JP3321602B2 - Selective lithium separating agent and method for producing the same - Google Patents
Selective lithium separating agent and method for producing the sameInfo
- Publication number
- JP3321602B2 JP3321602B2 JP2000036377A JP2000036377A JP3321602B2 JP 3321602 B2 JP3321602 B2 JP 3321602B2 JP 2000036377 A JP2000036377 A JP 2000036377A JP 2000036377 A JP2000036377 A JP 2000036377A JP 3321602 B2 JP3321602 B2 JP 3321602B2
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- JP
- Japan
- Prior art keywords
- lithium
- adsorption
- separating agent
- producing
- adsorbent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- Treatment Of Liquids With Adsorbents In General (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicon Compounds (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は新規なリチウム分離剤に
関するものである。更に詳しく言えば本発明はリチウム
に対する選択吸着性に優れ、かつ吸着容量及び吸着速度
が大きく、水溶液中で安定、かつ安価なリチウム吸着剤
の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel lithium separating agent. More specifically, the present invention relates to a method for producing a lithium adsorbent which is excellent in selective adsorptivity to lithium, has a large adsorption capacity and adsorption speed, is stable in an aqueous solution, and is inexpensive.
【０００２】[0002]
【従来の技術】近年、リチウムは、例えばセラミック
ス、グリース、空調用冷媒、医薬品、電池等の原料とし
て使用されており、また将来は、大容量電池、アルミニ
ウム合金材料、核融合燃料などに用いられる重要な物質
として注目されている。しかるに、我が国においてはリ
チウム鉱石資源がなく、リチウム金属やその化合物は全
量輸入しているのが現状である。一方、海水中には微量
のリチウムが含まれており、海水からリチウムを効率よ
く回収する技術の確立が強く要望されている。海水など
リチウムを含む希薄溶液から該リチウムを回収する方法
としては、共沈法や蒸発法などが提案されているが経済
的に大きな問題があり、吸着法がもっとも経済的である
と結論されている。そのため、リチウムに対し高い選択
吸着性を示し、かつ化学的に安定な吸着剤の開発が強く
要望されている。2. Description of the Related Art In recent years, lithium has been used as a raw material for, for example, ceramics, grease, refrigerants for air conditioning, pharmaceuticals, batteries and the like. It is attracting attention as an important substance. However, in Japan, there is no lithium ore resource, and at present, all lithium metal and its compounds are imported. On the other hand, seawater contains a trace amount of lithium, and there is a strong demand for establishing a technology for efficiently recovering lithium from seawater. As a method for recovering lithium from a dilute solution containing lithium such as seawater, a coprecipitation method or an evaporation method has been proposed, but there are major economic problems, and it has been concluded that the adsorption method is the most economical. I have. Therefore, there is a strong demand for the development of a chemically stable adsorbent that exhibits high selective adsorption to lithium.
【０００３】従来、リチウム吸着剤としては、ヒ酸トリ
ウム（「J. Inorg. Nucl. Chem.」第32巻、第1719ペー
ジ（1970））やアンチモン酸スズ（「Hydrometallurg
y」第12巻、第83ページ（1984））などが知られている
が、吸着量が低く実用には使用できない。Conventionally, lithium adsorbents include thorium arsenate ("J. Inorg. Nucl. Chem.", Vol. 32, p. 1719 (1970)) and tin antimonate ("Hydrometallurg").
y ", Vol. 12, p. 83 (1984)), but the amount of adsorption is low and cannot be used practically.
【０００４】また、加熱処理したリチウム含有マンガン
酸化物を酸処理して得られたリチウム吸着剤（特願 昭
６０−１１６２１）や、マグネシウムを含むマンガン−
アルミニウム複合酸化物の加熱処理物からマグネシウム
を酸で溶出して調製した複合型リチウム吸着剤が知られ
ている（特願 昭６１−２０８７２０）。これらの吸着
剤は海水からリチウムを選択的に吸着し、吸着量も大き
いが、実用性を考えるとまだ十分な性能には達していな
い。A lithium adsorbent (Japanese Patent Application No. 60-11621) obtained by subjecting a heat-treated lithium-containing manganese oxide to acid treatment, and a manganese-containing manganese oxide containing magnesium.
A composite lithium adsorbent prepared by eluting magnesium from a heat-treated aluminum composite oxide with an acid is known (Japanese Patent Application No. 61-208720). These adsorbents selectively adsorb lithium from seawater and have a large amount of adsorption, but have not yet achieved sufficient performance in view of practicality.
