JPS5820729A - Preparation of manganese oxide - Google Patents
Preparation of manganese oxideInfo
- Publication number
- JPS5820729A JPS5820729A JP11726581A JP11726581A JPS5820729A JP S5820729 A JPS5820729 A JP S5820729A JP 11726581 A JP11726581 A JP 11726581A JP 11726581 A JP11726581 A JP 11726581A JP S5820729 A JPS5820729 A JP S5820729A
- Authority
- JP
- Japan
- Prior art keywords
- manganese
- manganese oxide
- oxidation
- suspension
- oxidizing agent
- 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.)
- Pending
Links
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【発明の詳細な説明】
承発明は、酸化マンガンの製造方法に関し、詳述すれば
、特にフェライト用原料として好適な、酸化度が1.3
〜1・5で微粒子形状の酸化χ/がンを経済的に製造す
る方法に関する。DETAILED DESCRIPTION OF THE INVENTION The claimed invention relates to a method for producing manganese oxide, and more specifically, the invention relates to a method for producing manganese oxide, which has an oxidation degree of 1.3 and is particularly suitable as a raw material for ferrite.
1.5 relates to a method for economically producing oxidized χ/gun in the form of fine particles.
従来より、酸化マンガンは、攬々の方法で製造されてい
るが、それらの方法には、次のような問題点がある。例
えば、マンがン酸化物の解離反応による方法は、その解
離温度が940℃以上と高い。Conventionally, manganese oxide has been produced by many methods, but these methods have the following problems. For example, a method using a dissociation reaction of manganese oxide has a high dissociation temperature of 940° C. or higher.
また、低い温度で反応を進行させる場合においては、水
素を必要とするなどの欠点がある。さらに、炭酸マンが
ン、水酸化マ/がン、塩化マンガンなどからも酸化マン
ガンは得られるが、6塩の揮発性物質を除去するために
1000℃以上の高い温度での加熱が必要となる。Furthermore, when the reaction is allowed to proceed at low temperatures, there are drawbacks such as the need for hydrogen. Furthermore, manganese oxide can be obtained from manganese carbonate, manganese hydroxide, manganese chloride, etc., but heating at a high temperature of 1000°C or higher is required to remove the volatile substances of the hexasalt. .
しかも、上記のごとき方法は、鍋温での加熱に起因する
非経済性に加えて、フェライト用原料として用いられる
のに要求されるような酸化度が制御され且つ微細な粒子
から成る酸化マンガンを得ることはきわめて困難である
という欠点も有する。Moreover, in addition to being uneconomical due to heating at pot temperature, the above method does not require manganese oxide to be produced which has a controlled oxidation degree and consists of fine particles, which is required for use as a raw material for ferrite. It also has the disadvantage that it is extremely difficult to obtain.
すなわち、従来の方法によって、フェライト原料として
好適な酸化度1.3〜1.5の酸化マンガンを得るには
、加熱工程における操作条件をきわめて紙積に制御する
必要があり事実上不可能に近く、また、微細な酸化マン
がンを得るには、そのために別の工程を必要とする。In other words, in order to obtain manganese oxide with an oxidation degree of 1.3 to 1.5, which is suitable as a ferrite raw material, by the conventional method, it is necessary to control the operating conditions in the heating step extremely closely, which is virtually impossible. In addition, to obtain fine manganese oxide, another process is required.
そこで、本発明の目的は、上記のごとき欠点を−消し、
フェライト用原料として使用され得るような酸化度が制
御された微粒子の酸化マンガンを経済的に製造する方、
法を提供するにある。Therefore, the purpose of the present invention is to eliminate the above drawbacks,
A method for economically producing manganese oxide in the form of fine particles with a controlled degree of oxidation that can be used as a raw material for ferrite;
It is in providing the law.
