JPS6362545A - Lithium adsorbent and its production and recovering method for lithium by using same - Google Patents
Lithium adsorbent and its production and recovering method for lithium by using sameInfo
- Publication number
- JPS6362545A JPS6362545A JP61208719A JP20871986A JPS6362545A JP S6362545 A JPS6362545 A JP S6362545A JP 61208719 A JP61208719 A JP 61208719A JP 20871986 A JP20871986 A JP 20871986A JP S6362545 A JPS6362545 A JP S6362545A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- adsorbent
- acid
- soln
- magnesium
- 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 66
- 239000003463 adsorbent Substances 0.000 title claims abstract description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 61
- 238000000034 method Methods 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000002253 acid Substances 0.000 claims abstract description 16
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 239000011777 magnesium Substances 0.000 claims description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 238000010306 acid treatment Methods 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 22
- 239000000243 solution Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- JWOZORSLWHFOEI-UHFFFAOYSA-N [O--].[O--].[Mg++].[Mn++] Chemical compound [O--].[O--].[Mg++].[Mn++] JWOZORSLWHFOEI-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- -1 batteries Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MHUWZNTUIIFHAS-XPWSMXQVSA-N 9-octadecenoic acid 1-[(phosphonoxy)methyl]-1,2-ethanediyl ester Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C\CCCCCCCC MHUWZNTUIIFHAS-XPWSMXQVSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 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
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 229940047047 sodium arsenate Drugs 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明はリチウム吸着剤、その製造方法及びそれを用い
た希薄ｉＷ Ｍからのリチウム回収方法に関するもので
ある。ざらにｘｙｔ、、＜いえば、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、
その１該希薄溶液中で安定であって、毒性の少ない安価
なリチウム吸着剤、その製造方法及び前記吸着剤を用い
て、リチウムを含む希薄溶液から該リチウムを効率よく
、かつ容易に回収する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 lithium adsorbent, a method for producing the same, and a method for recovering lithium from dilute iWM using the same. In other words, it has excellent selective adsorption for lithium, and has a large adsorption capacity and speed.
Part 1: An inexpensive lithium adsorbent that is stable in the dilute solution and has low toxicity, a method for producing the same, and a method for efficiently and easily recovering lithium from a dilute solution containing lithium using the adsorbent. It is related to.
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
いられており、また将来、大容量電池、アリミニラム合
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］。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 are being considered for use in large-capacity batteries, aliminilum alloy materials, nuclear fusion fuels, etc. Demand for lithium is expected to increase significantly due to
“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、アンブリゴナイト、ペターライト、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とを原Ｆ４として製造されている
。The lithium metal and its compounds are currently produced from lithium-containing ores such as spodumene, ambrigonite, petalite, and levidolite, as well as from salt lakes and underground brine containing high lithium concentrations.
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
温泉水ここはかなりのリチウムを含有するものがあり、
また周囲をとり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, geothermal water and hot spring water in our country contain a considerable amount of lithium.
The surrounding ocean also contains trace amounts of lithium. Therefore, it is strongly desired to establish a technique for efficiently recovering lithium from these dilute solutions containing lithium.
従来の技術
従来、満水なとのリチウムを含む希薄溶澄から該リチウ
ムを回収する方法としては、ｆｆｆｌｌえば水酸化アル
ミニウム共沈法［［日本化学会第４３年金、講演要旨集
ＩＪ、第１２４０ページ（＋９８１） ］ 、ある第９
９巻、第５８５ページ（＋９８３） ］、 金属アルミ
ニウム〔「防錆管理」、第１９８２巻、第３６９ページ
コ、含水酸化スズ［「日本鉱業会誌」、第９９巻、第９
３３ベージ（１９８３） ］を用いる吸着法などが知ら
れている。Conventional technology Conventionally, as a method for recovering lithium from a dilute solution containing lithium, which is full of water, the aluminum hydroxide coprecipitation method [[43rd Annual Annual Meeting of the Chemical Society of Japan, Proceedings IJ, p. 1240] (+981) ], a certain 9th
Volume 9, page 585 (+983) ], Metallic aluminum [“Rust Prevention Management”, Volume 1982, page 369], Hydrous Tin Oxide [“Journal of the Japan Mining Association”, Volume 99, Volume 9
