈殿をよく洗浄した後炭酸リチウム溶液を得た。 According to the extraction and separation method of this embodiment, a sodium carbonate solution having a concentration of 1.5 mol/L was added to the lithium-containing raffinate, the volume ratio of the added sodium carbonate solution to the lithium-containing raffinate was 2:1, and after thoroughly washing the precipitate, a lithium carbonate solution was obtained.
本実施例の前記抽出・分離方法によれば、逆抽出プロセスでは、２ｍｏｌ／ＬのＨＣｌを逆抽出剤として使用し、逆抽出パラメータは添加した塩酸とニッケル・コバルト・マンガンを担持した有機相の体積比（Ａ／Ｏ）＝２：１、逆抽出温度２４℃、逆抽出段数１段、混合均一撹拌時間３０分、混合均一撹拌回転数３００ｒ／分であり、よく混ぜた後遠心分離機に入れ、遠心分離回転数８０００ｒ／分で１０分間遠心分離した後相分離してニッケル・コバルト・マンガン逆抽出液及び再生有機相を得た。 According to the extraction and separation method of this embodiment, in the back extraction process, 2 mol/L HCl was used as a back extraction agent, and the back extraction parameters were the volume ratio (A/O) of the added hydrochloric acid to the organic phase carrying nickel, cobalt, and manganese = 2:1, the back extraction temperature was 24°C, the number of back extraction stages was 1, the mixing uniform stirring time was 30 minutes, and the mixing uniform stirring rotation speed was 300 r/min. After mixing well, the mixture was placed in a centrifuge and centrifuged at a centrifugation rotation speed of 8000 r/min for 10 minutes, followed by phase separation to obtain a nickel, cobalt, and manganese back extract and a regenerated organic phase.
実施例１の抽出実験結果は、以下の通りである。 The results of the extraction experiment in Example 1 are as follows:
本実施例において、一段抽出を経た後、ニッケル・コバルト・マンガンの抽出率がいずれも９２％以上に達し、同時にラフィネート中で高純度のリチウム塩溶液が得られ、廃リチウム電池中のリチウムと遷移金属の有効な分離を実現した。 In this embodiment, after one-stage extraction, the extraction rates of nickel, cobalt, and manganese all reached 92% or more, and at the same time, a high-purity lithium salt solution was obtained in the raffinate, achieving effective separation of lithium and transition metals in waste lithium batteries.
本実施例により提供される疎水性深共晶溶媒とリン酸トリブチルの協同抽出剤及び廃リチウム電池浸出液中のリチウムと遷移金属を抽出・分離する方法のフローチャートは、図１に示される。 The flowchart of the synergistic extractant of hydrophobic deep eutectic solvent and tributyl phosphate provided in this embodiment and the method for extracting and separating lithium and transition metals in waste lithium battery leachate is shown in Figure 1.
本実施例の模擬廃リチウム電池の酸性浸出液の成分は、以下の通りである。 The components of the acid leachate from the simulated used lithium battery in this example are as follows:
本実施例の前記抽出・分離方法によれば、調製された模擬廃リチウム電池の水相は、ｐＨ＝６であり、
本実施例の前記抽出・分離方法によれば、調製された疎水性深共晶溶媒中のリドカインとｎ－デカン酸とが水素結合を介して結合し、その物質量の比は１：１となり、ｎ－デカン酸を加熱溶解した後、リドカインに加え、５０℃の水浴加熱条件下で混合して疎水性深共晶溶媒を得、
本実施例の前記抽出・分離方法によれば、調製された疎水性深共晶溶媒をリン酸トリブチルに添加し、添加したリン酸トリブチルと疎水性深共晶溶媒の体積比は４：６で、有機相を得、
本実施例の前記抽出・分離方法によれば、水相に調製された有機相を添加し、抽出プロセスパラメータは水相と有機相の体積比（Ａ／Ｏ）＝２：１、抽出温度３０℃、抽出段数１段、混合均一撹拌時間３０分、回転数５００ｒ／分であり、よく混ぜた後遠心分離機に入れ、遠心分離回転数８０００ｒ／分で３０分間遠心分離した後相分離してニッケル・コバルト・マンガンを担持した有機相及びリチウム含有ラフィネートを得た。
According to the extraction and separation method of this embodiment, the aqueous phase of the prepared simulated waste lithium battery has a pH of 6.
