JP2002282684A - Method for producing porous granular lithium adsorbent - Google Patents
Method for producing porous granular lithium adsorbentInfo
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- JP2002282684A JP2002282684A JP2001094350A JP2001094350A JP2002282684A JP 2002282684 A JP2002282684 A JP 2002282684A JP 2001094350 A JP2001094350 A JP 2001094350A JP 2001094350 A JP2001094350 A JP 2001094350A JP 2002282684 A JP2002282684 A JP 2002282684A
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- lithium
- water
- porous granular
- producing
- forming agent
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、リチウムに対する
選択吸着性が優れ、かつ吸着速度及び吸着容量が大き
く、水溶液中で安定で、かつ安価な多孔質粒状リチウム
吸着剤を製造するための新規な方法に関するものであ
る。The present invention relates to a novel porous granular lithium adsorbent which is excellent in selective adsorption to lithium, has a high adsorption rate and adsorption capacity, is stable in an aqueous solution, and is inexpensive. It is about the method.
【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、電池などの原料と
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、核融合燃料などの重要な原料である
が、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。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, and batteries. In the future, lithium will be used as an important material for large-capacity batteries, aluminum alloy materials, fusion fuels, and the like. Although it is a raw material, there is no lithium ore resource in Japan, and at present the lithium metal and its compounds are entirely imported.
【０００３】一方、海水、地下かん水及び地熱水などに
は微量のリチウムが含まれており、それらからリチウム
を効率よく回収する技術について、以前から研究が続け
られている。そして、これまでそれらリチウムを含む希
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、これらの方法は、エ
ネルギー面や設備面でコストがかかり、経済的に問題が
あるため、現在では吸着法が主流になりつつある。その
ため、リチウムに対し高い選択吸着性を示し、かつ吸着
速度及び吸着容量の大きい吸着剤の開発が強く要望され
ている。[0003] On the other hand, seawater, underground brackish water, geothermal water, and the like contain a trace amount of lithium, and research on a technique for efficiently recovering lithium therefrom has been continued. As a method of recovering the lithium from a dilute solution containing the lithium, a coprecipitation method or an evaporation method has been proposed. However, these methods are costly in terms of energy and equipment, and are economical. The adsorption method is now becoming mainstream due to problems in terms of quality. Therefore, there is a strong demand for the development of an adsorbent which exhibits high selective adsorption to lithium and has a large adsorption rate and a large adsorption capacity.
【０００４】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［「Ｈｙｄｒｏｍｅｔａｌｌｕｒｇｙ」，第１２
巻，第８３ページ（１９８４）］などが知られている
が、吸着速度及び吸着量が低く、実用的ではない。Conventionally, lithium adsorbents include thorium arsenate [“J. Inorg. Nucl. Chem.”, Vol. 32, p. 1719 (1970)] and tin antimonate [“Hydrometallurgy”, twelfth.
Vol. 83, p. 1984] is not practical because the adsorption speed and the adsorption amount are low.
【０００５】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（特開昭６
１−１７１５３５号公報）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（特開昭６３−６２５４６号公報）、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
きいという長所はあるが、実用化するには、まだ十分な
性能には達していない。Further, a lithium adsorbent obtained by subjecting a heat-treated lithium-containing manganese oxide to acid treatment (Japanese Patent Application Laid-Open No.
And a composite lithium adsorbent prepared by eluting magnesium with an acid from a heat-treated manganese-aluminum composite oxide containing magnesium (JP-A-63-62546). These adsorbents have the advantage of selectively adsorbing lithium from seawater and have a large amount of adsorption, but have not yet achieved sufficient performance for practical use.
【０００６】さらに、吸着剤とリチウム希薄溶液とを効
果的に吸着処理するために粉末状吸着剤が提案されてい
るが（特許第１８８８３６１号）、このものは、粒径が
大きくなると吸着速度が低下し、また吸着性能が不十分
になるという欠点がある。Further, a powdery adsorbent has been proposed for effectively adsorbing an adsorbent and a dilute lithium solution (Japanese Patent No. 1888361). However, this adsorbent has an increased adsorption speed as the particle size increases. However, there is a disadvantage that the adsorption performance is insufficient.