33 Bage (1983)] is known.
しかしながら、これらの方法はリチウムに対する吸着容
量及び吸着速度が小さいという欠点があって、実用化は
困難である。また、ヒ酸ナトリウム［ｒＪ、ｌｎｏｒｇ
、Ｎｕｃｌ、Ｃｈｅｍ、Ｊ第３２巻、第１７１９ページ
（＋９７０）Ｊ 、アンチモン酸スズ［ｒｓｏｌｖｅｎ
ｔ Ｅｘ−ｔｒａｃｔｉｏｎ ＆ Ｉｏｎ−Ｅｘｃｈａ
ｎｇｅＪ 、第１巻、第９７ページ（１９８３） ］な
ともリチウム吸着性を示すことが報告されているが、実
用化するには吸着性の向上などの課題が残されている。However, these methods have the disadvantage that the adsorption capacity and adsorption rate for lithium are low, making it difficult to put them into practical use. Also, sodium arsenate [rJ, lnorg
, Nucl, Chem, J Volume 32, Page 1719 (+970) J, Tin Antimonate [rsolven
t Ex-traction & Ion-Excha
ngeJ, Volume 1, Page 97 (1983)] has been reported to exhibit lithium adsorption properties, but issues such as improvement of adsorption properties remain for practical use.
このほかに、各種のイオンシーブ型の吸着剤がリチウム
に対して吸着性を示すことも報告されているが［ｒＮｅ
ｏｒｇａｎ、Ｍａｔ、Ｊ 、第９巻、第１０４１ベージ
（１９７３）、同誌、第１２巻、第１４５１ページ（１
９７６）］、に至っていない。In addition, it has been reported that various ion sieve type adsorbents exhibit adsorption properties for lithium.
organ, Mat, J, Vol. 9, No. 1041 page (1973), same magazine, Vol. 12, No. 1451 page (1
976)].
発明が解決しようとする問題点
リチウムを含む海水、地熱水、地下かん水などの希ａ（
Ｊ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沢吸着性に優れ、かつ吸着速度や吸
着容量が大きく、その１該希薄溶液中で安定であって、
毒性が少なく、ざらに吸脱着の繰り返し使用が可能であ
ることが要求される。Problems to be solved by the invention Rare a(
In order to practically adsorb and recover the lithium from J liquid,
It has excellent selective adsorption properties for lithium, and has a large adsorption rate and adsorption capacity. 1. It is stable in the dilute solution,
It is required to have low toxicity and be able to be used repeatedly by adsorption and desorption.
本発明の目的は、このような用件を満足しろる吸着剤、
その製造方法及び該吸着剤を用いて、リチウムを含む希
薄溶液から該リチウムを極めて効率よく回収する実用的
なリチウム回収方法を提供することになる。The object of the present invention is to provide an adsorbent that satisfies these requirements,
By using the manufacturing method and the adsorbent, a practical method for recovering lithium is provided, which can extremely efficiently recover lithium from a dilute solution containing lithium.
問題点を解決するための手段
本発明者らは種々断交を重ねた結果、特定の温度で加熱
して、調製されたマグネシウム・マンガン酸化物 （Ｍ
ｇ６Ｍｎ０Ｂ ）のリチウム溶出物が前記要チウムを極
めて効率よく、容易に回収しうろことを見出し、この知
見に基づいて本発明を完成するに至った。Means for Solving the Problems The inventors of the present invention made various attempts to solve the problem, and as a result, a magnesium-manganese oxide (M
It was discovered that the lithium eluate of g6Mn0B) can easily recover the essential lithium, and based on this knowledge, the present invention was completed.