According to the extraction and separation method of this embodiment, lidocaine and n-decanoic acid in the prepared hydrophobic deep eutectic solvent are bonded via hydrogen bonds, and the ratio of the amounts of substances is 1:1. After the n-decanoic acid is heated and dissolved, it is added to the lidocaine and mixed under a water bath heating condition of 50°C to obtain a hydrophobic deep eutectic solvent.
According to the extraction and separation method of this embodiment, the prepared hydrophobic deep eutectic solvent is added to tributyl phosphate, and the volume ratio of the added tributyl phosphate to the hydrophobic deep eutectic solvent is 4:6 to obtain an organic phase;
According to the extraction and separation method of this embodiment, the prepared organic phase was added to the aqueous phase, and the extraction process parameters were the volume ratio of the aqueous phase to the organic phase (A/O) = 2:1, the extraction temperature was 30°C, the number of extraction stages was 1, the mixing and uniform stirring time was 30 minutes, and the rotation speed was 500 r/min. After thorough mixing, the mixture was placed in a centrifuge and centrifuged at a centrifugation rotation speed of 8000 r/min for 30 minutes, followed by phase separation to obtain an organic phase carrying nickel, cobalt, and manganese, and a lithium-containing raffinate.
本実施例の前記抽出・分離方法によれば、リチウム含有ラフィネートに濃度１．５ｍｏｌ／Ｌの炭酸ナトリウム溶液を添加し、添加した炭酸ナトリウム溶液とリチウム含有ラフィネートの体積比は２：１であり、沈殿をよく洗浄した後炭酸リチウム溶液を得た。 According to the extraction and separation method of this embodiment, a sodium carbonate solution having a concentration of 1.5 mol/L was added to the lithium-containing raffinate, the volume ratio of the added sodium carbonate solution to the lithium-containing raffinate was 2:1, and after thoroughly washing the precipitate, a lithium carbonate solution was obtained.
本実施例の前記抽出・分離方法によれば、逆抽出プロセスでは、２ｍｏｌ／ＬのＨＣｌを逆抽出剤として使用し、逆抽出パラメータは添加した塩酸とニッケル・コバルト・マンガンを担持した有機相の体積比（Ａ／Ｏ）＝２：１、逆抽出温度２４℃、逆抽出段数１段、混合均一撹拌時間３０分、混合均一撹拌回転数３００ｒ／分であり、よく混ぜた後遠心分離機に入れ、遠心分離回転数８０００ｒ／分で１５分間遠心分離した後相分離してニッケル・コバルト・マンガン逆抽出液及び再生有機相を得た。 According to the extraction and separation method of this embodiment, in the back extraction process, 2 mol/L HCl was used as a back extraction agent, and the back extraction parameters were the volume ratio (A/O) of the added hydrochloric acid to the organic phase carrying nickel, cobalt, and manganese = 2:1, the back extraction temperature was 24°C, the number of back extraction stages was 1, the mixing uniform stirring time was 30 minutes, and the mixing uniform stirring rotation speed was 300 r/min. After mixing well, the mixture was placed in a centrifuge and centrifuged at a centrifugation rotation speed of 8000 r/min for 15 minutes, followed by phase separation to obtain a nickel, cobalt, and manganese back extract and a regenerated organic phase.
実施例２の抽出実験結果は、以下の通りである。 The results of the extraction experiment in Example 2 are as follows:
本実施例において、一段抽出を経た後、ニッケル・コバルト・マンガンの抽出率がいずれも９８％以上に達し、同時にラフィネート中で高純度のリチウム塩溶液が得られ、廃リチウム電池中のリチウムと遷移金属の有効な分離を実現した。 In this embodiment, after one-stage extraction, the extraction rates of nickel, cobalt, and manganese all reached 98% or more, and at the same time, a high-purity lithium salt solution was obtained in the raffinate, achieving effective separation of lithium and transition metals in waste lithium batteries.
本実施例により提供される疎水性深共晶溶媒とリン酸トリブチルの協同抽出剤及び廃リチウム電池浸出液中のリチウムと遷移金属を抽出・分離する方法のフローチャートは、図１に示される。 The flowchart of the synergistic extractant of hydrophobic deep eutectic solvent and tributyl phosphate provided in this embodiment and the method for extracting and separating lithium and transition metals in waste lithium battery leachate is shown in Figure 1.
