JPH0587448B2 - - Google Patents
Info
- Publication number
- JPH0587448B2 JPH0587448B2 JP12709586A JP12709586A JPH0587448B2 JP H0587448 B2 JPH0587448 B2 JP H0587448B2 JP 12709586 A JP12709586 A JP 12709586A JP 12709586 A JP12709586 A JP 12709586A JP H0587448 B2 JPH0587448 B2 JP H0587448B2
- Authority
- JP
- Japan
- Prior art keywords
- ferric oxide
- oxide particles
- particles
- hydrated ferric
- orthoferrite
- 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 - Fee Related
Links
- 239000000843 powder Substances 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 239000003513 alkali Substances 0.000 claims description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 13
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000010419 fine particle Substances 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 5
- 239000002245 particle Substances 0.000 description 62
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 229910000859 α-Fe Inorganic materials 0.000 description 6
- 229910052595 hematite Inorganic materials 0.000 description 5
- 239000011019 hematite Substances 0.000 description 5
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 5
- 239000006249 magnetic particle Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000007900 aqueous suspension Substances 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910003153 β-FeOOH Inorganic materials 0.000 description 3
- 229910002588 FeOOH Inorganic materials 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Compounds Of Iron (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、β−含水酸化第二鉄微粒子粉末の製
造法に関するものであり、詳しくは、高濃度反応
であつて且つ、短時間裡の反応が可能であること
に起因して生産性を高めることができる反応によ
り、粒度が微細なβ−含水酸化第二鉄微粒子粉末
を工業的、経済的に有利に提供することを目的と
する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing β-hydrated ferric oxide fine particle powder, and more specifically, it involves a high concentration reaction and a short time reaction. The object of the present invention is to provide industrially and economically advantageous β-hydrous ferric oxide fine particle powder with fine particle size through a reaction that can increase productivity due to the reaction being possible.
本発明に係るβ−含水酸化第二鉄微粒子粉末の
主な用途は、塗料用顔料粉末、ゴム・プラスチツ
ク用着色剤、磁性粒子粉末用出発原料、フエライ
ト用原料粉末及び触媒等である。 The main uses of the β-hydrated ferric oxide fine particles of the present invention include pigment powder for paints, colorants for rubber and plastics, starting materials for magnetic particle powders, raw material powders for ferrite, catalysts, etc.
β−含水酸化第二鉄粒子粉末は、赤褐色を呈し
ている為、顔料とビヒクルとを混合して塗料を製
造する際の塗料用顔料粉末として使用されてお
り、殊に、500Å程度以下の微粒子は紫外線吸収
効果並びに透明性を発現する等の特徴がある為、
紫外線吸収フイルム用透明性顔料粉末として使用
れており、更に、ゴム、プラスチツクに混練・分
散して着色剤としても使用されている。
Since β-hydrated ferric oxide particles have a reddish-brown color, they are used as pigment powders for paints when mixing pigments and vehicles to produce paints. Because it has characteristics such as ultraviolet absorption effect and transparency,
It is used as a transparent pigment powder for ultraviolet absorbing films, and is also used as a coloring agent by kneading and dispersing it into rubbers and plastics.
次に、β−含水酸化第二鉄粒子粉末は、磁気記
録用磁性粒子粉末を製造する際の出発原料として
も使用されている。即ち、針状晶マグヘマイト粒
子粉末、針状晶マグネタイト粒子粉末等の磁性粒
子粉末はβ−含水酸化第二鉄粒子粉末を加熱脱水
した後、還元するか、更に酸化することにより製
造されている。 Next, the β-hydrated ferric oxide particles are also used as a starting material when producing magnetic particles for magnetic recording. That is, magnetic particles such as acicular maghemite particles and acicular magnetite particles are produced by heating and dehydrating β-hydrated ferric oxide particles and then reducing or further oxidizing them.
また、β−含水酸化第二鉄粒子粉末は、フエラ
イト用原料粉末としても、使用されている。 Moreover, the β-hydrated ferric oxide particle powder is also used as a raw material powder for ferrite.