すなわち、本発明は、３００〜６００ ℃で加熱して調
製されたＭ：６ＭｎＱ８の酸処理生成物から成るリチウ
ム吸着剤、この吸着剤を、マグネシウムとマンガンの混
合物を３００〜６００℃の温度において加熱処理して肖
３６Ｍｎ０Ｂを調製したのち、酸で該マグネシウムを溶
出させることによって製造する方法、及びリチウムを吸
着分離させたのち、弱酸又は弱酸性水溶液を用いて該吸
着剤に吸着されたリチウムを溶離することによって、リ
チウムを回収する方法を提供するものである。That is, the present invention provides a lithium adsorbent consisting of an acid-treated product of M:6MnQ8 prepared by heating at 300-600°C; A method of manufacturing by treating to prepare 36Mn0B and then eluting the magnesium with acid, and after adsorbing and separating lithium, eluting the lithium adsorbed to the adsorbent using a weak acid or a weakly acidic aqueous solution. This provides a method for recovering lithium.
本発明において、吸着剤の製造に用いろマグネシウムと
マンガンの混合物は、例えば″マグネシウム塩溶液とマ
ンガン塩溶液との混合溶液にアルカリ性溶潰を加えて得
られる沈殿生成物を溶：αと分離することによって調製
されるが、もちろん、このような方法に限定されるもの
ではない・本発明の吸着剤は、このようにして得られた
マグネシウムとマンガンの混合物を３００〜６００℃、
好ましくは３００〜５００’Ｃの温度で加熱して、Ｍｇ
６ＭｎＯ８を調製したのち、該マグネシウムを酸で溶出
させろことによって得られる。Ｍｇ６Ｍｎ０Ｂはマグネ
シウムとマンガンの混合物を３００℃以上の温度で加熱
することによって調製される立方晶系の結晶である。７
００℃以上の温度で加熱処理して得られるＭｇ６ＭｎＯ
８は不安定で、その酸処理物はリチウムに対する吸着性
能がほとんどみられない。５００℃以下の温度で加熱調
製したものは、マグネシウムの溶出が容易であり、その
マグネシウム溶出物は構造が安定でリチウムに対して吸
着性を示した。特に４００℃で加熱処理したものは、箸
しく大きなリチウム吸着性を示す。また、加熱処理時間
は処理温度によって異なるが、一般に３０分〜５時間程
度で十分である。In the present invention, the mixture of magnesium and manganese used in the production of the adsorbent is obtained by, for example, adding alkaline dissolution to a mixed solution of a magnesium salt solution and a manganese salt solution, and separating the precipitated product from the solution α. However, the method is not limited to this method. The adsorbent of the present invention is prepared by heating the magnesium and manganese mixture obtained in this way at 300 to 600°C.
Preferably by heating at a temperature of 300 to 500'C, Mg
It is obtained by preparing 6MnO8 and then eluting the magnesium with acid. Mg6Mn0B is a cubic crystal prepared by heating a mixture of magnesium and manganese at temperatures above 300°C. 7
Mg6MnO obtained by heat treatment at a temperature of 00°C or higher
No. 8 is unstable, and its acid-treated product shows almost no adsorption performance for lithium. When prepared by heating at a temperature of 500° C. or lower, magnesium was easily eluted, and the magnesium eluted product had a stable structure and exhibited adsorption properties for lithium. Particularly, those heat-treated at 400°C exhibit extremely high lithium adsorption properties. Further, the heat treatment time varies depending on the treatment temperature, but generally about 30 minutes to 5 hours is sufficient.