【０００５】[0005]
【発明が解決しようとする課題】リチウムを含む海水な
どの希薄溶液から該リチウムを実用的に吸着回収するた
めには、リチウムに対する選択吸着性に優れ、かつ吸着
速度および吸着容量が大きく、その上、化学的に安定で
あり、吸着・脱着の繰り返しが可能である吸着剤の開発
が必要である。In order to practically adsorb and recover lithium from a dilute solution such as seawater containing lithium, it is required to have excellent selective adsorption to lithium, high adsorption speed and large adsorption capacity, It is necessary to develop an adsorbent that is chemically stable and capable of repeating adsorption and desorption.
【０００６】本発明は、このような要件を満足しうるリ
チウム吸着剤を提供することを目的としてなされたもの
である。[0006] The object of the present invention is to provide a lithium adsorbent which can satisfy such requirements.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、前記目的
を達成するために鋭意研究を重ねた結果、リチウムを含
むアルミナ−シリカ複合酸化物を加熱処理した後、酸処
理してリチウムを溶出したものが前記の要件を満たすリ
チウム分離剤であることを認め、本発明をなすに至っ
た。すなわち、本発明は、きわめて高濃度の塩溶液から
でも十分なリチウム吸着性を示す効率的な吸着剤を安価
に提供するものである。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, after heating a lithium-containing alumina-silica composite oxide containing lithium, an acid treatment was performed to convert lithium. It was recognized that the eluted product was a lithium separating agent satisfying the above requirements, and the present invention was accomplished. That is, the present invention provides an inexpensive efficient adsorbent that exhibits sufficient lithium adsorption even from a salt solution having a very high concentration.
【０００８】本発明におけるリチウムを含有するアルミ
ナ−シリカ複合酸化物は特定の方法で調製したものでな
く、各種の方法で調製したものが用いられる。[0008] The alumina-silica composite oxide containing lithium in the present invention is not prepared by a specific method, but is prepared by various methods.
【０００９】例えば、炭酸リチウム等のリチウム化合物
とアルミニウム水酸化物とケイ素の水酸化物等の化合物
を一定割合で混合し加熱する固相反応法、塩化アルミニ
ウム溶液とケイ酸イオンおよび水酸化リチウムを含む溶
液とを混合し、リチウム−ケイ素−アルミニウム複合水
酸化物を共沈させ、さらに加熱処理する共沈法、アルミ
ニウムイオンとケイ酸イオンを含む溶液からアルミナ−
シリカ複合物をあらかじめ共沈させた後、リチウム化合
物を一定割合で混合し加熱する共沈−固相反応法、等が
使用できる。For example, a solid-state reaction method in which a lithium compound such as lithium carbonate and a compound such as aluminum hydroxide and silicon hydroxide are mixed at a fixed ratio and heated, an aluminum chloride solution is mixed with silicate ions and lithium hydroxide. A solution containing aluminum ions and silicate ions is mixed with a solution containing aluminum ions and silicate ions by co-precipitation of a lithium-silicon-aluminum composite hydroxide, followed by heat treatment.
A co-precipitation-solid phase reaction method in which a silica compound is co-precipitated in advance, a lithium compound is mixed at a fixed ratio, and heated, can be used.
【００１０】アルミナ−シリカ複合酸化物中のシリコン
/アルミニウムモル比(Si/Al比)は吸着サイトの含量と酸
強度を上昇させるうえで重要である。Si/Al比は0.1〜10
の間で許されるが、0.5〜４が望ましい。また、リチウ
ムの含有量は１〜10％の間で許されるが、2〜6％が望ま
しい。Silicon in alumina-silica composite oxide
The aluminum / aluminum molar ratio (Si / Al ratio) is important in increasing the content of adsorption sites and acid strength. Si / Al ratio is 0.1 ~ 10
Is allowed, but 0.5 to 4 is desirable. Further, the content of lithium is allowed between 1% and 10%, but is preferably between 2% and 6%.
【００１１】リチウム含有アルミナ−シリカ複合酸化物
の加熱処理温度は３００度以上が、望ましくは４００度
以上が必要である。加熱とともに結晶化反応が進むが、
加熱時間は１０分以上は必要であり、望ましくは１時間
以上は必要である。[0011] The heat treatment temperature of the lithium-containing alumina-silica composite oxide should be 300 ° C or higher, preferably 400 ° C or higher. The crystallization reaction proceeds with heating,
The heating time must be at least 10 minutes, and preferably at least 1 hour.
