JPH07118019A - Production of manganese dioxide - Google Patents
Production of manganese dioxideInfo
- Publication number
- JPH07118019A JPH07118019A JP5225996A JP22599693A JPH07118019A JP H07118019 A JPH07118019 A JP H07118019A JP 5225996 A JP5225996 A JP 5225996A JP 22599693 A JP22599693 A JP 22599693A JP H07118019 A JPH07118019 A JP H07118019A
- Authority
- JP
- Japan
- Prior art keywords
- manganese dioxide
- manganese
- surface area
- permanganate
- added
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、比表面積の高い二酸化
マンガンの製造法に関するものである。FIELD OF THE INVENTION The present invention relates to a method for producing manganese dioxide having a high specific surface area.
【０００２】[0002]
【従来の技術】乾電池材料としての二酸化マンガンはチ
タン等を陽極とし、これを硫酸マンガン、塩化マンガ
ン、硝酸マンガン等のマンガン塩水溶液の電解液を介し
て陰極を配置し、これら両極間に電圧を印加して電解を
行って陽極上に析出した二酸化マンガンを剥離、粉砕、
中和、水洗、乾燥したものが多くもちいられている。ま
た、自動車排ガス等に含まれる大気汚染物質として知ら
れている一酸化炭素の接触酸化触媒の主要成分として用
いられている二酸化マンガンは、２価のマンガン化合物
を過マンガン酸カリウムなどの酸化剤で酸化する種々の
化学反応法で調製されている。例えば、特開昭51-71299
号では２価のマンガン化合物の硝酸酸性水溶液に過マン
ガン酸カリウムを添加して酸化する方法、特開昭 54-10
6099号では硫酸マンガンと炭酸ナトリウムとから調製し
た炭酸マンガンを過マンガン酸カリウム等の酸化剤で酸
化する方法、J. Am. Chem. Soc., 43 巻, 1982 (1921)
には硫酸マンガンの水溶液に硫酸を添加することで生成
した硫酸マンガンのスラリーを過マンガン酸カリウムで
酸化する方法が開示されている。2. Description of the Related Art Manganese dioxide as a dry battery material has titanium or the like as an anode, and a cathode is placed through the electrolyte of a manganese salt aqueous solution such as manganese sulfate, manganese chloride or manganese nitrate, and a voltage is applied between these electrodes. Applying electrolysis to remove manganese dioxide deposited on the anode, pulverize,
Most of them are neutralized, washed with water and dried. Manganese dioxide, which is used as the main component of the catalytic oxidation catalyst for carbon monoxide, which is known as an air pollutant contained in automobile exhaust gas, is a divalent manganese compound that is an oxidizing agent such as potassium permanganate. It is prepared by various chemical reaction methods that oxidize. For example, JP-A-51-71299
JP-A-54-10 discloses a method of adding potassium permanganate to a nitric acid acidic aqueous solution of a divalent manganese compound to oxidize it.
No. 6099, a method of oxidizing manganese carbonate prepared from manganese sulfate and sodium carbonate with an oxidizing agent such as potassium permanganate, J. Am. Chem. Soc., Vol. 43, 1982 (1921).
Discloses a method of oxidizing a slurry of manganese sulfate produced by adding sulfuric acid to an aqueous solution of manganese sulfate with potassium permanganate.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、これら
公知の方法は、製造法の観点からすると例えば、J. Am.
Chem. Soc., 43 巻, 1982 (1921) の方法では多量の硫
酸を使用し、その中和のための工程が必要とされ、それ
ゆえ工程が非常に煩雑であったり、多量の硫安が副生す
る等の問題点があった。また水酸化マンガンや炭酸マン
ガンなどを酸化して二酸化マンガンを得る公知の方法で
は低温では分解に長時間を要し酸化が十分に進まず高温
では粒子成長のために表面積の大きな二酸化マンガンが
得られないなどの欠点があった。二酸化マンガンは種々
の結晶形をとることが知られておりその結晶形が表面積
の決定要因の一つとなっている。つまり高比表面積の二
酸化マンガンを得るためには結晶形の制御が必要とされ
ていた。しかるに公知の方法では結晶形を制御すること
が困難なため表面積の大きい二酸化マンガンを再現性良
く調製することが出来なかった。そのため触媒性能も実
用上満足のいくものでないなどの問題点があった。However, these known methods are, for example, J. Am.