即ち、フエライトは、β−含水酸化第二鉄粒子
粉末等の主原料とBa，Sr，Ca若しくはPb化合物
等、又は、Zn，Mn，Ni，Mg、若しくはCu化合
物等の副原料とを混合し、加熱焼成、粉砕するこ
とにより製造されている。 That is, ferrite is produced by mixing main raw materials such as β-hydrated ferric oxide particles with auxiliary raw materials such as Ba, Sr, Ca, or Pb compounds, or Zn, Mn, Ni, Mg, or Cu compounds. It is manufactured by heating, baking, and pulverizing.
更に、β−含水酸化第二鉄粒子粉末は、触媒と
しても使用されている。 Additionally, β-hydrated ferric oxide particles have also been used as catalysts.
上記した通り、β−含水酸化第二鉄粒子粉末
は、様々の分野で使用されているが、いずれの分
野においても共通して要求される粒子粉末の特性
は、粒度の微細なβ−含水酸化第二鉄である。 As mentioned above, β-hydrous ferric oxide particles are used in various fields, but the characteristics commonly required in all fields are It is the second railway.
即ち、塗料の製造においては塗料化に際して、
ゴム・プラスチツクの製造においては混練に際し
て、β−含水酸化第二鉄粒子粉末を均一、且つ、
容易に分散させることが必要であり、その為に
は、できるだけ微細なβ−含水酸化第二鉄粒子粉
末が要求される。 In other words, in the production of paint, when turning it into a paint,
In the production of rubber and plastics, during kneading, β-hydrous ferric oxide particle powder is uniformly and
It is necessary to easily disperse the powder, and for that purpose, β-hydrous ferric oxide particles as fine as possible are required.
次に、磁気記録用磁性粒子粉末としては、磁気
記録媒体の低ノイズ化の為には、出来るだけ微粒
子であることが必要であり、出発原料であるβ−
含水酸化第二鉄も当然、微粒子であることが要求
される。 Next, magnetic particles for magnetic recording must be as fine as possible in order to reduce the noise of magnetic recording media, and the starting material β-
Naturally, the hydrous ferric oxide is also required to be fine particles.
また、フエライトの製造にあたつては、主原料
であるβ−含水酸化第二鉄微子粉末の粒度が微細
化すればする程、原料の均一混合が可能となり、
その結果、フエライト化反応の進行が容易とな
る。 In addition, when manufacturing ferrite, the finer the particle size of the β-hydrated ferric oxide fine powder, which is the main raw material, the more uniform the raw materials can be mixed.
As a result, the ferritization reaction progresses easily.
この事実は、例えば、粉体工学第７巻第８号
（1970年）第46頁の「フエライト化反応は粒度が
小さい程反応性は増大する。」なる記載から明ら
かである。 This fact is clear, for example, from the statement in Powder Engineering Vol. 7, No. 8 (1970), page 46, "The smaller the particle size of the ferrite reaction, the greater the reactivity."
更に、β−含水酸化第二鉄粒子粉末を触媒とし
て使用するに際しては、粒子が微細化すればする
程、触媒活性が向上する。 Furthermore, when using the β-hydrated ferric oxide particles as a catalyst, the finer the particles, the better the catalytic activity.
従来、β−含水酸化第二鉄粒子粉末の製造法と
しては、大別して二通りの方法が知られている。 Conventionally, methods for producing β-hydrated ferric oxide particles are broadly classified into two types.
その一つは、塩化第二鉄水溶液を加水分解する
方法であり、他の一つは、塩化第一鉄水溶液に酸
素含有ガスを通気して酸化反応を行うものであ
る。 One of them is a method of hydrolyzing a ferric chloride aqueous solution, and the other is a method of performing an oxidation reaction by passing an oxygen-containing gas through the ferrous chloride aqueous solution.
粒度が微細なβ−含水酸化第二鉄粒子粉末は、
現在最も要求されているところであるが、先ず、
反応鉄濃度と生成するβ−含水酸化第二鉄粒子の
粒度との関係について言えば、次の通りである。
上記した通りの公知方法による場合には、塩化鉄
の溶液濃度が薄くなる程、生成するβ−含水酸化
第二鉄粒子の粒度が微細化する傾向にあり、例え
ば、特公昭54−24918号公報の「第２図」に示さ
れている通り、塩化鉄の溶液濃度がそれぞれ0.5
モル／、0.3モル／及び0.1モル／の場合、
0.6μm程度、0.4μm程度及び0.3μm程度のβ−含
水酸化第二鉄粒子が得られており、塩化鉄の溶液
濃度が殊に、0.5モル／程度以上の高濃度反応
によつては、微細な、殊に、約0.1μm程度以下の
β−含水酸化第二鉄粒子粉末を得ることは困難で
あつた。
β-hydrous ferric oxide particle powder with fine particle size is
This is currently the most requested area, but first of all,
The relationship between the reaction iron concentration and the particle size of the generated β-hydrated ferric oxide particles is as follows.