【０００７】したがって、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の、
リチウムに対する選択吸着性に優れ、かつ吸着速度や吸
着容量が大きく、しかも希薄溶液中で安定である上、希
薄溶液の吸着処理が容易な形状を有する吸着剤の開発が
要望されている。Therefore, for practically adsorbing and recovering lithium from a dilute solution such as seawater containing lithium,
There is a demand for the development of an adsorbent that has excellent selective adsorption to lithium, has a large adsorption rate and adsorption capacity, is stable in a dilute solution, and has a shape that facilitates the adsorption treatment of a dilute solution.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、このような
事情のもとで、リチウムに対する選択吸着性が優れ、吸
着速度及び吸着容量が大きく、水溶液中で安定で、取り
扱いが容易なリチウム吸着剤を効率よく安価に製造する
方法を提供することを目的としてなされたものである。SUMMARY OF THE INVENTION Under such circumstances, the present invention provides a lithium adsorbent which is excellent in selective adsorption to lithium, has a high adsorption rate and adsorption capacity, is stable in an aqueous solution, and is easy to handle. The object of the present invention is to provide a method for producing an agent efficiently and at low cost.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、多孔質粒
状リチウム吸着剤の製造方法について鋭意研究を重ねた
結果、原料としてリチウム含有マンガン酸化物と水溶性
細孔形成剤と有機バインダーを用いて造粒し、この造粒
物から該水溶性細孔形成剤及びリチウムを溶出させるこ
とにより、前記機能を有する多孔質粒状リチウム吸着剤
が効率よく得られ、その目的を達成しうることを見出
し、この知見に基づいて本発明を完成するに至った。The present inventors have conducted intensive studies on a method for producing a porous granular lithium adsorbent. By using the granulated product and elute the water-soluble pore-forming agent and lithium from the granulated product, a porous granular lithium adsorbent having the above function can be efficiently obtained, and the object can be achieved. The present invention has been completed based on the findings.
【００１０】すなわち、本発明は、リチウム含有マンガ
ン酸化物粉末と水溶性細孔形成剤粉末と有機バインダー
とを混合し、造粒したのち、得られた粒状物を水中に投
入し、水溶性細孔形成剤を溶出させ、次いで酸性水溶液
と接触させてリチウムを溶出させることを特徴とする多
孔質粒状リチウム吸着剤の製造方法を提供するものであ
る。That is, according to the present invention, a lithium-containing manganese oxide powder, a water-soluble pore-forming agent powder and an organic binder are mixed and granulated, and the obtained granules are poured into water to form a water-soluble fine powder. It is intended to provide a method for producing a porous granular lithium adsorbent characterized by eluting a pore-forming agent and then contacting it with an acidic aqueous solution to elute lithium.
【００１１】[0011]
【発明の実施の形態】本発明の多孔質粒状リチウム吸着
剤の製造方法においては、原料としてリチウム含有マン
ガン酸化物、水溶性細孔形成剤及び有機バインダーが用
いられる。前記リチウム含有マンガン酸化物としては、
特に制限はないが、例えば、一般式 Ｌｉ1+xＭｎ2-xＯ4 （式中のｘは０≦ｘ＜１）で表わされる化合物を用いる
ことができる。このような化合物の好ましいものとして
は、Ｌｉ1.33Ｍｎ1.67Ｏ4やＬｉＭｎ2Ｏ4などを含むも
のが挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION In the method for producing a porous granular lithium adsorbent of the present invention, a lithium-containing manganese oxide, a water-soluble pore-forming agent and an organic binder are used as raw materials. As the lithium-containing manganese oxide,
Although there is no particular limitation, for example, a compound represented by the general formula Li 1 + x Mn 2-x O 4 (where x is 0 ≦ x <1) can be used. Preferred examples of such compounds include those containing Li 1.33 Mn 1.67 O 4 and LiMn 2 O 4 .