このようにして、３００〜６００℃で加熱して調製され
たＭｇ６Ｍｎ０ａから、該マグネシウムを溶出するのに
用いる故としては、０．０５〜ＩＮ程度のａ度を有する
塩酸や、硫酸、硝酸などの鉱酸の水溶）夜が好適である
が、該マグネシウムを容易に溶出することができ、かつ
リチウム吸着性能に悪影響を及ぼさないかぎり、これら
に限定されるものではない。Hydrochloric acid, sulfuric acid, nitric acid, etc. having a degree of a of about 0.05 to IN are used to elute the magnesium from Mg6Mn0a prepared by heating at 300 to 600°C in this way. Water dissolution of mineral acid) is preferred, but the method is not limited thereto as long as the magnesium can be easily eluted and does not adversely affect the lithium adsorption performance.
このようにして得られた吸着剤は、粉末状で用いてもよ
いし、バインダーなどを使用し粒状や繊維状に成形して
用いてもよい。The adsorbent thus obtained may be used in powder form, or may be formed into granules or fibers using a binder or the like.
本発明において用いるリチウムを含む希薄溶液としては
、例えば海水のみならず、地熱水、温泉水、鉱泉水、天
然ガスかん水なとの地下かん水、製塩かん水、工場廃液
などが挙げられる。Examples of the dilute solution containing lithium used in the present invention include not only seawater but also geothermal water, hot spring water, mineral spring water, underground brine such as natural gas brine, salt brine, factory waste liquid, and the like.
本発明においては、リチウムを含む希薄溶液に、前記の
ようにして得られた吸着剤を添加して、該リチウムを十
分に吸着せしめたのち、吸着剤を該溶液から分層して、
弱酸又は弱酸性水溶ｉ夜と接触させ、該リチウムを溶離
して回収するか、あるいは、粒状や繊維状に成形した吸
着剤を充填したカラムに、リチウムを含む希薄溶液を通
液することによって、該リチウムを吸着せしめたのち、
弱酸又は弱酸性水溶液を通液し、該リチウムを脱着して
回収することもできる。In the present invention, the adsorbent obtained as described above is added to a dilute solution containing lithium to sufficiently adsorb the lithium, and then the adsorbent is separated from the solution,
By contacting with a weak acid or a weakly acidic aqueous solution to elute and recover the lithium, or by passing a dilute solution containing lithium through a column packed with an adsorbent formed into granules or fibers, After adsorbing the lithium,
It is also possible to desorb and recover the lithium by passing a weak acid or a weakly acidic aqueous solution through it.
吸着したリチウムの溶ス１に用いる弱酸又は弱酸性水溶
液については、該リチウムを容易に溶離することができ
、かつ吸着剤の性能に悪影響を与えないかぎり、特に制
限はないが、通常０．０５〜ＩＮの濃度を有する塩酸や
、硫酸、硝酸などの水溶液が好適である。The weak acid or weak acidic aqueous solution used for the adsorbed lithium solution 1 is not particularly limited as long as it can easily elute the lithium and does not adversely affect the performance of the adsorbent, but it is usually 0.05 An aqueous solution of hydrochloric acid, sulfuric acid, nitric acid, etc. having a concentration of ~IN is suitable.
発明の効果
本発明のリチウム吸着剤は、特定の温度で加熱調製した
Ｍｇ３ＭｎＯ３のマグネシウム溶出物から成るものであ
って、リチウムに対する選択性に廃れ、かつ吸着量や吸
着速度が大きく、しかも吸、脱着の繰り返し使用が可能
で、その上、水ｍＫｌ中で安定であって、毒性の少ない
安価なものである。この吸着剤を用いることにより、リ
チウムを含む希薄ｉ？７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ろ。Effects of the Invention The lithium adsorbent of the present invention is composed of a magnesium eluate of Mg3MnO3 prepared by heating at a specific temperature. It can be used repeatedly, is stable in water (mKl), has little toxicity, and is inexpensive. By using this adsorbent, dilute i? It would be possible to recover the lithium from liquid 7 very efficiently and economically.
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。Example Next, the present invention will be explained in more detail with reference to Examples.