本発明者らは、該目的を達成するために研究を菖ねた結
果、硫酸マンがン水溶液とアンモニア水との反応によっ
て水酸化マンガンの懸濁液を形成させ、葭液中K、直接
、酸化剤を添加すれば、酸−化虻の制御が容易に行なわ
れつつ酸化マンガンを生成させることができ、その後、
濾過し乾燥処理ヰ
するだけで所望の酸化度を有し且つ微細な一化マンfン
を得ることができることを見出した。かくして、本発明
に従えば、硫酸マンガン水溶液とアンモニア水とを反応
させて、水酸化マン2//の懸濁液を形成させる工程、
前記lIi!濁液に酸化剤を添加して所望の酸化度の酸
化マンガンを得る工程、および該酸化マンがンを濾過し
乾燥する工程から成ることを特゛徴とする、酸化度が1
.!1〜1.5の酸化マンがンの製造方法が提供される
。(なお、本明細書において用いる酸化度という飴は、
酸化マンガンをMnOxとして表わしたときのXの値を
意味するものである。)
本発明における硫酸マンガン水溶液とアンモニア水とを
反応させて水酸化マンがンの懸濁液を形成させる工程は
、水酸化マンガンが効率的に生成され、はっ、不純物を
含有しないような条件で行なわれるべきである。したが
って、該反応は、Mn濃度が100〜220 f’/l
の硫酸インがン尿溶液に、1〜6Nのアンモニア水を添
加し、pH9,0〜10.2の条件下で行なわれること
が好ましい。硫酸マンがン水溶液中のMn 9度が10
0171以下では生産性、反応効率が悪くなり、220
t/を以上では溶解しない硫酸マンガンが存すること
になる。アンモニア水は、低lll−程、生成する水酸
化マンがン中に不純物の混入が無く良好であるが、1N
以下では生産性が悪くなり、一方、6N以上では不純物
の巻込みが多くなるため1N〜6Nの濃度のものを用い
るのが好ましい。The present inventors conducted research to achieve this objective, and found that a suspension of manganese hydroxide was formed by the reaction between an aqueous solution of manganese sulfate and aqueous ammonia, and K in the soybean solution was directly absorbed. By adding an oxidizing agent, manganese oxide can be generated while easily controlling oxidizing flies, and then,
It has been found that fine manganide having a desired degree of oxidation can be obtained by simply filtering and drying. Thus, according to the invention, reacting an aqueous manganese sulfate solution with aqueous ammonia to form a suspension of manganese hydroxide
Said lIi! The method is characterized by comprising a step of adding an oxidizing agent to the suspension to obtain manganese oxide with a desired degree of oxidation, and a step of filtering and drying the manganese oxide.
.. ! 1 to 1.5 is provided. (In addition, the candy called oxidation degree used in this specification is
It means the value of X when manganese oxide is expressed as MnOx. ) In the present invention, the step of reacting an aqueous manganese sulfate solution with aqueous ammonia to form a suspension of manganese hydroxide is carried out under conditions such that manganese hydroxide is efficiently produced and does not contain any impurities. It should be done in Therefore, the reaction is performed at a Mn concentration of 100 to 220 f'/l.
It is preferable to add 1 to 6N aqueous ammonia to the sulfuric acid urine solution under conditions of pH 9.0 to 10.2. Mn in manganese sulfate aqueous solution 9 degrees is 10
If it is less than 0171, productivity and reaction efficiency will be poor, and if it is less than 220
There will be manganese sulfate that does not dissolve above t/. The lower the ammonia water is, the better it is because there will be no impurities in the manganese hydroxide produced, but 1N
If it is less than 6N, the productivity will be poor, while if it is more than 6N, more impurities will be included, so it is preferable to use a concentration of 1N to 6N.
また、g)Hを9.0〜10.2とする理由は、マンガ
ンを能率よく酸化させるためである。す・なわちpHが
9・0以下になるとマンガンの酸化の能率は低下し、他
方、pHが10−.2以上となると硫酸マンが/水溶液
に含まれているアルカリ、アルカリ土類などの不純物の
混入が多くなるとともに、周知のように、水酸化マンが
ンの一部が錯イオンとなって浴けてマンガンの回収率を
低下させるので好ましくない。Moreover, the reason why g) H is set to 9.0 to 10.2 is to efficiently oxidize manganese. In other words, when the pH is below 9.0, the efficiency of manganese oxidation decreases, and on the other hand, when the pH is below 10. When the value is 2 or more, impurities such as alkali and alkaline earth contained in the manganese sulfate/aqueous solution increase, and as is well known, part of the manganese hydroxide becomes complex ions and becomes difficult to absorb in the bath. This is not preferable because it reduces the recovery rate of manganese.