When using the above-mentioned known method, the smaller the iron chloride solution concentration, the finer the particle size of the β-hydrated ferric oxide particles that are produced. As shown in "Figure 2", the concentration of iron chloride solution is 0.5.
In the case of mol/, 0.3 mol/ and 0.1 mol/,
β-hydrated ferric oxide particles of approximately 0.6 μm, 0.4 μm, and 0.3 μm have been obtained, and in some cases, the concentration of iron chloride in the solution is particularly high, such as 0.5 mol/min or more. In particular, it has been difficult to obtain β-hydrated ferric oxide particles having a particle size of approximately 0.1 μm or less.
従来、塩化鉄の溶液濃度が高い領域で微細なβ
−含水酸化第二鉄粒子を得る方法として前出特公
昭54−24918号公報に記載の方法がある。 Conventionally, fine β
- As a method for obtaining hydrous ferric oxide particles, there is a method described in the aforementioned Japanese Patent Publication No. 54-24918.
即ち、特公昭54−24918号公報に記載の方法は、
ホウ酸もしくはその塩を含む水溶液中で塩化第二
鉄を加熱下に加水分解するものである。しかしな
がら、この方法による場合には、ホウ酸もしくは
その塩の添加量が増加する程、生成するβ−含水
酸化第二鉄粒子の粒度が小さくなる傾向にあり、
塩化鉄の溶液濃度が0.5モル／程度の高濃度反
応で0.1μm程度以下の微細なβ−含水酸化第二鉄
粒子を得ようとすれば、ホウ酸もしくはその塩を
0.15モル／以上と多量に添加しなければなら
ず、従つて、生成するβ−含水酸化第二鉄粒子中
には不純物としてのホウ酸もしくはその塩が多量
に含有され、前述した各種分野における原料粉末
としては品質特性上好ましくない。 That is, the method described in Japanese Patent Publication No. 54-24918 is as follows:
Ferric chloride is hydrolyzed under heating in an aqueous solution containing boric acid or its salt. However, when using this method, the particle size of the generated β-hydrated ferric oxide particles tends to become smaller as the amount of boric acid or its salt added increases.
If you want to obtain fine β-hydrated ferric oxide particles of about 0.1 μm or less in a high-concentration reaction where the iron chloride solution concentration is about 0.5 mol/min, boric acid or its salt should be used.
A large amount of boric acid or its salt must be added as an impurity in the β-hydrated ferric oxide particles that are produced. It is unfavorable as a powder due to its quality characteristics.
次に、β−含水酸化第二鉄粒子の反応時間につ
いて言えば、上記した公知方法による場合には、
通常数時間以上が必要である。 Next, regarding the reaction time of β-hydrated ferric oxide particles, when using the above-mentioned known method,
Usually several hours or more are required.
そこで、不純物の原因となる添加剤を添加する
ことなく高濃度反応であつて、且つ、短時間裡の
反応により工業的、経済的に有利に微細なβ−含
水酸化第二鉄粒子を得る為の技術手段の確立が強
く要望されている。 Therefore, in order to obtain fine β-hydrous ferric oxide particles industrially and economically advantageously through a high-concentration reaction and a short reaction time without adding additives that cause impurities. There is a strong demand for the establishment of technical means for this.
本発明者は、不純物の原因となる添加剤を添加
することなく高濃度反応であつて、且つ、短時間
裡の反応により、工業的、経済的に有利に微細な
β−含水酸化第二鉄粒子を得るべく種々検討を重
ねた結果、本発明に到達したのである。
The present inventor has discovered that fine β-hydrated ferric oxide can be produced industrially and economically by a high-concentration reaction without the addition of additives that cause impurities, and a short reaction time. As a result of various studies to obtain particles, the present invention was arrived at.
