JPH0611650B2 - Manganese dioxide production method - Google Patents
Manganese dioxide production methodInfo
- Publication number
- JPH0611650B2 JPH0611650B2 JP60170889A JP17088985A JPH0611650B2 JP H0611650 B2 JPH0611650 B2 JP H0611650B2 JP 60170889 A JP60170889 A JP 60170889A JP 17088985 A JP17088985 A JP 17088985A JP H0611650 B2 JPH0611650 B2 JP H0611650B2
- Authority
- JP
- Japan
- Prior art keywords
- manganese
- manganese dioxide
- solution
- mol
- reaction
- 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
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Description
【発明の詳細な説明】 産業上の利用分野 本発明は二酸化マンガンの製造方法に関し、更に詳述す
るならば、アンモニア溶液に酸化剤及びマンガン塩溶液
を添加することによって二酸化マンガンを製造する化学
的方法に係わるものである。Description: FIELD OF THE INVENTION The present invention relates to a method for producing manganese dioxide, and more specifically, a chemical method for producing manganese dioxide by adding an oxidizing agent and a manganese salt solution to an ammonia solution. It is related to the method.
従来の技術 乾電池の陽極活物質などに用いられる二酸化マンガンは
高い純度と活性を有していなければならず、従来より、
このような要求を満たすものとして電解法による二酸化
マンガンが用いられてきた。しかしながら、電解二酸化
マンガンは高純度ではあるが、その製造の際に多量の電
力を消費するためコストの点から好ましくない。2. Description of the Related Art Manganese dioxide used as an anode active material for dry batteries must have high purity and activity.
Manganese dioxide produced by the electrolytic method has been used as a material satisfying such requirements. However, although electrolytic manganese dioxide has a high degree of purity, it consumes a large amount of electric power during its production, which is not preferable in terms of cost.
そこで、化成二酸化マンガン、即ち、化学的処理によ
り、電解二酸化マンガンに匹敵する二酸化マンガンを得
る方法が提案されており、そのような方法の一つとし
て、マンガン塩溶液中にアルカリを添加してMn（ＯＨ）
2とし、更にＯ2その他の酸化剤で酸化して二酸化マンガ
ンを製造する方法が知られている。Therefore, chemical manganese dioxide, that is, a method of obtaining manganese dioxide that is comparable to electrolytic manganese dioxide by chemical treatment has been proposed.As one of such methods, an alkali is added to a manganese salt solution to add Mn. (OH)
A method is known in which manganese dioxide is produced by converting it to 2, and then oxidizing it with O 2 or another oxidizing agent.
しかしながら、このようにいったん固体のMn(ＯＨ)2を
生成させ、該Mn(ＯＨ)2をアルカリ溶液中で酸化する反
応は、固体と液体の反応であり、かつ常に低アルカリ側
で反応を行っているため、反応速度が遅く、二酸化マン
ガンの製造に多くの時間を要することとなる。However, the reaction of once producing solid Mn (OH) 2 and oxidizing the Mn (OH) 2 in an alkaline solution is a reaction between a solid and a liquid, and the reaction is always performed on the low alkaline side. Therefore, the reaction rate is slow, and it takes a lot of time to produce manganese dioxide.
逆に、高アルカリ条件下で酸化反応を行う方法として、
例えばタンク中に水酸化ナトリウム溶液を入れ、該水酸
化ナトリウム溶液を撹拌しつつ、硫酸マンガン溶液と空
気を添加してδ型二酸化マンガンを得る方法が知られて
いる〔トランス エレクトロケミカル ソサエティー
（Trans.Electrochem.Soc.）第92巻、第12号、第７頁
（1947年）〕。この方法では得られる二酸化マンガンを
水酸化ナトリウム過剰のまま乾燥し、含有率90.5％の二
酸化マンガンを得ている。On the contrary, as a method of performing the oxidation reaction under highly alkaline conditions,
For example, a method is known in which a sodium hydroxide solution is placed in a tank, and a manganese sulfate solution and air are added while stirring the sodium hydroxide solution to obtain δ-type manganese dioxide (Trans Electrochemical Society (Trans. Electrochem.Soc.) Vol. 92, No. 12, page 7 (1947)]. In this method, the obtained manganese dioxide is dried with sodium hydroxide in excess and manganese dioxide with a content rate of 90.5% is obtained.