実施例１
１Ｍ塩化マグネシウム水溶ｉ ６００ｍＬとＩＭ塩化マ
ンガン水溶液１００ｍＬとの混合溶γ夜をかきまぜなが
ら、ｐＨｌ０．５以上になるまでアンモニア水（１：１
）を加えた。さらに３０％過酸化水素溶ｊ夜１００ｍＬ
を滴加した。生成物を母液中で３日間熟成したのち、ろ
別し、ｐＨ０，５のアンモニア水て数回洗浄した。生成
物中のマグネシウムとマンガン含量の原子比は５．８：
１であった。これを２００〜８００”Ｃで１時間加熱処
理してマグネシウム・マンガン酸化物を調製した。３０
０℃以上の加熱処理物は、Ｘ線回折試験の結果、いずれ
もＭｇ３Ｍｎ０Ｂであることを確；３した。この加熱生
成物１ｇを０．５ Ｎ塩酸溶）α１し中に加えて、２５
日間かきまぜたのち、生成物をろ別、洗浄し、７０℃で
乾燥した。このようにして得られた各種吸着剤５０ｍｇ
をそれぞれ２Ｌの天然海水中（ＬｉＷ度１７０μｇｉｇ
）に添加し、７日間かきまぜたのち、上澄液中のリチ
ウム濃度を定量してリチウム吸着量を求めた。その結果
を第１表に示す。Example 1 A mixed solution of 600 mL of 1M magnesium chloride aqueous solution and 100 mL of IM manganese chloride aqueous solution.
) was added. Add 100 mL of 30% hydrogen peroxide solution
was added dropwise. After aging the product in the mother liquor for 3 days, it was filtered off and washed several times with aqueous ammonia at pH 0.5. The atomic ratio of magnesium and manganese content in the product is 5.8:
It was 1. This was heat-treated at 200 to 800"C for 1 hour to prepare magnesium manganese oxide. 30
As a result of an X-ray diffraction test, it was confirmed that all of the heat-treated products at 0° C. or higher were Mg3Mn0B. 1 g of this heated product was dissolved in 0.5 N hydrochloric acid) α1 and added to 25
After stirring for several days, the product was filtered off, washed and dried at 70°C. 50 mg of various adsorbents obtained in this way
each in 2L of natural seawater (LiW degree 170μgig
) and stirred for 7 days, the lithium concentration in the supernatant was determined to determine the amount of lithium adsorbed. The results are shown in Table 1.
第 １ 表この表から明
らかなように、３００〜６００℃で加熱処理したものは
、リチウム吸着性を示すことが分る。Table 1 As is clear from this table, those heat-treated at 300 to 600°C exhibit lithium adsorption properties.
実方ｋＥグリ２
実施ηす１における試料Ｎ０３（加熱温度４００℃）の
ものについて、酸処理時間を変えた場合のリチウム吸着
性を調べた。その結果、第２表に示すように、酸処理時
間が長くなるにつれて、リチウム吸着性が増大し、酸処
理時間２０日で得られた吸着剤が最高の吸着性を示し、
さらに酸処理時間が長くなると吸着性能が低下する順向
が認められた。The lithium adsorption properties of sample N03 (heating temperature 400° C.) in Example 1 were investigated when the acid treatment time was varied. As a result, as shown in Table 2, as the acid treatment time increased, the lithium adsorption increased, and the adsorbent obtained with the acid treatment time of 20 days showed the highest adsorption ability.
Furthermore, it was observed that the adsorption performance decreased as the acid treatment time increased.
第 ２ 表実施例３
実施例２において、吸着性能が最も優れてぃた試料Ｎｏ
１０ （リチウム吸着ｆ１３．２ｍｇ／３） ０−５
ｇを０．０５Ｎ塩酸溶液５０ｍＬ中に入れて、室温で５
時間深ってリチウムの脱着を行った結果、脱着率は９０
％を示し、該吸着剤から容易に脱着てきることが認めら
れた。Table 2 Example 3 In Example 2, sample No. 2 had the best adsorption performance.