【００１２】加熱処理物からのリチウムの溶出はｐＨ３
以下の弱酸溶液で数時間以上、望ましくは１日以上処理
することによって達成できる。溶出に用いる酸としては
ｐＨ３以下の酸溶液であればよいが、望ましくは塩酸、
硫酸、硝酸、リン酸などの鉱酸がよい。The elution of lithium from the heat-treated product is pH 3
It can be achieved by treating with the following weak acid solution for several hours or more, preferably for one day or more. The acid used for elution may be an acid solution having a pH of 3 or less, but is preferably hydrochloric acid,
Mineral acids such as sulfuric acid, nitric acid and phosphoric acid are preferred.
【００１３】[0013]
【発明の効果】本発明の方法で調製した吸着剤は、吸着
サイトの酸強度が高く、かつリチウムに対する選択吸着
性にすぐれ、ナトリウムなどの共存元素が大量に含まれ
る溶液からでもリチウムを効率よく回収する。また、吸
着速度および吸着容量が極めて大きく、しかも水溶液中
で安定であり、実用的な吸着剤である。本発明の吸着剤
を用いることにより、希薄溶液から該リチウムを極めて
効率よく経済的に回収することができる。The adsorbent prepared by the method of the present invention has a high acid strength at the adsorption site, has excellent selective adsorption to lithium, and can efficiently convert lithium even from a solution containing a large amount of coexisting elements such as sodium. to recover. In addition, the adsorption rate and the adsorption capacity are extremely large, and are stable in an aqueous solution, and are practical adsorbents. By using the adsorbent of the present invention, the lithium can be extremely efficiently and economically recovered from a dilute solution.
【００１４】[0014]
【実施例】次に、実施例により本発明を更に詳細に説明
するが、本発明はこれらの例によってなんら限定される
ものではない。Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.
【００１５】実施例１ 炭酸リチウムと水酸化アルミニウムと二酸化ケイ素をL
i:Al:Siモル比を１：１：２となるように混合し、１０
００度で4時間加熱処理した。この加熱処理物を0.3Mの
硫酸溶液中に浸漬し、150度で5日間水熱処理し、リチウ
ムを抽出した。このとき80％のリチウムが抽出された。Example 1 Lithium carbonate, aluminum hydroxide and silicon dioxide were mixed with L
i: Al: Si molar ratio was mixed to be 1: 1: 2,
Heat treatment was performed at 00 degrees for 4 hours. This heat-treated product was immersed in a 0.3 M sulfuric acid solution and subjected to hydrothermal treatment at 150 ° C. for 5 days to extract lithium. At this time, 80% of lithium was extracted.
【００１６】リチウムを抽出した分離剤０．１ｇを１M
のNaClと0.01MのLiOHを含む混合溶液15ミリリットル中
に浸漬し、90度で1日間振とうし吸着実験を行った。吸
着前後のリチウム濃度からリチウム吸着率を求めた。リ
チウム吸着率は90％となり、選択的にリチウムが分離さ
れた。0.1 g of the separating agent from which lithium was extracted was added to 1 M
Was immersed in 15 ml of a mixed solution containing NaCl and 0.01M LiOH, and shaken at 90 ° C. for 1 day to perform an adsorption experiment. The lithium adsorption rate was determined from the lithium concentration before and after the adsorption. The lithium adsorption rate became 90%, and lithium was selectively separated.
【００１７】このことから、本発明の吸着剤は、高いリ
チウム選択吸着性能を有することは明らかである。From the above, it is apparent that the adsorbent of the present invention has high lithium selective adsorption performance.
【００１８】実施例２ 塩化アルミニウムとケイ酸ナトリウムをAl:Siモル比
１：３で混合し、ｐHを中性に調整して沈殿を生成さ
せ、水洗してアルミニウム−ケイ素共沈水酸化物を合成
した。この共沈物に炭酸リチウムをLi:Al比1：1となる
よう添加し、混合した後、８００度で4時間加熱処理し
た。この加熱処理物を0.3Mの硫酸溶液中に浸漬し、150
度で5日間水熱処理し、リチウムを抽出した。75％のリ
チウムが抽出された。Example 2 Aluminum chloride and sodium silicate were mixed at an Al: Si molar ratio of 1: 3, the pH was adjusted to neutral to form a precipitate, and the precipitate was washed with water to synthesize an aluminum-silicon coprecipitated hydroxide. did. Lithium carbonate was added to this coprecipitate so as to have a Li: Al ratio of 1: 1. After mixing, the mixture was heated at 800 ° C. for 4 hours. This heat-treated product was immersed in a 0.3 M sulfuric acid solution,
Hydrothermal treatment was performed for 5 days to extract lithium. 75% of the lithium was extracted.