この方法においてもNaOHとMnとの錯イオンガ出来にく
く、Mn(OH)2が生成するために、MnＯ2の製造に多くの時
間を要する。Even in this method, it is difficult to form a complex ion of NaOH and Mn, and Mn (OH) 2 is produced, so that it takes a long time to produce MnO 2 .
また、特公昭31−6722号明細書は、硫酸マンガン溶液、
若しくは酸化マンガン鉱を硫酸（またはＳＯｘガスの回
収により製造された硫酸）に溶解して得られる硫酸マン
ガン溶液に、アンモニアと酸素の混合ガスを吹込みこと
によってマンガンを酸化して二酸化マンガンを得る方法
を開示している。Further, Japanese Patent Publication No. 316722 discloses a manganese sulfate solution,
Alternatively, manganese oxide is obtained by blowing a mixed gas of ammonia and oxygen into a manganese sulfate solution obtained by dissolving manganese oxide ore in sulfuric acid (or sulfuric acid produced by collecting SO x gas). A method is disclosed.
しかしながら、この方法ではアンモニアと酸素の混合ガ
スを吹き込むため、引火性のアンモニアガスと酸素を混
合することとなり、爆発の危険性を伴う。また、アンモ
ニアによる大気汚染も深刻な問題である。However, in this method, since a mixed gas of ammonia and oxygen is blown, flammable ammonia gas and oxygen are mixed with each other, and there is a risk of explosion. Air pollution due to ammonia is also a serious problem.
発明が解決しようとする問題点 そこで、本発明は、このような従来法の状況に鑑みて、
乾電池活物質として使用することのできる高品位、高純
度の二酸化マンガンを新規な化学的処理によって短時間
で且つ安全に製造することのできる方法を提供せんとす
るものである。Problems to be Solved by the Invention Therefore, the present invention, in view of the situation of such a conventional method,
It is an object of the present invention to provide a method by which high-quality, high-purity manganese dioxide that can be used as a dry battery active material can be safely produced in a short time by a novel chemical treatment.
問題点を解決するための手段 そこで、本発明者等は前記目的を達成すべく種々検討、
研究した結果、従来の化成二酸化マンガンの製法におい
ては固体のMn(ＯＨ)2を経由するための反応速度が遅く
なるのであり、またアンモニアと酸素の混合ガスを使用
するために安全性に欠けると考えられるが、このような
問題は錯イオンを形成しやすいアンモニア溶液を使用す
ることにより解決でき、これが上記目的を達成するうえ
で極めて有効であることを見出した。本発明はかかる新
規知見に基づき完成されたものである。Means for Solving the Problems Therefore, the present inventors have conducted various studies to achieve the above-mentioned object,
As a result of research, in the conventional method for producing chemical conversion manganese dioxide, the reaction rate for passing through solid Mn (OH) 2 becomes slow, and it is not safe because it uses a mixed gas of ammonia and oxygen. It is conceivable that such a problem can be solved by using an ammonia solution that easily forms complex ions, and it has been found that this is extremely effective in achieving the above object. The present invention has been completed based on such new findings.
即ち、本発明の二酸化マンガンの製造方法は、アンモニ
ア溶液に酸化剤およびマンガン塩溶液を添加することに
よってマンガン塩を速やかに二酸化マンガンに酸化する
ことを特徴とする。That is, the method for producing manganese dioxide of the present invention is characterized by rapidly oxidizing a manganese salt into manganese dioxide by adding an oxidizing agent and a manganese salt solution to an ammonia solution.
本発明による二酸化マンガンの製造方法は、通常次のよ
うな一連の製造工程に従って行われる。即ち、アンモニ
ア溶液を密閉容器に入れ、Ｏ2ガスを必要量だけ吹き込
みながらスターラーで撹拌する。しかる後、マンガン塩
溶液を徐々に添加して、アンモニアとマンガンの錯イオ
ンを作らせつつ、マンガンを酸化して速やかに二酸化マ
ンガンとする。得られる二酸化マンガンを濾過して分取
し、水洗後、乾燥する。The method for producing manganese dioxide according to the present invention is usually performed according to the following series of production steps. That is, the ammonia solution is put in a closed container and stirred with a stirrer while blowing a required amount of O 2 gas. Thereafter, a manganese salt solution is gradually added to form a complex ion of ammonia and manganese, and manganese is oxidized to quickly become manganese dioxide. The obtained manganese dioxide is filtered, separated, washed with water, and dried.