即ち、本発明は、アルカリオルソフエライトと
該アルカリオルソフエライト中の鉄に対し等モル
以上のハロゲン化物とを含むpH2以下の水溶液を
70℃以上の温度で加熱して上記アルカリオルソフ
エライトを加水分解することによりβ−含水酸化
第二鉄微粒子を生成させることよりなるβ−含水
酸化第二鉄粒子粉末の製造法である。 That is, the present invention provides an aqueous solution with a pH of 2 or less containing an alkali orthoferrite and a halide in an amount equal to or more than the same mole relative to iron in the alkali orthoferrite.
This is a method for producing β-hydrated ferric oxide particle powder, which comprises generating β-hydrated ferric oxide fine particles by hydrolyzing the alkali orthoferrite by heating at a temperature of 70° C. or higher.
先ず、本発明において最も重要な点は、鉄原料
としてアルカリオルソフエライトを用いた場合に
は、微細な、殊に、約0.1μm以下のβ−含水酸化
第二鉄粒子を、所望する場合には約0.01μm程度
の超微細なβ−含水酸化第二鉄粒子までもを得る
ことができる点である。
First, the most important point in the present invention is that when alkali orthoferrite is used as the iron raw material, fine β-hydrous ferric oxide particles, especially about 0.1 μm or less, can be formed if desired. The point is that even ultrafine β-hydrated ferric oxide particles of about 0.01 μm can be obtained.
本発明において、微細なβ−含水酸化第二鉄粒
子が得られる理由について、本発明者はβ−含水
酸化第二鉄粒子が短時間裡に生成することから、
β−含水酸化第二鉄粒子の生成反応速度が非常に
早いことによるものと考えている。 In the present invention, the reason why fine β-hydrated ferric oxide particles are obtained is that the β-hydrated ferric oxide particles are generated in a short period of time.
It is believed that this is due to the extremely fast production reaction rate of β-hydrated ferric oxide particles.
本発明においては、鉄原料であるアルカリオル
ソフエライトが固体えあることに起因して高濃度
反応、殊に、鉄濃度が1.0モル／以上の反応が
可能であつて、且つ、数時間程度以下の短時間裡
の反応が可能であることに起因して生産性を高め
ることがきる反応により、β−含水酸化第二鉄粒
子を工業的、経済的に有利に得ることができ、ま
た、不純物の原因となる添加剤を添加しない為、
品質特性上好ましいβ−含水酸化第二鉄粒子を得
ることができる。 In the present invention, since the alkali orthoferrite, which is the iron raw material, is solid, it is possible to perform a high concentration reaction, especially a reaction with an iron concentration of 1.0 mol/or more, and a reaction time of several hours or less. β-hydrated ferric oxide particles can be industrially and economically advantageously obtained by a reaction that can be carried out in a short period of time and can increase productivity. Because no additives are added that may cause
β-hydrated ferric oxide particles having favorable quality characteristics can be obtained.
次に、本発明方法実施にあたつての諸条件につ
いて述べる。 Next, various conditions for carrying out the method of the present invention will be described.
本発明において使用されるアルカリオルソフエ
ライトとしては、Na，Ｋ，Li等のオルソフエラ
イトがある。 The alkali orthoferrite used in the present invention includes orthoferrites such as Na, K, and Li.
アルカリオルソフエライトは、いずれの方法に
より得られたものでもよく、例えば、酸化第二鉄
と炭酸アルカリとの混合物を700℃以上の温度で
加熱焼成るすことにより得ることができる。 Alkali orthoferrite may be obtained by any method, for example, by heating and calcining a mixture of ferric oxide and alkali carbonate at a temperature of 700° C. or higher.
本発明におけるハロゲン化物水溶液としては、
HCl，NaCl，KCl，KBr，NaBr，KI及びNal等
の水溶液を使用することができる。 The halide aqueous solution in the present invention includes:
Aqueous solutions such as HCl, NaCl, KCl, KBr, NaBr, KI and Nal can be used.
ハロゲン化物の量は、アルカリオルソフエライ
ト中の鉄に対し等モル以上である。 The amount of halide is at least equimolar to iron in the alkali orthoferrite.