The method of Chem. Soc., Vol. 43, 1982 (1921) uses a large amount of sulfuric acid and requires a step for neutralizing the sulfuric acid. Therefore, the step is very complicated and a large amount of ammonium sulfate is added. There were problems such as birth. Further, in the known method of oxidizing manganese hydroxide or manganese carbonate to obtain manganese dioxide, decomposition takes a long time at a low temperature and oxidation does not proceed sufficiently, so that at a high temperature manganese dioxide having a large surface area is obtained due to particle growth. There was a defect such as not being. Manganese dioxide is known to take various crystal forms, and the crystal form is one of the determinants of the surface area. That is, control of the crystal form was required to obtain manganese dioxide having a high specific surface area. However, since it is difficult to control the crystal form by the known method, manganese dioxide having a large surface area could not be prepared with good reproducibility. Therefore, there was a problem that the catalyst performance was not satisfactory in practice.
【０００４】[0004]
【問題点を解決するための手段】本発明らは、上記の課
題を解決するため鋭意検討した結果、本発明を完成する
に至ったものである。すなわち、本発明は、過マンガン
酸塩と２価のマンガン化合物を原料とする二酸化マンガ
ンの製造法において、いずれか一方の水溶液に他の一方
を固体で添加し酸化、熟成することを特徴とする高比表
面積の二酸化マンガンの製造法である。[Means for Solving the Problems] The inventors of the present invention have completed the present invention as a result of extensive studies to solve the above problems. That is, the present invention is characterized in that, in a method for producing manganese dioxide using a permanganate salt and a divalent manganese compound as raw materials, one of the aqueous solutions is added with the other solid, and the mixture is oxidized and aged. This is a method for producing high specific surface area manganese dioxide.
【０００５】本発明らは、過マンガン酸塩と２価のマン
ガン化合物から二酸化マンガンを調製する条件、および
相変化について詳細に検討した結果、過マンガン酸塩と
２価のマンガン化合物とから鉱酸を使うことなく高比表
面積を持ち、一酸化炭素の接触酸化反応に対し、極めて
高い触媒活性を持った二酸化マンガンを調製出来ること
を見い出し、本発明を完成するに至った。The present inventors have made detailed studies on the conditions for preparing manganese dioxide from permanganate and a divalent manganese compound, and on the phase change. It has been found that manganese dioxide having a high specific surface area and an extremely high catalytic activity for the catalytic oxidation reaction of carbon monoxide can be prepared without using the above, and has completed the present invention.
【０００６】本発明において、２価のマンガン化合物は
硫酸マンガン、硫酸アンモニウムマンガン、硝酸マンガ
ン又は塩化マンガンであることが好ましい。また本発明
で用いる過マンガン酸塩は、過マンガン酸カリウム、過
マンガン酸ナトリウム、過マンガン酸バリウム等であ
り、これら過マンガン酸塩の二種以上を併用しても良
い。過マンガン酸塩と２価のマンガン化合物のモル比
は、0.5〜2.0であり、好ましくは、0.6〜1.5である。0.
5 より小さいと十分な酸化が起こらないため活性の高い
二酸化マンガンとはならず、2.0 より大きいと過マンガ
ン酸塩の使用量が多過ぎて不経済となる。２価のマンガ
ン化合物の水溶液に過マンガン酸塩を固体で添加する場
合の２価のマンガン化合物水溶液の濃度は 0.5〜6.0mol
／ｌであることが好ましく、また、過マンガン酸塩の水
溶液に２価のマンガン化合物を固体で添加する場合の過
マンガン酸塩水溶液の濃度は 0.5〜2.0 mol／ｌ である
ことが好ましい。かかる酸化、熟成の温度は、20゜ 〜15
0℃ であり、好ましくは40゜ 〜90℃である。20℃よりも
低いと十分な速度で酸化処理が進行せず、又 150℃より
も高いと活性の高いマンガン酸化物とはならない。ま
た、かかる酸化、熟成の時間は、温度にもよるが、通
常、 0.1〜48時間であり、好ましくは 0.5〜24時間であ
る。In the present invention, the divalent manganese compound is preferably manganese sulfate, ammonium manganese sulfate, manganese nitrate or manganese chloride. The permanganate used in the present invention is potassium permanganate, sodium permanganate, barium permanganate and the like, and two or more of these permanganates may be used in combination. The molar ratio of the permanganate and the divalent manganese compound is 0.5 to 2.0, preferably 0.6 to 1.5. 0.