本実施例の模擬廃リチウム電池の酸性浸出液の成分は、以下の通りである。 The components of the acid leachate from the simulated used lithium battery in this example are as follows:
本実施例の前記抽出・分離方法によれば、調製された模擬廃リチウム電池の水相は、ｐＨ＝３であり、
本実施例の前記抽出・分離方法によれば、調製された疎水性深共晶溶媒中のリドカインとｎ－デカン酸とが水素結合を介して結合し、その物質量の比は１：１となり、ｎ－デカン酸を加熱溶解した後、リドカインに加え、５０℃の水浴加熱条件下で混合して疎水性深共晶溶媒を得、
本実施例の前記抽出・分離方法によれば、調製された疎水性深共晶溶媒をリン酸トリブチルに添加し、添加したリン酸トリブチルと疎水性深共晶溶媒の体積比は４：６で、有機相を得、
本実施例の前記抽出・分離方法によれば、水相に調製された有機相を添加し、抽出プロセスパラメータは水相と有機相の体積比（Ａ／Ｏ）＝３：１、抽出温度２４℃、抽出段数１段、混合均一撹拌時間３０分、回転数３００ｒ／分であり、よく混ぜた後遠心分離機に入れ、遠心分離回転数８０００ｒ／分で１０分間遠心分離した後相分離してニッケル・コバルト・マンガンを担持した有機相及びリチウム含有ラフィネートを得た。
According to the extraction and separation method of this embodiment, the aqueous phase of the simulated waste lithium battery prepared has a pH of 3,
According to the extraction and separation method of this embodiment, lidocaine and n-decanoic acid in the prepared hydrophobic deep eutectic solvent are bonded via hydrogen bonds, and the ratio of the amounts of substances is 1:1. After the n-decanoic acid is heated and dissolved, it is added to the lidocaine and mixed under a water bath heating condition of 50°C to obtain a hydrophobic deep eutectic solvent.
According to the extraction and separation method of this embodiment, the prepared hydrophobic deep eutectic solvent is added to tributyl phosphate, and the volume ratio of the added tributyl phosphate to the hydrophobic deep eutectic solvent is 4:6, to obtain an organic phase;
According to the extraction and separation method of this embodiment, the prepared organic phase was added to the aqueous phase, and the extraction process parameters were the volume ratio of the aqueous phase to the organic phase (A/O) = 3:1, the extraction temperature was 24°C, the number of extraction stages was 1, the mixing and uniform stirring time was 30 minutes, and the rotation speed was 300 r/min. After thorough mixing, the mixture was put into a centrifuge and centrifuged at a centrifugation rotation speed of 8000 r/min for 10 minutes, followed by phase separation to obtain an organic phase carrying nickel, cobalt, and manganese, and a lithium-containing raffinate.
本実施例の前記抽出・分離方法によれば、リチウム含有ラフィネートに濃度１．５ｍｏｌ／Ｌの炭酸ナトリウム溶液を添加し、添加した炭酸ナトリウム溶液とリチウム含有ラフィネートの体積比は２：１であり、沈殿をよく洗浄した後炭酸リチウム溶液を得た。 According to the extraction and separation method of this embodiment, a sodium carbonate solution having a concentration of 1.5 mol/L was added to the lithium-containing raffinate, the volume ratio of the added sodium carbonate solution to the lithium-containing raffinate was 2:1, and after thoroughly washing the precipitate, a lithium carbonate solution was obtained.
本実施例の前記抽出・分離方法によれば、逆抽出プロセスでは、２ｍｏｌ／ＬのＨＣｌを逆抽出剤として使用し、逆抽出パラメータは添加した塩酸とニッケル・コバルト・マンガンを担持した有機相の体積比（Ａ／Ｏ）＝２：１、逆抽出温度２４℃、逆抽出段数１段、混合均一撹拌時間３０分、混合均一撹拌回転数３００ｒ／分であり、よく混ぜた後遠心分離機に入れ、遠心分離回転数８０００ｒ／分で１０分間遠心分離した後相分離してニッケル・コバルト・マンガン逆抽出液及び再生有機相を得た。 According to the extraction and separation method of this embodiment, in the back extraction process, 2 mol/L HCl was used as a back extraction agent, and the back extraction parameters were the volume ratio (A/O) of the added hydrochloric acid to the organic phase carrying nickel, cobalt, and manganese = 2:1, the back extraction temperature was 24°C, the number of back extraction stages was 1, the mixing uniform stirring time was 30 minutes, and the mixing uniform stirring rotation speed was 300 r/min. After mixing well, the mixture was placed in a centrifuge and centrifuged at a centrifugation rotation speed of 8000 r/min for 10 minutes, followed by phase separation to obtain a nickel, cobalt, and manganese back extract and a regenerated organic phase.