【００１２】これらのリチウム含有マンガン酸化物は公
知であり、従来知られている任意の方法、例えば、炭酸
リチウムや硝酸リチウムなどのリチウム化合物と、水酸
化酸化マンガンや炭酸マンガンなどのマンガン化合物を
所定の割合で混合し、３５０℃以上の温度で数時間程度
加熱処理する固相反応法により、調製することができ
る。These lithium-containing manganese oxides are known. For example, a lithium compound such as lithium carbonate or lithium nitrate and a manganese compound such as manganese hydroxide oxide or manganese carbonate can be prepared by any known method. , And heat-treated at a temperature of 350 ° C. or more for about several hours.
【００１３】また、水溶性細孔形成剤としては、アルカ
リ金属のハロゲン化物、炭酸塩、炭酸水素塩、硝酸塩、
硫酸塩及びリン酸塩のような水溶性無機塩が好ましい
が、その他の水溶性発泡剤も用いることができる。これ
らは１種を単独で用いてもよいし、２種以上を組み合わ
せて用いてもよい。The water-soluble pore-forming agents include alkali metal halides, carbonates, bicarbonates, nitrates, and the like.
Water-soluble inorganic salts such as sulfates and phosphates are preferred, but other water-soluble blowing agents can be used. One of these may be used alone, or two or more may be used in combination.
【００１４】本発明においては、前記のリチウム含有マ
ンガン酸化物及び水溶性細孔形成剤は、それぞれ粉末の
形態で用いられる。リチウム含有マンガン酸化物粉末の
粒径としては、特に制限はないが、平均粒径が通常０．
１〜１０μｍ、好ましくは１〜１０μｍの範囲にあるも
のが有利である。水溶性細孔形成剤の粒径は、得られる
多孔質粒状リチウム吸着剤の細孔径の点から、好ましく
は０．１〜１００μｍの範囲、より好ましくは１〜１０
０μｍの範囲である。また、平均粒径は、通常１〜７０
μｍ、好ましくは１０〜５０μｍの範囲である。In the present invention, each of the lithium-containing manganese oxide and the water-soluble pore-forming agent is used in the form of a powder. The particle size of the lithium-containing manganese oxide powder is not particularly limited, but the average particle size is usually 0.1.
Those having a range of 1 to 10 μm, preferably 1 to 10 μm are advantageous. The particle size of the water-soluble pore-forming agent is preferably in the range of 0.1 to 100 µm, more preferably 1 to 10 from the viewpoint of the pore size of the obtained porous granular lithium adsorbent.
The range is 0 μm. The average particle size is usually 1 to 70.
μm, preferably in the range of 10 to 50 μm.
【００１５】次に、有機バインダーとしては特に制限は
ないが、熱可塑性樹脂が好ましい。この熱可塑性樹脂と
しては、例えばポリ塩化ビニル、アクリロニトリル系共
重合体、ポリスルホン、ポリアミドイミド、ポリエステ
ル、アセチルセルロースなどが挙げられる。これらは１
種を単独で用いてもよいし、２種以上を組み合わせて用
いてもよいが、これらの中で、特にポリ塩化ビニルが好
適である。The organic binder is not particularly limited, but is preferably a thermoplastic resin. Examples of the thermoplastic resin include polyvinyl chloride, acrylonitrile copolymer, polysulfone, polyamideimide, polyester, acetylcellulose and the like. These are 1
The seeds may be used alone or two or more kinds may be used in combination. Among them, polyvinyl chloride is particularly preferable.