等モル未満である場合には、β−含水酸化第二
鉄粒子中にヘマタイト粒子が混在してくる。 If the amount is less than equimolar, hematite particles will be mixed in the β-hydrated ferric oxide particles.
本発明におけるアルカリオルソフエライトを含
むハロゲン化物水溶液のpHは、２以下となるよ
うに調整される。 The pH of the aqueous halide solution containing alkali orthoferrite in the present invention is adjusted to 2 or less.
pHが２を越える場合には、β−含水酸化第二
鉄粒子中にヘマタイト粒子が混在してくる。 When the pH exceeds 2, hematite particles are mixed in the β-hydrated ferric oxide particles.
pHの調整は、塩酸、硫酸、酢酸等を用いて行
うことができる。 Adjustment of pH can be performed using hydrochloric acid, sulfuric acid, acetic acid, etc.
本発明における反応温度は、70℃以上である。 The reaction temperature in the present invention is 70°C or higher.
70℃未満である場合には、加水分解反応が生起
せず、β−含水酸化第二鉄粒子を生成させること
ができない。70℃以上であればβ−含水酸化第二
鉄粒子を生成させることができるが、100℃以上
である場合には、オートクレーブ等の特殊な装置
が必要であり、工業性、経済性を考慮すれば100
℃以下で十分である。 If the temperature is lower than 70°C, no hydrolysis reaction occurs and β-hydrated ferric oxide particles cannot be produced. β-hydrous ferric oxide particles can be generated at temperatures above 70°C, but when temperatures are above 100°C, special equipment such as an autoclave is required, and industrial efficiency and economic efficiency must be considered. 100
℃ or less is sufficient.
〔実施例〕 次に、実施例により、本発明を説明する。〔Example〕 Next, the present invention will be explained by examples.
尚、以下の実施例における粒子の長軸、軸比
（長軸：短軸）は、いずれも電子顕微鏡写真から
測定した数値の平均値で示した。 In addition, the long axis and axial ratio (long axis: short axis) of the particles in the following examples are both shown as average values of numerical values measured from electron micrographs.
実施例 １
酸化第二鉄粒子2000gとNa2CO32000gとの混合
物を800℃で１時間加熱焼成した後、水洗するこ
とによりうぐいす色を呈した焼成物を得た。この
うぐいす色を呈した焼成物は、Ｘ線回折の結果、
ナトリウムオルソフエライト（NaFeO2）であつ
た。Example 1 A mixture of 2,000 g of ferric oxide particles and 2,000 g of Na 2 CO 3 was fired at 800° C. for 1 hour, and then washed with water to obtain a fired product exhibiting a light blue color. As a result of X-ray diffraction, this light brown fired product was found to be
It was sodium orthoferrite (NaFeO 2 ).
上記ナトリウムオルソフエライト222gを含む
水懸濁液中に5N−HCl水溶液400mlを添加混合し
た後、水を加えて全容を１（鉄濃度は2.0モ
ル／に該当する。）とし（この時のpHは0.7で
あつた。）、80℃の温度で10分間攪拌することによ
り赤褐色沈澱を生成させた。この時のpHは2.8で
あつた。 After adding and mixing 400 ml of 5N-HCl aqueous solution to the aqueous suspension containing 222 g of the above sodium orthoferrite, water was added to bring the total volume to 1 (the iron concentration corresponds to 2.0 mol/) (at this time the pH was 0.7), and a reddish brown precipitate was produced by stirring at a temperature of 80°C for 10 minutes. The pH at this time was 2.8.
この赤褐色沈澱は、図１に示すＸ線回折に示さ
れる通り、β−FeOOHであり、図２に示す電子
顕微鏡写真（×50000）から明らかな通り、長軸
0.03μm、軸比（長軸：短軸）５：１の針状粒子
であつた。 This reddish-brown precipitate is β-FeOOH, as shown in the X-ray diffraction shown in Figure 1, and as is clear from the electron micrograph (×50000) shown in Figure 2, the long axis
They were acicular particles of 0.03 μm and an axial ratio (long axis: short axis) of 5:1.
