JPH0626660B2 - New manufacturing method of lithium adsorbent - Google Patents
New manufacturing method of lithium adsorbentInfo
- Publication number
- JPH0626660B2 JPH0626660B2 JP63083497A JP8349788A JPH0626660B2 JP H0626660 B2 JPH0626660 B2 JP H0626660B2 JP 63083497 A JP63083497 A JP 63083497A JP 8349788 A JP8349788 A JP 8349788A JP H0626660 B2 JPH0626660 B2 JP H0626660B2
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- manganese
- magnesium
- adsorbent
- magnesium content
- 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
Links
- 229910052744 lithium Inorganic materials 0.000 title claims description 35
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 34
- 239000003463 adsorbent Substances 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000011777 magnesium Substances 0.000 claims description 50
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 37
- 229910052749 magnesium Inorganic materials 0.000 claims description 37
- 125000005385 peroxodisulfate group Chemical group 0.000 claims description 2
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 20
- 238000001179 sorption measurement Methods 0.000 description 20
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 19
- 229910052748 manganese Inorganic materials 0.000 description 19
- 239000011572 manganese Substances 0.000 description 19
- 238000010828 elution Methods 0.000 description 16
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 14
- 229910018663 Mn O Inorganic materials 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000013535 sea water Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- -1 seawater Chemical compound 0.000 description 2
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- ZIGCAHUFDDOFRE-UHFFFAOYSA-L manganese(2+);oxygen(2-);dihydroxide Chemical compound [OH-].[OH-].[O-2].[O-2].[Mn+2].[Mn+2].[Mn+2] ZIGCAHUFDDOFRE-UHFFFAOYSA-L 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Landscapes
- Treatment Of Liquids With Adsorbents In General (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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の製造方法に関するものであ
る。更に詳しく言えば、リチウムに対する選択吸着性が
優れ、かつ吸着容量及び吸着速度が大きく、リチウム希
薄溶液中で安定であって、毒性が少なく安価なリチウム
吸着剤の製造方法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing a lithium adsorbent. More specifically, it relates to a method for producing a lithium adsorbent which is excellent in selective adsorption to lithium, has a large adsorption capacity and adsorption rate, is stable in a dilute lithium solution, has low toxicity, and is inexpensive.
近年、リチウム金属およびその化合物は、多くの分野、
例えば、セラミックス、電池、吸収型冷媒、医薬品など
に用いられており、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て
おり、リチウムの重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（1981）〕。し
かしながら、我が国はリチウム鉱石資源に乏しく、リチ
ウム原料は海外からの輸入に依存している現状である。
このため、海水、地熱水、地下かん水などのリチウムを
含む溶液からの吸着採取技術の確立が強く要望されてい
る。In recent years, lithium metal and its compounds have been used in many fields,
For example, it is used in ceramics, batteries, absorption-type refrigerants, pharmaceuticals, etc., and is expected to be used as large-capacity batteries, aluminum alloy materials, fusion fuels, etc. in the future, and lithium is expected to increase significantly in importance. (The Journal of the Japan Mining Industry, Vol. 97, p. 221 (1981)). However, Japan is poor in lithium ore resources, and the lithium raw material currently depends on imports from abroad.
For this reason, there is a strong demand for the establishment of adsorption collection technology from solutions containing lithium, such as seawater, geothermal water, and ground brackish water.
本発明は、これら希薄リチウム溶液からのリチウム採取
用に開発した吸着剤の製造方法である。The present invention is a method for producing an adsorbent developed for extracting lithium from these dilute lithium solutions.
従来、海水、地熱水、地下かん水などのリチウムを含む
希薄溶液からの該リチウムを採取分離するために、種々
の吸着剤が開発されている。それらのうち、高性能吸着
剤の１つとして、Ｍg ２Ｍn Ｏ４を原料とするイオンふ
るい型マンガン酸化物吸着剤がある〔日本海水学会第38
年会要旨集、第17（1987）〕、〔特開昭63−64919
号〕。Conventionally, various adsorbents have been developed to collect and separate lithium from dilute solutions containing lithium such as seawater, geothermal water, and ground brackish water. Among them, as one of the high-performance adsorbents, there is an ion sieve type manganese oxide adsorbent made of Mg 2 Mn O 4 as a raw material [Japan Society of Sea Water 38th
Annual Meeting Summary, No. 17 (1987)], [JP-A-63-64919
issue〕.