【００１６】この有機バインダーは溶液として用いられ
る。この有機バインダー溶液の調製に使用される溶媒と
しては、前記熱可塑性樹脂を溶解しうる有機溶媒、例え
ばＮ，Ｎ‐ジメチルホルムアミド、アセトニトリル、ア
セトンシアンヒドリンなどが挙げられる。これらは単独
で用いてもよいし、２種以上を組み合わせて用いてもよ
い。This organic binder is used as a solution. Examples of the solvent used for preparing the organic binder solution include organic solvents capable of dissolving the thermoplastic resin, such as N, N-dimethylformamide, acetonitrile, and acetone cyanohydrin. These may be used alone or in combination of two or more.
【００１７】有機バインダー溶液の調製に、このような
有機溶媒を用いる場合、前記水溶性細孔形成剤として
は、塩化ナトリウム及び塩化カリウムが好適である。例
えば、温度１０〜３０℃におけるＮ，Ｎ‐ジメチルホル
ムアミドに対する塩化カリウムの溶解度は１〜２ｍｇ／
１００ｇ程度であり、塩化ナトリウムの溶解度は３〜５
ｍｇ／１００ｇ程度であって、極めて難溶性である。一
方、水に対する溶解度は、いずれも２７ｇ／１００ｇ以
上であり、易溶性である。有機バインダー溶液における
有機バインダーの濃度としては、通常５〜２０質量％の
範囲内で選ばれる。When such an organic solvent is used for preparing the organic binder solution, sodium chloride and potassium chloride are preferred as the water-soluble pore-forming agent. For example, the solubility of potassium chloride in N, N-dimethylformamide at a temperature of 10 to 30 ° C is 1 to 2 mg /
The solubility of sodium chloride is about 3 to 5
It is about mg / 100 g, and is extremely poorly soluble. On the other hand, the solubility in water is 27 g / 100 g or more in each case, and it is easily soluble. The concentration of the organic binder in the organic binder solution is usually selected within the range of 5 to 20% by mass.
【００１８】本発明方法においては、まず前記のリチウ
ム含有マンガン酸化物粉末と水溶性細孔形成剤粉末と有
機バインダーとを混合して造粒用組成物を調製する。こ
の際、各成分の使用割合については、水溶性細孔形成剤
粉末は、リチウム含有マンガン酸化物粉末１００質量部
当り、好ましくは１〜５０質量部、より好ましくは２〜
２０質量部の範囲で選ばれる。一方、有機バインダー
は、リチウム含有マンガン酸化物粉末１００質量部当
り、２〜４０質量部、好ましくは１０〜３０質量部の範
囲内で選ばれる。In the method of the present invention, first, a lithium-containing manganese oxide powder, a water-soluble pore-forming agent powder and an organic binder are mixed to prepare a granulation composition. At this time, as for the use ratio of each component, the water-soluble pore-forming agent powder is preferably 1 to 50 parts by mass, more preferably 2 to 100 parts by mass per 100 parts by mass of the lithium-containing manganese oxide powder.
It is selected in the range of 20 parts by mass. On the other hand, the organic binder is selected within the range of 2 to 40 parts by mass, preferably 10 to 30 parts by mass per 100 parts by mass of the lithium-containing manganese oxide powder.
【００１９】このようにして調製された混合物を、ゆっ
くりかきまぜられている凝固液中に徐々に滴下し、球状
に凝固させて造粒する。この際、凝固液としては、有機
バインダー中の有機溶媒に対し相容性を有するが、有機
バインダー及び水溶性細孔形成剤を実質上溶解しないも
のを用いることができる。このような凝固液としては、
例えば水とエチルアルコールとの等容量混合物などを挙
げることができる。このようにして形成された粒状物の
粒径は、通常０．５〜８ｍｍ、好ましくは１〜５ｍｍの
範囲である。The mixture thus prepared is gradually dropped into a slowly stirred coagulating liquid, and is coagulated into a sphere and granulated. At this time, as the coagulating liquid, a liquid which has compatibility with the organic solvent in the organic binder but does not substantially dissolve the organic binder and the water-soluble pore-forming agent can be used. As such a coagulating liquid,
For example, an equal volume mixture of water and ethyl alcohol can be used. The particle size of the granular material thus formed is usually in the range of 0.5 to 8 mm, preferably 1 to 5 mm.
