JPH0665611B2 - Method for producing α-iron oxyhydroxide - Google Patents
Method for producing α-iron oxyhydroxideInfo
- Publication number
- JPH0665611B2 JPH0665611B2 JP60014068A JP1406885A JPH0665611B2 JP H0665611 B2 JPH0665611 B2 JP H0665611B2 JP 60014068 A JP60014068 A JP 60014068A JP 1406885 A JP1406885 A JP 1406885A JP H0665611 B2 JPH0665611 B2 JP H0665611B2
- Authority
- JP
- Japan
- Prior art keywords
- iron oxyhydroxide
- axial ratio
- ferrous
- carbonate
- temperature
- 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
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- Compounds Of Iron (AREA)
- Hard Magnetic Materials (AREA)
Description
【発明の詳細な説明】 （イ）産業上の利用分野 本発明は、形状が米粒状乃至紡錘状で、粒度が均一な任
意の軸比を有するα−オキシ水酸化鉄の製造方法に関す
るものであり、詳しくは平均粒子径が０．４μｍ以下で
且つ軸比が２〜８の任意の軸比を有するα−オキシ水酸
化鉄の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a method for producing α-iron oxyhydroxide having a rice grain shape or a spindle shape and an arbitrary axial ratio with a uniform grain size. More specifically, the present invention relates to a method for producing α-iron oxyhydroxide having an average particle size of 0.4 μm or less and an axial ratio of 2 to 8.
（ロ）従来の技術 近年、磁気記録媒体用磁性粉の諸物性に対する要求が多
様化し、磁気ヘッド材料面からは低保磁力の磁性鉄粉、
ＤＩＳＣ及び垂直磁気記録用材料面からは低軸比の磁性
粉が要望されている。(B) Conventional technology In recent years, the demands for various physical properties of magnetic powder for magnetic recording media have diversified, and magnetic coercive force of magnetic iron powder,
From the viewpoint of DISC and perpendicular magnetic recording materials, magnetic powder having a low axial ratio is desired.
従来より高軸比の磁性粉及びその原料の一つであるα−
オキシ水酸化鉄の製造法については種々報告されている
が、低軸比の磁性粉及びα−オキシ水酸化鉄の製造法の
報告は殆ど見当たらない。Conventionally, magnetic powder with a high axial ratio and α- which is one of its raw materials
Although various methods of producing iron oxyhydroxide have been reported, reports of methods of producing magnetic powder having a low axial ratio and α-iron oxyhydroxide are hardly found.
粒度が均一な非針状α−オキシ水酸化鉄の製造方法とし
て、例えば特公昭５２−４２４３７号公報では、第一鉄
塩を一旦水酸化第一鉄とし、次に該水酸化第一鉄を酸性
炭酸塩で炭酸第一鉄とした後、酸素含有ガスで酸化し紡
錘状のα−オキシ水酸化鉄を製造している。As a method for producing non-acicular α-iron oxyhydroxide having a uniform particle size, for example, in JP-B-52-42437, a ferrous salt is once used as ferrous hydroxide, and then the ferrous hydroxide is added. After making ferrous carbonate with acidic carbonate, it is oxidized with oxygen-containing gas to produce spindle-shaped α-iron oxyhydroxide.
又、特開昭５７−８８０３６号公報では、炭酸ソーダ等
の炭酸塩水溶液に第一鉄塩を添加し、生成した炭酸第一
鉄の懸濁液を非酸化性状態で数時間撹拌熟成後、PHを調
節しながら酸素含有ガスで酸化し非針状のα−オキシ水
酸化鉄を製造している。Further, in JP-A-57-88036, a ferrous salt is added to an aqueous solution of a carbonate such as sodium carbonate, and the resulting ferrous carbonate suspension is stirred and aged for several hours in a non-oxidizing state. We manufacture non-acicular α-iron oxyhydroxide by oxidizing with oxygen-containing gas while adjusting PH.
