JPH01203039A - Adsorbent indicating new lithium selectivity and manufacture thereof - Google Patents
Adsorbent indicating new lithium selectivity and manufacture thereofInfo
- Publication number
- JPH01203039A JPH01203039A JP2827188A JP2827188A JPH01203039A JP H01203039 A JPH01203039 A JP H01203039A JP 2827188 A JP2827188 A JP 2827188A JP 2827188 A JP2827188 A JP 2827188A JP H01203039 A JPH01203039 A JP H01203039A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- adsorbent
- li2tio3
- adsorption
- acidic solution
- 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.)
- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 47
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000003463 adsorbent Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000003929 acidic solution Substances 0.000 claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 22
- 229910007848 Li2TiO3 Inorganic materials 0.000 abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract description 3
- 150000007513 acids Chemical class 0.000 abstract description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 2
- 239000011707 mineral Substances 0.000 abstract description 2
- 150000007524 organic acids Chemical class 0.000 abstract description 2
- 235000005985 organic acids Nutrition 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 150000003609 titanium compounds Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- -1 batteries Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は新規なリチウム選択性を示す吸着剤及びその製
造方法に関するものである。さらに詳しくいえば、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
量や吸着速度が大きく、その上希薄溶液中で安定であっ
て、毒性の少ない安価な吸着剤及びその製造方法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a novel adsorbent exhibiting lithium selectivity and a method for producing the same. More specifically, the present invention relates to an inexpensive adsorbent that has excellent selective adsorption for lithium, has a large adsorption capacity and adsorption rate, is stable in dilute solutions, and has low toxicity, and a method for producing the same. It is.
従来の技術
近年、リチウム金属及びその化合物は、多くの分野、例
えばセラミックス、電池、冷媒吸着剤、医薬品などに用
いられておシ、また将来、大容量電池、アルミニウム合
金材料、核融合燃料などとしての利用が考えられること
から、リチウムの需要の著しい増大が見込まれている〔
「日本鉱業会誌」第９７巻、第２２１ページ〕。BACKGROUND OF THE INVENTION In recent years, lithium metal and its compounds have been used in many fields, such as ceramics, batteries, refrigerant adsorbents, and pharmaceuticals, and in the future, they will be used in large-capacity batteries, aluminum alloy materials, nuclear fusion fuels, etc. Demand for lithium is expected to increase significantly due to the potential use of lithium.
“Journal of the Japan Mining Association,” Volume 97, Page 221].
前記リチウム金属及びその化合物は、現在上としてスポ
ジューメン、アングリコナイト、ベターライト、レビド
ライトなどのリチウム含有鉱石、及びリチウム濃度の高
い塩湖や地下かん水などを原料として製造されている。The lithium metal and its compounds are currently produced using lithium-containing ores such as spodumene, angliconite, betterite, and levidolite, and salt lakes and underground brine with high lithium concentration as raw materials.
しかるに、わが国においては、前記のようなリチウム鉱
石資源がなく、リチウム金属やその化合物は全量輸入に
依存しているのが現状である。−方、わが国の地熱水や
温泉水にはかなシのリチウムを含有するものがあり、ま
た周囲をとシまく海洋中にも微量のリチウムが含まれて
いる。したがって、これらのリチウムを含む希薄溶液か
ら該リチウムを効率よく回収する技術を確立することが
強く要望されている。However, our country does not have the above-mentioned lithium ore resources, and currently relies entirely on imports for lithium metal and its compounds. - On the other hand, some geothermal water and hot spring water in Japan contain small amounts of lithium, and trace amounts of lithium are also contained in the surrounding oceans. Therefore, it is strongly desired to establish a technique for efficiently recovering lithium from these dilute solutions containing lithium.