【００２０】次いで、この粒状物を水中に投入して、該
粒状物中に含まれている水溶性細孔形成剤を溶出させ
る。この溶出操作は、該細孔形成剤が、実質上全部溶出
するまで繰り返し行うことができる。この溶出操作によ
り、多孔質粒状物が形成される。Next, the granules are put into water to elute the water-soluble pore-forming agent contained in the granules. This elution operation can be repeated until the pore-forming agent is substantially completely eluted. By this elution operation, a porous granular material is formed.
【００２１】次に、このようにして得られた多孔質粒状
物に酸性水溶液を接触させて、リチウムを溶出させる。
上記酸性水溶液としては、塩酸、硫酸、硝酸などの鉱酸
を含む、ｐＨ３以下の弱酸性水溶液が好ましい。このリ
チウムの溶出処理は、通常数時間以上、好ましくは２日
間以上行うのがよい。このようにしてリチウムの溶出処
理を行ったのち、十分に洗浄し、さらに乾燥処理するこ
とにより、多孔質粒状リチウム吸着剤が得られる。Next, an acidic aqueous solution is brought into contact with the porous granules thus obtained to elute lithium.
As the acidic aqueous solution, a weakly acidic aqueous solution containing a mineral acid such as hydrochloric acid, sulfuric acid, and nitric acid and having a pH of 3 or less is preferable. This lithium elution treatment is usually performed for several hours or more, preferably for two days or more. After performing the elution treatment of lithium in this way, by sufficiently washing and further drying, a porous granular lithium adsorbent can be obtained.
【００２２】このようにして得られた多孔質粒状リチウ
ム吸着剤は、通常内部まで０．１μｍ以上の細孔が多数
形成されており、水分子（直径０．２８ｎｍ）やリチウ
ムイオン（直径０．１４６ｎｍ）が容易に吸着サイトと
接触できる構造を有している。The porous granular lithium adsorbent thus obtained usually has a large number of pores of 0.1 μm or more formed inside, and water molecules (diameter 0.28 nm) and lithium ions (diameter 0. 8 nm). 146 nm).
【００２３】この多孔質粒状リチウム吸着剤は、蜂の巣
状形態を保っており、該粒状吸着剤の内部までリチウム
イオンが短時間に浸透できる。したがって、吸着速度が
大きく効果的にイオン交換が進行でき、海水のようなリ
チウム希薄溶液からでも吸着速度は大きい。This porous granular lithium adsorbent maintains a honeycomb shape, and lithium ions can permeate into the particulate adsorbent in a short time. Accordingly, the adsorption rate is large and the ion exchange can proceed effectively, and the adsorption rate is high even from a lithium-dilute solution such as seawater.
【００２４】[0024]
【実施例】次に、実施例により本発明をさらに詳細に説
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.
【００２５】実施例 水酸化酸化マンガンと炭酸リチウムを用いてリチウムと
マンガンの混合物（モル比８：１０）を調製した。これ
を粉砕したのち、るつぼにとり、４００℃で４時間加熱
処理して、リチウム含有マンガン酸化物を合成した。こ
のものはＸ線分析の結果、Ｌｉ1.33Ｍｎ1.67Ｏ4相が形
成されていることが確認された。Example A mixture of lithium and manganese (molar ratio: 8:10) was prepared using manganese hydroxide and lithium carbonate. After pulverized, the mixture was placed in a crucible and heat-treated at 400 ° C. for 4 hours to synthesize a lithium-containing manganese oxide. As a result of X-ray analysis, it was confirmed that a Li 1.33 Mn 1.67 O 4 phase was formed.