次いで、本発明の方法においては、上記のようにして得
られた水酸化マンガンの懸濁液に、直接、酸化剤を添加
することによって酸化マンガンが製造される。酸化剤と
しては、各種の酸化剤が使用可能でめゐが、水酸化マン
がンとの反応性や後の処理工程を考慮すれば、過酸化水
素水、酸素、または空気を用いるのが好適である。かく
して、本発明に従えば、液状の酸化剤を用いる場合には
、その濃度を制御することによって、得られる酸化マン
ガンの酸化度を容易に制御することができる。Next, in the method of the present invention, manganese oxide is produced by directly adding an oxidizing agent to the suspension of manganese hydroxide obtained as described above. Various oxidizing agents can be used as the oxidizing agent, but in consideration of reactivity with manganese hydroxide and subsequent processing steps, it is preferable to use hydrogen peroxide, oxygen, or air. It is. Thus, according to the present invention, when a liquid oxidizing agent is used, the degree of oxidation of the obtained manganese oxide can be easily controlled by controlling its concentration.
例えば、過酸化水素水を用いる場合にはその濃度は1〜
15パ一セント濃度とすることによって、所望の酸化度
(1,3〜1.5)の酸化マンがンを得ることができる
。過酸化水素水の濃度が15/量−セント濃度以上では
vno2となつ、でしまい、一方、1パ一セント濃度以
下では生産性が悪く実用的でない。また、酸素や空気を
酸化剤として用いる場合には、その吹き込み速度や吹き
込み時間を調節することによって、得られる酸化マンガ
ンの酸化度を容易に制御することができる。なお、酸化
剤として、複数の酸化剤を混合して用いることもできる
。For example, when using hydrogen peroxide, the concentration is between 1 and
By setting the concentration to 15 percent, manganese oxide with a desired degree of oxidation (1.3 to 1.5) can be obtained. If the concentration of the hydrogen peroxide solution is more than 15/volume-cent concentration, it will become vno2, whereas if it is less than 1 percent concentration, the productivity will be poor and it will not be practical. Further, when oxygen or air is used as an oxidizing agent, the degree of oxidation of the obtained manganese oxide can be easily controlled by adjusting the blowing speed and blowing time. Note that a mixture of a plurality of oxidizing agents can be used as the oxidizing agent.
最後に、本発明の方法においては、酸化剤の添加によっ
て所望の酸化度まで酸化して得られた酸化マンがンを濾
過し乾燥処理する。Finally, in the method of the present invention, the manganese oxide obtained by oxidizing to a desired degree of oxidation by adding an oxidizing agent is filtered and dried.
このようにして、本発明の方法に従えば、短時間で、し
かも低い温度(室温)で、所望の酸化度の酸化マンがン
を得ることができる。また、高濃度での処理であるため
に大量生産に適している。In this manner, according to the method of the present invention, manganese oxide having a desired degree of oxidation can be obtained in a short time and at a low temperature (room temperature). In addition, since it is processed at a high concentration, it is suitable for mass production.
さらに、水酸化マンガンの微粒子がそのまま酸化される
ため、得られる酸化マンガンは、粒子の状態が常に均一
で、1〜5μの大きさの比較的粒度構成が整った微細な
形状を成す、このように、本発明によって得られた酸化
マンガンは、微粒子であり、しかも仮焼するなどの工程
を必要としないなどの利点もあるために、フェライト用
原料としても好適なものである。Furthermore, since the fine particles of manganese hydroxide are oxidized as they are, the obtained manganese oxide is always in a uniform state and has a fine shape with a relatively uniform particle size structure of 1 to 5 μm. In addition, the manganese oxide obtained by the present invention has the advantage that it is fine particles and does not require steps such as calcining, so it is suitable as a raw material for ferrite.
添付図面は、本発明の方法を実施するのに好適な装置の
1例を示すものである。硫酸マンガン水浴液とアンモニ
ア水とを反応させる場合、攪拌機1と邪魔板4とを備え
る該装置内に硫酸マンガン水溶液を装入し、一方、ノズ
ル2を通してアンモニア水を導入する。水酸化マンがン
の懸濁液を酸化する場合には、ガス吹込みノズル3を通
して酸素や空気のごときガスを吹込′□み、または、ノ
ズル2を通してアンモニア水のごとき液状酸化剤を導入
し、あるいは、それらの酸化剤をノズル2と3を併用し
て混合導入する。生成物は、ドレン口5から取り出され
ろう
以下に本発明の実施例を掲げる。The accompanying drawing shows an example of a suitable apparatus for carrying out the method of the invention. When a manganese sulfate water bath solution and ammonia water are reacted, the manganese sulfate aqueous solution is charged into the apparatus equipped with a stirrer 1 and a baffle plate 4, while ammonia water is introduced through a nozzle 2. When oxidizing a suspension of manganese hydroxide, a gas such as oxygen or air is blown through the gas blowing nozzle 3, or a liquid oxidizing agent such as aqueous ammonia is introduced through the nozzle 2. Alternatively, these oxidizing agents are mixed and introduced using nozzles 2 and 3 in combination. The product will be removed from the drain port 5. Examples of the invention are listed below.