実施例３の抽出実験結果は、以下の通りである。 The results of the extraction experiment in Example 3 are as follows:
本実施例において、一段抽出を経た後、ニッケル・コバルト・マンガンの抽出率がいずれも９３％以上に達し、同時にラフィネート中で高純度のリチウム塩溶液が得られ、廃リチウム電池中のリチウムと遷移金属の有効な分離を実現した。 In this embodiment, after one-stage extraction, the extraction rates of nickel, cobalt, and manganese all reached 93% or more, and at the same time, a high-purity lithium salt solution was obtained in the raffinate, achieving effective separation of lithium and transition metals in waste lithium batteries.
本実施例により提供される疎水性深共晶溶媒とリン酸トリブチルの協同抽出剤及び廃リチウム電池浸出液中のリチウムと遷移金属を抽出・分離する方法のフローチャートは、図１に示される。 The flowchart of the synergistic extractant of hydrophobic deep eutectic solvent and tributyl phosphate provided in this embodiment and the method for extracting and separating lithium and transition metals in waste lithium battery leachate is shown in Figure 1.
本実施例の模擬廃リチウム電池の酸性浸出液の成分は、以下の通りである。 The components of the acid leachate from the simulated used lithium battery in this example are as follows:
本実施例の前記抽出・分離方法によれば、調製された模擬廃リチウム電池の水相は、ｐＨ＝３であり、
本実施例の前記抽出・分離方法によれば、調製された疎水性深共晶溶媒中のリドカインとｎ－デカン酸とが水素結合を介して結合し、その物質量の比は１：１となり、ｎ－デカン酸を加熱溶解した後、リドカインに加え、５０℃の水浴加熱条件下で混合して疎水性深共晶溶媒を得、
本実施例の前記抽出・分離方法によれば、調製された疎水性深共晶溶媒をリン酸トリブチルに添加し、添加したリン酸トリブチルと疎水性深共晶溶媒の体積比は４：６で、有機相を得、
本実施例の前記抽出・分離方法によれば、水相に調製された有機相を添加し、抽出プロセスパラメータは水相と有機相の体積比（Ａ／Ｏ）＝１：３、抽出温度２４℃、抽出段数１段、混合均一撹拌時間３０分、回転数３００ｒ／分であり、よく混ぜた後遠心分離機に入れ、遠心分離回転数８０００ｒ／分で１０分間遠心分離した後相分離してニッケル・コバルト・マンガンを担持した有機相及びリチウム含有ラフィネートを得た。
According to the extraction and separation method of this embodiment, the aqueous phase of the simulated waste lithium battery prepared has a pH of 3,
According to the extraction and separation method of this embodiment, lidocaine and n-decanoic acid in the prepared hydrophobic deep eutectic solvent are bonded via hydrogen bonds, and the ratio of the amounts of substances is 1:1. After the n-decanoic acid is heated and dissolved, it is added to the lidocaine and mixed under a water bath heating condition of 50°C to obtain a hydrophobic deep eutectic solvent.
According to the extraction and separation method of this embodiment, the prepared hydrophobic deep eutectic solvent is added to tributyl phosphate, and the volume ratio of the added tributyl phosphate to the hydrophobic deep eutectic solvent is 4:6, to obtain an organic phase;
According to the extraction and separation method of this embodiment, the prepared organic phase was added to the aqueous phase, and the extraction process parameters were the volume ratio of the aqueous phase to the organic phase (A/O) = 1:3, the extraction temperature was 24°C, the number of extraction stages was 1, the mixing and uniform stirring time was 30 minutes, and the rotation speed was 300 r/min. After thorough mixing, the mixture was put into a centrifuge and centrifuged at a centrifugation rotation speed of 8000 r/min for 10 minutes, followed by phase separation to obtain an organic phase carrying nickel, cobalt, and manganese, and a lithium-containing raffinate.