（ハ）発明が解決しようとする問題点 上述のように、特公昭５２−４２４３７号公報のα−オ
キシ水酸化鉄の製造方法は、第一鉄塩を一旦水酸化第一
鉄とし、次に炭酸第一鉄に変換する等煩雑な製造方法で
ある。(C) Problems to be Solved by the Invention As described above, in the method for producing α-iron oxyhydroxide disclosed in JP-B-52-42437, the ferrous salt is once made into ferrous hydroxide and then This is a complicated manufacturing method such as conversion to ferrous carbonate.
又、特開昭５７−８８０３６号公報のα−オキシ水酸化
鉄の製造方法も炭酸第一鉄の撹拌による熟成、PHを調節
しながらの酸化が必要である事等これ又煩雑な製造方法
である。Also, the method for producing α-iron oxyhydroxide disclosed in JP-A-57-88036 is a complicated production method such as aging of ferrous carbonate by stirring and oxidation while adjusting PH. is there.
而も、何れのα−オキシ水酸化鉄の製造方法も任意の軸
比を有するα−オキシ水酸化鉄の製造方法を提供するも
のではない。Moreover, none of the methods for producing α-iron oxyhydroxide provides a method for producing α-iron oxyhydroxide having an arbitrary axial ratio.
（ニ）問題点を解決するための手段 本発明者らは、任意の軸比を有するα−オキシ水酸化鉄
の製造方法について鋭意検討の結果、本発明を完成した
ものである。(D) Means for Solving the Problems The present inventors have completed the present invention as a result of earnest studies on a method for producing α-iron oxyhydroxide having an arbitrary axial ratio.
即ち、本発明は、ガス吹き込み管を有する撹拌槽を用
い、炭酸アンモニウム水溶液に硫酸第一鉄等の第一鉄塩
水溶液を非酸化状態で添加して炭酸第一鉄の縣濁液を
得、該炭酸第一鉄縣濁液に２５〜７０℃の温度で、且つ
温度を制御して酸素含有ガスを通気することにより、平
均粒子径が０．４μｍ以下で、軸比が２〜８で、粒度が
均一な低軸比の米粒状乃至紡錘状で、且つ前記の範囲で
所望の軸比を有するα−オキシ水酸化鉄を得ることを特
徴とするα−オキシ水酸化鉄の製造方法に関する。That is, the present invention, using a stirring tank having a gas blowing tube, to obtain a suspension of ferrous carbonate by adding a ferrous sulfate aqueous solution such as ferrous sulfate to the ammonium carbonate aqueous solution in a non-oxidized state, By passing an oxygen-containing gas through the ferrous carbonate suspension at a temperature of 25 to 70 ° C. and controlling the temperature, the average particle diameter is 0.4 μm or less, and the axial ratio is 2 to 8, The present invention relates to a method for producing α-iron oxyhydroxide, which is characterized by obtaining α-iron oxyhydroxide having a low axial ratio of rice grains or a spindle shape with a uniform particle size and having a desired axial ratio within the above range.
反応系の温度は２５〜７０℃である必要があり、２０℃
未満では米粒状乃至紡錘状のα−オキシ水酸化鉄は生成
しない。又、７０℃を越えるとマグネタイトが生成する
ようになる。酸化反応温度を２５〜７５℃の範囲で、一
定の反応温度に制御することにより、生成するα−オキ
シ水酸化鉄の軸比を２〜８の範囲の任意の軸比にする事
ができる。この場合、酸化温度が高くなるにつれて生成
するα−オキシ水酸化鉄の軸比は、高くなる。The temperature of the reaction system needs to be 25 to 70 ° C, 20 ° C
When the amount is less than the above, rice granular or spindle-shaped α-iron oxyhydroxide is not formed. Further, when it exceeds 70 ° C., magnetite is generated. By controlling the oxidation reaction temperature to a constant reaction temperature in the range of 25 to 75 ° C., the axial ratio of the α-iron oxyhydroxide produced can be set to any axial ratio in the range of 2 to 8. In this case, the axial ratio of α-iron oxyhydroxide produced increases as the oxidation temperature increases.
本発明は、アルカリとして炭酸アンモニウムを使用する
為その緩衝作用により系のPH変動が小さい為、均一なα
−オキシ水酸化鉄が生成する。In the present invention, since ammonium carbonate is used as the alkali, the pH fluctuation of the system is small due to its buffering effect, so that a uniform α
-Iron oxyhydroxide is produced.