【００２６】このリチウム含有マンガン酸化物１０ｇ
に、水溶性細孔形成剤として、塩化カリウム（平均粒径
２８μｍ、粒子径１．５〜１００μｍ）０．５０ｇを加
え、混合機を用いて３０分間混合した。その混合物を１
０分割してそれぞれの組成中の塩化カリウムを定量した
結果、その混合比は４．７〜５．４質量％で均一性が認
められた。10 g of this lithium-containing manganese oxide
To the mixture was added 0.50 g of potassium chloride (average particle size: 28 μm, particle size: 1.5 to 100 μm) as a water-soluble pore-forming agent, and the mixture was mixed using a mixer for 30 minutes. The mixture is 1
As a result of quantifying potassium chloride in each composition by dividing it into 0 parts, the mixture ratio was 4.7 to 5.4% by mass and uniformity was recognized.
【００２７】ポリ塩化ビニル（重合度６８０）２．５ｇ
を３３ｍｌのＮ，Ｎ‐ジメチルホルムアミドに溶解した
のち、これに上記で得られた混合物１０ｇを加え、さら
に混合してスラリーを調製した。2.5 g of polyvinyl chloride (degree of polymerization 680)
Was dissolved in 33 ml of N, N-dimethylformamide, 10 g of the mixture obtained above was added thereto, and the mixture was further mixed to prepare a slurry.
【００２８】このスラリーをろ斗の下端に細管（内径１
ｍｍ）を取り付けたものに移し入れた。下部の凝固液
（水とエチルアルコールの等容混合液）４００ｍｌ中へ
毎分１００〜１５０滴の速度で滴下した。凝固液は約１
６０ｒｐｍで撹拌し、試料に回転運動を与えながら、球
状体に凝固させて造粒した。すなわち、ポリ塩化ビニル
の溶媒であるＮ，Ｎ‐ジメチルホルムアミドは多量の凝
固液と溶解混合するが、ポリ塩化ビニルは凝固液には不
溶性であるため固形物となり、有機バインダーとしての
役割を果す。This slurry is placed at the lower end of a funnel in a thin tube (with an inner diameter of 1).
mm). The solution was dropped at a rate of 100 to 150 drops per minute into 400 ml of the lower coagulating liquid (a mixture of equal volumes of water and ethyl alcohol). Coagulation liquid is about 1
The mixture was stirred at 60 rpm, and solidified into a spherical body and granulated while giving rotational movement to the sample. That is, N, N-dimethylformamide, which is a solvent for polyvinyl chloride, is dissolved and mixed with a large amount of coagulation liquid, but polyvinyl chloride is insoluble in the coagulation liquid and becomes a solid, thus serving as an organic binder.
【００２９】次に、この粒状物（粒径２．５〜３．５ｍ
ｍ）１０ｇを蒸溜水１リットルに入れ、撹拌して細孔形
成剤の塩化カリウムを溶出させた。１日後、新しい水１
リットルと取り替え、このような処理を３回繰り返した
結果、塩化カリウムの溶出率は９８％に達した。この処
理により多孔質粒状物を調製することができた。Next, the granules (particle size: 2.5 to 3.5 m)
m) 10 g was placed in 1 liter of distilled water and stirred to elute potassium chloride as a pore-forming agent. One day later, new water 1
The treatment was repeated three times, and the elution rate of potassium chloride reached 98%. By this treatment, a porous granular material could be prepared.
【００３０】この多孔質粒状物５ｇを０．５モル／リッ
トル濃度の塩酸溶液１リットル中に入れ、２日間浸漬し
てリチウムを溶出させた。それを分離したのち、水洗、
乾燥（７０℃）して多孔質粒状リチウム吸着剤を製造し
た。5 g of this porous granular material was placed in 1 liter of a 0.5 mol / liter hydrochloric acid solution and immersed for 2 days to elute lithium. After separating it, wash with water,
After drying (70 ° C.), a porous granular lithium adsorbent was produced.
【００３１】前記多孔質粒状物及び多孔質粒状リチウム
吸着剤の表面部と断面部について走査電子顕微鏡で観察
した。その結果、いずれも１〜１００μｍ程度の細孔と
考えられる黒色の点が無数観察された。その分布は均質
であり、本発明により粒状体内部まで多孔構造が形成さ
れていることが認められた。The surface and cross section of the porous granular material and porous granular lithium adsorbent were observed with a scanning electron microscope. As a result, countless black points, which are considered to be pores of about 1 to 100 μm, were observed. The distribution was homogeneous, and it was confirmed that a porous structure was formed up to the inside of the granular material according to the present invention.