ところで、チタン酸化物については、これまで種々の結
晶形態のものが知られておシ、例えば天然鉱石として、
ルチル、アナタース、プルカイトなどがあるが、これら
はいずれもリチウム吸着性を示さない。また、最近、層
状のチタン酸アルカリを酸処理し、アルカリ金属イオン
を溶出させて成る層状のチタン酸化物が報告されている
〔「窯業協会誌」第９４巻、第６２１ページ（１９８６
年〕〕。By the way, titanium oxide has been known in various crystal forms, for example, as a natural ore,
There are rutile, anatase, pulchite, etc., but none of these exhibit lithium adsorption properties. In addition, a layered titanium oxide produced by acid-treating a layered alkali titanate to elute alkali metal ions has recently been reported [Ceramic Industry Association Journal, Vol. 94, p. 621 (1986
Year〕〕.
しかしながら、このものはリチウム吸着性を示すものの
、ナトリウムやカリウムに対する選択性が十分に高くな
いため、海水のようにすＩ−ＩＪウムやカリウムがリチ
ウムと共に大量に共存する場合には、リチウム用吸着剤
としては不適である。However, although this material exhibits lithium adsorption properties, its selectivity for sodium and potassium is not sufficiently high, so when a large amount of I-IJum and potassium coexist with lithium, such as in seawater, it is difficult to adsorb lithium. It is unsuitable as a drug.
発明が解決しようとする課題
本発明は、リチウムに対する選択吸着性に優れ、かつ吸
着容量や吸着速度が大きい上に、希薄溶液中で安定であ
って、毒性が少なく、しかも製造コストの低い新規な吸
着剤を提供することを目的としてなされたものである。Problems to be Solved by the Invention The present invention provides a novel material that has excellent selective adsorption for lithium, has a large adsorption capacity and adsorption rate, is stable in dilute solutions, has little toxicity, and is low in production cost. This was done for the purpose of providing an adsorbent.
課題を解決するための手段
本発明者らは、先に原料としてＭｇ２ＭｎＯ４を用い、
これを酸処理することによシ、リチウム選択吸着性の優
れたマンガン酸化物を得ることに成功したが、本発明者
らは、リチウムとチタンの複合酸化物についても同じよ
うに研究を進めた結果、Ｌｉ２ＴｉＪ を原料として用
い、これを酸処理して、その中のリチウムを溶出させる
ことにより、前記目的を達成しうろことを見い出し、こ
の知見に基づいて本発明を完成するに至った。Means for Solving the Problems The present inventors first used Mg2MnO4 as a raw material,
By treating this with acid, we succeeded in obtaining manganese oxide with excellent lithium selective adsorption properties, but the present inventors also conducted research on composite oxides of lithium and titanium in the same way. As a result, it was discovered that the above object could be achieved by using Li2TiJ as a raw material and treating it with acid to elute the lithium therein. Based on this knowledge, the present invention was completed.
すなわち、本発明は、Ｌｉ２ＴｉＯ３の酸処理物であっ
て、リチウム選択性を示し、かつ主要なＸ線回折ピーク
が、
４．７４±０．０３ 強
４．５４±０．０３ 中
２．４６±０．０５中
１．７２±０．０３弱
１．５２±０．０３ 弱
であるチタン酸化物系吸着剤を提供するものである。That is, the present invention is an acid-treated product of Li2TiO3, which exhibits lithium selectivity and whose main X-ray diffraction peaks are: 4.74±0.03 strong 4.54±0.03 medium 2.46± The present invention provides a titanium oxide-based adsorbent that has a strength of 1.72±0.03 of 0.05 and 1.52±0.03 of 0.05.
このものは、Ｌｉ２ＴｉＯ３をｐＨ５以下の酸性溶液で
処理し、その中のリチウムを溶出させることにより、製
造することができる。This material can be produced by treating Li2TiO3 with an acidic solution having a pH of 5 or less and eluting the lithium therein.