尚、本発明において炭酸アンモニウムを使用する代りに
炭酸ソーダを使用し、３０〜５０℃で反応したところ、
米粒状乃至紡錘状のα−オキシ水酸化鉄は生成したがそ
の軸比は５であった。In the present invention, sodium carbonate was used instead of ammonium carbonate, and the reaction was carried out at 30 to 50 ° C.,
Rice grain-shaped or spindle-shaped α-iron oxyhydroxide was produced, but its axial ratio was 5.
又、本発明は、生成炭酸第一鉄を撹拌等の操作による長
時間熟成を行う必要はない。Further, in the present invention, it is not necessary to age the produced ferrous carbonate for a long time by an operation such as stirring.
以下、本発明につき詳細に説明する。尚、純粋な炭酸ア
ンモニウムは市販されていないのでアンモニアと重炭酸
アンモニウムを等モル溶解したものを使用した。Hereinafter, the present invention will be described in detail. Since pure ammonium carbonate is not commercially available, a solution obtained by dissolving equimolar amounts of ammonia and ammonium bicarbonate was used.
（ト）発明の効果 本発明によると、形状が米粒状乃至紡錘状で、粒度が均
一で平均粒子径が０．４μｍ以下であり、且つ軸比が２
〜８の範囲の任意の軸比を有するα−オキシ水酸化鉄の
製造が可能である。(G) Effect of the Invention According to the present invention, the shape is rice grain or spindle shape, the particle size is uniform, the average particle size is 0.4 μm or less, and the axial ratio is 2
It is possible to produce α-iron oxyhydroxide with any axial ratio in the range of ˜8.
α−オキシ水酸化鉄の軸比は、炭酸第一鉄を酸素含有ガ
スで酸化する時の温度により制御する事が出来る。温度
が高くなるにつれ生成するα−オキシ水酸化鉄の軸比は
上昇する。The axial ratio of α-iron oxyhydroxide can be controlled by the temperature at which ferrous carbonate is oxidized with an oxygen-containing gas. The axial ratio of α-iron oxyhydroxide formed increases with increasing temperature.
α−オキシ水酸化鉄の粒子径は、生成した炭酸第一鉄の
酸化反応時の酸素分圧と酸素含有ガス量即ち、酸化反応
速度で制御する事が出来る。酸素量が多い程粒子径は小
さくなる。The particle size of α-iron oxyhydroxide can be controlled by the oxygen partial pressure and the oxygen-containing gas amount during the oxidation reaction of the produced ferrous carbonate, that is, the oxidation reaction rate. The larger the amount of oxygen, the smaller the particle size.
又、α−オキシ水酸化鉄の粒子径の分布は、炭酸アンモ
ニウムの濃度により制御する事が可能であり、炭酸アン
モニウムの濃度が０．５モル／１の時、その分布は最も
狭いものとなる。Further, the particle size distribution of α-iron oxyhydroxide can be controlled by the concentration of ammonium carbonate, and when the concentration of ammonium carbonate is 0.5 mol / 1, the distribution becomes the narrowest. .
本発明は、アルカリとして炭酸アンモニウムを使用する
為その緩衝作用により系のPH変動が小さい。In the present invention, ammonium carbonate is used as the alkali, so that the pH fluctuation of the system is small due to its buffering action.
又、本発明は、生成炭酸第一鉄を撹拌等の操作による熟
成を行う必要はない。Further, in the present invention, it is not necessary to age the produced ferrous carbonate by an operation such as stirring.
以下、実施例をもって本発明を更に詳細に説明する。
尚、純粋な炭酸アンモニウムは市販されていないのでア
ンモニアと重炭酸アンモニウムを等モル溶解したものを
使用した。Hereinafter, the present invention will be described in more detail with reference to Examples.
Since pure ammonium carbonate is not commercially available, a solution obtained by dissolving equimolar amounts of ammonia and ammonium bicarbonate was used.