本実施例の前記抽出・分離方法によれば、リチウム含有ラフィネートに濃度１．５ｍｏｌ／Ｌの炭酸ナトリウム溶液を添加し、添加した炭酸ナトリウム溶液とリチウム含有ラフィネートの体積比は２：１であり、沈殿をよく洗浄した後炭酸リチウム溶液を得た。 According to the extraction and separation method of this embodiment, a sodium carbonate solution having a concentration of 1.5 mol/L was added to the lithium-containing raffinate, the volume ratio of the added sodium carbonate solution to the lithium-containing raffinate was 2:1, and after thoroughly washing the precipitate, a lithium carbonate solution was obtained.
本実施例の前記抽出・分離方法によれば、逆抽出プロセスでは、２ｍｏｌ／ＬのＨＣｌを逆抽出剤として使用し、逆抽出パラメータは添加した塩酸とニッケル・コバルト・マンガンを担持した有機相の体積比（Ａ／Ｏ）＝２：１、逆抽出温度２４℃、逆抽出段数１段、混合均一撹拌時間３０分、混合均一撹拌回転数３００ｒ／分であり、よく混ぜた後遠心分離機に入れ、遠心分離回転数８０００ｒ／分で１０分間遠心分離した後相分離してニッケル・コバルト・マンガン逆抽出液及び再生有機相を得た。 According to the extraction and separation method of this embodiment, in the back extraction process, 2 mol/L HCl was used as a back extraction agent, and the back extraction parameters were the volume ratio (A/O) of the added hydrochloric acid to the organic phase carrying nickel, cobalt, and manganese = 2:1, the back extraction temperature was 24°C, the number of back extraction stages was 1, the mixing uniform stirring time was 30 minutes, and the mixing uniform stirring rotation speed was 300 r/min. After mixing well, the mixture was placed in a centrifuge and centrifuged at a centrifugation rotation speed of 8000 r/min for 10 minutes, followed by phase separation to obtain a nickel, cobalt, and manganese back extract and a regenerated organic phase.
実施例４の抽出実験結果は、以下の通りである。 The results of the extraction experiment in Example 4 are as follows:
本実施例において、一段抽出を経た後、ニッケル・コバルト・マンガンの抽出率がいずれも９９％以上に達し、同時にラフィネート中で高純度のリチウム塩溶液が得られ、廃リチウム電池中のリチウムと遷移金属の有効な分離を実現した。 In this embodiment, after one-stage extraction, the extraction rates of nickel, cobalt, and manganese all reached 99% or more, and at the same time, a high-purity lithium salt solution was obtained in the raffinate, achieving effective separation of lithium and transition metals in waste lithium batteries.
本実施例により提供される疎水性深共晶溶媒とリン酸トリブチルの協同抽出剤及び廃リチウム電池浸出液中のリチウムと遷移金属を抽出・分離する方法のフローチャートは、図１に示される。 The flowchart of the synergistic extractant of hydrophobic deep eutectic solvent and tributyl phosphate provided in this embodiment and the method for extracting and separating lithium and transition metals in waste lithium battery leachate is shown in Figure 1.
本実施例の模擬廃リチウム電池の酸性浸出液の成分は、以下の通りである。 The components of the acid leachate from the simulated used lithium battery in this example are as follows:
本実施例の前記抽出・分離方法によれば、調製された模擬廃リチウム電池の水相は、ｐＨ＝３であり、
本実施例の前記抽出・分離方法によれば、調製された疎水性深共晶溶媒中のリドカインとｎ－デカン酸とが水素結合を介して結合し、その物質量の比は１：１となり、ｎ－デカン酸を加熱溶解した後、リドカインに加え、５０℃の水浴加熱条件下で混合して疎水性深共晶溶媒を得、
本実施例の前記抽出・分離方法によれば、調製された疎水性深共晶溶媒をリン酸トリブチルに添加し、添加したリン酸トリブチルと疎水性深共晶溶媒の体積比は４：６で、有機相を得、
本実施例の前記抽出・分離方法によれば、水相に調製された有機相を添加し、抽出プロセスパラメータは水相と有機相の体積比（Ａ／Ｏ）＝１：２、抽出温度２４℃、抽出段数１段、混合均一撹拌時間３０分、回転数３００ｒ／分であり、よく混ぜた後遠心分離機に入れ、遠心分離回転数８０００ｒ／分で１０分間遠心分離した後相分離してニッケル・コバルト・マンガンを担持した有機相及びリチウム含有ラフィネートを得た。
According to the extraction and separation method of this embodiment, the aqueous phase of the simulated waste lithium battery prepared has a pH of 3,
According to the extraction and separation method of this embodiment, lidocaine and n-decanoic acid in the prepared hydrophobic deep eutectic solvent are bonded via hydrogen bonds, and the ratio of the amounts of substances is 1:1. After the n-decanoic acid is heated and dissolved, it is added to the lidocaine and mixed under a water bath heating condition of 50°C to obtain a hydrophobic deep eutectic solvent.