本発明において原料として用いられるＬｉ２ＴｉＯ３は
１２例えばＬｉ２００３とＴｌＯ２とをモル比１：ｌの
割合で混合して、約８００℃の温度で数時間加熱処理す
ることによシ、あるいはリチウムの水酸化物、酸化物、
重炭酸塩、硝酸塩、ハロゲン化物などと、チタンの含水
酸化物、酸化物、硝酸塩、ハロゲン化物などとを適当な
組合せで混合したのち、４００℃以上の温度で加熱処理
することにより、製造することができる。この際、初期
混合物中のリチウム量としては、チタンの２倍モル以上
存在する必要がある。２倍モル未満の場合には、異なっ
た結晶形態の化合物、例えばＬｉ、、Ｔｉ、、６，０４
、アナタース、ルチルなどが生成するため、リチウム吸
着性が著しく低下する。Li2TiO3 used as a raw material in the present invention can be prepared by mixing 12, for example, Li2003 and TlO2 at a molar ratio of 1:1, and heating the mixture at a temperature of about 800°C for several hours, or by preparing lithium hydroxide. , oxide,
Produced by mixing bicarbonates, nitrates, halides, etc. with hydrous oxides, oxides, nitrates, halides, etc. of titanium in an appropriate combination, and then heating the mixture at a temperature of 400°C or higher. Can be done. At this time, the amount of lithium in the initial mixture needs to be at least twice the mole of titanium. If the amount is less than 2 times the molar amount, compounds with different crystal forms, such as Li, Ti, 6,04
, anatase, rutile, etc., resulting in a significant decrease in lithium adsorption.
本発明においては、前記Ｌｉ２ＴｉＯ３はｐＨ５以下の
酸性溶液で処理され、その中のリチウムが溶出される。In the present invention, the Li2TiO3 is treated with an acidic solution having a pH of 5 or less, and lithium therein is eluted.
この酸性溶液は、例えば塩酸、硫酸、硝酸、リン酸など
の鉱酸や、ギ酸、酢酸などの有機酸を用いて、ｐＨ５以
下、好ましくは２以下になるように調製される。前記酸
はそれぞれ単独で用いてもよいし、２種以上を混合して
用いてもよい。This acidic solution is prepared to have a pH of 5 or less, preferably 2 or less, using a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid, or an organic acid such as formic acid or acetic acid. The above acids may be used alone or in combination of two or more.
リチウムの溶出処理は、前記酸性溶液中に、原料のＬｉ
２ ＴｉＯ３を通常室温において１時間以上、好１し
くけ数日間浸せきし、かきまぜることにょシ行われる。In the lithium elution treatment, the raw material Li is added to the acidic solution.
2 TiO3 is usually soaked at room temperature for at least 1 hour, preferably for several days, and then stirred.
このようにしてリチウムを溶出させたのち、固形物を通
常用いられている手段にょシ取り出し、水洗後、好１し
くけ７０℃以下の温度において乾燥することによシ、所
望の吸着剤が得られる。After eluting the lithium in this way, the solid material is taken out by a commonly used means, washed with water, and dried preferably at a temperature below 70°C to obtain the desired adsorbent. It will be done.
この吸着剤のＸ線回折特性を下記に示す。なお、比較上
し７ＡＳＴＭカードＡ３３ ８３１記載（Ｄ Ｌｉ２Ｔ
ｉＯ３のＸ線回折特性を併記する。The X-ray diffraction characteristics of this adsorbent are shown below. For comparison, 7ASTM card A33 831 (D Li2T
The X-ray diffraction characteristics of iO3 are also shown.