10 (Lithium adsorption f13.2mg/3) 0-5
g in 50 mL of 0.05N hydrochloric acid solution and stirred at room temperature for 5 minutes.
As a result of desorption of lithium over time, the desorption rate was 90.
%, and it was recognized that it could be easily desorbed from the adsorbent.
特許出願人 工業技術院長 飯 塚 幸 三指定代理
人 工業技術院四国工業技術試験所管 域 和
彦Patent applicant: Director of the Agency of Industrial Science and Technology Kozo Iizuka Designated agent: Agency of Industrial Science and Technology, Shikoku Industrial Technology Testing Jurisdiction Kazu Area
Hiko
Claims (1)
Ｏ＿８の酸処理生成物から成るリチウム吸着剤。 ２ マグネシウムとマンガンのモル比が１２：２〜１の
ものを、３００〜６００℃の温度において加熱処理して
Ｍｇ＿６ＭｎＯ＿８を調製したのち、これを酸で処理し
て、マグネシウムを溶出させることを特徴とするリチウ
ム吸着剤の製造方法。 ３ リチウムを含む希薄溶液中に、３００〜６００℃の
温度で加熱して調製されたＭｇ＿６ＭｎＯ＿８のマグネ
シウム溶出物から成る吸着剤を加え、リチウムを吸着分
離させたのち、弱酸又は弱酸性水溶液を用いて前記吸着
剤に吸着されたリチウムを溶離することを特徴とする希
薄溶液からのリチウム回収方法。[Claims] 1 Mg_6Mn prepared by heating at 300 to 600°C
Lithium adsorbent consisting of the acid treatment product of O_8. 2 Mg_6MnO_8 is prepared by heat-treating magnesium and manganese in a molar ratio of 12:2 to 1 at a temperature of 300 to 600°C, and then this is treated with acid to elute the magnesium. A method for producing a lithium adsorbent. 3. Add an adsorbent consisting of a magnesium eluate of Mg_6MnO_8 prepared by heating at a temperature of 300 to 600°C into a dilute solution containing lithium, adsorb and separate lithium, and then add it to a dilute solution containing lithium. A method for recovering lithium from a dilute solution, comprising eluting lithium adsorbed on the adsorbent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61208719A JPS6362545A (en) | 1986-09-03 | 1986-09-03 | Lithium adsorbent and its production and recovering method for lithium by using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61208719A JPS6362545A (en) | 1986-09-03 | 1986-09-03 | Lithium adsorbent and its production and recovering method for lithium by using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6362545A true JPS6362545A (en) | 1988-03-18 |
| JPH0357814B2 JPH0357814B2 (en) | 1991-09-03 |
Family
ID=16560948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61208719A Granted JPS6362545A (en) | 1986-09-03 | 1986-09-03 | Lithium adsorbent and its production and recovering method for lithium by using same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6362545A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732829A (en) * | 2017-01-04 | 2017-05-31 | 潍坊学院 | A kind of preparation method of manganese aluminium base lithium ion extraction material |
| CN106732830A (en) * | 2017-01-04 | 2017-05-31 | 潍坊学院 | A kind of preparation method of the manganese titanium-based lithium ion extraction material of magnesium |
| CN106824302A (en) * | 2017-01-04 | 2017-06-13 | 潍坊学院 | A kind of preparation method of the titanium-based lithium ion extraction material of magnesium |
-
1986
- 1986-09-03 JP JP61208719A patent/JPS6362545A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732829A (en) * | 2017-01-04 | 2017-05-31 | 潍坊学院 | A kind of preparation method of manganese aluminium base lithium ion extraction material |
| CN106732830A (en) * | 2017-01-04 | 2017-05-31 | 潍坊学院 | A kind of preparation method of the manganese titanium-based lithium ion extraction material of magnesium |
| CN106824302A (en) * | 2017-01-04 | 2017-06-13 | 潍坊学院 | A kind of preparation method of the titanium-based lithium ion extraction material of magnesium |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0357814B2 (en) | 1991-09-03 |
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