この吸着剤はＭg ２Ｍn Ｏ４を塩酸、硝酸などの鉱酸あ
るいは有機酸で処理して大部分のマグネシウムを溶出除
去して製造されている。すなわち、結晶構造を保ちつつ
マグネシウムを溶出除去して形成される微細孔がリチウ
ム吸着に関与すると考えられている。従って、リチウム
吸着性能を向上させるためには残存マグネシウム量をで
きるだけ小さくすることが望ましい。しかしながら、こ
の酸処理において、吸着剤の骨格を形成するマンガンが
10％程度溶解するため、吸着剤の収率が低下し、非経済
的である。また、マンガンの溶解は結晶構造の不安定化
につながり、リチウム吸着性能の低下の原因となる。This adsorbent is produced by treating Mg 2 Mn O 4 with a mineral acid such as hydrochloric acid or nitric acid or an organic acid to elute and remove most of magnesium. That is, it is considered that fine pores formed by elution and removal of magnesium while maintaining the crystal structure are involved in lithium adsorption. Therefore, it is desirable to reduce the amount of residual magnesium as much as possible in order to improve the lithium adsorption performance. However, in this acid treatment, the manganese forming the skeleton of the adsorbent
Since it dissolves about 10%, the yield of the adsorbent decreases, which is uneconomical. Further, the dissolution of manganese leads to destabilization of the crystal structure, which causes a reduction in lithium adsorption performance.
Ｍg ２Ｍn Ｏ４からリチウム吸着剤の製造においては、
結晶構造を壊さずにマグネシウムを溶出除去する必要が
ある。すなわち、マンガンの溶解損失量を可及的に抑制
するとともに、マグネシウムの溶出速度が大きく、しか
も安価な処理方法が要求される。更に得られる吸着剤は
リチウム選択吸着性が大きく、化学的および物理的に安
定したものが望ましい。本発明の目的は、このような要
件を満足しうる製造方法を提供することである。In the production of a lithium adsorbent from Mg 2 Mn O 4 ,
It is necessary to elute and remove magnesium without destroying the crystal structure. That is, there is required a treatment method that suppresses the dissolution loss of manganese as much as possible, has a high elution rate of magnesium, and is inexpensive. Further, it is desirable that the adsorbent obtained has a large lithium selective adsorption property and is chemically and physically stable. An object of the present invention is to provide a manufacturing method that can satisfy such requirements.
本発明者らは種々の製造方法について研究を重ねた結
果、酸性かつ酸化性を示す溶液をＭg ２Ｍn Ｏ４からの
マグネシウム溶出剤として用いることにより、容易に前
記要件を解決しうることを認め、本発明をなすに至っ
た。すなわち、マンガン酸化物はマンガンの原子価が大
きくなると耐酸性を示すことに着目し、酸化剤の共存の
もとで該マグネシウムを溶出除去することを考案した。As a result of repeated studies on various production methods, the present inventors have found that the above requirements can be easily solved by using an acidic and oxidizing solution as a magnesium eluent from Mg 2 Mn O 4. The present invention has been completed. That is, focusing on the fact that manganese oxide exhibits acid resistance when the valence of manganese increases, it was devised to elute and remove the magnesium in the presence of an oxidizing agent.
酸性かつ酸化性を示す溶液としては、酸性酸化剤を含む
溶液あるいは酸化剤と酸の混合物を含む溶液のいずれも
用いることができるが、処理操作の点からは酸性酸化物
を含む溶液が好ましい。酸性酸化物としてはペルオクソ
二硫酸塩、臭素などが使用可能であるが、溶解度や経済
性の面からペルオクソ二硫酸アンモニウムが好ましい。
ペルオクソ二硫酸アンモニウムの水溶液を加温すると、
次式のように分解する。As the solution which is acidic and oxidizable, either a solution containing an acidic oxidizing agent or a solution containing a mixture of an oxidizing agent and an acid can be used, but a solution containing an acidic oxide is preferable from the viewpoint of treatment operation. As the acidic oxide, peroxodisulfate, bromine and the like can be used, but ammonium peroxodisulfate is preferable from the viewpoint of solubility and economy.
When an aqueous solution of ammonium peroxodisulfate is heated,
Decompose like the following formula.