According to the extraction and separation method of this embodiment, the prepared hydrophobic deep eutectic solvent is added to tributyl phosphate, and the volume ratio of the added tributyl phosphate to the hydrophobic deep eutectic solvent is 4:6, to obtain an organic phase;
According to the extraction and separation method of this embodiment, the prepared organic phase was added to the aqueous phase, and the extraction process parameters were the volume ratio of the aqueous phase to the organic phase (A/O) = 1:2, the extraction temperature was 24°C, the number of extraction stages was 1, the mixing and uniform stirring time was 30 minutes, and the rotation speed was 300 r/min. After thorough mixing, the mixture was placed in a centrifuge and centrifuged at a centrifugation rotation speed of 8000 r/min for 10 minutes, followed by phase separation to obtain an organic phase carrying nickel, cobalt, and manganese, and a lithium-containing raffinate.
本実施例の前記抽出・分離方法によれば、リチウム含有ラフィネートに濃度１．５ｍｏｌ／Ｌの炭酸ナトリウム溶液を添加し、添加した炭酸ナトリウム溶液とリチウム含有ラフィネートの体積比は２：１であり、沈殿をよく洗浄した後炭酸リチウム溶液を得た。 According to the extraction and separation method of this embodiment, a sodium carbonate solution with a concentration of 1.5 mol/L was added to the lithium-containing raffinate, the volume ratio of the added sodium carbonate solution to the lithium-containing raffinate was 2:1, and after thoroughly washing the precipitate, a lithium carbonate solution was obtained.
本実施例の前記抽出・分離方法によれば、逆抽出プロセスでは、２ｍｏｌ／ＬのＨＣｌを逆抽出剤として使用し、逆抽出パラメータは添加した塩酸とニッケル・コバルト・マンガンを担持した有機相の体積比（Ａ／Ｏ）＝２：１、逆抽出温度２４℃、逆抽出段数１段、混合均一撹拌時間３０分、混合均一撹拌回転数３００ｒ／分であり、よく混ぜた後遠心分離機に入れ、遠心分離回転数８０００ｒ／分で１０分間遠心分離した後相分離してニッケル・コバルト・マンガン逆抽出液及び再生有機相を得た。 According to the extraction and separation method of this embodiment, in the back extraction process, 2 mol/L HCl was used as a back extraction agent, and the back extraction parameters were the volume ratio (A/O) of the added hydrochloric acid to the organic phase carrying nickel, cobalt, and manganese = 2:1, the back extraction temperature was 24°C, the number of back extraction stages was 1, the mixing uniform stirring time was 30 minutes, and the mixing uniform stirring rotation speed was 300 r/min. After mixing well, the mixture was placed in a centrifuge and centrifuged at a centrifugation rotation speed of 8000 r/min for 10 minutes, followed by phase separation to obtain a nickel, cobalt, and manganese back extract and a regenerated organic phase.
実施例５の抽出実験結果は、以下の通りである。 The results of the extraction experiment in Example 5 are as follows:
本実施例において、一段抽出を経た後、ニッケル・コバルト・マンガンの抽出率がいずれも９８％以上に達し、同時にラフィネート中で高純度のリチウム塩溶液が得られ、廃リチウム電池中のリチウムと遷移金属の有効な分離を実現した。
In this embodiment, after one-stage extraction, the extraction rates of nickel, cobalt and manganese all reached 98% or more, and at the same time, a high-purity lithium salt solution was obtained in the raffinate, and effective separation of lithium and transition metals in waste lithium batteries was realized.