【００３２】前記多孔質粒状リチウム吸着剤（粒径２．
５〜３．５ｍｍ）を内径２ｃｍのカラムに入れ、天然海
水（リチウム濃度１７０ｐｐｂ）を空間速度４００ｈ-1
の条件で通水した。吸着時間１５日及び３０日でのリチ
ウム吸着量は５ｍｇ／ｇ及び８ｍｇ／ｇであった。The porous granular lithium adsorbent (particle size: 2.
5 to 3.5 mm) in a column having an inner diameter of 2 cm, and natural seawater (lithium concentration 170 ppb) at a space velocity of 400 h -1.
Water was passed under the following conditions. The lithium adsorption amounts at the adsorption time of 15 days and 30 days were 5 mg / g and 8 mg / g.
【００３３】比較例 実施例と同じリチウム含有マンガン酸化物を用い、かつ
水溶性細孔形成剤を使用しなかったこと以外は、実施例
に準拠して粒状リチウム吸着剤を製造した。この粒状吸
着剤（粒径２．５〜３．５ｍｍ）について、天然海水を
用いて実施例と同様な条件で吸着実験を行った。吸着時
間１５日及び３０日でのリチウム吸着量は２ｍｇ／ｇ及
び４ｍｇ／ｇであった。Comparative Example A granular lithium adsorbent was produced according to the example except that the same lithium-containing manganese oxide as in the example was used and no water-soluble pore-forming agent was used. About this granular adsorbent (particle diameter of 2.5 to 3.5 mm), an adsorption experiment was performed using natural seawater under the same conditions as in the example. The lithium adsorption amounts at adsorption times of 15 days and 30 days were 2 mg / g and 4 mg / g.
【００３４】実施例のように多孔化処理を行った吸着剤
は無処理吸着剤に比べてリチウム吸着量は大きく、その
吸着速度は約２倍に向上した。このように本発明の多孔
質粒状リチウム吸着剤は優れた性能を示した。このこと
から、本発明の多孔質粒状リチウム吸着剤は、海水のよ
うな低濃度リチウム溶液から容易にリチウムを回収でき
ることは明らかである。The adsorbent which has been subjected to the porous treatment as in the example has a larger lithium adsorption amount than the untreated adsorbent, and the adsorption speed is improved about twice. Thus, the porous granular lithium adsorbent of the present invention showed excellent performance. From this, it is clear that the porous granular lithium adsorbent of the present invention can easily recover lithium from a low-concentration lithium solution such as seawater.