本発明の方法において使用するアンモニア溶液の濃度は
高い方が錯イオンの生成には好ましく、0.5〜15モル／
の範囲で可能であり、更に好ましくは2.5〜15モル／
の範囲である。アンモニア溶液の濃度が低い場合には
反応溶液量が大きくなるので経済的でなく、また15モル
／よるも高くなるとアンモニア溶液を作製することが
困難となる。The higher the concentration of the ammonia solution used in the method of the present invention, the more preferable it is for the production of complex ions.
Is possible, and more preferably 2.5 to 15 mol /
Is the range. When the concentration of the ammonia solution is low, the amount of the reaction solution becomes large, which is not economical, and when it is higher than 15 mol / mol, it becomes difficult to prepare the ammonia solution.
また、アンモニア溶液に添加するマンガン塩の種類は、
マンガンの硫酸塩、塩酸塩若しくは硝酸塩であり、また
はこれらの混合物であってもよい。The type of manganese salt added to the ammonia solution is
It may be manganese sulphate, hydrochloride or nitrate, or a mixture thereof.
これらのマンガン塩の濃度は0.2〜４モル／のものを
使用することができ、好ましくは0.5〜２モル／の濃
度である。マンガン塩濃度が高くなると、溶液中にMn
(ＯＨ)2の生成が多くなり、MnＯ2生成速度が遅くなるか
らであり、逆に低い場合には反応液量が大になって経済
的でないからである。The concentration of these manganese salts may be 0.2 to 4 mol / l, preferably 0.5 to 2 mol / l. As the manganese salt concentration increases, Mn
This is because the amount of (OH) 2 produced increases and the MnO 2 production rate becomes slower. On the contrary, when the amount is low, the amount of the reaction solution becomes large and it is not economical.
更に、アンモニア溶液とマンガンとのモル比(ＮＨ４Ｏ
Ｈ／Mn)は2.0〜10の範囲とすることができ2.4〜４とす
ることが好ましい。ＮＨ４ＯＨの比率が小さいと、二酸
化マンガンの生成反応が遅くなり、また大きいと過剰の
ＮＨ４ＯＨが残ることとなって経済的でない。Furthermore, the molar ratio of the ammonia solution and manganese (NH 4 O
H / Mn) can be in the range of 2.0 to 10, and preferably 2.4 to 4. If the ratio of NH 4 OH is small, the reaction for producing manganese dioxide becomes slow, and if it is large, excess NH 4 OH remains, which is not economical.
次に、本発明の方法において使用する酸化剤としてはＯ
2、Ｈ2、Ｏ3、Ｏ2添加空気、空気などを利用することが
でき、これらの酸化剤を組み合せて使用することもでき
る。特に、Ｏ2や空気を溶液中に吹き込んで酸化するこ
とは、安価で且つ簡単な方法である。Next, the oxidant used in the method of the present invention is O.
2 , H 2 , O 3 , O 2 -added air, air, etc. can be used, and these oxidizing agents can also be used in combination. In particular, blowing O 2 or air into the solution for oxidation is an inexpensive and simple method.
反応温度に関しては、一般に溶液の温度が高い程、反応
温度は大となる。しかし逆に溶液中におけるＯ2の溶解
度は低下するので、高温で反応を行うためには加圧が必
要となる。従って、常圧で本発明の方法を行うには、０
〜80℃の範囲の温度が利用でき、特に５〜20の範囲とす
ることが好ましく、オートクレープ等の密閉容器内で加
圧状態で反応を行う場合には、250℃まで反応温度を上
げることが可能で、反応速度は著しく促進される。Regarding the reaction temperature, generally, the higher the temperature of the solution, the higher the reaction temperature. However, on the contrary, since the solubility of O 2 in the solution decreases, pressurization is required to carry out the reaction at a high temperature. Therefore, to carry out the method of the present invention at atmospheric pressure, 0
A temperature in the range of -80 to 80 ° C can be used, and a range of 5 to 20 is particularly preferable. When carrying out the reaction under pressure in a closed container such as an autoclave, increase the reaction temperature to 250 ° C. Is possible and the reaction rate is significantly enhanced.