本発明の吸着剤 Ｌｉ２Ｔｉ０５（ＡＳ
Ｔ ３３−８３１）
４．７４ 強 ４．８０
強４．５４ 中 ４．３４
弱２．４６ 中
２．５０ 中ｔ、２３
巷；春春 中 ２．０７
強１．７２ 弱 １．９
０ 弱１．５２ 弱
１．６０ 弱１．４７中
このように、本発明の吸着剤は、出発原料のＬｉ２Ｔｉ
Ｏ３とほとんど同様なＸａ回折特性を示すが、該吸着剤
と原料Ｌｉ２ＴｉＯ３のＸ線回折特性の相違点は、チタ
ンの新規な形態の形成に際して、わずかにピーク位置の
変化がみられることである。Adsorbent of the present invention Li2Ti05 (AS
T 33-831) 4.74 strong 4.80
Strong 4.54 Medium 4.34
Weak 2.46 Medium
2.50 Middle T, 23rd Street; Spring Spring Middle 2.07
Strong 1.72 Weak 1.9
0 Weak 1.52 Weak
1.60 weak 1.47 In this way, the adsorbent of the present invention has a starting material of Li2Ti
Although it exhibits almost the same Xa diffraction characteristics as O3, the difference between the X-ray diffraction characteristics of the adsorbent and the raw material Li2TiO3 is that there is a slight change in the peak position when a new form of titanium is formed.
発明の効果
本発明の吸着剤は、リチウムの吸着に適した微細孔を有
しており、リチウムに対する選択吸着性に優れ、かつ吸
着速度及び吸着容量が犬きく、しかも毒性がなく、水溶
液中で安定であることから、希薄溶液、例えば海水や地
熱水などから、効率よくリチウムを回収することができ
る。また、本発明の吸着剤は、リチウム以外の有用物質
回収用吸着剤や有害物質除去用吸着剤などとしても用い
ることができる。さらに、本発明の吸着剤として用いら
れるチタン化合物は、電池活性電極材料などとしても使
用することができる。Effects of the Invention The adsorbent of the present invention has micropores suitable for adsorbing lithium, has excellent selective adsorption for lithium, has excellent adsorption rate and adsorption capacity, is non-toxic, and can be used in aqueous solutions. Because it is stable, lithium can be efficiently recovered from dilute solutions such as seawater and geothermal water. Further, the adsorbent of the present invention can be used as an adsorbent for recovering useful substances other than lithium, an adsorbent for removing harmful substances, and the like. Furthermore, the titanium compound used as the adsorbent of the present invention can also be used as a battery active electrode material.
実施例 次に実施例によシ本発明をさらに詳細に説明する。Example Next, the present invention will be explained in more detail with reference to Examples.
実施例１
アナタース型含水酸化チタン（表面積２００ ｔｒ？／
り）と炭酸リチウムとを、Ｌｉ ： Ｔｉ原子比が２：
１となるように混合したのち、８００℃で４時間加熱処
理して、Ｌｉ２ＴｉＯ３を調製した。この加熱処理物１
りを０．２Ｎ塩酸溶液３を中に加えて、ｌＯ日日間きま
ぜたのち、生成物をろ別し、洗浄後、７０℃で乾燥して
吸着剤を調製した。第１表に得られた加熱処理物及び吸
着剤のＸ線回折特性を示す。なお、比較のために、ＡＳ
ＴＭカード３３−８３１記載のＬｉ２ＴｉＯ３のＸ線回
折特性を示す。Example 1 Anatase type hydrated titanium oxide (surface area 200 tr?/
Li) and lithium carbonate at a Li:Ti atomic ratio of 2:
1, and then heat-treated at 800° C. for 4 hours to prepare Li2TiO3. This heat treated product 1
After adding 0.2N hydrochloric acid solution 3 to the mixture and stirring for 10 days, the product was filtered, washed, and dried at 70°C to prepare an adsorbent. Table 1 shows the X-ray diffraction characteristics of the heat-treated product and adsorbent. For comparison, AS
The X-ray diffraction characteristics of Li2TiO3 described in TM Card 33-831 are shown.
第 １ 表
加熱処理物（Ｌｉ２Ｔｉ０５）のＸ線回折特性は、ＡＳ
ＴＭカード記載のものと極めてよく一致した。Table 1 The X-ray diffraction characteristics of the heat-treated product (Li2Ti05) are as follows:
It matched extremely well with what was written on the TM card.