２（ＮＨ４）２Ｓ２Ｏ８＋２Ｈ２Ｏ→ ４ＮＨ４ＨＳＯ４＋Ｏ２ ＮＨ４ＨＳＯ４→ＮＨ４ ＋＋Ｈ＋＋ＳＯ４ 2- この生成水素イオンとＭg ２Ｍn Ｏ４中のマグネシウム
とがイオン交換するためマグネシウムが溶出してくる。
一方、生成酸素が酸化作用を示し、マンガン酸化物の溶
解を抑制する。すなわち、マンガンの原子価を４価に保
ち、弱酸性溶液中で不溶性化合物とする。従って、処理
温度は高温ほど反応が促進される。望もしくは80〜90℃
がよい。ペルオクソ二硫酸アンモニウムの濃度は 0.25
〜 2Ｎが好適であるが、これに限定するものではない。
固体比は処理温度90℃、ペルオクソ二硫酸アンモニウム
濃度 1〜 2Ｎの場合には 5g ／ 100ml以下が好適であ
る。2 (NH 4 ) 2 S 2 O 8 + 2H 2 O → 4NH 4 HSO 4 + O 2 NH 4 HSO 4 → NH 4 + + H + + SO 4 2- This generated hydrogen ion and magnesium in Mg 2 MnO 4 are ions Magnesium elutes for replacement.
On the other hand, the generated oxygen has an oxidizing effect and suppresses the dissolution of manganese oxide. That is, the valence of manganese is kept tetravalent, and the compound is made insoluble in a weakly acidic solution. Therefore, the higher the processing temperature is, the more the reaction is promoted. Hope or 80 ~ 90 ℃
Is good. Ammonium peroxodisulfate concentration is 0.25
2 N is preferable, but not limited to this.
When the treatment temperature is 90 ° C. and the concentration of ammonium peroxodisulfate is 1 to 2 N, the solid ratio is preferably 5 g / 100 ml or less.
本発明の製造方法によれば、マンガンの溶解損失率を
0.5％以下に抑制することができる。しかもリチウム吸
着性能に関与する吸着剤中のマグネシウム含有量を任意
に調節することができるため、最高の吸着性能を発現す
る吸着剤を容易に、かつ高収率に製造できる。吸着剤は
毒性がなく、水溶液中で安定であり、しかもリチウム吸
着性能は従来のものより優れており、吸着剤中のリチウ
ム吸着量は鉱石なみになる。According to the production method of the present invention, the dissolution loss rate of manganese
It can be suppressed to 0.5% or less. Moreover, since the magnesium content in the adsorbent, which is involved in the lithium adsorbing performance, can be arbitrarily adjusted, the adsorbent exhibiting the highest adsorbing performance can be easily produced in a high yield. The adsorbent is non-toxic, stable in aqueous solution, and has better lithium adsorption performance than conventional ones, and the amount of lithium adsorbed in the adsorbent is similar to that of ore.
本法で製造した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。By using the adsorbent produced by this method, the lithium can be extremely efficiently and economically recovered from the dilute solution.
次に実施例により、本発明を更に詳細に説明する。 Next, the present invention will be described in more detail with reference to examples.
実施例１ 水酸化酸化マンガンと水酸化マグネシウムをモル比で
１：２の割合で粉砕混合したものを900 ℃で２時間加熱
処理して、原料のＭg ２Ｍn Ｏ４を合成した。Example 1 Manganese hydroxide oxide and magnesium hydroxide were pulverized and mixed at a molar ratio of 1: 2, and heat-treated at 900 ° C. for 2 hours to synthesize a raw material Mg 2 Mn O 4 .
このＭg ２Ｍn Ｏ４（マグネシウム含有率28.5％）１g
を 250ml容量の三角フラスコにとり、２Ｎ−ペルオクソ
二硫酸アンモニウム溶液 100mlを加え、50〜90℃に加温
してマグネシウムを溶出した。そのときの生成物中のマ
グネシウム含有率を求めた結果を第１図に示す。この図
から明らかなように処理温度が高くなるほど反応は促進
され、マグネシウム含有率は小さくなった。マグネシウ
ム含有率２％以下のものが、高いリチウム吸着性を示す
ことから、処理温度は90℃、時間2 〜 6時間がよいこと
がわかった。1g of this Mg 2 Mn O 4 (magnesium content 28.5%)
Was placed in a 250 ml Erlenmeyer flask, 100 ml of a 2N-peroxodisulfate ammonium solution was added, and the mixture was heated to 50 to 90 ° C. to elute magnesium. The results of determining the magnesium content in the product at that time are shown in FIG. As is clear from this figure, the reaction was promoted and the magnesium content decreased as the treatment temperature increased. It was found that the treatment temperature of 90 ° C. and the time of 2 to 6 hours are good because the magnesium content of 2% or less shows a high lithium adsorption property.