また、本発明の方法は０〜50気圧の反応圧で行うことが
可能である。Further, the method of the present invention can be carried out at a reaction pressure of 0 to 50 atm.
作用 本発明の方法によると、溶液中に多量に存在するＮＨ4
ＯＨにマンガン塩溶液を添加するため、ＮＨ4ＯＨとMn
の可溶性錯イオンが生成し、害錯イオンは酸化剤によっ
て速やかに活性な二酸化マンガンに酸化される。従って
本発明の方法は液体−液体反応であり、従来のMn(ＯＨ)
2を経由する固体−液体反応に比べで反応速度が著しく
速くなる。特に反応初期においては高濃度のアンモニア
溶液中にマンガン塩を添加するので錯イオンを形成しや
すい。本発明の方法を用いて常圧で二酸化マンガンを製
造する場合には、従来のMn(ＯＨ)2を経由する反応に比
べて反応時間を1/5〜1/10に短縮することが可能であ
る。Action According to the method of the present invention, NH 4 present in a large amount in the solution
To add manganese salt solution to OH, NH 4 OH and Mn
Soluble complex ions are produced, and the harmful complex ions are rapidly oxidized to active manganese dioxide by an oxidizing agent. Therefore, the method of the present invention is a liquid-liquid reaction, and the conventional Mn (OH) 2
The reaction rate is significantly faster than the solid-liquid reaction via 2 . Particularly at the initial stage of the reaction, since the manganese salt is added to the high-concentration ammonia solution, complex ions are easily formed. When manganese dioxide is produced under atmospheric pressure using the method of the present invention, the reaction time can be shortened to 1/5 to 1/10 as compared with the conventional reaction via Mn (OH) 2. is there.
また、本発明の方法は、アンモニア溶液中にＯ2ガスを
吹き込むので、アンモニアと酸素の混合ガスを吹き込む
従来法のような爆発の危険性もなく、安全である。Further, since the method of the present invention blows O 2 gas into the ammonia solution, it is safe without the risk of explosion unlike the conventional method of blowing a mixed gas of ammonia and oxygen.
更に、密閉容器で反応を行う場合には、必要量のＯ2の
みを吹き込み、過剰なＯ2を供給しないので、アンモニ
アによる大気汚染の心配もない。Further, when the reaction is carried out in a closed vessel, blowing only O 2 the required amount, does not provide excess O 2, there is no fear of air pollution with ammonia.
実施例 以下に本発明の方法を実施例に基づき更に具体的に説明
するが、本発明の範囲はこれら実施例により何等制限さ
れない。Examples Hereinafter, the method of the present invention will be described more specifically based on examples, but the scope of the present invention is not limited to these examples.
実施例１ アンモニア溶液とマンガンとのモル比(ＮＨ4ＯＨ／Mn)
と得られる二酸化マンガンの含有率との関係を調べるた
め以下の実験を行った。即ち、５の密閉容器に14モル
／の濃度のアンモニア溶液を適量入れ、撹拌しながら
Ｏ2ガスを0.05気圧で吹き込み、1.5モル／の濃度の硫
酸マンガン溶液を３／６hrの速度で添加した。反応温
度は20℃であった。ＮＨ4ＯＨ／Mnモル比を2.0〜10の間
の各種の値となるように設定して行った実験の結果を第
１図に示す。図から明らかなように、ＮＨ4ＯＨ／Mnモ
ル比が３以上で含有率84％以上の二酸化マンガンが得ら
れた。Example 1 Molar ratio of ammonia solution and manganese (NH 4 OH / Mn)
The following experiment was conducted in order to investigate the relationship between the content and the content of manganese dioxide obtained. That is, an appropriate amount of 14 mol / concentration ammonia solution was placed in a closed container 5 and O 2 gas was blown at 0.05 atm while stirring, and a 1.5 mol / concentration manganese sulfate solution was added at a rate of 3/6 hr. The reaction temperature was 20 ° C. The results of an experiment conducted by setting the NH 4 OH / Mn molar ratio to various values between 2.0 and 10 are shown in FIG. As is clear from the figure, manganese dioxide having a NH 4 OH / Mn molar ratio of 3 or more and a content of 84% or more was obtained.