実施例 ２
実施例１で得られたナトリウムオルソフエライ
トを用い、該ナトリウムオルソフエライト222g
を含む水懸濁液中にNaCl120g及び5N−H2SO4水
溶液400mlを添加混合した後、水を加えて全容を
１（鉄濃度は2.0モル／に該当する。）とし
（この時のpHは0.7であつた。）、80℃の温度で10
分間攪拌することにより赤褐色沈澱を生成させ
た。この時のpHは2.6であつた。Example 2 Using the sodium orthoferrite obtained in Example 1, 222 g of the sodium orthoferrite
After adding and mixing 120 g of NaCl and 400 ml of 5N-H 2 SO 4 aqueous solution to an aqueous suspension containing 0.7), 10 at a temperature of 80℃
A reddish brown precipitate was formed by stirring for a minute. The pH at this time was 2.6.
この赤褐色沈澱は、Ｘ線回折の結果、β−
FeOOHであり、図３に示す電子顕微鏡写真（×
50000）から明らかな通り、長軸0.02μm、軸比
（長軸：短軸）５：１の針状粒子であつた。 As a result of X-ray diffraction, this reddish brown precipitate was found to be β-
It is FeOOH, and the electron micrograph shown in Figure 3 (×
50000), they were acicular particles with a long axis of 0.02 μm and an axial ratio (long axis: short axis) of 5:1.
実施例 ３
実施例１で得られたナトリウムオルソフエライ
トを用い、該ナトリウムオルソフエライト444g
を含む水懸濁液中に1ON−HCl水溶液600mlを添
加混合した後、水を加えて全容を１（鉄濃度は
4.0モル／に該当する。）とし（この時のpHは
0.5であつた。）、90℃の温度で10分間攪拌するこ
とにより赤褐色沈澱を生成させた。この時のpH
は5.1であつた。Example 3 Using the sodium orthoferrite obtained in Example 1, 444 g of the sodium orthoferrite
After adding and mixing 600 ml of 1ON-HCl aqueous solution to the aqueous suspension containing
This corresponds to 4.0 mol/. ) (at this time the pH is
It was 0.5. ), a reddish-brown precipitate was produced by stirring for 10 minutes at a temperature of 90°C. pH at this time
was 5.1.
この赤褐色沈澱は、Ｘ線回折の結果、β−
FeOOHであり、電子顕微鏡観察の結果、長軸
0.07μm、軸比（長軸：短軸）６：１の針状粒子
であつた。 As a result of X-ray diffraction, this reddish brown precipitate was found to be β-
It is FeOOH, and as a result of electron microscopy observation, the long axis
They were acicular particles with a diameter of 0.07 μm and an axial ratio (long axis: short axis) of 6:1.
比較例 １
ナトリウムオルソフエライトを含む水懸濁液中
に5N−CH3COOH水溶液300ml及びNaCl180gを
添加混合した後、水を加えて全容を１とした
後、H2SO4を添加してpH2.5とした以外は、実施
例１と同様にして赤褐色沈澱を生成させた。Comparative Example 1 After adding and mixing 300 ml of 5N-CH 3 COOH aqueous solution and 180 g of NaCl to an aqueous suspension containing sodium orthoferrite, water was added to bring the total volume to 1, and then H 2 SO 4 was added to bring the pH to 2. A reddish brown precipitate was produced in the same manner as in Example 1 except that the value was changed to 5.
この赤褐色沈澱は、図４に示すＸ線回折に示す
通り、β−FeOOH粒子中にヘマタイト粒子が混
在するものであつた。 As shown in the X-ray diffraction shown in FIG. 4, this reddish brown precipitate contained hematite particles mixed in β-FeOOH particles.
図４中、ピークＡはβ−FeOOHのピークを示
し、ピークＢはヘマタイトのピークを示す。 In FIG. 4, peak A indicates the peak of β-FeOOH, and peak B indicates the peak of hematite.
比較例 ２
反応温度を65℃とした以外は、実施例１と同様
にして30分間攪拌したが、うぐいす色のナトリウ
ムオルソフエライトが水溶液中に懸濁したままで
あり何ら変化もなかつた。Comparative Example 2 The mixture was stirred for 30 minutes in the same manner as in Example 1 except that the reaction temperature was 65°C, but the light blue sodium orthoferrite remained suspended in the aqueous solution and no change occurred.