また、本発明の吸着剤は、Ｌｉ２ＴｉＯ３と比較して、
わずかながら面間隔が変化しているが、元の構造を維持
していることは明らかである。Furthermore, compared to Li2TiO3, the adsorbent of the present invention has
Although the interplanar spacing has changed slightly, it is clear that the original structure is maintained.
第２表に、これらのチタン化合物のリチウム含量を示す
。本発明の吸着剤は、Ｌｉ２ＴｉＯ３よりすチウム含量
が著しく少なく、極めて微細な空隙をもつ新規な吸着剤
であることは明らかである。Table 2 shows the lithium content of these titanium compounds. It is clear that the adsorbent of the present invention is a novel adsorbent with a significantly lower lithium content than Li2TiO3 and extremely fine voids.
第 ２ 表
実施例２
実施例１において調製した吸着剤について、０．２Ｍ
ＮＨ４Ｃｌ−０，２Ｍ ＮＨ３緩衝溶液（ｐＨ８，３）
中における、リチウム、ナトリウム、カリウムの吸着性
を調べた。Table 2 Example 2 For the adsorbent prepared in Example 1, 0.2M
NH4Cl-0.2M NH3 buffer solution (pH 8.3)
The adsorption properties of lithium, sodium, and potassium were investigated.
すなわち、吸着剤５０ｍｇを、それぞれ１ ｍ Ｍの濃
度でリチウム、ナトリウム及びカリウムを含む緩衝溶液
１５ゴに加え、７日間かき筐ぜた。吸着前後のアルカリ
金属イオン濃度を原子吸光法で定量し、吸着率を求めた
。結果を第３表に示す。That is, 50 mg of the adsorbent was added to 15 g of a buffer solution containing lithium, sodium, and potassium at a concentration of 1 mM each, and stirred for 7 days. The alkali metal ion concentration before and after adsorption was determined by atomic absorption spectrometry to determine the adsorption rate. The results are shown in Table 3.
第 ３ 表
この結果から、本発明の吸着剤は、リチウム選択吸着性
が優れていることは明らかである。Table 3 From the results, it is clear that the adsorbent of the present invention has excellent lithium selective adsorption properties.
比較例
アナタース型含水酸化チタンと炭酸リチウムとを、Ｌｉ
： Ｔｉ原子比が、それぞれ帆５：１、ｌ：ｌとなる
ように混合したのち、８００℃で４時間加熱処理した。Comparative Example Anatase-type hydrous titanium oxide and lithium carbonate were
: They were mixed so that the Ti atomic ratios were 5:1 and 1:1, respectively, and then heat-treated at 800° C. for 4 hours.
Ｌｉ： Ｔｉ原子比が０．５ ： １の場合、加熱処理
物はルチルとＬｉ１．Ｈ”１．６６０４の混合物となり
、Ｌｉ ： Ｔｉ原子比がｌ二ｌの場合、加熱処理物は
主にＬ １ ｒ 、ａｓ Ｔ Ｉ １．６ｓ Ｏ４とな
った。When the Li:Ti atomic ratio is 0.5:1, the heat-treated product contains rutile and Li1. When the Li:Ti atomic ratio was 121, the heat-treated product was mainly L 1 r , as T I 1.6s O4.
これらの加熱処理物それぞれ１２を０．５Ｎ塩酸溶液３
を中に加えて、ＩＯ日日間きまぜたのち、生成物をろ別
し、洗浄後７０℃で乾燥してチタン化合物を調製した。12 of each of these heat-treated products was mixed with 3 of a 0.5N hydrochloric acid solution.
After stirring for 10 days, the product was filtered, washed, and dried at 70°C to prepare a titanium compound.