Claims (5)
（１）水相の調製：廃リチウム電池浸出液の成分を模擬し、リチウム、ニッケル、コバルト、及びマンガンの金属イオンを含む水相を調製し、その際、水相のｐＨは、２～６、有価金属含有量はそれぞれＬｉ＝３００～４００ｍｇ／Ｌ、Ｎｉ＝１３００～１５００ｍｇ／Ｌ、Ｃｏ＝６００～７００ｍｇ／Ｌ、Ｍｎ＝８００～９００ｍｇ／Ｌとする工程、
（２）疎水性深共晶溶媒の調製：リドカインとｎ－デカン酸とは、水素結合を介して結合し、その物質量の比は１：１となり、ｎ－デカン酸を加熱溶解した後、前記リドカインに加え、５０℃の水浴加熱条件下で混合して疎水性深共晶溶媒を得る工程、
（３）有機相の調製：前記工程（２）で得られた疎水性深共晶溶媒とリン酸トリブチルを混合して有機相を得て、その際、有機相中のリン酸トリブチルと疎水性深共晶溶媒の体積比は６：４～４：６とする工程、
（４）前記工程（１）で得られた水相に前記工程（３）で得られた有機相を添加して混合抽出し、遠心分離して相分離した後、ニッケル・コバルト・マンガンを担持した有機相及びリチウム含有ラフィネートを得る工程、
（５）前記工程（４）のリチウム含有ラフィネートに沈殿剤を添加して炭酸リチウム沈殿物を得る工程、及び、
（６）前記工程（４）のニッケル・コバルト・マンガンを担持した有機相に逆抽出剤を添加してニッケル・コバルト・マンガン逆抽出液及び再生有機相を得る工程
を含む
ことを特徴とする抽出法。 A synergistic extraction method for selectively separating lithium and transition metals from waste batteries using a hydrophobic deep eutectic solvent, comprising:
(1) Preparation of an aqueous phase: preparing an aqueous phase containing lithium, nickel, cobalt, and manganese metal ions by simulating the components of a waste lithium battery leachate, with the aqueous phase having a pH of 2 to 6 and a valuable metal content of Li=300 to 400 mg/L, Ni=1,300 to 1,500 mg/L, Co=600 to 700 mg/L, and Mn=800 to 900 mg/L, respectively ;
(2) Preparation of hydrophobic deep eutectic solvent: Lidocaine and n-decanoic acid are bonded via hydrogen bonds, and the ratio of the amounts of substances is 1:1. After heating and dissolving n-decanoic acid, the mixture is added to the lidocaine and mixed under a water bath heating condition of 50°C to obtain a hydrophobic deep eutectic solvent;
(3) Preparation of an organic phase: mixing the hydrophobic deep eutectic solvent obtained in the step (2) with tributyl phosphate to obtain an organic phase, in which the volume ratio of tributyl phosphate to the hydrophobic deep eutectic solvent in the organic phase is 6:4 to 4:6;
(4) adding the organic phase obtained in the step (3) to the aqueous phase obtained in the step (1), mixing and extracting the mixture, and then centrifuging to separate the phases, to obtain an organic phase carrying nickel, cobalt and manganese and a lithium-containing raffinate;
(5) adding a precipitant to the lithium-containing raffinate of the step (4) to obtain a lithium carbonate precipitate; and
(6) A method for extraction comprising the step of adding a stripping agent to the organic phase carrying nickel-cobalt-manganese from the step (4) to obtain a nickel-cobalt-manganese stripped solution and a regenerated organic phase.
請求項１に記載の抽出法。 The organic phase prepared in step (3) contains a substance of the following structural formula:
請求項１に記載の抽出法。 The extraction process according to claim 1, wherein the extraction process parameters in the step (4) are: a volume ratio (A/O) of the added aqueous phase to the organic phase = 3:1 to 1:3, an extraction temperature of 10 to 30°C, a number of extraction stages of 1, a mixing and uniform stirring time of 20 to 30 minutes, and a mixing and uniform stirring rotation speed of 200 to 500 r/min; the aqueous phase and the organic phase are thoroughly mixed and then placed in a centrifuge, and centrifuged at a centrifugation rotation speed of 6000 to 8000 r/min for 10 to 30 minutes, followed by phase separation, to obtain an organic phase carrying nickel, cobalt, and manganese and a lithium-containing raffinate.
請求項１に記載の抽出法。 2. The extraction method according to claim 1, wherein the precipitant added in step (5) is a 1.5 mol/L sodium carbonate solution, and the volume ratio of the added sodium carbonate to the lithium-containing raffinate is 2.