（ヘ）実施例 実施例１ 撹拌機付１．５の反応容器に、窒素ガスの流通下濃度
１モル／の炭酸アンモニウム溶液０．５を仕込み撹
拌する。この溶液に温度３０℃で濃度０．４モル／の
硫酸第一鉄溶液０．５をゆっくり滴下する。次に生成
した炭酸第一鉄の懸濁液を３０℃で３０分間保持した
後、空気を３０℃で３．２／minの割合で吹込む。酸
化反応は６Hrで終了した。得られたα−オキシ水酸化鉄
は米粒状で軸比２．５、長軸径０．１５μｍの均一な粒
子であった。第１図は、その電子顕微鏡写真（倍率４０
０００倍）である。(F) Examples Example 1 A reaction vessel equipped with a stirrer, 1.5, is charged with 0.5 mol of ammonium carbonate solution having a concentration of 1 mol / nitrogen gas under stirring and stirred. 0.5 mol of ferrous sulfate solution having a concentration of 0.4 mol / mol is slowly added dropwise to this solution at a temperature of 30 ° C. Next, the suspension of ferrous carbonate thus produced is held at 30 ° C. for 30 minutes, and then air is blown at 30 ° C. at a rate of 3.2 / min. The oxidation reaction was completed at 6 hours. The obtained α-iron oxyhydroxide was a rice grain-like uniform particle having an axial ratio of 2.5 and a major axis diameter of 0.15 μm. Figure 1 shows the electron micrograph (magnification 40
000 times).
実施例２ 酸化反応を５０℃で５時間行った以外は、実施例１と同
様に処理した。得られたα−オキシ水酸化鉄は紡錘状で
軸比５長軸径０．２５μｍの均一な粒子であった。第２
図は、その電子顕微鏡写真（倍率４００００倍）であ
る。Example 2 The same treatment as in Example 1 was carried out except that the oxidation reaction was carried out at 50 ° C. for 5 hours. The obtained α-iron oxyhydroxide was a spindle-shaped, uniform particle having an axial ratio of 5 and a major axis diameter of 0.25 μm. Second
The figure is an electron micrograph (magnification: 40,000 times).
実施例３ 空気吹き込み量を６．４／minとし酸化反応を２．５
時間行った以外は、実施例２と同様に処理した。得られ
たα−オキシ水酸化鉄は紡錘状で軸比５長軸径０．１５
μｍの均一な粒子であった。第３図は、その電子顕微鏡
写真（倍率４００００倍）である。Example 3 The amount of air blown was 6.4 / min and the oxidation reaction was 2.5.
The same treatment as in Example 2 was carried out except that the treatment was carried out for a time. The obtained α-iron oxyhydroxide has a spindle shape and an axial ratio of 5 major axis diameter of 0.15.
It was a uniform particle of μm. FIG. 3 is an electron micrograph (magnification: 40,000 times).
実施例４ 酸化反応を７０℃で５時間行った以外は、実施例１と同
様に処理した。得られたα−オキシ水酸化鉄は紡錘状で
軸比８長軸径０．３５μｍの均一な粒子であった。第４
図は、その電子顕微鏡写真（倍率４００００倍）であ
る。Example 4 The same treatment as in Example 1 was carried out except that the oxidation reaction was carried out at 70 ° C. for 5 hours. The obtained α-iron oxyhydroxide was a spindle-shaped uniform particle having an axial ratio of 8 major axis diameter of 0.35 μm. Fourth
The figure is an electron micrograph (magnification: 40,000 times).
比較例１ 酸化反応を２０℃で８時間行った以外は、実施例１と同
様に処理した。得られたα−オキシ水酸化鉄は不均一で
無定形な粒子であった。Comparative Example 1 The same treatment as in Example 1 was carried out except that the oxidation reaction was carried out at 20 ° C. for 8 hours. The obtained α-iron oxyhydroxide was inhomogeneous and amorphous particles.
比較例２ ２モル／の炭酸アンモニウムを使用した以外は、実施
例１と同様に処理した。得られたα−オキシ水酸化鉄は
軸比２長軸径０．３μｍであったが、粒子径分布が広か
った。Comparative Example 2 The same treatment as in Example 1 was carried out except that 2 mol / ammonium carbonate was used. The obtained α-iron oxyhydroxide had an axial ratio of 2 and a major axis diameter of 0.3 μm, but had a wide particle size distribution.