これらチタン化合物それぞれ５０■を、実施例２と同じ
緩衝溶液１５ｍｔ中に加え、７日間かきまぜて、リチウ
ム、ナトリウム、カリウムの吸着性を調べた。その結果
を第４表に示す。50 μ of each of these titanium compounds were added to 15 mt of the same buffer solution as in Example 2, stirred for 7 days, and the adsorption properties of lithium, sodium, and potassium were examined. The results are shown in Table 4.
第 ４ 表
この結果から、リチウム選択吸着性を示さないことは明
らかである。Table 4 From the results, it is clear that lithium selective adsorption is not exhibited.
Claims (1)
選択性を示し、かつ次に示すＸ線回折ピークを有する吸
着剤。 面間隔（Å）：相対強度 ４．７４±０．０３：強 ４．５４±０．０３：中 ２．４６±０．０５：中 １．９３±０．０５：中 １．７２±０．０３：弱 １．５２±０．０３：弱 ２ Ｌｉ＿２ＴｉＯ＿３をｐＨ５以下の酸性溶液で処理
し、その中のリチウムを溶出させることを特徴とする、
特許請求の範囲第１項記載の吸着剤の製造方法。[Scope of Claims] 1. An adsorbent that is an acid-treated product of Li_2TiO_3, exhibits lithium selectivity, and has the following X-ray diffraction peak. Planar spacing (Å): Relative strength 4.74±0.03: Strong 4.54±0.03: Medium 2.46±0.05: Medium 1.93±0.05: Medium 1.72±0. 03: Weak 1.52 ± 0.03: Weak 2 Li_2TiO_3 is treated with an acidic solution of pH 5 or less to elute the lithium therein.
A method for producing an adsorbent according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2827188A JPH01203039A (en) | 1988-02-08 | 1988-02-08 | Adsorbent indicating new lithium selectivity and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2827188A JPH01203039A (en) | 1988-02-08 | 1988-02-08 | Adsorbent indicating new lithium selectivity and manufacture thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01203039A true JPH01203039A (en) | 1989-08-15 |
| JPH0525541B2 JPH0525541B2 (en) | 1993-04-13 |
Family
ID=12243920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2827188A Granted JPH01203039A (en) | 1988-02-08 | 1988-02-08 | Adsorbent indicating new lithium selectivity and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01203039A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682296A (en) * | 2013-08-16 | 2014-03-26 | 东莞上海大学纳米技术研究院 | Preparation method for nanoscale lithium titanate material with high specific capacity |
| WO2018203522A1 (en) * | 2017-05-01 | 2018-11-08 | テイカ株式会社 | Power storage device composition, power storage device separator using power storage device composition, and power storage device |
| CN110474122A (en) * | 2019-07-25 | 2019-11-19 | 湖南邦普循环科技有限公司 | A kind of method and the lithium ion sieve preparing lithium ion sieve using LiMn2O4 waste material |
-
1988
- 1988-02-08 JP JP2827188A patent/JPH01203039A/en active Granted
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682296A (en) * | 2013-08-16 | 2014-03-26 | 东莞上海大学纳米技术研究院 | Preparation method for nanoscale lithium titanate material with high specific capacity |
| WO2018203522A1 (en) * | 2017-05-01 | 2018-11-08 | テイカ株式会社 | Power storage device composition, power storage device separator using power storage device composition, and power storage device |
| JPWO2018203522A1 (en) * | 2017-05-01 | 2020-05-14 | テイカ株式会社 | Power storage device composition, power storage device separator using the power storage device composition, and power storage device |
| US11302993B2 (en) | 2017-05-01 | 2022-04-12 | Tayca Corporation | Power storage device composition, power storage device separator using power storage device composition, and power storage device |
| CN110474122A (en) * | 2019-07-25 | 2019-11-19 | 湖南邦普循环科技有限公司 | A kind of method and the lithium ion sieve preparing lithium ion sieve using LiMn2O4 waste material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0525541B2 (en) | 1993-04-13 |
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