JPH03262530A - Manganese dioxide for adsorbing lithium and preparation thereof - Google Patents
Manganese dioxide for adsorbing lithium and preparation thereofInfo
- Publication number
- JPH03262530A JPH03262530A JP6006090A JP6006090A JPH03262530A JP H03262530 A JPH03262530 A JP H03262530A JP 6006090 A JP6006090 A JP 6006090A JP 6006090 A JP6006090 A JP 6006090A JP H03262530 A JPH03262530 A JP H03262530A
- Authority
- JP
- Japan
- Prior art keywords
- manganese dioxide
- lithium
- peroxidation
- degree
- reduction treatment
- 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
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 123
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 47
- 238000005502 peroxidation Methods 0.000 claims abstract description 19
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 hydrazine compound Chemical class 0.000 claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 abstract description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000377 hydrazine sulfate Inorganic materials 0.000 abstract 1
- 239000012493 hydrazine sulfate Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- SWGZHHCRMZDRSN-BTJKTKAUSA-N (Z)-but-2-enedioic acid 1-phenoxypropan-2-ylhydrazine Chemical compound OC(=O)\C=C/C(O)=O.NNC(C)COC1=CC=CC=C1 SWGZHHCRMZDRSN-BTJKTKAUSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910011197 Li2Co Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910016978 MnOx Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、種々の金属イオンを含有する溶液から、選択
的にリチウムを吸着するリチウム吸着用二酸化マンガン
及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to manganese dioxide for lithium adsorption that selectively adsorbs lithium from solutions containing various metal ions, and a method for producing the same.
〈従来の技術及び発明が解決しようとする課動これまで
、他の金属イオンと共存するリチウムイオンを選択的に
回収する方法としては、有機溶媒で抽出する方法（米国
特許第３、３０７．９２２号明細書）及び可溶性アルミ
ニウム塩を用いる共沈法（米国特許第２．９６４．３８
１号明細書）が知られている。しかし、これらの方法は
リチウム含量の高い溶液中からリチウムを回収するには
比較的良好な結果を示すが、海水などのようにリチウム
含量の低い溶液からの回収には多量の有機溶媒又は塩類
を必要とするので不適当である。<Issues to be solved by the prior art and the invention Up to now, as a method for selectively recovering lithium ions coexisting with other metal ions, there has been a method of extraction with an organic solvent (U.S. Pat. No. 3,307,922). 2.964.38) and a coprecipitation method using soluble aluminum salts (U.S. Pat. No. 2.964.38)
1) is known. However, although these methods show relatively good results in recovering lithium from solutions with high lithium content, they require the use of large amounts of organic solvents or salts when recovering lithium from solutions with low lithium content, such as seawater. It is inappropriate because it requires
また、Ｍｎ系吸着剤（λ型ＭｎＯ，）とＬｉ塩とを混合
し、熱処理した後に、Ｌｉを溶出する方法があるが、Ｌ
１吸着量が満足できる地のではなかった（Ｍｎ： Ｌｉ
＝２： １モル此程度、っまｔ＋Ｌｉが４％程度し
かＭｎ化合物中に吸着できない）。In addition, there is a method in which a Mn-based adsorbent (λ type MnO,) and Li salt are mixed, heat treated, and then Li is eluted.
1 adsorption amount was not satisfactory (Mn: Li
=2: Only about 4% of 1 mole of Li can be adsorbed into the Mn compound).
本発明は、以上述べた事情に鑑み、リチウムを効率よく
選択的に回収し得るリチウム吸着用二酸化マンガン及び
その製造方法を提供することを目的とする。SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, an object of the present invention is to provide manganese dioxide for adsorbing lithium, which can efficiently and selectively recover lithium, and a method for producing the same.
く課題を解決するための手段〉
本発明者らは、前記目的を達成するために鋭意研究を重
ねた結果、二酸化マンガンをヒドラジン化合物で還元し
て得られた過酸化度の低い二酸化マンガンが、大きいリ
チウム吸着能を有することを見出し、この知見に基いて
本発明を完成した。Means for Solving the Problems> As a result of intensive research to achieve the above object, the present inventors found that manganese dioxide with a low degree of peroxidation obtained by reducing manganese dioxide with a hydrazine compound, It was discovered that it has a large lithium adsorption capacity, and the present invention was completed based on this knowledge.
かかる知見に基づき、本発明に係るリチウム吸着用の二
酸化マンガンの構成は、還元処理したリチウム吸着用二
酸化マンガンであって、還元処理後の二酸化マンガンの
過酸化度が１．４５〜１．９５であることを特徴とする
。Based on this knowledge, the composition of the manganese dioxide for lithium adsorption according to the present invention is reduced-treated manganese dioxide for lithium adsorption, and the degree of peroxidation of the manganese dioxide after the reduction treatment is 1.45 to 1.95. characterized by something.