実施例２ 実施例１と同じＭg ２Ｍn Ｏ４１g を 250ml容量の三角
フラスコにとり、 0.1〜 3Ｎのペルオクソ二硫酸アンモ
ニウム溶液 100mlを加え、90℃で４時間処理した。その
ときのマグネシウム含有率およびマンガン溶出率を求
め、ペルオクソ二硫酸アンモニウムの濃度の影響を調べ
た。その結果を第２図に誌す。ペルオクソ二硫酸アンモ
ニウムの濃度が 0.25 〜 3Ｎではマグネシウム含有率
2.5％以下が得られた。一方、マンガン溶出率は 0.5〜
2Ｎの範囲では 0.5％以下であったがペルオクソ二硫酸
アンモニウム濃度がさらに高くなると溶出率が大きくな
った。これらのことからペルオクソ二硫酸アンモニウム
の濃度は 0.5〜 2Ｎが適当であることがわかった。実施
例３ １Ｎおよび２Ｎのペルオクソ二硫酸アンモニウム溶液 1
00mlを 250ml容量の三角フラスコにとり、実施例１と同
じＭg ２Ｍn Ｏ４を1 〜15g 加え、90℃で４時間処理し
た。その結果を第３図に示す。この結果からペルオクソ
二硫酸アンモニウムの濃度が１Ｎの場合は、固液比 5g
／100 ml、２Ｎの場合には固液比 7g ／ 100ml以下にお
いてマグネシウム含有率４％以下のものが得られた。こ
のようにペルオクソ二硫酸アンモニウム濃度に応じて好
適な固液比があることがわかった。Example 2 1 g of Mg 2 Mn O 4 as in Example 1 was placed in an Erlenmeyer flask having a capacity of 250 ml, 100 ml of a 0.1 to 3N ammonium peroxodisulfate solution was added, and the mixture was treated at 90 ° C. for 4 hours. At that time, the magnesium content rate and the manganese elution rate were obtained, and the influence of the concentration of ammonium peroxodisulfate was investigated. The results are shown in Fig. 2. Magnesium content when ammonium peroxodisulfate concentration is 0.25 to 3N
Less than 2.5% was obtained. On the other hand, manganese elution rate is 0.5 ~
In the range of 2N, it was 0.5% or less, but the elution rate increased as the ammonium peroxodisulfate concentration became higher. From these facts, it was found that an appropriate concentration of ammonium peroxodisulfate is 0.5 to 2N. Example 3 1N and 2N ammonium peroxodisulfate solution 1
00 ml was placed in a 250 ml Erlenmeyer flask, 1 to 15 g of the same Mg 2 Mn O 4 as in Example 1 was added, and the mixture was treated at 90 ° C. for 4 hours. The results are shown in FIG. From this result, when the concentration of ammonium peroxodisulfate is 1N, the solid-liquid ratio is 5 g.
In the case of / 100 ml and 2N, a magnesium content of 4% or less was obtained at a solid-liquid ratio of 7 g / 100 ml or less. Thus, it was found that there is a suitable solid-liquid ratio depending on the ammonium peroxodisulfate concentration.