本発明におけるβ−含水酸化第二鉄粒子粉末の
製造法によれば、前出実施例に示した通り、鉄原
料としてアルカリオルソフエライトを用いること
に起因して反応速度が早いことにより、微細な、
殊に、0.1μm以下のβ−含水酸化第二鉄粒子を得
ることができるので、塗料用顔料粉末、ゴム・プ
ラスチツク用着色剤、磁性粒子粉末用出発原料、
フエライト用原料粉末及び触媒として好適であ
る。
According to the method for producing β-hydrated ferric oxide particles of the present invention, as shown in the previous example, the reaction rate is fast due to the use of alkali orthoferrite as the iron raw material, so fine particles are produced. ,
In particular, β-hydrated ferric oxide particles of 0.1 μm or less can be obtained, so they can be used as pigment powders for paints, colorants for rubber and plastics, starting materials for magnetic particle powders,
Suitable as raw material powder and catalyst for ferrite.
また、本発明においては、高濃度反応であつ
て、且つ、短時間裡の反応が可能であることに起
因して生産性を高めることができる反応により、
工業的、経済的に有利にβ−含水酸化第二鉄粒子
を得ることができる。 In addition, in the present invention, the reaction can be performed at a high concentration and in a short period of time, thereby increasing productivity.
β-hydrated ferric oxide particles can be obtained industrially and economically advantageously.
図１は実施例１で得られたβ−含水酸化第二鉄
粒子のＸ線回折図である。図１中、ピークＡはβ
−含水酸化第二鉄を示す。図２及び図３は、いず
れもβ−含水酸化第二鉄粒子の粒子構造を示す電
子顕微鏡写真（×50000）であり、それぞれ、実
施例１及び実施例２で得られたβ−含水酸化第二
鉄粒子粉末である。図４は、比較例１で得られた
粒子粉末のＸ線回折図である。
図４中、ピークＡはβ−含水酸化第二鉄、ピー
クＢはヘマタイトを示す。
FIG. 1 is an X-ray diffraction diagram of β-hydrated ferric oxide particles obtained in Example 1. In Figure 1, peak A is β
- indicates hydrated ferric oxide. 2 and 3 are electron micrographs (×50000) showing the particle structure of β-hydrated ferric oxide particles, and they are the β-hydrated ferric oxide particles obtained in Example 1 and Example 2, respectively. It is a di-iron particle powder. FIG. 4 is an X-ray diffraction diagram of the particles obtained in Comparative Example 1. In FIG. 4, peak A indicates β-hydrated ferric oxide, and peak B indicates hematite.
Claims (1)
ソフエライト中の鉄に対し等モル以上のハロゲン
化物とを含むpH2以下の水溶液を70℃以上の温度
で加熱して上記アルカリオルソフエライトを加水
分解することによりβ−含水酸化第二鉄微粒子を
生成させることを特徴とするβ−含水酸化第二鉄
微粒子粉末の製造法。1. Beta-hydrated by heating an aqueous solution with a pH of 2 or less containing an alkali orthoferrite and a halide in an amount equal to or more than the same mole relative to iron in the alkali orthoferrite at a temperature of 70°C or higher to hydrolyze the alkali orthoferrite. A method for producing a β-hydrated ferric oxide fine particle powder, which comprises producing ferric oxide fine particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12709586A JPS62283822A (en) | 1986-05-31 | 1986-05-31 | Production of fine beta-ferric oxide hydrate particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12709586A JPS62283822A (en) | 1986-05-31 | 1986-05-31 | Production of fine beta-ferric oxide hydrate particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62283822A JPS62283822A (en) | 1987-12-09 |
| JPH0587448B2 true JPH0587448B2 (en) | 1993-12-16 |
Family
ID=14951459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12709586A Granted JPS62283822A (en) | 1986-05-31 | 1986-05-31 | Production of fine beta-ferric oxide hydrate particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62283822A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4058822B2 (en) * | 1997-09-30 | 2008-03-12 | 住友金属鉱山株式会社 | Selective permeable membrane coating solution, selective permeable membrane and selective permeable multilayer membrane |
| DE10221310A1 (en) * | 2002-05-14 | 2003-12-11 | Trespaphan Gmbh | Highly active beta nucleation additive for polypropylene |
-
1986
- 1986-05-31 JP JP12709586A patent/JPS62283822A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62283822A (en) | 1987-12-09 |
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