一方の、リチウム吸着用二酸化マンガンの製造方法は、
二酸化マンガンをヒドラジン化合物で還元することを特
徴とする。On the other hand, the method for producing manganese dioxide for lithium adsorption is as follows:
It is characterized by reducing manganese dioxide with a hydrazine compound.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明でリチウム吸着用二酸化マンガンとは、還元処理
後の過酸化度が１，４５〜１，９５の低過酸化度の二酸
化マンガンをいい、還元処理される二酸化マンガンとし
ては、例えば電解法により得たγ型二酸化マンガン、こ
のγ型二酸化マンガンを熱処理して得たβ型二酸化マン
ガン、化学的に合成した化学二酸化マンガン、電解中あ
るいは化学合成中にリン酸を用いてリンを含有させてな
るリン含有二酸化マンガン等を挙げる乙とができる。In the present invention, manganese dioxide for adsorbing lithium refers to manganese dioxide with a low peroxidation degree of 1,45 to 1,95 after reduction treatment, and manganese dioxide to be subjected to reduction treatment includes, for example, electrolytic method. The obtained γ-type manganese dioxide, the β-type manganese dioxide obtained by heat-treating the γ-type manganese dioxide, the chemically synthesized chemical manganese dioxide, and the γ-type manganese dioxide obtained by adding phosphorus using phosphoric acid during electrolysis or chemical synthesis. Examples include phosphorus-containing manganese dioxide, etc.
リチウム吸着用二酸化マンガンとしては過酸化度が１．
４５〜１．９５とするのが好ましい。Manganese dioxide for lithium adsorption has a peroxidation degree of 1.
It is preferable to set it as 45-1.95.
これは、１．４５未満に還元することは困難であり、ま
た１、９５を超えるとリチウム吸着能の増大効果が少な
くなり、共に好ましくないからである。This is because it is difficult to reduce the number to less than 1.45, and if it exceeds 1.95, the effect of increasing the lithium adsorption capacity will be reduced, both of which are undesirable.
還元処理は、とドラジン化合物の水溶液を用いるのが好
ましく、この処理液中のヒドラジン化合物の濃度を０．
０５〜０．５ ｍｊ ／ Ｉとすることにより、低過酸
化度が１．４５〜１．９５の範囲の二酸化マンガンを得
ることができる。In the reduction treatment, it is preferable to use an aqueous solution of a hydrazine compound, and the concentration of the hydrazine compound in this treatment solution is set to 0.
By setting it as 05 to 0.5 mj/I, manganese dioxide with a low peroxidation degree in the range of 1.45 to 1.95 can be obtained.
またヒドラジン化合物としては、抱水ヒドラジン、硫酸
とドラジン、塩酸ヒドラジン等の還元用ヒドラジンを例
示できる。Examples of the hydrazine compound include hydrazine for reduction, such as hydrazine hydrate, sulfuric acid and drazine, and hydrazine hydrochloride.
また、この還元の際の還元処理時間及び温度は、１０分
〜１時間、２０〜８０℃の条件とするのがよい。The reduction treatment time and temperature during this reduction are preferably 10 minutes to 1 hour and 20 to 80°C.
還元処理後の二酸化マンガンは、濾過、乾燥させた後月
いればよい。The manganese dioxide after reduction treatment can be used for a month after being filtered and dried.
このように還元処理された過酸化度が１．４５〜１．９
５の低過酸化度の二酸化マンガンは、各種イオンの含有
した溶液からリチウムのみを選択的に吸着するリチウム
吸着剤として用いて好適である。The degree of peroxidation after reduction treatment is 1.45 to 1.9.
Manganese dioxide having a low degree of peroxidation No. 5 is suitable for use as a lithium adsorbent that selectively adsorbs only lithium from a solution containing various ions.
第１図に本発明に係るリチウム吸着用二酸化マンガンが
リチウムイオンを吸着する状態を示す。FIG. 1 shows a state in which the manganese dioxide for lithium adsorption according to the present invention adsorbs lithium ions.
同図に示すように、低過酸化度二酸化マンガンからなる
リチウム吸着剤は、該吸着剤の内部又は表面に、多量の
水酸基を有しており、この水酸基のプロトンがリチウム
イオンとｐＨによっては璽換して（アルカリ側で口換す
る）吸着することにより、リチウムイオンを多量に吸着
できる。As shown in the figure, a lithium adsorbent made of manganese dioxide with a low peroxide degree has a large amount of hydroxyl groups inside or on the surface of the adsorbent, and the protons of these hydroxyl groups can interact with lithium ions depending on the pH. A large amount of lithium ions can be adsorbed by exchanging the lithium ions (exchanging them with the alkaline side).