If it is less than 5, sufficient oxidation does not occur and manganese dioxide with high activity is not obtained. If it is more than 2.0, the amount of permanganate used is too large, which is uneconomical. When the permanganate is added as a solid to the aqueous solution of the divalent manganese compound, the concentration of the aqueous solution of the divalent manganese compound is 0.5 to 6.0 mol.
The concentration of the aqueous solution of permanganate is preferably 0.5 to 2.0 mol / l when the divalent manganese compound is added as a solid to the aqueous solution of permanganate. The temperature for such oxidation and aging is 20 ° to 15 °
The temperature is 0 ° C, preferably 40 ° to 90 ° C. If it is lower than 20 ° C, the oxidation treatment does not proceed at a sufficient rate, and if it is higher than 150 ° C, it does not become a highly active manganese oxide. The time for such oxidation and aging depends on the temperature, but is usually 0.1 to 48 hours, preferably 0.5 to 24 hours.
【０００７】[0007]
【実施例】以下、本発明を実施例により具体的に説明す
る。 実施例１ 水250gに過マンガン酸カリウム60g を溶解し、撹拌しな
がら90℃に加温する。次に、この水溶液に硫酸マンガン
4〜5水和物129gを添加し、添加終了後90℃で１時間撹
拌した。その後、濾過、１ｌの水で３回洗浄を行い、12
0℃ で15時間乾燥して二酸化マンガン80g を得た。比表
面積は350m2／gであった。EXAMPLES The present invention will be specifically described below with reference to examples. Example 1 60 g of potassium permanganate is dissolved in 250 g of water and heated to 90 ° C. with stirring. Next, add manganese sulfate to this aqueous solution.
129 g of 4-5 hydrate was added, and after the addition was completed, the mixture was stirred at 90 ° C. for 1 hour. Then, filter, wash 3 times with 1 liter of water, and
After drying at 0 ° C for 15 hours, 80 g of manganese dioxide was obtained. The specific surface area was 350 m 2 / g.
【０００８】実施例２ 水360gに硫酸アンモニウムマンガン ６水和物222gを溶
解し、撹拌しながら90℃に加温する。次に、この水溶液
に過マンガン酸カリウム60g を添加し、添加終了後70℃
で６時間撹拌した。その後、濾過、１ｌの水で３回洗浄
を行い、 120℃で15時間乾燥して二酸化マンガン79g を
得た。比表面積は372m2／gであった。Example 2 222 g of ammonium manganese sulfate hexahydrate was dissolved in 360 g of water and heated to 90 ° C. with stirring. Next, add 60 g of potassium permanganate to this aqueous solution, and add 70
And stirred for 6 hours. Then, filtration, washing with 1 l of water three times, and drying at 120 ° C. for 15 hours gave 79 g of manganese dioxide. The specific surface area was 372 m 2 / g.
【０００９】比較例１ 水250gに過マンガン酸カリウム60g を溶解し、撹拌しな
がら90℃に加温する。次に、この水溶液に、水250gに硫
酸マンガン 4〜5水和物129gを溶解した水溶液を添加
し、添加終了後90℃で１時間撹拌した。その後、濾過、
１ｌの水で３回洗浄を行い、120℃ で15時間乾燥して二
酸化マンガン76g を得た。 比表面積は200m2／gであっ
た。Comparative Example 1 60 g of potassium permanganate is dissolved in 250 g of water and heated to 90 ° C. with stirring. Next, to this aqueous solution was added an aqueous solution in which 129 g of manganese sulfate 4-5 hydrate was dissolved in 250 g of water, and after the addition was completed, the mixture was stirred at 90 ° C. for 1 hour. Then filtration,
It was washed 3 times with 1 l of water and dried at 120 ° C. for 15 hours to obtain 76 g of manganese dioxide. The specific surface area was 200 m 2 / g.