図１、図２、図３、図４は、それぞれ実施例１、実施例
２、実施例３、実施例４におけるα−オキシ水酸化鉄の
電子顕微鏡写真（４００００倍）である。1, FIG. 2, FIG. 3, and FIG. 4 are electron micrographs (× 40,000) of α-iron oxyhydroxide in Example 1, Example 2, Example 3, and Example 4, respectively.
───────────────────────────────────────────────────── フロントページの続き 審判の合議体 審判長 渡辺 順之 審判官 足立 法也 審判官 徳永 英男 (56)参考文献 特開 昭59−232922（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page Judgment panel Judgment Chair Judge Watanabe Judge Judge Adachi Hoya Adachi Judge Hideo Tokunaga (56) References JP 59-232922 (JP, A)
Claims (2)
酸アンモニウム水溶液に硫酸第一鉄等の第一鉄塩水溶液
を非酸化状態で添加して炭酸第一鉄の縣濁液を得、該炭
酸第一鉄縣濁液に２５〜７０℃の温度で、且つ温度を制
御して酸素含有ガスを通気することにより、平均粒子径
が０．４μｍ以下で、軸比が２〜８で、粒度が均一な低
軸比の米粒状乃至紡錘状で、且つ前記の範囲で所望の軸
比を有するα−オキシ水酸化鉄を得ることを特徴とする
α−オキシ水酸化鉄の製造方法。1. A stirrer having a gas blowing tube is used to add an aqueous solution of ferrous salt such as ferrous sulfate in a non-oxidized state to an aqueous solution of ammonium carbonate to obtain a suspension of ferrous carbonate. By passing an oxygen-containing gas through the ferrous carbonate suspension at a temperature of 25 to 70 ° C. and controlling the temperature, the average particle size is 0.4 μm or less, the axial ratio is 2 to 8, and the particle size is Is a granular or spindle-shaped rice having a uniform low axial ratio, and α-iron oxyhydroxide having a desired axial ratio within the above range is obtained.
０．６モル／１、硫酸第一等の第一鉄塩水溶液の濃度が
０．０５〜０．４モル／１であり、且つ反温度が２５〜
７０℃である事を特徴とする特許請求の範囲第一項記載
の製造方法。2. The concentration of the ammonium carbonate aqueous solution is 0.3-.
0.6 mol / 1, the concentration of a ferrous salt aqueous solution such as primary sulfuric acid is 0.05 to 0.4 mol / 1, and the counter temperature is 25 to
The method according to claim 1, wherein the temperature is 70 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60014068A JPH0665611B2 (en) | 1985-01-28 | 1985-01-28 | Method for producing α-iron oxyhydroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60014068A JPH0665611B2 (en) | 1985-01-28 | 1985-01-28 | Method for producing α-iron oxyhydroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61174119A JPS61174119A (en) | 1986-08-05 |
| JPH0665611B2 true JPH0665611B2 (en) | 1994-08-24 |
Family
ID=11850780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60014068A Expired - Lifetime JPH0665611B2 (en) | 1985-01-28 | 1985-01-28 | Method for producing α-iron oxyhydroxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0665611B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0726878B1 (en) * | 1993-11-01 | 1999-05-12 | Minnesota Mining And Manufacturing Company | Process for making goethite |
| DE10010940A1 (en) * | 2000-03-06 | 2001-09-13 | Bayer Ag | Production of iron oxide yellow, useful for pigmenting building material, e.g. concrete, or plastics or as disperse dye, involves adding iron-II sulfate or chloride solution to alkaline solution and oxidation under specified conditions |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59232922A (en) * | 1983-06-15 | 1984-12-27 | Dainippon Ink & Chem Inc | Manufacture of spindle-shaped goethite having high axial ratio |
-
1985
- 1985-01-28 JP JP60014068A patent/JPH0665611B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61174119A (en) | 1986-08-05 |
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