請求項１に記載の抽出法。
The extraction method according to claim 1, wherein in the stripping process of step (6), 2 mol/L HCl is used as a stripping agent, the stripping parameters are a volume ratio (A/O) of the added hydrochloric acid to the organic phase carrying nickel, cobalt and manganese of 2:1, a stripping temperature of 24°C, a stripping stage number of 1, a mixing uniform stirring time of 30 minutes, and a mixing uniform stirring rotation speed of 300 r/min. After thorough mixing, the mixture is placed in a centrifuge and centrifuged at a centrifugation rotation speed of 8000 r/min for 10 minutes, followed by phase separation to obtain a nickel, cobalt and manganese stripped solution and a regenerated organic phase.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020515719A (en) | 2018-01-10 | 2020-05-28 | 北京工業大学 | Method for separating nickel and cobalt from solution |
| CN112553481A (en) | 2020-12-11 | 2021-03-26 | 中南大学 | Production method of electrolytic manganese |
| WO2021134515A1 (en) | 2019-12-30 | 2021-07-08 | 荆门市格林美新材料有限公司 | Battery-level ni-co-mn mixed solution and preparation method for battery-level mn solution |
| CN115029556A (en) | 2022-06-14 | 2022-09-09 | 桐乡市思远环保科技有限公司 | Method for recycling waste lithium ion battery cathode material |
| JP2023022934A (en) | 2021-08-04 | 2023-02-16 | 国立大学法人九州大学 | Recovery apparatus of metal, and recovery method of metal |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US10522884B2 (en) * | 2012-04-04 | 2019-12-31 | Worcester Polytechnic Institute | Method and apparatus for recycling lithium-ion batteries |
| US9957459B2 (en) * | 2014-11-03 | 2018-05-01 | Exxonmobil Research And Engineering Company | Low transition temperature mixtures or deep eutectic solvents and processes for preparation thereof |
| CN106319228B (en) * | 2016-08-26 | 2018-06-19 | 荆门市格林美新材料有限公司 | A kind of method of synchronous recycling nickel cobalt manganese in manganese waste slag from nickel and cobalt containing |
| US11591670B2 (en) * | 2019-06-24 | 2023-02-28 | William Marsh Rice University | Recycling Li-ion batteries using green chemicals and processes |
| CN111187911A (en) * | 2020-01-15 | 2020-05-22 | 中国科学院过程工程研究所 | Method for selectively extracting lithium in waste ternary batteries by using functionalized ionic liquid |
| CN111270073A (en) * | 2020-02-03 | 2020-06-12 | 广东省稀有金属研究所 | Method for recovering valuable metals from leachate of waste lithium ion battery electrode material |
| US11932557B2 (en) * | 2020-06-30 | 2024-03-19 | University Of Kentucky Research Foundation | Detection and extraction of plastic contaminants within water using hydrophobic deep eutectic solvents |
| CN111850302B (en) * | 2020-07-16 | 2021-11-09 | 中国科学院青海盐湖研究所 | Method for extracting metal ions from lithium battery |
| CN112226632B (en) * | 2020-09-11 | 2022-06-21 | 江苏大学 | Method for selectively extracting and precipitating lithium in lithium mother liquor by using hydrophobic eutectic solvent |
| CN112522517A (en) * | 2020-11-30 | 2021-03-19 | 北京博萃循环科技有限公司 | Method for recycling nickel, cobalt, manganese and lithium |
| CN112662877B (en) * | 2020-12-02 | 2023-12-12 | 广西科技师范学院 | Method for preparing high-purity nickel sulfate from electrolytic manganese sulfide slag |
| CN114438343B (en) * | 2022-01-24 | 2023-03-17 | 中国科学院过程工程研究所 | Difunctional hydrophobic eutectic solvent for selectively extracting lithium and preparation method and application method thereof |
| CN115074551B (en) * | 2022-06-29 | 2023-10-17 | 北京工业大学 | Synergistic extraction method for selectively separating lithium and transition metal from waste battery by using hydrophobic eutectic solvent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020515719A (en) | 2018-01-10 | 2020-05-28 | 北京工業大学 | Method for separating nickel and cobalt from solution |
| WO2021134515A1 (en) | 2019-12-30 | 2021-07-08 | 荆门市格林美新材料有限公司 | Battery-level ni-co-mn mixed solution and preparation method for battery-level mn solution |
| CN112553481A (en) | 2020-12-11 | 2021-03-26 | 中南大学 | Production method of electrolytic manganese |
| JP2023022934A (en) | 2021-08-04 | 2023-02-16 | 国立大学法人九州大学 | Recovery apparatus of metal, and recovery method of metal |
| CN115029556A (en) | 2022-06-14 | 2022-09-09 | 桐乡市思远环保科技有限公司 | Method for recycling waste lithium ion battery cathode material |
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