実施例２ 硫酸マンガン溶液の濃度と得られる二酸化マンガンの含
有率との関係を調べるため以下の実験を行った。即ち、
マンガンとして0.1〜４モル／の各種濃度の硫酸マン
ガン溶液を使用して、ＮＨ4ＯＨ／Mnモル比を3.0とし、
その他の条件は実施例１と同様の条件および方法で二酸
化マンガンを製造した。その結果を第２図に示すが、硫
酸マンガン濃度を２モル／以下にすることによって、
84％以上の高含有率の二酸化マンガンが得られた。Example 2 The following experiment was conducted in order to investigate the relationship between the concentration of the manganese sulfate solution and the content rate of the obtained manganese dioxide. That is,
Using manganese sulfate solutions with various concentrations of 0.1 to 4 mol / mol as manganese, the NH 4 OH / Mn molar ratio is 3.0,
Other conditions were the same as in Example 1 and manganese dioxide was produced. The results are shown in FIG. 2. By setting the manganese sulfate concentration to 2 mol / or less,
A high content of manganese dioxide of 84% or more was obtained.
実施例３ 常圧における反応温度と二酸化マンガンの含有率との関
係を調べるために以下の実験を行った。即ち、ＮＨ4Ｏ
Ｈ／Mnモル比を3.0に固定し、その他の条件は実施例１
と同じとし、０〜80℃の間の各種温度で二酸化マンガン
を製造した。その結果を第３図に示すが、図から明らか
なように、５〜20℃の間で含有率84％以上の二酸化マン
ガンが得られた。Example 3 The following experiment was conducted in order to investigate the relationship between the reaction temperature at normal pressure and the content of manganese dioxide. That is, NH 4 O
The H / Mn molar ratio was fixed at 3.0, and other conditions were as in Example 1.
Same as above, but manganese dioxide was produced at various temperatures between 0 and 80 ° C. The results are shown in FIG. 3, and as is clear from the figure, manganese dioxide having a content of 84% or more was obtained between 5 and 20 ° C.
実施例４ 加圧状態における反応温度と二酸化マンガンの含有率と
の関係を調べるために以下の実験を行った。即ち、密閉
容器内にＯ2ガスを導入して、該容器内における圧力
を、その温度における自成圧力とし、他は実施例３と同
条件で40〜250℃の各種温度で二酸化マンガンを製造し
た。得られた結果を第４図に示す。図から明らかなよう
に、加圧状態では100℃以上で二酸化マンガンの品位が
上がり、高含有率のものが得られた。Example 4 The following experiment was conducted in order to investigate the relationship between the reaction temperature and the content rate of manganese dioxide in a pressurized state. That is, O 2 gas was introduced into the closed container, and the pressure in the container was made to be the self-made pressure at that temperature, and otherwise manganese dioxide was produced at various temperatures of 40 to 250 ° C. under the same conditions as in Example 3. did. The obtained results are shown in FIG. As is clear from the figure, under a pressurized condition, the quality of manganese dioxide increased at 100 ° C or higher, and a high content of manganese dioxide was obtained.
実施例５ アンモニア溶液濃度と二酸化マンガンの含有率との関係
を調べるために以下の実験を行った。即ち、ＮＨ4ＯＨ
／Mnモル比を3.0に固定し、0.1〜15モル／の各種濃度
のアンモニア溶液を用いて、その他の条件は実施例１と
同じにして二酸化マンガンの製造を行った。その結果を
第５図に示すが、２モル／以上の濃度で良好な結果を
得た。Example 5 The following experiment was conducted in order to investigate the relationship between the ammonia solution concentration and the manganese dioxide content. That is, NH 4 OH
/ Mn molar ratio was fixed to 3.0, and manganese dioxide was produced under the same conditions as in Example 1 except that ammonia solution having various concentrations of 0.1 to 15 mol / was used. The results are shown in FIG. 5, and good results were obtained at a concentration of 2 mol / mol or more.
発明の効果 以上、詳しく説明したように、本発明の二酸化マンガン
の製造方法によると、高品位、高純度の二酸化マンガン
を短時間で且つ安全に製造することができ、従って乾電
池用二酸化マンガンの製造コストを低減することが可能
となった。Effects of the Invention As described in detail above, according to the method for producing manganese dioxide of the present invention, high-quality, high-purity manganese dioxide can be produced safely in a short time, and therefore, the production of manganese dioxide for dry batteries is possible. It has become possible to reduce costs.