実施例1
Mn濃度150 tt/lの硫酸マンガン水溶液を作成
した。Example 1 A manganese sulfate aqueous solution with a Mn concentration of 150 tt/l was prepared.
ついで、上述の硫酸マンがン水溶液を図に示す攪拌機を
備えた反応槽に入れ2より2Nのアンモニア水を少量ず
つ添加した。このよう・にしてアンモニア水を添加し、
pH9,8で白色の水酸化マンがンを得た後、さらに攪
拌を続けなから6/9−セント濃度の過酸化水素水を少
量ずつ2より添加し、水酸化マンガンを酸化した。Next, the above-described aqueous solution of manganese sulfate was placed in a reaction tank equipped with a stirrer as shown in the figure, and 2N aqueous ammonia was added little by little. Add ammonia water in this way,
After obtaining white manganese hydroxide at pH 9.8, while stirring was continued, hydrogen peroxide solution with a concentration of 6/9 cents was added little by little to oxidize the manganese hydroxide.
酸化反応によって得られた褐色の生成物を5より取抄出
して濾過し、水洗した後に、140℃の温度で乾燥した
結果、第1表に示したとおりの組成をもつ微粒子の酸化
マンガンが得られた。The brown product obtained by the oxidation reaction was extracted from No. 5, filtered, washed with water, and dried at a temperature of 140°C. As a result, fine particles of manganese oxide having the composition shown in Table 1 were obtained. It was done.
第 1 表
なお、第1表及び以下の表におけるT、Mn(Tota
lMn)とは、生成酸化マンガンのMn品位(Mn 含
有量)を重量%で表わしたものである。Table 1 In addition, T, Mn (Tota
lMn) is the Mn grade (Mn content) of the produced manganese oxide expressed in weight %.
実施例2:
un a& 150 f/Jの硫酸9ンf7水溶液41
を作成し、実施例1と同様に反応槽内で白色の沈殿物を
生成せしめた後、3より02 ガスを毎分2Jの割合
で吹き込みながら、201. jO160,90分の攪
拌処理をし九〇
これにより得られた酸化マンが7を実施例1と同様KN
過および水洗し、乾燥処理し声とζろ−2表に示したと
うりの組成を有した微粒子の酸化マンがンが得られた。Example 2: Un a & 150 f/J of sulfuric acid 9 N f7 aqueous solution 41
After creating a white precipitate in the reaction tank in the same manner as in Example 1, 201. JO160, stirred for 90 minutes, and the resulting oxidized manganese 7 was mixed with KN as in Example 1.
After filtering, washing with water, and drying, fine particles of manganese oxide having the composition shown in Table 2 were obtained.
第2#!中で明らかなようKm什条件(吹込み量と時間
)Kよって酸什マンがンの組成は替化し、本実施例では
、A2〜7が最適条件である。2nd #! As is clear from the above, the composition of the oxidized manganese varies depending on the Km conditions (injection amount and time), and in this example, A2 to A7 are the optimum conditions.
M211i!
実施例3:
実施例2と同様の操作を繰シ返した。但し、02ガスの
かわ)K9気を用い、90,180 分の酸化反応を行
ない一過乾燥処理し九結果、第3辰に示したとうりの組
成を有した微粒子の酸化マンがン妙1得られた。M211i! Example 3: The same operation as in Example 2 was repeated. However, an oxidation reaction was carried out for 90,180 minutes using K9 gas instead of 02 gas, followed by temporary drying, and as a result, fine particles of oxidized manganese having the composition shown in the third section were obtained. It was done.
本wm例奄実施例2と同様、酸化条件によ・りで酸化マ
ンがンの組成は賛化し、本害施例ではム2゜3および4
に示す条件下に所望の酸化度のものが得られることがわ
かった・
#!3表
4、図面の簡単な貌&114 □図面は、本発
明の方法を寮施するのに好逼な袈−〇餉部断函図である
。As in Example 2, the composition of manganese oxide becomes favorable depending on the oxidation conditions, and in this example, the composition of manganese oxide becomes favorable depending on the oxidation conditions.
It was found that the desired degree of oxidation could be obtained under the conditions shown in #! 3 Table 4, Brief outline of the drawings & 114 □ The drawings are cross-section diagrams of the shank section suitable for applying the method of the present invention to the dormitory.