これに対し、従来例に係るＭｎ系（λＷＩＭ ｎ Ｏ，
）吸着剤は、第２図に示すように焼成して水分を飛ばし
て合成していたためにリチウムイオンを吸着し得ろす〜
イドが、Ｍｎイオンの欠損部分しかなかったため、リチ
ウムイオンを吸着できる部分が少なかったと思料される
。On the other hand, the conventional Mn system (λWIM n O,
) As shown in Figure 2, the adsorbent was synthesized by firing to remove water, so it was able to adsorb lithium ions.
It is thought that because the id had only a defective portion of Mn ions, there were few portions that could adsorb lithium ions.
く実 施 例〉
以下、本発明を実施例及び比較例に基づき具体的に説明
する。EXAMPLES The present invention will be specifically described below based on Examples and Comparative Examples.
実施例１
加温装雪を設けた内容積２１の処理槽内に満たされ？：
０．０５ ｍｏｌ ／ ｌ抱水ヒドラジン水溶液中に、
電解二酸化マンガン（γ型ＭｎＯ２）１００ｇを投入し
撹拌しながら反応温度５０℃で２０分間反応させた後、
常法の濾過、乾燥処理を行ない低過酸化度の二酸化マン
ガンを得た。このときの過酸化度を第１表に示す。Example 1 A treatment tank with an internal volume of 21 equipped with a heating snow cover was filled with water. :
In a 0.05 mol/l hydrazine hydrate aqueous solution,
After adding 100 g of electrolytic manganese dioxide (γ-type MnO2) and reacting with stirring at a reaction temperature of 50°C for 20 minutes,
Manganese dioxide with a low degree of peroxidation was obtained by performing conventional filtration and drying processes. The degree of peroxidation at this time is shown in Table 1.
得られた低過酸化度の二酸化マンガン１００ｇを、リチ
ウム３０ｇを含有する溶液ｌｌ中に入れ、７５℃に加温
し、ｐＨを１０に調整した状態で２００時間撹拌する。100 g of the obtained manganese dioxide with a low peroxidation degree is placed in 1 l of a solution containing 30 g of lithium, heated to 75° C., and stirred for 200 hours while adjusting the pH to 10.
その後、常法に従い濾過、乾燥をし、低過酸化度の二酸
化マンガン中のリチウム含有を測定し、リチウム吸着率
を求めた。Thereafter, it was filtered and dried according to a conventional method, and the lithium content in manganese dioxide with a low degree of peroxidation was measured to determine the lithium adsorption rate.
その結果を第１表に示す。The results are shown in Table 1.
実施例２〜４
実＃１例１の抱水ヒドラジン濃度を０．１ｍｏｌ／Ｉ、
０．２ｍｏｌ／ｊ、０．５ｍｏｌ／Ｊとした以外は実施
例１と同様に操作して低過酸化度の二酸化マンガンを得
た後、実施例１と同様に操作して各々のリチウム吸着率
を求めた。Examples 2-4 Fruit #1 The concentration of hydrazine hydrate in Example 1 was 0.1 mol/I,
After obtaining manganese dioxide with a low degree of peroxidation by operating in the same manner as in Example 1 except that the amounts were 0.2 mol/j and 0.5 mol/J, each lithium adsorption rate was obtained by operating in the same manner as in Example 1. I asked for
各々の結果を第１表に示す。The results are shown in Table 1.
実施例５
加温装置を設けた内容積３１の電解槽に陽極としてチタ
ン板、陰極として黒鉛板をそれぞれ交互に懸吊せしめ、
電解槽の底部に硫酸マンガンおよびリンｌｌ溶液からな
る電解補給液の添加管を設けたものを使用した。Example 5 A titanium plate as an anode and a graphite plate as a cathode were alternately suspended in an electrolytic cell with an internal volume of 31 equipped with a heating device,
The electrolytic cell used had an addition tube for an electrolytic replenishment solution consisting of manganese sulfate and phosphorus solution at the bottom.
電解補給液は、硫酸マンガン溶液にリン酸を０．５ｇ／
ｌとなるように調整した。The electrolytic replenishment solution is 0.5g/0.5g of phosphoric acid in manganese sulfate solution.
It was adjusted to be 1.