【００３５】[0035]
【発明の効果】本発明方法で製造した多孔質粒状リチウ
ム吸着剤は、吸着剤内部まで無数の微細孔構造を保って
いるため、吸着速度及び吸着容量が極めて大きく、しか
もリチウムに対する選択吸着性に優れ、水溶液中で安定
であり、実用的な吸着剤である。本発明に係る多孔質粒
状リチウム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 porous granular lithium adsorbent produced by the method of the present invention maintains an infinite number of microporous structures inside the adsorbent, so that the adsorption speed and the adsorption capacity are extremely large, and the selective adsorbability to lithium is improved. Excellent, stable in aqueous solution, and practical. By using the porous granular lithium adsorbent according to the present invention, the lithium can be extremely efficiently and economically recovered from a dilute solution.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 チトラカー ラメシュ 香川県高松市林町2217番14 経済産業省産 業技術総合研究所四国工業技術研究所内 (72)発明者 加納 博文 香川県高松市林町2217番14 経済産業省産 業技術総合研究所四国工業技術研究所内 (72)発明者 大井 健太 香川県高松市林町2217番14 経済産業省産 業技術総合研究所四国工業技術研究所内 Ｆターム(参考） 4G066 AA13A AA14D AA26A AA26B AA32A AA33A AA34D AA43A AA47A AA50A AA53A AC15D BA22 CA45 DA07 FA03 FA11 FA12 FA21 FA22 FA26 FA34 FA37 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Chitracar Ramesh 22217-14, Hayashi-cho, Takamatsu-shi, Kagawa Prefecture Within Shikoku Institute of Industrial Technology, National Institute of Advanced Industrial Science and Technology (72) Inventor Hirofumi Kano Hayashi-cho, Takamatsu-shi, Kagawa 2217-14 Ministry of Economy, Trade and Industry, National Institute of Advanced Industrial Science and Technology (Shikoku Industrial Technology Research Institute) Reference) 4G066 AA13A AA14D AA26A AA26B AA32A AA33A AA34D AA43A AA47A AA50A AA53A AC15D BA22 CA45 DA07 FA03 FA11 FA12 FA21 FA22 FA26 FA34 FA37
Claims (8)
性細孔形成剤粉末と有機バインダーとを混合し、造粒し
たのち、得られた粒状物を水中に投入し、水溶性細孔形
成剤を溶出させ、次いで酸性水溶液と接触させてリチウ
ムを溶出させることを特徴とする多孔質粒状リチウム吸
着剤の製造方法。1. A method comprising mixing a lithium-containing manganese oxide powder, a water-soluble pore-forming agent powder, and an organic binder, granulating the mixture, and pouring the obtained granules into water to form a water-soluble pore-forming agent. A method for producing a porous granular lithium adsorbent, which comprises eluted and then contacted with an acidic aqueous solution to elute lithium.
求項１記載の多孔質粒状リチウム吸着剤の製造方法。2. The porous granular material according to claim 1, wherein the lithium-containing manganese oxide is a compound represented by a general formula: Li 1 + x Mn 2-x O 4 (where x is 0 ≦ x <1). A method for producing a lithium adsorbent.
請求項１又は２記載の多孔質粒状リチウム吸着剤の製造
方法。3. The method for producing a porous granular lithium adsorbent according to claim 1, wherein the water-soluble pore-forming agent is a water-soluble inorganic salt.
化物、炭酸塩、炭酸水素塩、硝酸塩、硫酸塩及びリン酸
塩の中から選ばれた少なくとも１種である請求項３記載
の多孔質粒状リチウム吸着剤の製造方法。4. The porous granular material according to claim 3, wherein the water-soluble inorganic salt is at least one selected from halides, carbonates, bicarbonates, nitrates, sulfates and phosphates of alkali metals. A method for producing a lithium adsorbent.
チウム含有マンガン酸化物粉末１００質量部当り、１〜
５０質量部の範囲で選ばれる請求項１ないし４のいずれ
かに記載の多孔質粒状リチウム吸着剤の製造方法。5. The use ratio of the water-soluble pore-forming agent powder is 1 to 100 parts by mass of the lithium-containing manganese oxide powder.
The method for producing a porous granular lithium adsorbent according to any one of claims 1 to 4, which is selected in a range of 50 parts by mass.
請求項１ないし５のいずれかに記載の多孔質粒状リチウ
ム吸着剤の製造方法。6. The method for producing a porous granular lithium adsorbent according to claim 1, wherein the organic binder is a thermoplastic resin.
請求項６記載の多孔質粒状リチウム吸着剤の製造方法。7. The method for producing a porous granular lithium adsorbent according to claim 6, wherein the thermoplastic resin is polyvinyl chloride.
含有マンガン酸化物１００質量部当り、２〜４０質量部
の範囲で選ばれる請求項１ないし７のいずれかに記載の
多孔質粒状リチウム吸着剤の製造方法。8. The porous particulate lithium adsorbent according to claim 1, wherein the proportion of the organic binder used is selected in the range of 2 to 40 parts by mass per 100 parts by mass of the lithium-containing manganese oxide. Production method.
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