実施例４ 実施例１と同じＭg ２Ｍn Ｏ４３g を 250ml容量の三角
フラスコにとり、２Ｎ−ペルオクソ二硫酸アンモニウム
溶液 100mlを加え、90℃で 0.5〜 8時間処理した。その
ときの生成物中のマグネシウム含有率とマンガン溶出率
を求めた。その結果を第４図に示す。また、生成物のリ
チウム吸着性能を調べた。吸着実験は吸着剤50mgを２ｌ
の天然海水に加え、25℃で５日間かきまぜて行った。そ
の後、吸着剤をろ別、水洗し、さらに塩酸で分解溶解し
たのち、そのリチウム量を定量し、吸着率を求めた。そ
れらのマグネシウム含有率とリチウム吸着率との関係を
第５図に示す。第５図から明らかなように、マグネシウ
ム含有率９％以下のものがリチウム吸着性を示し、さら
にその含有率 0.3〜 2％のものが高いリチウム吸着性を
示した。一方、その製造処理時間は第４図および第５図
から２〜４時間が好適であることがわかった。その場合
のマンガン溶出率は 0.05 ％以下であり、無視できる程
度であった、このように本発明の製造方法によれば、Ｍ
g ２Ｍn Ｏ４より高性能なリチウム吸着剤をマンガンの
溶解損失量を極めて小さい条件、すなわち、高収率で容
易に製造できる。Example 4 3 g of Mg 2 Mn O 4 as in Example 1 was placed in a 250 ml Erlenmeyer flask and 100 ml of 2N-ammonium peroxodisulfate solution was added, followed by treatment at 90 ° C. for 0.5 to 8 hours. The magnesium content and manganese elution rate in the product at that time were obtained. The results are shown in FIG. Also, the lithium adsorption performance of the product was examined. Adsorption experiment was conducted with 2 l
Was added to the natural seawater of, and the mixture was stirred at 25 ° C for 5 days. After that, the adsorbent was filtered off, washed with water, decomposed and dissolved in hydrochloric acid, and the amount of lithium was quantified to determine the adsorption rate. The relationship between the magnesium content rate and the lithium adsorption rate is shown in FIG. As is clear from FIG. 5, those having a magnesium content of 9% or less exhibited lithium adsorption, and those having a magnesium content of 0.3 to 2% exhibited high lithium adsorption. On the other hand, it was found from FIG. 4 and FIG. 5 that the manufacturing processing time is preferably 2 to 4 hours. The manganese elution rate in that case was 0.05% or less, which was negligible. Thus, according to the production method of the present invention, M
A lithium adsorbent having higher performance than g 2 Mn O 4 can be easily produced under the condition that the amount of manganese dissolution loss is extremely small, that is, in high yield.
比較例 実施例１と同じＭg ２Ｍn Ｏ４ 0.75 g を 250ml容量の
三角フラスコにとり、これに 0.05 〜 1.25 Ｎの塩酸溶
液および硝酸溶液 250mlを加え、25℃で55日間処理し
た。そのときの生成物中のマグネシウム含有率およびマ
ンガン溶出率を求めた。その結果を第６図および第７図
に示す。これらの図から明らかなように、酸濃度が 0.0
5 Ｎの場合には、マンガンの溶解性は認められないが、
マグネシウム含有率が大きく、リチウム吸着性を示さな
かった、 0.25 Ｎの場合には処理時間45〜55日におい
て、マグネシウム含有率２％程度のものが得られたが、
その場合のマンガンの溶出率は 9〜10％になった。更に
1.25 Ｎの場合には、マグネシウム含有率０％のものが
得られたが、マンガンの溶出率も増加し、その値は12％
以上に達した。このように酸溶液のみの処理方法の場合
には、高いリチウム吸着性を発現する吸着剤（マグネシ
ウム含有率５％以下）を製造する際、約10％のマンガン
の溶出を伴う欠点が認められた。Comparative Example The same Mg 2 MnO 4 0.75 g as in Example 1 was placed in a 250 ml Erlenmeyer flask, and 0.05 to 1.25 N hydrochloric acid solution and 250 ml nitric acid solution were added thereto, and the mixture was treated at 25 ° C. for 55 days. The magnesium content and manganese elution rate in the product at that time were determined. The results are shown in FIGS. 6 and 7. As is clear from these figures, the acid concentration is 0.0
In the case of 5 N, the solubility of manganese is not recognized,
The magnesium content was high and did not show lithium adsorption. In the case of 0.25 N, a magnesium content of about 2% was obtained in the treatment time of 45 to 55 days.
In that case, the elution rate of manganese was 9 to 10%. Further
In the case of 1.25 N, a magnesium content of 0% was obtained, but the elution rate of manganese also increased, and the value was 12%.
The above is reached. As described above, in the case of the treatment method using only the acid solution, when producing an adsorbent (magnesium content of 5% or less) exhibiting high lithium adsorbability, a drawback accompanied by elution of about 10% manganese was observed. .