【００１０】実施例３ 実施例１、実施例２、比較例１および市販電解法の二酸
化マンガンを用いて公知の方法に従って酸化触媒を製造
した。硫酸銅CuSO4・5H20 50gを水250mlに溶解して得ら
れる硫酸銅水溶液（0.79mol/l）に 30％苛性ソーダ水溶
液を溶液pHが約10になるまで添加し水酸化銅の沈澱を得
る。 この沈澱を濾液pHが7.5以下になるまで十分洗浄す
る。次に実施例１、実施例２、比較例１または市販電解
法の二酸化マンガン各10g に水を加えてスラリーとした
ものに上述の水酸化銅3.9gを加えて十分攪拌混合した
後、 濾過、洗浄、120℃、15時間乾燥して二酸化マンガ
ン−酸化銅系酸化触媒を製造した。以下、これらの触媒
をそれぞれ触媒A、B、CまたはDとする。これら粉末状触
媒1gを300mlのガラス容器にいれ、一酸化炭素20％を含
む空気を導入密封し70℃ で接触反応させ反応に伴う一
酸化炭素の減少速度をFT-IR分光光度計を用いて 2200cm
-1の一酸化炭素の吸収強度を測定することにより決定し
た。 その結果一酸化炭素が始めの濃度の1/10になるま
でに要する時間は 触媒A、B、C、D それぞれ13分、12
分、16分および33分であった。本実施例による二酸化マ
ンガンを主体とした二酸化マンガン−酸化銅系酸化触媒
が一酸化炭素除去に優れた性能を持つことがわかる。Example 3 An oxidation catalyst was produced according to a known method using Example 1, Example 2, Comparative Example 1 and manganese dioxide of a commercial electrolysis method. Copper sulfate sulfate CuSO 4 · 5H 2 0 50g dissolved in 250ml water to obtain a copper sulfate aqueous solution (0.79mol / l) 30% caustic soda solution is added until the solution pH is about 10 to obtain a copper hydroxide precipitate . The precipitate is thoroughly washed until the pH of the filtrate is 7.5 or less. Next, water was added to 10 g each of manganese dioxide of Example 1, Example 2, Comparative Example 1 or the commercial electrolysis method to make a slurry, and 3.9 g of the above-mentioned copper hydroxide was added and sufficiently stirred and mixed, followed by filtration, After washing and drying at 120 ° C. for 15 hours, a manganese dioxide-copper oxide-based oxidation catalyst was manufactured. Hereinafter, these catalysts will be referred to as catalysts A, B, C or D, respectively. 1 g of these powdered catalysts were placed in a 300 ml glass container, air containing 20% carbon monoxide was introduced, and the mixture was hermetically sealed and contacted at 70 ° C to determine the rate of decrease of carbon monoxide accompanying the reaction using an FT-IR spectrophotometer. 2200 cm
-1 was determined by measuring the absorption intensity of carbon monoxide. As a result, the time required for carbon monoxide to reach 1/10 of the initial concentration was 13 minutes for catalysts A, B, C, and 12 for catalyst D, respectively.
Minutes, 16 minutes and 33 minutes. It can be seen that the manganese dioxide-copper oxide-based oxidation catalyst mainly composed of manganese dioxide according to this example has excellent performance for removing carbon monoxide.