この補給液を前記電解槽に注入しながら、電解するに際
して、電解液の組成をマンガン５０ｇ／ｊ、硫酸８０ｇ
／ｌとなるように調整し、電解は電解浴の温度を９５±
１℃に保ち、電流密度１００ Ａ ／ ｒｒ？で行なっ
た。While injecting this replenishing solution into the electrolytic cell, the composition of the electrolytic solution is changed to 50g/j of manganese and 80g/j of sulfuric acid.
/l, and for electrolysis, the temperature of the electrolytic bath was adjusted to 95±
Maintained at 1°C, current density 100 A/rr? I did it.
電解終了後、電解二酸化マンガンが電着した陽極板を取
り出し、常法の後処理を実施し、リンを含有するリン含
有二酸化マンガンを得た。After the electrolysis was completed, the anode plate on which the electrolytic manganese dioxide was electrodeposited was taken out and subjected to a conventional post-treatment to obtain phosphorus-containing manganese dioxide containing phosphorus.
得られたリン含有二酸化マンガンを用いて、実施例１と
ゝ同様に操作し、リチウム吸着率を求めた。The obtained phosphorus-containing manganese dioxide was operated in the same manner as in Example 1 to determine the lithium adsorption rate.
その結果を第１表に示す。The results are shown in Table 1.
実ｍ例６
炭酸マンガンと塩素酸カリウムとの混合物を３００℃に
加熱して、化学二酸化マンガンを得た。Practical Example 6 A mixture of manganese carbonate and potassium chlorate was heated to 300°C to obtain chemical manganese dioxide.
この得られた化学二酸化マンガンを用い実施例１と同様
に操作し、リチウム吸着率を求めた。The obtained chemical manganese dioxide was operated in the same manner as in Example 1 to determine the lithium adsorption rate.
その結果を第１表に示す。The results are shown in Table 1.
実施例７
実施例１で用いた電解二酸化マンガンを酸性溶液中でス
ラリーにして３８０〜４５０℃に加温してβ型二酸化マ
ンガンを得た。Example 7 The electrolytic manganese dioxide used in Example 1 was slurried in an acidic solution and heated to 380 to 450°C to obtain β-type manganese dioxide.
この得られたβ型二酸化マンガンを用い、実施例１と同
様に操作し、リチウム吸着率を求めた。The obtained β-type manganese dioxide was operated in the same manner as in Example 1 to determine the lithium adsorption rate.
その結果を第１！！に示す。The results are number one! ! Shown below.
比較例ｌ
Ｍｎ０．１００ ｇとＬｉ２Ｃｏ、 ２３．４ ｇ （
Ｍｎ： Ｌｉ＝２： １のモル比）を混合し、ｓｓｏ℃
で６時間、８５０℃で１４時間空気中において熱処理し
、スピネル型二酸化マンガンを得た。Comparative Example 1 0.100 g of Mn and 23.4 g of Li2Co (
Mn:Li=2:1 molar ratio) was mixed and heated at sso°C.
The mixture was heat-treated at 850° C. for 6 hours and in air at 850° C. for 14 hours to obtain spinel-type manganese dioxide.
このスピネル型二酸化マンガン３０ｇを４Ｎの硫酸中に
１７０時間浸漬した後、２１の純水で洗浄して、λ型二
酸化マンガンを得た。After immersing 30 g of this spinel type manganese dioxide in 4N sulfuric acid for 170 hours, it was washed with 21 pure water to obtain λ type manganese dioxide.
この得られたλ型二酸化マンガンを用いて、実施例１と
同様にリチウム吸着を行い、そのリチウム吸着率を求め
た。Using the obtained λ-type manganese dioxide, lithium adsorption was performed in the same manner as in Example 1, and the lithium adsorption rate was determined.
その畔果を、第１表に示す。The fruits are shown in Table 1.
比較例２
実施例１で用いた電解二酸化マンガン（γ型Ｍｎ０２）
を還元処理を行なわず、リチウム吸着を行いそのリチウ
ム吸着率を求めた。Comparative Example 2 Electrolytic manganese dioxide (γ-type Mn02) used in Example 1
was subjected to lithium adsorption without reduction treatment, and the lithium adsorption rate was determined.
その結果を第１表に示す。The results are shown in Table 1.
尚実施例、比較例で吸着されたリチウムは、ｐＨが酸性
側の溶液に漬けることにより、簡単に脱着する。Note that the lithium adsorbed in the Examples and Comparative Examples is easily desorbed by immersing it in a solution with an acidic pH.