2;液体導入ノズル、3;fス吹込みノズル。2; liquid introduction nozzle; 3; f-s blowing nozzle.
Claims (1)
製造方法であって、硫酸マンガン水溶液とアンモニア水
とを反応させて、水酸化マンガンの懸濁液を形成させる
工程、前記懸濁液に酸化剤を添加して所望の酸化度の酸
化マンガンを得る工程、および該酸化マンガンを濾過し
乾燥する工程から成ることを特徴とする前記方法。 (2)硫酸マンガン水溶液とアンモニア水との反応が、
Mn 濃[1DO〜220 f/lにオイテ1〜6Nの
アンモニア水を添加し、G)H9−0〜10.2の条件
下で行なわれる前記第(1)項に記載の酸化マンガンの
製造方法。 131 酸化剤が、過酸化水素水、酸素または空気か
ら成る前記第f11項又は第(21項に記載の酸化マン
ガンの製造方法7[Claims] 111 A method for producing manganese oxide having an M degree of 1.3 to 1.5, which comprises reacting an aqueous solution of manganese sulfate with aqueous ammonia to form a suspension of manganese hydroxide. The method comprises the following steps: adding an oxidizing agent to the suspension to obtain manganese oxide with a desired degree of oxidation, and filtering and drying the manganese oxide. (2) The reaction between manganese sulfate aqueous solution and ammonia water is
The method for producing manganese oxide according to the above item (1), which is carried out by adding 1 to 6N ammonia water to Mn concentration [1DO to 220 f/l, and performing under the conditions of G) H9-0 to 10.2. . 131 The method for producing manganese oxide according to item f11 or item (21), wherein the oxidizing agent is hydrogen peroxide, oxygen, or air.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11726581A JPS5820729A (en) | 1981-07-27 | 1981-07-27 | Preparation of manganese oxide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11726581A JPS5820729A (en) | 1981-07-27 | 1981-07-27 | Preparation of manganese oxide |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS5820729A true JPS5820729A (en) | 1983-02-07 |
Family
ID=14707473
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP11726581A Pending JPS5820729A (en) | 1981-07-27 | 1981-07-27 | Preparation of manganese oxide |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5820729A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59223236A (en) * | 1983-06-02 | 1984-12-15 | Chuo Denki Kogyo Kk | Production of high purity manganese compound |
JPS60127917A (en) * | 1983-12-14 | 1985-07-08 | Amada Co Ltd | Cutting control method and device for sawing machine |
JPS6219319A (en) * | 1985-07-17 | 1987-01-28 | Amada Co Ltd | Lifting control method for hack sawing machine and device thereof |
US6039390A (en) * | 1996-08-20 | 2000-03-21 | Donnelly Corporation | Chromogenic window assembly construction and other chromogenic devices |
JP2001261343A (en) * | 2000-03-17 | 2001-09-26 | Unitika Ltd | Super fine particle of trimanganese tetraoxide and method of producing the same |
JP2003002654A (en) * | 2001-06-21 | 2003-01-08 | Naoaki Kumagai | Method for producing layered lithium manganese complex oxide and lithium secondary battery |
-
1981
- 1981-07-27 JP JP11726581A patent/JPS5820729A/en active Pending
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59223236A (en) * | 1983-06-02 | 1984-12-15 | Chuo Denki Kogyo Kk | Production of high purity manganese compound |
JPH0310578B2 (en) * | 1983-06-02 | 1991-02-14 | Chuo Denki Kogyo Co | |
JPS60127917A (en) * | 1983-12-14 | 1985-07-08 | Amada Co Ltd | Cutting control method and device for sawing machine |
JPS6219319A (en) * | 1985-07-17 | 1987-01-28 | Amada Co Ltd | Lifting control method for hack sawing machine and device thereof |
JPH0526606B2 (en) * | 1985-07-17 | 1993-04-16 | Amada Co Ltd | |
US6039390A (en) * | 1996-08-20 | 2000-03-21 | Donnelly Corporation | Chromogenic window assembly construction and other chromogenic devices |
US6493128B1 (en) | 1996-08-20 | 2002-12-10 | Donnelly Corporation | Chromogenic window assembly construction and other chromogenic devices |
JP2001261343A (en) * | 2000-03-17 | 2001-09-26 | Unitika Ltd | Super fine particle of trimanganese tetraoxide and method of producing the same |
JP2003002654A (en) * | 2001-06-21 | 2003-01-08 | Naoaki Kumagai | Method for producing layered lithium manganese complex oxide and lithium secondary battery |
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