第１図は、本発明の方法によって二酸化マンガンを製造
する際のアンモニア溶液とマンガンとのモル比と、得ら
れる二酸化マンガン含有率との関係を示す図、 第２図は、硫酸マンガン溶液の濃度と得られる二酸化マ
ンガン含有率との関係を示す図、 第３図は、常圧における反応温度と得られる二酸化マン
ガン含有率との関係を示す図、 第４図は、加圧状態における反応温度と得られる二酸化
マンガン含有率との関係を示す図、 第５図は、アンモニア溶液濃度と得られる二酸化マンガ
ン含有率との関係を示す図である。FIG. 1 is a diagram showing the relationship between the molar ratio of an ammonia solution and manganese when producing manganese dioxide by the method of the present invention and the obtained manganese dioxide content, and FIG. 2 is the concentration of the manganese sulfate solution. And FIG. 3 is a diagram showing the relationship between the obtained manganese dioxide content, FIG. 3 is a diagram showing the relationship between the reaction temperature at atmospheric pressure and the obtained manganese dioxide content, and FIG. 4 is the reaction temperature under pressure. The figure which shows the relationship with the obtained manganese dioxide content rate, and FIG. 5 is a figure which shows the relationship between the ammonia solution concentration and the obtained manganese dioxide content rate.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 落合 弘 新潟県中頚城郡妙高高原町大字田口272番 地 中央電気工業株式会社内 (72)発明者 相見 政巳 新潟県中頚城郡妙高高原町大字田口272番 地 中央電気工業株式会社内 (72)発明者 新山 正徳 新潟県中頚城郡妙高高原町大字田口272番 地 中央電気工業株式会社内 (72)発明者 宮下 孝洋 新潟県中頚城郡妙高高原町大字田口272番 地 中央電気工業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hiroshi Ochiai, 272 Taguchi, Myokokogen Town, Nakakubiki-gun, Niigata Prefecture, Chuo Electric Industry Co., Ltd. Address Chuo Denki Kogyo Co., Ltd. (72) Inventor Masanori Niiyama Taguchi 272, Myokokogen-cho, Nakakubiki-gun, Niigata Pref. Address: Central Electric Industry Co., Ltd.
Claims (9)
液を添加することによってマンガン塩を速やかに二酸化
マンガンに酸化することを特徴とする二酸化マンガンの
製造方法。1. A method for producing manganese dioxide, which comprises rapidly oxidizing a manganese salt into manganese dioxide by adding an oxidizing agent and a manganese salt solution to an ammonia solution.
／であることを特徴とする特許請求の範囲第１項に記
載の方法。2. The method according to claim 1, wherein the ammonia solution has a concentration of 0.5 to 15 mol / mol.
塩若しくは硝酸塩、またはこれらの混合物であることを
特徴とする特許請求の範囲第１項または第２項に記載の
方法。3. The method according to claim 1 or 2, wherein the manganese salt is a manganese sulfate, a hydrochloride or a nitrate, or a mixture thereof.
して0.2〜４モル／であることを特徴とする特許請求
の範囲第１項乃至第３項のいずれかに記載の方法。4. The method according to claim 1, wherein the manganese salt solution has a manganese concentration of 0.2 to 4 mol / mol.
が２〜10であることを特徴とする特許請求の範囲第１項
乃至第４項のいずれかに記載の方法。5. The method according to any one of claims 1 to 4, wherein the molar ratio of the ammonia solution and manganese is 2 to 10.
空気若しくは空気またはこれらの混合物であることを特
徴とする特許請求の範囲第１項乃至第５項のいずれかに
記載の方法。6. The method according to any one of claims 1 to 5, wherein the oxidizing agent is O 2 , H 2 O 2 , O 3 , O 2 added air, air or a mixture thereof. The method described in crab.
を特徴とする特許請求の範囲第１項乃至第６項のいずれ
かに記載の方法。7. The method according to any one of claims 1 to 6, wherein the oxidation reaction is carried out at a temperature of 0 to 80 ° C.
Ｏ2ガスを吹き込みながら撹拌し、前記マンガン塩溶液
を添加することを特徴とする特許請求の範囲第１項乃至
第６項のいずれかに記載の方法。8. The method according to claim 1, wherein the manganese salt solution is added while stirring while blowing O 2 gas into the ammonia solution placed in a closed container. The method described in.