【００１９】リチウムを抽出した分離剤０．１ｇを１M
のNaClと0.01MのLiOHを含む混合溶液15ミリリットル中
に浸漬し、90度で1日間浸透し吸着実験を行った。吸着
前後のリチウム濃度からリチウム吸着率を求めた。リチ
ウム吸着率は80％となり、選択的にリチウムが分離され
た。このことから、本発明の吸着剤は、高いリチウム選
択吸着性能を有することは明らかである。0.1 g of the separating agent from which lithium was extracted was added to 1 M
Was immersed in 15 ml of a mixed solution containing NaCl and 0.01 M LiOH, and permeated at 90 ° C. for 1 day to perform an adsorption experiment. The lithium adsorption rate was determined from the lithium concentration before and after the adsorption. The lithium adsorption rate was 80%, and lithium was selectively separated. From this, it is clear that the adsorbent of the present invention has high lithium selective adsorption performance.
【００２０】実施例３ 実施例１でリチウムを吸着した吸着剤50mgを0.1規定の
塩酸溶液50ミリリットル中に入れ、24時間撹拌した。撹
拌後、上澄みのリチウム濃度を測定しリチウム脱着率を
求めたところ、90%となった。このことから、該分離剤
は吸着だけでなく脱着も容易に進むことは明らかであ
る。Example 3 50 mg of the adsorbent that had adsorbed lithium in Example 1 was placed in 50 ml of a 0.1 N hydrochloric acid solution and stirred for 24 hours. After stirring, the lithium concentration of the supernatant was measured to determine the lithium desorption rate, which was 90%. From this, it is clear that the separating agent easily proceeds not only in adsorption but also in desorption.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 槇田 洋二 香川県高松市林町2217番14号 工業技術 院四国工業技術研究所内 審査官 新居田 知生 (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 20/00 - 20/34 ────────────────────────────────────────────────── ─── continued (72) of the front page inventor Makita Yoji Kagawa Prefecture, Takamatsu Shirin-cho, 2217 No. No. 14 industrial technology Institute Shikoku industrial technology research Institute within the examiner new home field Tomoo (58) investigated the field (Int.Cl. 7, (DB name) B01J 20/00-20/34
Claims (2)
化物の加熱処理物からリチウムを酸で溶出して調製した
リチウム分離剤。1. A lithium separating agent prepared by eluting lithium from a heat-treated alumina-silica composite oxide containing lithium with an acid.
化物を３５０度以上の温度で加熱した後、酸処理してリ
チウムを溶出させることを特徴とするリチウム分離剤の
製造方法。2. A method for producing a lithium separating agent, comprising heating an alumina-silica composite oxide containing lithium at a temperature of 350 ° C. or higher, and then performing an acid treatment to elute lithium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000036377A JP3321602B2 (en) | 2000-02-15 | 2000-02-15 | Selective lithium separating agent and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000036377A JP3321602B2 (en) | 2000-02-15 | 2000-02-15 | Selective lithium separating agent and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001224957A JP2001224957A (en) | 2001-08-21 |
| JP3321602B2 true JP3321602B2 (en) | 2002-09-03 |
Family
ID=18560424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000036377A Expired - Lifetime JP3321602B2 (en) | 2000-02-15 | 2000-02-15 | Selective lithium separating agent and method for producing the same |
Country Status (1)
| Country | Link |
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| JP (1) | JP3321602B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106379903A (en) * | 2016-08-30 | 2017-02-08 | 浙江阿斯克建材科技股份有限公司 | Technology for preparing refined diatomite |
| CN110639467A (en) * | 2019-10-18 | 2020-01-03 | 华东理工大学 | Preparation method of magnetic aluminum salt lithium adsorbent |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012193088A (en) * | 2011-03-17 | 2012-10-11 | Taiheiyo Cement Corp | Method for manufacturing positive electrode active material for lithium-ion battery |
| CN102872792A (en) * | 2012-08-28 | 2013-01-16 | 常州大学 | Composite adsorbing material for removing lithium ions in natural water and preparation method thereof |
| JP6406524B2 (en) * | 2014-02-06 | 2018-10-17 | 日産化学株式会社 | Silica-based fine particle sol and method for producing the same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106379903A (en) * | 2016-08-30 | 2017-02-08 | 浙江阿斯克建材科技股份有限公司 | Technology for preparing refined diatomite |
| CN106379903B (en) * | 2016-08-30 | 2019-01-25 | 浙江阿斯克建材科技股份有限公司 | A kind of process preparing fine diatomite |
| CN110639467A (en) * | 2019-10-18 | 2020-01-03 | 华东理工大学 | Preparation method of magnetic aluminum salt lithium adsorbent |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001224957A (en) | 2001-08-21 |
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