第１図は、本発明の製造方法によるＭg ２Ｍn Ｏ４から
のマグネシウムの溶出性を示したものである。すなわ
ち、処理温度50〜90℃における処理時間と生成物中のマ
グネシウム含有率との関係を表した。▲−▲は処理温度
50℃、■−■は処理温度80℃、●−●は処理温度90℃の
場合である。 第２図はマグネシウム含有率およびマンガン溶出率に及
ぼすペルオクソ二硫酸アンモニウム濃度の影響を調べた
ものである。縦軸左はマグネシウム含有率（％）を表
し、●−●で示した。縦軸右はマンガン溶出率（％）を
表し、▲−▲で示した。 第３図はペルオクソ二硫酸アンモニウム溶液の濃度、１
Ｎおよび２Ｎの場合での固液比と生成物中のマグネシウ
ム含有率との関係を調べたものである。▲−▲は１Ｎ、
●−●は２Ｎの場合である。 第４図は固液比 3g ／ 100mlの場合での処理時間とマグ
ネシウム含有率およびマンガン溶出率との関係を調べた
ものである。縦軸左はマグネシウム含有率を表し、●−
●で示した。縦軸右はマンガン溶出率を表し、▲−▲で
示した。 第５図は吸着中のマグネシウム含有率とリチウム吸着率
の一例を示すグラフであり、横軸はマグネシウム含有率
（％）、縦軸はリチウム吸着率を表す。 第６図は塩酸溶液を用いた場合である。○−○、●−●
は 0.05 Ｎ、△−△、▲−▲は 0.25 Ｎ、□−□、■−
■は 1.25 Ｎの場合である。 第７図は硝酸溶液を用いた場合である。 ○−○、●−●は 0.05 Ｎ、△−△、▲−▲は 0.25
Ｎ、□−□、■−■は 1.25 Ｎの場合である。FIG. 1 shows the elution property of magnesium from Mg 2 Mn O 4 by the production method of the present invention. That is, the relationship between the treatment time at the treatment temperature of 50 to 90 ° C. and the magnesium content in the product was shown. ▲-▲ is the processing temperature
50 ℃, ■-■ is the processing temperature of 80 ℃, ●-● is the processing temperature of 90 ℃. FIG. 2 shows the effect of ammonium peroxodisulfate concentration on the magnesium content and manganese elution rate. The left side of the vertical axis represents the magnesium content rate (%), which is indicated by ●-●. The manganese elution rate (%) is shown on the right of the vertical axis, and is shown by ▲-▲. Figure 3 shows the concentration of ammonium peroxodisulfate solution, 1
The relationship between the solid-liquid ratio in the cases of N and 2N and the magnesium content in the product was investigated. ▲-▲ is 1N,
●-● is for 2N. FIG. 4 shows the relationship between the treatment time and the magnesium content and manganese elution rate when the solid-liquid ratio was 3 g / 100 ml. The left side of the vertical axis represents the magnesium content rate, and-
Shown with ●. The right side of the vertical axis represents the elution rate of manganese, which is indicated by ▲-▲. FIG. 5 is a graph showing an example of the magnesium content rate and the lithium adsorption rate during adsorption, wherein the horizontal axis represents the magnesium content rate (%) and the vertical axis represents the lithium adsorption rate. FIG. 6 shows the case where a hydrochloric acid solution is used. ○ − ○, ● − ●
Is 0.05 N, △-△, ▲-▲ is 0.25 N, □-□, ■-
■ is for 1.25 N. FIG. 7 shows the case of using a nitric acid solution. ○-○, ●-● is 0.05 N, △-△, ▲-▲ is 0.25
N, □-□, and ■-■ are for 1.25 N.
Claims (1)
溶液あるいは臭素水で処理して、大部分のマグネシウム
を溶出除去することを特徴とするリチウム吸着剤の製造
方法。1. A method for producing a lithium adsorbent, characterized in that Mg 2 MnO 4 is treated with a solution containing peroxodisulfate or bromine water to elute and remove most of magnesium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63083497A JPH0626660B2 (en) | 1988-04-04 | 1988-04-04 | New manufacturing method of lithium adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63083497A JPH0626660B2 (en) | 1988-04-04 | 1988-04-04 | New manufacturing method of lithium adsorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01254246A JPH01254246A (en) | 1989-10-11 |
| JPH0626660B2 true JPH0626660B2 (en) | 1994-04-13 |
Family
ID=13804116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63083497A Expired - Lifetime JPH0626660B2 (en) | 1988-04-04 | 1988-04-04 | New manufacturing method of lithium adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0626660B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117957057B (en) * | 2023-12-21 | 2026-01-02 | 广东邦普循环科技有限公司 | A composite lithium extraction adsorbent, its preparation method and application |
-
1988
- 1988-04-04 JP JP63083497A patent/JPH0626660B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01254246A (en) | 1989-10-11 |
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