還元処理後のＭ ｎ Ｏｘ値
二酸化マンガン１００重量部中のリチウム含有量第１表
の結果に示すように、実施例１〜７で得られた低過酸化
度の二酸化マンガンは、比較例１，２と比較して、低い
過酸化度を有すると共に、高いＬｉ吸着率を有すること
が判明した。MnOx value after reduction treatment Lithium content in 100 parts by weight of manganese dioxide As shown in the results in Table 1, manganese dioxide with a low degree of peroxidation obtained in Examples 1 to 7 was compared to Comparative Example 1, It was found that it had a lower degree of peroxidation and a higher Li adsorption rate compared to No. 2.
ま７た、実施例１〜４のγ型ＭｎＯ２に比べて、実施例
５，６のリン含有Ｍ ｎ Ｏ，、化学Ｍ ｎ Ｏ，は、
特に高い吸着能を有している。これは、リン含有Ｍ ｎ
Ｏ２及び化学Ｍ ｎ Ｏ，は、比表面積が大で、結合
水を多く持っているからであると思料する。Moreover, compared to the γ-type MnO2 of Examples 1 to 4, the phosphorus-containing MnO, chemical MnO, of Examples 5 and 6,
It has particularly high adsorption capacity. This is the phosphorus-containing M n
This is thought to be because O2 and chemical M n O, have a large specific surface area and contain a large amount of bound water.
〈発明の効果〉
以上述べたように、本発明のリチウム吸着用二酸化マン
ガンは、還元処理をして過酸化度を１．４５〜１．９５
とすることにより、高いリチウム吸着能を有し、リチウ
ム回収用材料として用いて好適である。<Effects of the Invention> As described above, the manganese dioxide for lithium adsorption of the present invention is reduced to a degree of peroxidation of 1.45 to 1.95.
As a result, it has a high lithium adsorption capacity and is suitable for use as a lithium recovery material.
第１図は本発明に係るリチウム吸着剤のリチウム吸着状
態を示す状態図、第２図は従来例に係るリチウム吸着剤
のリチウム吸着状態を示す状態図である。FIG. 1 is a state diagram showing the lithium adsorption state of the lithium adsorbent according to the present invention, and FIG. 2 is a state diagram showing the lithium adsorption state of the lithium adsorbent according to the conventional example.
Claims (1)
て、 還元処理後の二酸化マンガンの過酸化度が １．４５〜１．９５であることを特徴とするリチウム吸
着用二酸化マンガン。 ２）二酸化マンガンをヒドラジン化合物で還元すること
を特徴とするリチウム吸着用二酸化マンガンの製造方法
。[Scope of Claims] 1) Manganese dioxide for lithium adsorption that has been subjected to a reduction treatment, characterized in that the degree of peroxidation of the manganese dioxide after the reduction treatment is 1.45 to 1.95. . 2) A method for producing manganese dioxide for lithium adsorption, which comprises reducing manganese dioxide with a hydrazine compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6006090A JP2847417B2 (en) | 1990-03-13 | 1990-03-13 | Manganese dioxide for lithium adsorption and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6006090A JP2847417B2 (en) | 1990-03-13 | 1990-03-13 | Manganese dioxide for lithium adsorption and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03262530A true JPH03262530A (en) | 1991-11-22 |
| JP2847417B2 JP2847417B2 (en) | 1999-01-20 |
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ID=13131165
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08173796A (en) * | 1994-09-02 | 1996-07-09 | Sakai Chem Ind Co Ltd | Nitrogen oxide oxidizing adsorbent and nitrogen oxide removing method |
| JP2008534423A (en) * | 2005-03-30 | 2008-08-28 | エスケー エネルギー 株式会社 | Spherical manganese carbonate precipitation method and product produced thereby |
| JP2011251862A (en) * | 2010-06-01 | 2011-12-15 | Tosoh Corp | Manganese oxide and method for producing the same |
| JP2014205617A (en) * | 2014-06-12 | 2014-10-30 | 東ソー株式会社 | Manganese oxide and method for producing lithium manganate using the same |
-
1990
- 1990-03-13 JP JP6006090A patent/JP2847417B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08173796A (en) * | 1994-09-02 | 1996-07-09 | Sakai Chem Ind Co Ltd | Nitrogen oxide oxidizing adsorbent and nitrogen oxide removing method |
| JP2008534423A (en) * | 2005-03-30 | 2008-08-28 | エスケー エネルギー 株式会社 | Spherical manganese carbonate precipitation method and product produced thereby |
| JP2011251862A (en) * | 2010-06-01 | 2011-12-15 | Tosoh Corp | Manganese oxide and method for producing the same |
| JP2014205617A (en) * | 2014-06-12 | 2014-10-30 | 東ソー株式会社 | Manganese oxide and method for producing lithium manganate using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2847417B2 (en) | 1999-01-20 |
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