【００１１】[0011]
【発明の効果】本発明の二酸化マンガン製造法は、製造
方法の観点からすると、鉱酸の使用量が少なく、また中
和による硫安等の副生が少ないなどクリーンでコスト的
にも有利であるなどの利点がある。一方、製造される二
酸化マンガンも触媒性能にとり基本的に重要な要素であ
る比表面積が大きく一酸化炭素などの酸化除去に優れた
性能を示すものである。この様に、本発明によれば、触
媒性能の安定した信頼性の高い二酸化マンガンを工業的
に有利に製造することが出来る。From the viewpoint of the production method, the method for producing manganese dioxide of the present invention is advantageous in terms of cleanness and cost, since the amount of mineral acid used is small and the by-products such as ammonium sulfate due to neutralization are small. There are advantages such as. On the other hand, the manganese dioxide produced also has a large specific surface area, which is a fundamentally important factor for the catalytic performance, and exhibits excellent performance in removing oxidization of carbon monoxide and the like. As described above, according to the present invention, manganese dioxide having stable catalytic performance and high reliability can be industrially advantageously produced.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｂ０１Ｊ 23/34 ＺＡＢ Ａ 8017−4Ｇ (72)発明者 池田 圭一 神奈川県横浜市栄区笠間町1190番地 三井 東圧化学株式会社内 (72)発明者 徳満 政弘 神奈川県横浜市栄区笠間町1190番地 三井 東圧化学株式会社内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Reference number within the agency FI Technical indication location // B01J 23/34 ZAB A 8017-4G (72) Inventor Keiichi Ikeda Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa 1190 Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Masahiro Tokuman 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
を原料とする二酸化マンガンの製造法において、いずれ
か一方の水溶液に他の一方を固体で添加し酸化、熟成す
ることを特徴とする高比表面積の二酸化マンガンの製造
法。1. A method for producing manganese dioxide using a permanganate salt and a divalent manganese compound as raw materials, wherein the other is added as a solid to one of the aqueous solutions, and the mixture is oxidized and aged. A method for producing manganese dioxide with a specific surface area.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5225996A JPH07118019A (en) | 1993-08-27 | 1993-09-10 | Production of manganese dioxide |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5-212459 | 1993-08-27 | ||
| JP21245993 | 1993-08-27 | ||
| JP5225996A JPH07118019A (en) | 1993-08-27 | 1993-09-10 | Production of manganese dioxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07118019A true JPH07118019A (en) | 1995-05-09 |
Family
ID=26519241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5225996A Pending JPH07118019A (en) | 1993-08-27 | 1993-09-10 | Production of manganese dioxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07118019A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004011376A1 (en) * | 2002-07-26 | 2004-02-05 | Sued-Chemie Catalysts Japan, Inc. | Manganese compound, process for producing the same, and method of utilization of the same |
| JP2008280242A (en) * | 2008-06-23 | 2008-11-20 | Sud-Chemie Catalysts Inc | Manganese compound |
| JP2011045806A (en) * | 2009-08-25 | 2011-03-10 | Sud-Chemie Catalysts Inc | Gaseous mercury removal agent and method for removing gaseous mercury in gas including metal mercury and/or vapor |
| JP2012245444A (en) * | 2011-05-25 | 2012-12-13 | Nippon Steel Corp | Method for desulfurizing and denitrating sintering furnace exhaust gas |
| CN106315680A (en) * | 2016-08-16 | 2017-01-11 | 陕西师范大学 | Coralline porous delta-MnO2 and preparation method thereof |
| US9938168B2 (en) | 2015-03-13 | 2018-04-10 | Korea Institute Of Science And Technology | Apparatus and method for water treatment using in-situ activation of manganese dioxide catalyst |
-
1993
- 1993-09-10 JP JP5225996A patent/JPH07118019A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004011376A1 (en) * | 2002-07-26 | 2004-02-05 | Sued-Chemie Catalysts Japan, Inc. | Manganese compound, process for producing the same, and method of utilization of the same |
| JP2008280242A (en) * | 2008-06-23 | 2008-11-20 | Sud-Chemie Catalysts Inc | Manganese compound |
| JP2011045806A (en) * | 2009-08-25 | 2011-03-10 | Sud-Chemie Catalysts Inc | Gaseous mercury removal agent and method for removing gaseous mercury in gas including metal mercury and/or vapor |
| JP2012245444A (en) * | 2011-05-25 | 2012-12-13 | Nippon Steel Corp | Method for desulfurizing and denitrating sintering furnace exhaust gas |
| US9938168B2 (en) | 2015-03-13 | 2018-04-10 | Korea Institute Of Science And Technology | Apparatus and method for water treatment using in-situ activation of manganese dioxide catalyst |
| CN106315680A (en) * | 2016-08-16 | 2017-01-11 | 陕西师范大学 | Coralline porous delta-MnO2 and preparation method thereof |
| CN106315680B (en) * | 2016-08-16 | 2018-12-07 | 陕西师范大学 | A kind of porous δ-MnO of coralliform2Preparation method |
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