特徴とする特許請求の範囲第８項に記載の方法。9. The method according to claim 8, wherein the reaction is carried out at a temperature of 0 to 250 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60170889A JPH0611650B2 (en) | 1985-08-02 | 1985-08-02 | Manganese dioxide production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60170889A JPH0611650B2 (en) | 1985-08-02 | 1985-08-02 | Manganese dioxide production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6230622A JPS6230622A (en) | 1987-02-09 |
| JPH0611650B2 true JPH0611650B2 (en) | 1994-02-16 |
Family
ID=15913195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60170889A Expired - Lifetime JPH0611650B2 (en) | 1985-08-02 | 1985-08-02 | Manganese dioxide production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0611650B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0386481U (en) * | 1989-12-25 | 1991-09-02 | ||
| JP2001261343A (en) * | 2000-03-17 | 2001-09-26 | Unitika Ltd | Super fine particle of trimanganese tetraoxide and method of producing the same |
| CN1308245C (en) * | 2005-03-30 | 2007-04-04 | 山东师范大学 | Method for synthesizing nano material of manganese dioxide in dandelion and stick shape |
| KR101171961B1 (en) | 2010-04-02 | 2012-08-08 | 주식회사 이엔드디 | Process for preparing Mn3O4 |
| JP5756525B2 (en) * | 2010-12-20 | 2015-07-29 | ▲海▼洋王照明科技股▲ふん▼有限公司 | Manufacturing method and use of manganese dioxide nanorods |
| CN116550320B (en) * | 2023-05-12 | 2024-02-02 | 河北地质大学 | Synthesis method of manganese dioxide nano material with neuron-like cell structure |
-
1985
- 1985-08-02 JP JP60170889A patent/JPH0611650B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6230622A (en) | 1987-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107093741B (en) | A kind of preparation method of high magnification nickel cobalt lithium aluminate cathode material | |
| EP4269337A1 (en) | Method for recovering lithium in lithium iron phosphate waste and application thereof | |
| CA2354918C (en) | Process for the preparation of vanadyl/vanadous sulphate crystal products or solutions | |
| CN112093785B (en) | Method for efficiently recycling lithium in lithium iron phosphate cathode waste and preparing iron phosphate for battery | |
| US6193947B1 (en) | Process for preparing layered rock-salt type lithium manganese oxide by mixed alkaline hydrothermal method | |
| KR970706620A (en) | SYNTHESIS METHOD FOR ALKALINE METAL INTERCALATION MATERIALS | |
| US20240055684A1 (en) | Preparation method of heterosite iron phosphate and application thereof | |
| CN110010990A (en) | There is the method for the nickel-cobalt-manganese ternary material of alumina-coated layer using retired lithium ion battery as raw material preparation | |
| CN113415813A (en) | Method for recovering lithium nickel cobalt manganese from waste ternary battery material | |
| Ooi et al. | Lithium-ion insertion/extraction reaction with λ-MnO2 in the aqueous phase | |
| JPH0611650B2 (en) | Manganese dioxide production method | |
| CN111137869A (en) | Preparation method of lithium iron phosphate | |
| CN113422040A (en) | Preparation method of medium-high nickel ternary material subjected to pre-oxidation treatment of precursor and lithium salt | |
| CN112563604A (en) | Method for regenerating anode material of waste lithium ion battery | |
| CN114585756A (en) | Method for recycling lithium batteries | |
| CN107863531A (en) | A kind of method that anode material for lithium-ion batteries is prepared using siderite | |
| JPH10125345A (en) | Manufacture of vanadium electrolyte | |
| CN114751390B (en) | Multi-ion doped battery-level ferric phosphate material and preparation method thereof | |
| CN106517345B (en) | Method for preparing ultrafine manganese dioxide by using potassium permanganate and potassium manganate | |
| JP2000072441A (en) | Production of vanadium sulfate solution | |
| GB2023558A (en) | Process for the Production of Electrochemically Active Lead Dioxide | |
| JPH08217458A (en) | Production of nickel hydroxide containing manganese(iii) | |
| CN86105859A (en) | Particulate manganese dioxide composites and preparation method thereof | |
| CN116265386A (en) | Preparation method of phosphate positive electrode material | |
| JPS5983938A (en) | Preparation of manganese dioxide |